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  • Computational Chemistry and Molecular Modeling  (8,042)
  • Physical Chemistry  (3,728)
  • Bone
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Skeletal radiology 29 (2000), S. 548-552 
    ISSN: 1432-2161
    Keywords: Key words Melorheostosis ; Dysplasia ; Bone ; Lower extremity ; Radiographs ; Specimen radiographs
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Melorheostosis is an unusual mesenchymal dysplasia, which commonly presents on radiographs as longitudinal bars of hyperostosis in osseous structures. We present a case of melorheostosis in the lower extremity of a 20-year-old woman for which detailed radiologic– pathologic correlation was achieved due to amputation of the involved limb.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Pediatric nephrology 14 (2000), S. 629-635 
    ISSN: 1432-198X
    Keywords: Key words Histomorphometry ; In situ hybridization histochemistry ; Molecular morphometry ; Immunohistochemistry ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Quantitative histomorphometric assessment of bone biopsies represents a powerful and informative method for the study of metabolic bone diseases. It is the gold standard against which the noninvasive ”diagnostic” markers of bone metabolism as well as newly available therapeutic modalities are tested. With the rapid progress in technology of molecular biology, identification of systemic and local biomolecules known to regulate bone metabolism can now be achieved. The study of localization, levels of expression, and synthesis of these factors in bone and its microenvironment is possible through applications of in situ hybridization histochemistry (ISHH) and immunohistochemistry (IHC). Application of ISHH allows study of specific mRNA expression. IHC determines the presence and distribution of target protein in cells. These two methodologies provide the link between the cellular processes of mRNA transcription and translation to the working protein. Combining the established bone histomorphometric techniques with ISHH and IHC elevates the study of bone to new heights, i.e., cellular and molecular mechanistic issues can now be studied.
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  • 3
    ISSN: 1432-198X
    Keywords: Key words Renal disease ; Bone ; Muscle ; Renal osteopathy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Bone structure and muscular strength of 30 children with renal disease were investigated by peripheral computed tomography and grip strength. Sixteen children suffered from nephrotic syndrome (NS) and had previously been treated with corticosteroids. Fourteen children suffered from chronic renal failure (CRF) ranging from mild renal failure to end-stage renal disease. Six children had received kidney transplants and corticosteroids for immunosuppression. There was a significant decrease in grip strength of children with NS (SD –0.91± 1.5; P=0.042) and children with CRF (SD –1.38±1.4; P〈0.001) compared with normal children. Furthermore, there was a significant correlation between cortical area and grip strength in all children with renal disease (r=0.92; P〈0.0001). Trabecular bone mineral density did not correlate well with grip strength. These findings resemble results found in healthy children. Trabecular bone mineral density was significantly elevated in children with CRF compared with normal children (SD 1.14±1.4; P=0.008).Grip strength as a marker of muscle mass and cortical area as a marker of bone strength correlate well in children with renal disease, similar to the correlation in healthy children. Grip strength is significantly lower in children with NS and CRF compared with normal children. These data suggest that muscular impairment could be involved in renal osteopathy.
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  • 4
    ISSN: 1433-0385
    Keywords: Schlüsselwörter: Tissue Engineering ; Mesenchymale Stammzellen ; Knochen ; Knorpel. ; Keywords: Tissue engineering ; Mesenchymal stem cells ; Bone ; Cartilage.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract. Tissue engineering offers the possibility to fabricate living substitutes for tissues and organs by combining histogenic cells and biocompatible carrier materials. Pluripotent mesenchymal stem cells are isolated and subcultured ex vivo and then their histogenic differentiation is induced by external factors. The fabrication of bone and cartilage constructs, their combinations and gene therapeutic approaches are demonstrated. Advantages and disadvantages of these methods are described by in vitro and in vitro testing. The proof of histotypical function after implantation in vivo is essential. The use of autologous cells and tissue engineering methods offers the possibility to overcome the disadvantages of classical tissue reconstruction – donor site morbidity of autologous grafts, immunogenicity of allogenic grafts and loosening of alloplastic implants. Furthermore, tissue engineering widens the spectrum of surgical indications in bone and cartilage reconstruction.
    Notes: Zusammenfassung. Tissue engineering ermöglicht die Herstellung lebender Konstrukte zum Gewebeersatz durch die Kombination histogener Zellen und biokompatiblen Trägermaterialien. Pluripotente mesenchymale Stammzellen können isoliert, ex vivo vermehrt und ihre gewebetypische Differenzierung durch Faktoren induziert werden. Es wird die Herstellung von Knochen- und Knorpelkonstrukten, deren Kombination sowie gentherapeutische Ansätze dargestellt. Vor- und Nachteile der Methoden werden durch in vitro und in vivo Testung beschrieben. Essentiell ist der Nachweis der gewebetypischen Funktion der Konstrukte nach Implantation in den Defekt. Die Verwendung autogener Zellen und Methoden des Tissue engineerings bietet die Möglichkeit die Probleme des klassischen Gewebeersatzes – Morbidität der autogenen Spenderstelle, Immunogenität des allogenen Transplantats und Lockerung von alloplastischen Implantaten – zu überwinden und erweitert das Indikationsspektrum in der rekonstruktiven Chirurgie.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 10 (2000), S. 1832-1835 
    ISSN: 1432-1084
    Keywords: Key words: Platyspondyly ; MRI ; Progressive pseudorheumatoid dysplasia ; Bone ; Osteochondrodysplasia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. A rare case of progressive pseudorheumatoid dysplasia (PPD) in a 9-year-old girl is presented. Clinically, chronic painless swollen joints, accompanied by progressive motion restriction and progressive walking difficulties, were found. Radiologically, there was enlargement of the epimetaphyseal portions of the large joints, metacarpal heads, and phalanges, and generalized platyspondyly with irregular delineation of the endplates of the vertebral bodies. The radioclinical features at the peripheral joints were originally misdiagnosed as juvenile rheumatoid arthritis (JRA), and the structural spinal abnormalities were neglected and interpreted as Scheuermann's disease. However, the absence of active inflammatory parameters argues against JRA, whereas the low age of onset of the irregularities at the vertebral endplates is an argument against the diagnosis of Scheuermann's disease. The combination of the dysplastic abnormalities of the spine, with platyspondyly and Scheuermann-like lesions at an unusually low age of onset, and radiological features mimicking JRA of the peripheral joints, is the clue to the diagnosis of this rare autosomal-recessive disease. This case is the first to document the MRI features of PPD of the spine.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of bone and mineral metabolism 18 (2000), S. 305-316 
    ISSN: 1435-5604
    Keywords: Key words Utah paradigm ; Bone ; Joint ; Ligament ; Biomechanics ; Osteoporosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In a 1960 paradigm of skeletal physiology, effector cells (chondroblasts, fibroblasts, osteoblasts, osteoclasts, etc.) regulated by nonmechanical agents wholly determined the architecture, strength, and health of bones, joints, fascia, ligaments, and tendons. Biomechanical and tissue-level phenomena had no roles in that paradigm. Subsequent studies and evidence slowly revealed skeletal tissue-level mechanisms and their functions, including biomechanical ones, as well as "game rules" that seem to govern them. That slow discovery process found that effector cells are only parts of tissue-level mechanisms, as kidney cells are only parts of nephrons and wheels are only parts of cars. Normally all those things help to determine skeletal architecture, strength, and health, and adding them to the 1960 paradigm led to the still-evolving Utah paradigm of skeletal physiology that concerns, in part, how load-bearing skeletal organs adapt to the voluntary mechanical loads on them. That caused controversies this article does not try to resolve; instead, it describes some issues they concern. In that regard, controversy can depend on how one assesses the relevance of facts to a problem more than on their accuracy. If a paradigm added new facts to a former one and the new one's advocates viewed all those facts as relevant, but the former's advocates questioned the relevance of some of the new facts, their views about a problem could differ even though each view depended on accurate facts. Readers would make their own judgments about the bearing of those ideas on this article's content.
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  • 7
    ISSN: 1433-0385
    Keywords: Schlüsselwörter: Gentherapie ; Knochen ; Fraktur ; Wachstumsfaktoren. ; Keywords: Gene therapy ; Bone ; Fracture ; Growth factors.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract. Gene therapy in orthopedic surgery is a new technic based on the idea of biological tissue healing. External gene segments are transferred to cells that overexpress growth factors locally to achieve this effect. The influence of growth factors on fracture healing is very well documented in the literature. Experimental data demonstrate that defect healing in bone can be accelerated by the application of different cytokines in vivo. Gene transfer is a promising, new technic of in situ tissue engineering that will enter clinics within the next decade.
    Notes: Zusammenfassung. Gentherapie in der Orthopädischen Chirurgie ist eine neue Technik, die auf der Idee basiert, die biologische Gewebeheilung zu unterstützen. Um dies zu erreichen, werden externe Gensegmente auf Zellen transferiert, die in Folge vermehrt Wachstumsfaktoren im Bereich der Fraktur produzieren. Die Wirkung von Wachstumsfaktoren auf die Frakturheilung ist gut dokumentiert. Die bislang durchgeführten tierexperimentellen Studien demonstrieren eine gute Beeinflussbarkeit der knöchernen Defektheilung. Der Gentransfer kann als eine neue erfolgversprechende Technik des in situ Tissue Engineering angesehen werden, mit deren klinischer Anwendung in der nächsten Dekade gerechnet werden darf.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Annals of biomedical engineering 28 (2000), S. 1200-1209 
    ISSN: 1573-9686
    Keywords: Bone ; Bone fluid ; Mixing ; Lacunar-canalicular porosity ; Metabolism ; Mass transport ; Poroelasticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract A mathematical model is developed to explain the fundamental conundrum as to how during cyclic mechanical loading there can be net solute (e.g., nutrient, tracer) transport in bone via the lacunar-canalicular porosity when there is no net fluid movement in the canaliculi over a loading cycle. Our hypothesis is that the fluid space in an osteocytic lacuna facilitates a nearly instantaneous mixing process of bone fluid that creates a difference in tracer concentration between the inward and outward canalicular flow and thus ensures net tracer transport to the osteocytes during cyclic loading, as has been shown experimentally. The sequential spread of the tracer from the osteonal canal to the lacunae is investigated for an osteon experiencing sinusoidal loading. The fluid pressure in the canaliculi is calculated using poroelasticity theory and the mixing process in the lacunae is then simulated computationally. The tracer concentration in lacunae extending radially from the osteonal canal to the cement line is calculated as a function of the loading frequency, loading magnitude, and number of loading cycles as well as the permeability of the lacunar-canalicular porosity. Our results show that net tracer transport to the lacunae does occur for cyclic loading. Tracer transport is found to increase with higher loading magnitude and higher permeability and to decrease with increasing loading frequency. This work will be helpful in designing experimental studies of tracer movement and bone fluid flow, which will enhance our understanding of bone metabolism as well as bone adaptation. © 2000 Biomedical Engineering Society. PAC00: 8716Uv, 8719Rr, 8716Ac
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Supportive care in cancer 8 (2000), S. 398-404 
    ISSN: 1433-7339
    Keywords: Key words Bisphosphonate ; Hypercalcemia ; Breast cancer ; Bone ; Osteoclast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Bisphosphonates are now the standard treatment for tumor-induced hypercalcemia (TIH), and pamidronate can normalize serum Ca in at least 90% of the patients treated for the first time. However, there are few data on the treatment of TIH when it recurs, and published results are contradictory. We studied 29 patients with solid tumors, 14 of whom had breast cancer and all of whom were naive to bisphosphonate therapy. They were retreated with pamidronate (median dose 1 mg/kg for both courses) for recurrence of TIH after a median interval of 78 (range 7–297) days. Fourteen of them, 7 of whom had breast cancer, were treated a third time 28 (range 5–79) days after the second course (median dose of pamidronate 1.5 mg/kg). Baseline Ca levels were not significantly different before each course, but the nadirs after each treatment progressively increased, 9.3±0.2 mg/dl, 10.5±0.3 mg/dl, and 12.3±0.4 mg/dl after the 1st, 2nd and 3rd administrations, respectively (P〈0.05). The percentage of treatment failures also progressively increased: 10%, 31% and 85% (P〈0.05). This decreased hypocalcemic effect was essentially observed in patients without bone metastases or with tumors other than breast cancer. Thus, in patients without bone metastases, Ca levels did not decrease at all after the 3rd course, whereas the responses were not significantly different between the three courses in patients with bone metastases. Baseline urinary hydroxyproline, a marker of bone resorption, increased progressively from course to course, especially in patients with bone metastases or breast cancer, but this was not the case for parameters of bone formation. There was also a progressive increase in PTHrP levels accompanied by an increase in the number of patients with enhanced kidney reabsorption of Ca and a decrease in the threshold for Pi excretion, which was significant in patients without bone metastases. In conclusion, pamidronate was progressively less efficient when hypercalcemia recurred. This was observed mainly in patients with hypercalcemia of humoral origin. Tumor progression is accompanied by an enhanced release of osteolytic factors, notably PTHrP, that increase bone resorption and enhance kidney calcium reabsorption, especially in patients without bone metastases. When both phenomena occur, the response to bisphosphonates becomes minimal and the usefulness of therapy questionable.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Virchows Archiv 436 (2000), S. 74-81 
    ISSN: 1432-2307
    Keywords: Key words Ochronosis ; Bone ; Cartilage ; Arthropathy ; Alkaptonuria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  An ochronotic femoral head has been studied morphologically under the light and the electron microscope. Its articular cartilage showed the alterations already reported in the literature, mainly consisting of erosions of the surface, pigment accumulation in chondrocytes and intercellular matrix, chondrocyte degeneration, the formation of pigmented, calcified and uncalcified microshards, and the presence of granulation tissue with macrophagic cells. The changes in bone were less severe than those in cartilage. Pigment was present in the calcified matrix. This did not seem to disturb the organization of the bone tissue, although it was diffusely osteoporotic, perhaps because of limb disuse. The preservation of calcified matrix might depend on the fact that its collagen fibrils are encrusted by mineral substance, which avoids the dangerous effects that the deposition of ochronotic pigment induces in the fibrils of soft connective tissues. On the other hand, the newly formed osteoid matrix remains uncalcified for too short a time to be modified by the pigment. Diffuse or granular pigmentation was found in a few osteocytes, while several of them were condensed or reduced to cellular fragments. Bone resorption often occurred near these osteocytes. However, this did not seem to alter the degree of bone remodelling, possibly because of the relatively low numbers of degenerated or dead osteocytes. Pigment was also contained in the cytoplasmic vacuoles of otherwise active osteoclasts, whereas it was not found in osteoblasts. On the whole, ochronosis in bone seems to induce the same changes as in other connective tissues. However, their severity appears to be limited by calcification, which prevents modifications in collagen fibrils, and by bone remodelling, which to some extent eliminates the oldest, pigment-richest parts of the tissue.
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  • 11
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    Journal of orthopaedics and traumatology 1 (2000), S. 11-16 
    ISSN: 1590-9999
    Keywords: Key words Hydroxyapatite ; Bone ; Interface ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We performed a back-scattered electron microscopy analysis of the interface between newly formed bone and hydroxyapatite coating, in an experimental rabbit model. Twenty cylinders made of Ti6A14V and coated with hydroxyapatite at different crystallinity were implanted in the distal femural canal and retrieved at 4, 8, 26 an 34 weeks. Crystallinity of the coating varied from 90% to 60% and thickness varied between 50 and 100 μm. Osteocytes were detectable a few micrometers in proximity of the coating. They produced new bone which was so tightly apposed to the coating that high magnification BSEM did not resolve any discontinuity at the interface. This was not observed in uncoated implants. Degradation of the hydroxyapatite coating is not a simple hydrolytic process because newly formed bone is remodelled in areas were a tight apposition with hydroxyapatite is present. The coatint itself is likely to be attacked by the resorptive action of multinucleated giant cells and osteoclasts. In conclusion, response to coated samples is morphologically characterized by tight apposition with bone. The substitution of areas of the coating by newly formed bone is possible.
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  • 12
    ISSN: 1615-3146
    Keywords: Key words Alkaline phosphatase ; Bone ; Lectin precipitation ; Fracture ; Osteoblast activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Serum activity of bone specific alkaline phosphatase, a product of differentiated osteoblasts, is thought to mirror fracture healing. The precise time course after various conditions involving bone healing is, however, poorly described. The aim of our study was to evaluate sequential changes of bone alkaline phosphatase over a period of 20 weeks in traumatized patients with and without bone injuries. The bone isoenzyme of alkaline phosphatase was determined in frozen serum samples using a new automated procedure based on the wheat germ lectin precipitation method. Patients were stratified into different groups: 1. ST – soft tissue injury without bone participation; 2. DF – diaphysial fracture of tibia or femur; 3. MT – patients suffering from multiple traumas; 4. PF – proximal femur fracture, treated with dynamic hip screw; and 5. EP – femur neck fracture, treated with cemented endoprosthesis. Similar values were obtained in all measured groups on the day of admission (ST 35.83±6.15 U/l; PF 27.37±4.43 U/l; EP 31.09±7.42 U/l). In the following measurements, enzyme activity decreased significantly in all groups to reach a nadir within the first week, ranging between 41 and 82% of the activity immediatly postoperative. Thereafter, a substantial increase occurred in all groups investigated. In the ST group, this increase led to an activity level that was comparable to the first posttraumatic value (39.06±7.81 U/l). In contrast, average values in all other groups revealed a further increase, which was significantly elevated compared to measurements taken the first day after trauma (DF 74.36±10.84 U/l; MT 177.87±30.0 U/l; PF 93.39±22.08 U/l; EP 51,52±7.33 U/l). Additionally, the time to reach the peak in enzyme activity differed between groups. In the MT group, it was observed as early as 3 weeks after injury, in the DF group the peak was reached as late as 6 weeks after trauma. The results of the study indicate that bone alkaline phophatase activity undergoes a specific pattern of changes after trauma. It may be assumed that the initial decrease is part of a general stress response to trauma and operation. The subsequent increase seems to depend from the magnitude of bone repair and the type of fracture healing, e.g. diaphysial fracture healing takes longer time than cancellous bone healing. These results seem to be a useful basis in order to establish a laboratory monitoring of fracture healing in subsequent studies.
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  • 13
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    Materials research innovations 3 (2000), S. 313-323 
    ISSN: 1433-075X
    Keywords: Keywords Glass ; Cell cycle ; Genes ; Bone ; Bioactive materials ; Osteogenesis ; Prostheses ; Omplants ; Ageing ; Osteoblasts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Many of the present generation biomaterials are still based upon the early concept that implantable materials should be bioinert and therefore designed to evoke minimal tissue response, if none. However, a growing body of clinical data demonstrates that the long survivability of these materials is hampered by high rates of failure, which is primarily attributed to interfacial instability. It has therefore become understood that this approach is not optimal. Modern approaches implicate the use of biomaterials that can actively interact with tissues and induce their intrinsic repair and regenerative potential. This involves control over the cell cycle, the molecular framework that controls cell proliferation and differentiation. Class A bioactive glass-ceramic materials were the first materials shown to endorse these properties and, depending upon the rate of resorption and release of ions, can create chemical gradients with specific biological actions over cells and tissues. Optimising this bioactive regenerative capacity of Bioactive glass-ceramics offers great hope for producing biomaterials that can stimulate growth, repair, and regeneration of any human tissue.
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  • 14
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    European journal of plastic surgery 23 (2000), S. 301-304 
    ISSN: 1435-0130
    Keywords: Key words Titanium ; Implants ; Bone ; TOF–SIMS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In order to study commercially pure (CP) titanium bone interaction and integration mechanism, titanium implant bone interface formed for 1, 3 and 6 months was examined and analyzed by advanced TOF–SIMS analysis. The results obtained show: 1) Titanium and bone tissue integrated closely; 2) The action between CP titanium and bone tissue is a reactive process; both physical and chemical integration occur at the titanium–bone interface; 3) Titanium diffuses into the bone tissue, though the diffusion density is limited; 4) The diffusion area of titanium into bone tissue noted during the follow-up period is up to 100 μm. In this paper the titanium bone integration mechanism was studied, both at molecular and anatomic level.
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  • 15
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    European journal of plastic surgery 23 (2000), S. 423-428 
    ISSN: 1435-0130
    Keywords: Key words Absorbable ; Bone ; Membrane ; Osteogenesis ; Polyglycolide ; Tissue engineering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  This study is part of a series of studies evaluating self-reinforced polyglycolide (SR-PGA) membranes. The aim of this study was to evaluate the effect of SR-PGA membrane on osteogenesis in order to assess its use in tissue engineering and bone regeneration. SR-PGA membranes (15×20 mm) were implanted over the femoral diaphyseal bone of 27 Wistar rats (over the periosteum). Each membrane was stabilized using a Dexon suture cerclage. Rats were followed-up for 1, 2, 3, 6, 8, 15 and 30 weeks. Histology and microradiography were used to evaluate bone formation. The membranes were excised and tested for their tensile strength properties, the results of which are published in a separate report. Bone formation periosteally was seen in 21/27 cases (77.8%, confidence interval 57.7–91.4). It occurred in all cases at 1, 2 and 3 weeks. At 6 weeks, it was seen in three out of four cases but at 8 weeks, only in one out of three cases. Bone formation seen as thickened cortex was detected at 15 weeks in all of the three cases and at 30 weeks in three out of six cases. Hence, bone formation was seen in most of the cases when SR-PGA membranes were applied around rats’ femora. They can be recommended for use in bone tissue engineering and regeneration.
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  • 16
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    Skeletal radiology 28 (1999), S. 90-95 
    ISSN: 1432-2161
    Keywords: Key words DXA ; Bone ; Cadaver ; Biomechanics ; Metastases ; Fracture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Objective. To determine whether the load-bearing capacity of human proximal femora with metastatic defects can be predicted from the bone mineral content. Design. The bone mineral content (BMC) of the total proximal femur was measured by dual-energy X-ray absorptiometry (DXA). The femurs were loaded so as to simulate stair ascent or external rotation. Patients. Simulated lytic defects were created using specialized cutting tools in the intertrochanteric region of 32 human cadaveric femora. Bone density measurements were made before and after creating defects. Results. A linear relation could be used to predict failure load from BMC or bone mineral density. The slope of the linear relation was greater for loads representing external rotation than for loads representing stair ascent. The linear relations suggest that the BMC measurements account for both the density of the host bone and the amount of bone removed by the defect. Conclusions. The data suggest that between 70% and 80% of the variation in failure load of human femora with lytic metastatic defects can be predicted from the BMC and that relations between BMC and failure load are sensitive to the type of loading. Combined with information on the loads associated with the activities of daily living, these data may be used to help identify patients in whom prophylactic stabilization might prevent a pathologic fracture.
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  • 17
    ISSN: 1432-5233
    Keywords: Key words Non-enzymatic glycosylation ; Advanced glycation endproducts ; Receptor for advanced glycation endproducts ; Diabetes mellitus ; Osteoblasts ; Bone ; Osteopenia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Advanced glycation endproducts have been implicated in the development of diabetic complications. In addition, these products could also mediate certain bone alterations such as diabetic osteopenia. Several receptors specific for advanced glycation endproduct-modified proteins have been characterized in different cell types, contributing to the recognition and degradation of senescent proteins. In the present report, we investigated the possible presence of advanced glycation endproduct-binding proteins on osteoblast-like cells. Both UMR106 and MC3T3E1 cell lines express specific advanced glycation endproduct-binding sites, with an affinity constant between 0.4 and 1.7 · 106 M−1, depending on the stage of osteoblastic differentiation; and with a receptor capacity of 1.5–2.0 · 107 sites/cell. Osteoblast-like cells were also found to participate both in the uptake and degradation of advanced glycation endproduct-modified bovine serum albumin at 37°C. Radiolabelled ligand blotting studies confirmed the presence of several membrane binding proteins, with apparent molecular masses of 50, 45–40, 30, 25 and 18 kDa; the major bands corresponded to 30 and 25 kDa proteins. This study provides evidence of the presence of advanced glycation endproduct-specific binding sites, and for their regulation with the stage of differentiation, in two osteoblast-like cells in culture.
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  • 18
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    European journal of orthopaedic surgery & traumatology 9 (1999), S. 251-254 
    ISSN: 1432-1068
    Keywords: Bone ; Scintigraphy ; symptomatic ; Knee ; Arthroplasty ; Os ; Scintigraphie ; Genou ; Arthroplastie ; Symptomatique
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Objectif: Evaluation de la scintigraphie osseuse dans l'arthroplastie totale de genou douloureux. Lieu: Hôpital universitaire, Maastricht et Hôpital Maasland, Sittard. Projet: Investigation clinique retrospective. Méthode: Les dossiers cliniques de 27 patients ayant subi une scintigraphie de l'os, ont été étudiés afin d'analyser les plaintes et la façon de décider le diagnostic. Ces patients avaient des symptômes persistants après l'arthroplastie totale du genou. En plus ont été étudiées les radiographies conventionelles et les scanographies isotopes, sans connaître les dossiers cliniques. Sur la base de ces données nous avons évalué les cas dans lesquels la scanographie isotope du genou a contribué de façon décisive au traitement future. Résultats: La scanographie isotope ne contribue pas à la planification du traitement, si l'examen physique ou les radiographies conventionelles n'ont pas apporté de diagnostic clinique. Il s'agissait ici de 37 % des patients de cette série. Dans les cas où le diagnostic clinique était fait, la scanographie isotope a influencé la décision de diagnostic de 65 % des patients. Cependant, pour les autres patients avec diagnostic clinique (35 %), ce ne fut pas le cas. Conclusion : La répresentation radionucléide est de valeur limitée dans le diagnostic d'une arthroplastie symptomatique totale du genou. Elle peut supporter ou rejeter un diagnostic clinique mais entraînera rarement un changement de traitement, dans l'absence de constatations anormales pendant les examens physiques ou radiologiques.
    Notes: Summary Objective: Determination of the value of bone scanning in symptomatic total knee arthroplasties. Setting Academic Hospital Maastricht and Maasland Hospital Sittard. Design: Retrospective clinical investigation. Method: The clinical reports of 27 patients, who underwent a bone scintigraphic study, were investigated for complaints and analysis of diagnostic decision making. These patients had persistent symptoms after total knee arthroplasty. In addition, conventional radiographs and the isotope scans were studied without knowledge of the clinical records. Based on these data we evaluated in which cases isotope scanning of the knee had contributed decisively to the further treatment. Results: Isotope scanning did not contribute to the treatment planning if physical examination or conventional radiographs had not led to a clinical diagnosis. This comprised 37% of the patients in our series. If a clinical diagnosis was present, isotope scanning did influence decision making in 65% of the patients. However in the remaining patients with a clinical diagnosis (35%) this was not the case. Conclusion: Radionuclide imaging is of limited value in the diagnostic process of symptomatic total knee arthroplasty. It may support or reject a clinical diagnosis, but in the absence of abnormal findings at physical examinations or radiologic studies, it seldom will induce a change in treatment
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  • 19
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    European journal of orthopaedic surgery & traumatology 9 (1999), S. 161-165 
    ISSN: 1432-1068
    Keywords: Bone ; Bone substitutes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Biocompatible calcium phosphate ceramics has been used for several years in orthopeadic surgery. We have been using two new synthetic biphasic calcium phosphate ceramics (BCP) since September 1996 for bone defect filling in any orthopaedic or trauma operation where autograft use was not possible or even wanted. The first, Eurocer 400® has 300 to 500 micron wide macropores with a totally interconnected porosity. This salt seed like product can be used in bone defect filling, when solidity is not a major concern. The second, Eurocer 200® has not totally interconnected 200 micron large pores. Its main characteristic is a mechanical resistance up to 30 Mpa. We use it in any case of weight-bearing surgery. Different sizes and presentation forms are available and will be chosen according to the recipient site shape. We report one hundred and fifty cases with a six to thirty month follow-up. In one third of the patients hip revision surgery was addressed. Another third concerned recent trauma or sequelae cases,.whereas the last third involved cold orthopaedic procedures. General principles are the need of a living and non-infected site after thorough debridement if necessary. Osteocompatibility of calcium phosphate ceramic is confirmed by our results. We report no mechanical failure. In all cases X-rays show a progressive integration, with new bone formation. Our substitutes have been histologically studied in nine cases, four to fifteen months after implantation. New bone formation around and in the substitute is impressive. Indeed, their good mechanical properties without loss of biological quality is the most relevant feature of these BCPs, leading to a wider indication field; therefore we have now abandoned the use of any bony auto, allo or xenograft.
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  • 20
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    Diseases of the colon & rectum 42 (1999), S. 1225-1227 
    ISSN: 1530-0358
    Keywords: Colon cancer ; Adenocarcinoma ; Intramuscular metastasis ; Bone ; Heterotopic ossification ; Soft tissue tumor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract PURPOSE: This report presents a patient who developed severe buttock pain because of an ossified intramuscular metastasis from a sigmoid colon cancer. METHODS: This is a case report and review of the literature for intramuscular metastasis from colon cancer. RESULTS: Computed tomography and magnetic resonance imaging showed a soft-tissue mass with heavy calcification. Histologically, mature compact bone was observed with adenocarcinoma cells dispersed among the bony trabeculae. CONCLUSION: When an intramuscular mass is seen, even if it contains extensive calcification, metastasis from colon cancer should be included in differential diagnosis.
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  • 21
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    International journal of legal medicine 112 (1999), S. 195-197 
    ISSN: 1437-1596
    Keywords: Key words Trauma ; Calcification ; Bone ; Embolism ; Autopsy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Notes: Abstract Embolism of bone marrow to the lungs is a quite frequent finding after trauma but transport and deposition of solid bone is rarely seen, which may simply be because pulmonary calcifications are not recognized as bone fragments. We report on three patients with embolism of bone spicules to small lung arteries of about 0.5 mm in diameter which were plentiful in two of the patients on postmortem examination. However, the true nature of the emboli was only recognizable after decalcification of lung tissues. It appears that trauma occurring in a septic bone lesion has the greatest chance to provoke bone embolism. The bone spicules do not usually occlude vessel lumina and thus do not severely disturb the blood circulation in the lungs. The bone fragments become covered by endothelium and can remain recognizable for months or even years.
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  • 22
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    Mund-, Kiefer- und Gesichtschirurgie 3 (1999), S. 140-145 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Konfokale Laser-Scanning-Mikroskopie ; Dunkelfeldmikroskopie ; Bisbenzimidmarkierung ; Knochen ; Strahlenfolgen ; Radiogener Osteozytentod ; Key words Confocal laser scanning microscopy ; Microscopy ; Bisbenzimide labelling ; Bone ; Radiation effects ; Osteocytes ; Osteoradionecrosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Early radiation effects on human bone may lead to osteoradionecrosis (ORN). Direct bone cellular lesions [28] as well as fibrous degeneration of blood vessels [21] are considered to be pathologically relevant. Only few data on initial subclinical radiation effects are available. Patients were grouped according to the dose of radiation and clinical findings. Group 1: sound human bone of lower jaw, mostly collected during orthodontic surgery (n = 10 patients); group 2: specimens of lower jaw from patients with ORN (n = 12 patients); group 3: specimens of lower jaw from patients with head and neck cancer who were preoperatively treated with 36 Gy radiation; group 4: specimens of lower jaw from patients with head and neck cancer (n = 9) who were treated with 60–70 Gy radiation. Specimens were studied by confocal laser scanning microscopy (CLSM), by conventional light microscopy (DL) and by flourescence darkfield microscopy (DFM) after bisbenzimide staining (H 33258) of the viable cellular nuclei. For the correlating study of identical areas in CLSM and DL the specimens were prepared according to the sawing and grinding technique [8]. All the radiated bony specimens, regardless of the dose of radiation, showed areas of extensive or total loss of vitality of the osteocytes. This finding was also evident after 36 Gy and a short interval between radiation and sample collection (group 3). Additionally, in CLSM micromorphologic lesions of the lamellate structure were seen. With these results we can confirm the loss of vitality of the osteocytes as an initial radiation effect as described earlier [10, 23, 28]. In addition to these findings, alteration of the lamellate microstructure was found in the early phase after radiation. The functional and mechanical significance of these findings should be the subject of further studies.
    Notes: Für die infizierte Osteoradionekrose (IORN) des Kiefers werden unterschiedliche pathogenetische Mechanismen initialer Strahlenfolgen im Knochen diskutiert: Wichtige Parameter sind dabei die direkte Zellschädigung der Osteozyten [28] und die Gefäßfibrosierung [21]. Bislang liegen wenige Kenntnisse zum Ausmaß der initialen, subklinischen Veränderungen vor. 4 Probengruppen wurden anhand verschiedener Patientenkollektive definiert: Gruppe 1: gesunde Unterkieferproben meist von orthodontischen Operationen (n = 10 Patienten); Gruppe 2: Unterkieferproben mit manifester IORN (n = 12 Patienten); Grruppe 3: Unterkieferproben nach 36 Gy präoperativer Radio(chemo)therapie (n = 9 Patienten); Gruppe 4: Unterkieferproben nach 60–70 Gy Bestrahlung ohne Hinweise auf IORN (n = 9 Patienten). Alle Proben wurden histotomographisch mit konfokaler Laser-Scanning-Mikroskopie (CLSM), durchlichtmikroskopisch (DL) und dunkelfeldmikroskopisch (DFM) nach Fluoreszenzmarkierung des intakten Zellkerns (Bisbenzimid H 33258) untersucht. Korrelierende Histologien identischer Probenareale erfolgten an Trenndünnschliffen [8]. Als Ergebnisse wurden gefunden: 1. Alle unterschiedlich bestrahlte Knochenproben zeigten Areale mit weitgehendem bis vollständigem Verlust vitaler Osteozyten. Diese Strahlenfolge trat auch schon nach 36 Gy und kurzem Intervall bis zur Operation (Gruppe 3) auf. 2. Im CLSM zeigten sich zusätzlich mikromorphologische Veränderungen der lamellären Struktur, die zwischen den Probengruppen progredient waren. Hieraus können folgende Schlußfolgerungen gezogen werden: 1. Der vorbeschriebene Vitalitätsverlust der Osteozyten [10, 23, 28] konnte als sehr frühe, initiale, radiogene Läsion bestätigt werden. 2. Zusätzlich zeigten sich Veränderungen der lamellären Mikroarchitektur des Knochens als frühe und im Gruppenvergleich progrediente Strahlenläsion. Die mikromechanisch funktionelle Bedeutung dieser Veränderung muß in weiterführenden Untersuchungen eruiert werden.
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  • 23
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    Annals of biomedical engineering 27 (1999), S. 508-516 
    ISSN: 1573-9686
    Keywords: Angiogenesis ; Artery ; Bone ; Creeping substitution ; Leukocytes ; Osteocytes ; Reperfusion injury ; Trauma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract An in vivo model has been developed for chronic observation of the effects of ischemia on cortical bone remodeling and perfused vascularity. Diaphragm occluders were implanted around the right common iliac artery of four rabbits and inflated to produce 10 h of ischemia to the limb. Microcirculation was monitored with intravital microscopy of injected fluorescent microspheres and FITC-Dextran 70 through a bone window, the tibial bone chamber implant (BCI). Bone resorption and apposition in the BCI were indicated with mineralization dyes. Between 2 and 12 h following release of the occluder, secondary ischemia/no-reflow and other evidence of reperfusion injury were observed. Vessel damage was suggested by abnormally high leakage of FITC-D70 from the few vessels perfused during secondary ischemia. In the weeks following occluder release perfused vasculature increased beyond pre-occlusion levels. Net bone resorption reached a maximum when vascularity passed normal levels. In order to further validate the arterial occlusion model for osteonecrosis, techniques for (1) confirming bone death and (2) detecting increased leukocyte adherence to endothelial cells were added. The dead cell stain Ethidium homodimer-1 was used to tag dead osteocytes immediately after occlusion and produced a measure designated “osteonecrosis index.” To detect leukocytes adhering to vessel walls, carboxyfluorescein diacetate, succinimidyl ester was injected at occluder release. An increase in the number of adherent leukocytes was detected. © 1999 Biomedical Engineering Society. PAC99: 8764Rr, 8717-d, 8719Tt
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  • 24
    ISSN: 1433-7347
    Keywords: Key words Anterior cruciate ; ligament reconstruction ; Bone ; tunnel enlargement ; Hamstring ; tendons ; Magnetic resonance ; imaging ; Radiographic evaluation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Sports Science
    Notes: Abstract The aim of this study was to describe the contrast-enhanced magnetic resonance imaging (MRI) appearance of bone tunnel enlargement detected on radiography after anterior cruciate ligament (ACL) reconstruction with semitendinosus and gracilis tendon endobutton (STG-endobutton) fixation technique. Fourteen patients with a STG-endobutton ACL reconstruction were examined 3 months (n = 1), 1 year (n = 1) and 2 years (n = 12) postoperatively. An age- and sex-matched group with a bone–patellar tendon–bone (BTB) autograft ACL reconstruction with similar follow-up was taken as control. Data on clinical examination, laxity and isokinetic muscle torque measurements, anteroposterior and lateral view radiography were obtained, and knee scores (Lysholm and Tegner) were collected. Contrast-enhanced MRI was performed in the STG-endobutton group with a 1.5-T imager. There were no statistical differences between the groups with respect to clinical findings, stability tests, or knee scores. In the STG-endobutton group the average femoral and tibial bone tunnel diameter detected on anteroposterior view radiography had increased at 2-year follow-up by 33% and 23%, respectively. On MRI the ligamentous graft itself was not enhanced by the contrast medium whereas periligamentous tissue within and around the STG graft bundles showed mild contrast enhancement. In conclusion, the MRI results suggest that enhancing periligamentous tissue accumulated in and around the STG graft associated with the tunnel expansion. In spite of the significant bone tunnel enlargement observed on the follow-up radiography the STG-endobutton knees were stable and the patients satisfied.
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  • 25
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    European journal of trauma 25 (1999), S. 230-236 
    ISSN: 1615-3146
    Keywords: Aneurysmatische Knochenzyste ; Knochentumor ; Hand ; Aneurysmal bone cyst ; Bone ; Hand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract The aneurysmal bone cyst localizised at the longfingers of the hand is an extremely rare clinical entity, particularly considering the age and the distinct aggressiveness in our case. In this specific case of a 53-year-old male the differentialdiagnosis as well as problems of the aneurysmal bone cyst with affection of the phalangeal bone will be discussed. Furthermore the various possibilities of therapy will be focussed on. At first the patient was treated with curettage followed by bone grafting. Already 5 months later a local recurrence appeared. The proximal phalangeal bone and the metacarpophalangeal joint V were almost distroyed. Aiming at preservation of a high funcionality of the hand we amputated the 5th finger in the metacarpophalangeal joint.
    Notes: Zusammenfassung Die aneurysmatische Knochenzyste mit Lokalisation an der Hand, insbesondere an den Phalangen, ist ein extrem seltenes Krankheitsbild. Auch das Alter des Patienten und die ausgeprägte Aggressivität unseres Falles sind bemerkenswert. Anhand der Krankengeschichte eines 53jährigen Mannes mit Befall der Grundphalanx des fünften Fingers der rechten Hand werden die Problemstellung bzw. Differentialdiagnose verdeutlicht und die verschiedenen Therapiemöglichkeiten besprochen. In unserem Fall wurde zunächst eine Kürettage mit anschließender Spongiosaaufftüllung durchgeführt. Bereits nach fünf Monaten kam es zu einem aggressiven Rezidiv mit Zerstörung der gesamten Grundphalanx und des Grundgelenks, so daß wir uns schließlich unter Berücksichtigung der bestmöglichen Funktion der Hand für eine Amputation des Kleinfingers entschieden haben.
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  • 26
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    Reproduktionsmedizin 15 (1999), S. 405-409 
    ISSN: 1434-808X
    Keywords: Schlüsselwörter Estrogenrezeptoren ; Knochen ; Arteriosklerose ; Endometrium ; Zentralnervensystem ; Key words Estrogen receptors ; Bone ; Arteriosclerosis ; Endometrium ; Central nervous system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Almost each cell in the body is estrogen-receptive. The strength of estrogen influence on organs or organ systems, however, may vary. Thus, estrogen withdrawal may have more or less severe pathophysiological consequences. Recently, the existence of two estrogen receptors has been established (estrogen receptor α and β = ERα and ERβ and several splice variants of these two basic receptor types have been desribed). This, together with our increasing knowledge about tissue-specific enhancer and repressor genes now allows a better understanding of the organ-specific effects of estrogens. In view of gynecological endocrinology, hormone replacement therapy with estrogens is beneficial for most organs in the body (bone, cardiovascular system, CNS). However, pure estrogen therapy may have deleterious effects in the endometrium of the uterus because it may initiate the development of uterine cancer. In the uterus of most species studied so far, no ERβ but only the classical ERα gene has been described. Hence, drug companies have now intensively begun to search for ERβ-specific estrogens. The first, relatively specific, non-steroidal product that addresses primarily the ERβ is the drug raloxifen, which has been recently introduced clinically. However, also some natural phyto-estrogens appear to be ERβ-specific.
    Notes: Zusammenfassung Fast jede Körperzelle ist estrogenrezeptiv. Es gibt allerdings Organe und Organsysteme, die besonders unter dem Einfluß von Estrogenen stehen und die sich bei Estrogenmangel krankhaft verändern können. Die vielfältigen Wirkungen von Estrogenen konnten nicht vollständig verstanden werden, solange die Existenz von nur einem Estrogenrezeptor quasi ein Dogma war. Erst die Klonierung eines zweiten (Estrogenrezeptor β = ERβ) sowie das bessere Verständnis von gewebespezifischen Enhancer- und Repressor-Genen konnten die vielfältigen und z. T. organspezifischen Wirkungen der Estrogene aufklären. Aus der Sicht der gynäkologischen Endokrinologie ist die Hormonersatztherapie mit Estrogenen für fast alle Organe des Körpers (Knochen, Herz-Kreislauf-System, Zentralnervensystem) segensreich. Eine nicht gestagenbegleitete Estrogentherapie kann allerdings verheerende Folgen am Endometrium mit Entwicklung eines Corpus-Karzinoms haben. Da der Uterus praktisch kein ERβ sondern nur den klassischen ERα exprimiert, hat eine intensive Suche nach ERβ-spezifischen Estrogenen begonnen. Ein erstes, halbwegs spezifisches nicht-steroidales Produkt scheint das kürzlich in die Klinik eingeführte Raloxifen zu sein, aber auch einige Phytoestrogene scheinen ERβ-spezifisch zu wirken.
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  • 27
    ISSN: 1432-2161
    Keywords: Key words Hemangiopericytoma ; Brain ; Bone ; Metastasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Two cases of osseous hemangiopericytoma are presented that were initially diagnosed as primary in origin, but later reclassified as metastases, after a history of resection for an intracranial tumor was discovered. An intracranial source should be excluded before an isolated osseous tumor is determined to be a primary hemangiopericytoma.
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  • 28
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    Skeletal radiology 27 (1998), S. 346-349 
    ISSN: 1432-2161
    Keywords: Key words Neurofibromatosis ; Malignant peripheral nerve sheath tumor ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Malignant peripheral nerve sheath tumors (MPNSTs) are uncommon sarcomas that almost always arise in soft tissue. They can develop in pre-existing neurofibromas or schwannomas, de novo from peripheral nerves, or following radiation therapy. Primary intraosseous MPNST is rare and has been reported most frequently in the mandible. Of the reported cases involving the long bones, none has been associated with neurofibromatosis type 1 (NF-1). We report a case of MPNST arising in the femur in a patient with NF-1.
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  • 29
    ISSN: 1432-198X
    Keywords: Key words: Neonatal Bartter syndrome ; Bone ; Cal- cium ; Heparin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The neonatal Bartter syndrome (NBS) is associated with a complex disorder of mineral metabolism in children, including hypercalciuria, nephrocalcinosis, and diminished bone mineral density. Although cyclooxygenase inhibition usually brings about improvement in these findings, there is a variable component which is resistant to such therapy in many children. The factor mediating this disorder has not been identified. Blood and urine from 12 children with NBS were examined. When compared with samples from normal children and adults, all (NBS) sera reduced bone calcium uptake in a bone disc bioassay. This effect persisted in the presence of parathyroid hormone (PTH) antibody and PTH receptor blockade, indicating that neither PTH nor PTH related peptide was responsible. It was eliminated by indomethacin, suggesting that prostanoid generation was essential. Protamine was also inhibitory, as was the addition of ecteola, an anion binder. Activity could be recovered from ecteola by elution with hypertonic buffer. Urine samples from children with NBS had the same calcitropic effect. The agent was removed by ecteola and recovered by hypertonic elution. Activity was eliminated by protamine and by heparinase, but not by trypsin digestion. Size exclusion centrifugation showed that the activity was associated with a material between 10 and 30 kilodaltons. Finally, urine ecteola eluates from NBS patients raised serum concentrations of calcium after intraperitoneal injection in rats. These data suggest that children with NBS have a calcitropic substance in their serum and urine which is not found in normal individuals. The substance is heparin like, and mediates its effects through prostanoid production. These studies provide additional evidence against a direct renal cause of the urinary calcium disturbance characteristic of the disorder.
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  • 30
    ISSN: 1423-0127
    Keywords: Muscular dystrophy ; Central nuclei ; Avian muscle ; Inflammation ; Dwarfism ; Lymphocyte ; Mechanochemical transducer ; Bone ; Steroid ; Fiber splitting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Muscular dystrophy has long been believed to be characterized by degeneration and abortive regeneration of muscle fibers (the muscle degeneration theory), but unfortunately its pathogenesis is still unclear and an effective treatment has yet to be developed. As a challenge to the theory, we have proposed an alternative muscle-defective-growth theory and a further bone muscle growth imbalance hypothesis supposing possible defects in bone-growth-dependent muscle growth based on our findings in hereditary dystrophic dy mice (C57BL/6Jdy/dy). This review presents some new insights into the pathogenesis of the disease along with our hypothesis, focusing on the physiological meaning of centronucleation, one of the major pathological changes commonly observed in dystrophic muscles of man and experimental animals.
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  • 31
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    European spine journal 7 (1998), S. 257-259 
    ISSN: 1432-0932
    Keywords: Key words Angiomatosis ; Bone ; Osteolysis ; Cervical spine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The case of a 21/2-year-old boy with diffuse cystic angiomatosis of bone is presented. No evidence of visceral involvement was recorded. The clinical, radiographic and histologic findings during the course of the disease process are discussed. At the age of 15 years the patient died of neurologic alterations developed due to massive osteolysis and collapse of the cervical spine, and severe dyspnoea, secondary to persistent bilateral pleural effusions.
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  • 32
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    Experimental biology online 3 (1998), S. 1-15 
    ISSN: 1430-3418
    Keywords: Bone ; Cell behaviour ; Chondrocyte ; Endothelia ; Epitenon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The motile behaviour, growth and reactions of osteoblasts, chondrocytes, epitenal cells and endothelia to culture on extended concave surfaces inside tubes is reported. Time-lapse video observations show that these cells can be successfully grown in quartz tubes for up to 21days. The cells would attach to the concave surfaces even when the radius of curvature was as low as 25 μm. The cells attached to the walls were not oriented. As culturing progressed the chondrocytes, osteoblasts and epitenon cells tended to detach from the walls of the tubes, forming long cords of cells attached to the walls at a few points only. Endothelial cells did not detach. These cords showed extensive lamellipodial activity at their points of attachment to the tube wall. The cells in these cords do not show contact inhibition of movement.
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  • 33
    ISSN: 1432-2277
    Keywords: Key words Knee joint ; Vascularized graft ; Bone ; Transplantation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Four transplantations of an allogeneic vascularized human knee joint were performed at the Trauma Center Murnau between April 1996 and July 1997. The indication for the procedure was the total loss of the knee joint including the extensor apparatus due to severe trauma. These were the first transplants of this type. Management of patients started with closure of soft-tissue defects. After successful completion, stabilization was achieved with femoral and tibial nails plus a temporary arthroplasty. AB0 compatibility and a negative cross-match were the main criteria for selecting patients for transplantation. Interlocking compression nails were used for osteosynthesis. Vascular anastomoses between graft and recipient vessels were established by the end-to-side technique. Immunosuppression was started as a quadruple induction therapy for 3 days, then reduced to a two-drug maintenance therapy with cyclosporine and azathioprine. Six months posttransplantation the osteotomies were bridged by callus and the patients became completely mobile. Radiographic and histological examinations revealed vital graft tissue.
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  • 34
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    Mund-, Kiefer- und Gesichtschirurgie 2 (1998), S. 141-145 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Konfokale Laser-Scanning-Mikroskopie ; Knochen ; Histotomographie ; Key words Confocal laser scanning microscopy ; Bone ; Histotomography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Objectives: Fixation (formalin), decalcification (sections) or mechanical treatment (grinding) all bear the risk of artifacts occurring during hard-tissue histology. Because studies on the etiology of pathological changes mostly focus on subclinical lesions, artifacts can simulate early changes or even be superimposed on existing changes. The objective of this study was to determine how artifacts can be reduced. Material and methods: In confocal laser scanning microscopy (CLSM) a focused laser beam scans the surface of the specimens and penetrates into the tissue. The intensity of the remitted light is recorded. The confocal effect is due to an extremely small aperture (pinhole), excluding light from out-of-focus planes of the sample. By stepwise movement of the object table, a tomographic series of tomographic images is obtained. Sound cortical bone samples of the lower jaw (n = 20) were studied by light microscopy and by CLSM, visualizing identical areas of a ground sectioned sample after H & E staining. Additionally, embedded and fresh blocks of tissue of the same bone sample were studied histotomographically in the CLSM. Results: (1) Light microscopic micromorphology of cortical bone can be visualized adequately in the CLSM; (2) many structures that can be visualized by light microscopy only after special staining (e.g., osteozyte processes) can be visualized by the CLSM using sample blocks without pretreatment. Conclusion: (1) Nondestructive subsurface histotomography by CLSM totally excludes mechanical artifacts; (2) physicochemical artifacts can be handled more easily because fresh samples can be studied; (3) pseudo-three-dimensional imaging allows histological interpretation of the tissue that is equivalent to macroscopic tomographic techniques (CT, MRT).
    Notes: Durch Fixierung (Formalin), Entkalkung (Schnitte) oder mechanische Bearbeitung (Schliffe) besteht bei der Hartgewebshistologie das Risiko physikalisch-chemischer oder mechanischer Artefakte. Da Studien zur Ätiopathogenese pathologischer Veränderungen meist auf subklinische Läsionen zielen, besteht die Gefahr, daß Artefakte frühe Veränderungen vortäuschen oder vorhandene überdecken. Es wird der Frage einer artefaktminimierten Histologie nachgegangen. Bei der konfokalen Laser-Scanning-Mikroskopie (CLSM) rastert ein monochromatischer Laserstrahl über die Probenoberfläche und dringt in das Gewebe ein. Die Intensität der remittierten Strahlung wird in einem Detektor gemessen. Durch eine konfokale Blende (pinhole) erreicht nur Laserlicht aus einer extrem dünnen In-Fokus-Ebene den Detektor, so daß schrittweises Bewegen des Objekttischs eine tomographische Serie von Einzelbildern visualisiert. Gesunde kortikale Knochenproben des Unterkiefers (n = 20) wurden durchlichtmikroskopisch und im CLSM untersucht: Dabei wurden identische Probenareale an Dünnschliffen nach HE-Färbung visualisiert. Außerdem wurden eingebettete und frische Gewebeblöcke derselben Knochenproben im CLSM histotomographiert. Als Ergebnisse wurden gefunden: 1. Lichtmikroskopische Mikromorphologie kortikalen Knochens ist im CLSM valide visualisierbar. 2. Viele lichtmikroskopisch erst nach Spezialfärbungen darstellbare Strukturen (z.B. Osteozytenfortsätze) können im CLSM an Probenblöcken ohne Vorbereitung mikroskopiert werden. Hieraus können folgende Schlußfolgerungen gezogen werden: 1. Die zerstörungsfreie Histotomographie des CLSM unter der Probenoberfläche vermeidet mechanische Artefakte völlig. 2. Physikalisch-chemische Artefakte werden kontrollierbar, da auch frische Proben mikroskopiert werden können. 3. Die pseudo-dreidimensionale Darstellung erlaubt eine histologische Gewebeinterpretation, die makroskopischen Schichtbildverfahren (CT, MRT) vergleichbar ist.
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  • 35
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    Mund-, Kiefer- und Gesichtschirurgie 2 (1998), S. S37 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Kalzium ; Phosphat ; Hydroxylapatit ; Zement ; Knochenersatz ; Augmentation ; Key words Calcium ; Phosphate ; Hydroxyapatite ; Cement ; Bone ; Augmentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary A new stoechiometric mixture of 27% dicalcium-phosphate (DCPA) and 73% tetra-calcium-phosphate (TTCP) can be prepared with water intraoperatively to a paste that subsequently sets to a structurally stabile implant composed of hydroxyapatite (HA). Primary setting time is about 20 min; pH during setting ranges from 6.5 to 8.5. There is no relevant curing heat or expansion or contraction. Compressive strength is about 50 MPa, tensile strength about 8 MPa. Over a period of about 4 h in physiological milieu, the cement converts to hydroxyapatite. This product is no longer redissolvable in normal body fluid. This cement can be used for non-load-bearing applications especially in craniofacial bone surgery. Cranial defects due to tumour or trauma as well as deficits in the facial skeleton may be reconstructed using this new biomaterial. In nine of ten patients we used the hydroxyapatite cement successfully for reconstructions in the craniofacial area. Fluid control of the operation field and implant site is extremely important and sometimes difficult to achieve. Further applications could be all non-load-bearing augmentations such as filling of blocked paranasal sinuses, of dentoalveolar cysts and defects following dental apectomy or fixation of implanted hearing-aid electrodes. The perspectives for the hydroxyapatite cement include its application as a carrier for osteogenic protein preparations, especially because of its isothermic reaction and intrinsic osteoconductive characteristics.
    Notes: Zusammenfassung Ein neuer Kalziumphosphatzement besteht aus 73% Tetrakalziumphosphat und 27% Kalziumhydrogenphosphat. Er bindet bei Körpertemperaturen nach Zugabe von Wasser innerhalb von 20 min ab. Innerhalb von 4 h wird der Zement zu Hydroxylapatitkristallen umgesetzt und damit wasserunlöslich. Der Abbindeprozeß verläuft nahezu isotherm im pH-Bereich von 6,5–8,5 ohne Schrumpfung. Die Druckfestigkeit liegt im ausgehärteten Zustand oberhalb von 50 MPa, die Zugfestigkeit bei mehr als 8 Mpa. Der Zement ist für alle nicht lasttragenden Knochenaugmentationen und Knochenersatzanwendungen insbesondere am Gesichtsschädel geeignet. Bei 9 von 10 Patienten benutzten wir den Zement erfolgreich für Rekonstruktionen im kraniofazialen Bereich. Beim klinischen Einsatz muß besonders auf sorgfältige Trockenlegung des Operations- und Implantationsfelds geachtet werden. Weitere Anwendungsmöglichkeiten sind das Auffüllen von ausgeräumten und verblockten Schädelhöhlen, die Fixation von implantierten Hörelektroden in der Hals-Nasen-Ohren-Heilkunde sowie das Auffüllen von Zysten und Wurzelspitzenresektionsdefekten in der dentoalveolären Chirurgie. Besondere Perspektiven bietet der Hydroxylapatitzement wegen seiner isothermen Abbindereaktion und seiner intrinsischen osteokonduktiven Eigenschaften als Trägermaterial für osteogene Proteinkomplexe.
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  • 36
    ISSN: 1434-5196
    Keywords: Key words Identification ; Forensic osteology ; DNA typing ; PCR ; Brain ; Bone ; Schlüsselwörter Identifikation ; Forensische ; Osteologie ; DNA-Typisierung ; PCR ; Gehirn ; Knochen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Ein weitgehend skelettierter Kleinkind-Schädel konnte mittels forensisch-anthropologischer Befunderhebung klassifiziert und mittels erfolgreicher DNA-PCR-Typisierung am Hirnbrei, nicht jedoch am Schädelknochen identifiziert werden. Die vorgestellte Kasuistik belegt eindrücklich, daß eine sorgfältige forensisch-anthropologische Befunderhebung eine wesentliche Grundlage für die molekularbiologische Identifizierung an Skeletteilen bildet und daß auch an fortgeschritten fäulnisverändertem Gehirn bei feuchtem Lagerungsmilieu eine DNA-PCR-Typisierung erfolgreich sein kann.
    Notes: Abstract The skull of a small child, which was largely devoid of soft tissue, was classified according to forensic/anthropological findings and could be identified on the basis of DNA typing by PCR using residual brain tissue, but not bone. This case illustrates the fact that careful forensic/anthropological investigation is an important basis for molecular biological identification from skeletal remains and that DNA typing by PCR may even be possible on brain tissue that has been exposed to damp conditions and is an advanced state of decomposition.
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  • 37
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    Clinical rheumatology 17 (1998), S. 47-51 
    ISSN: 1434-9949
    Keywords: Bone ; Fatigue ; Stress fracture ; Stress reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Stress fractures are being increasingly reported as a common cause of morbidity in both healthy populations and those withunderlying diseases involving abnormal bone. An insight into the types and pathogenesis of stress fractures is necessary to considering the diagnosis, management and prevention of such conditions. The classification, aetiology and aspects of management are discussed.
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  • 38
    ISSN: 1432-0878
    Keywords: Key words Osteoclasts ; Osteoblasts ; Osteocytes ; Bone ; Substance P (SP) ; Neurokinin-1 receptor (NK1-R) ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Substance P (SP) is a neuropeptide that is released from axons of sensory neurons and causes signal transduction through the activation of the neurokinin-1 receptor (NK1-R). The present study demonstrates the distribution of SP-like-immunoreactive (SP-LI) axons and the localization of NK1-Rs in rat bone tissue using the avidin-biotin-peroxidase complex method. Axons with SP-LI were commonly found near the trabecular bone in the temporal bone marrow, but they were only sparsely distributed in the mandible, femur, and tibia. Immunoreactivity for NK1-Rs was found on the plasma membrane and in the cytoplasm of the osteoclasts. In the osteoblasts and osteocytes, a small number of weak, punctate immunoreactive products of NK1-Rs were distributed close to the plasma membrane. At the electron-microscopic level, immunoreactivity for NK1-R was distributed mainly in the whole cytoplasm, except for the clear zone of the osteoclasts, and in pit-like structures along the plasma membrane. The NK1-R-immunoreactive structures in the cytoplasm were divided into two types of organelles, consisting of vesicular and vacuolar structures (probably transport vesicles and early endosomes). In the osteoblasts and osteocytes, the number of NK1-R-positive vesicular structures was fewer than in the osteoclasts. These results thus suggest that SP secreted by the sensory axons could directly modulate bone metabolism via NK1-Rs.
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  • 39
    ISSN: 1432-0878
    Keywords: Key words Osteoclast ; Bone ; Bone resorption ; Alveolar bone ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Glutaraldehyde-formaldehyde fixed undecalcified alveolar bone from 7-day-old rats was prepared for light and electron microscopy. Colloidal lanthanum was used as an ultrastructural tracer, and both random and semi-serial sections were examined. Lanthanum penetrated the infoldings of the ruffled border and some nearby vacuoles and vesicles. The majority of vacuoles and vesicles were lanthanum-free. Some osteoclast profiles contained a large vacuole with a cell enclosed in its interior. The enclosed cell exhibited an irregular nucleus containing condensed peripheral chromatin, intact cytoplasmic organelles, conspicuous rough endoplasmic reticulum and large blebs on the cell surface. These features are characteristic of osteoblasts or bone-lining cells or immature osteocytes which may be undergoing apoptosis or necrosis. The observation of remnants of cellular structures within internalized osteoclast vacuoles, together with the above results, suggests that osteoclasts engulf and probably degrade dying osteoblasts/bone-lining cells or immature osteocytes.
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  • 40
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The apparent rate constants of formation (k1) and hydrolysis (k2) of the Schiff bases formed between pyridoxal and polyallylamine has been fitted to a kinetic scheme that involve the different protonated species in the reaction medium and the individual rate constants of formation (k1i) and hydrolysis (k2i). The (k1i) values precludes an acid catalyzed intramolecular process. The effects of hydrophobic medium due to the presence of the macromolecule on the reaction is also discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 1-6, 1998.
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  • 41
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    International Journal of Chemical Kinetics 30 (1998), S. 21-29 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of ozone with a series of unsaturated oxygenates and with 1-pentene has been studied at ambient T (287-296 K) and p=1 atm. of air. Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 0.22±0.05 for 2 (5H)-furanone, 1.08±0.20 for methacrolein, 1.74±0.20 for crotonaldehyde, 5.84±0.39 for methylvinyl ketone, 1.05±0.15 for methyl acrylate, 3.20±0.47 for vinyl acetate, 59.0±8.7 for cis-3-hexenyl acetate, 154±30 for ethylvinyl ether, ≥(315±23) for linalool, and 10.9±1.4 for 1-pentene. The results are compared to literature data for the compounds studied and for other unsaturated oxygenates, and are discussed in terms of reactivity toward ozone as a function of the nature, number, and position of the oxygen-containing substituents (SINGLEBOND)CHO, (SINGLEBOND)C(O)R, (SINGLEBOND)C(O)OR, and (SINGLEBOND)OC(O)R. Atmospheric implications are briefly examined. © 1998 John Wiley & Sons, Inc. Int. J Chem Kinet: 30: 21-29, 1998.
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  • 42
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    International Journal of Chemical Kinetics 30 (1998), S. 55-61 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tartaric acid oxidation by vanadium(V) in sulfuric acid medium was investigated spectrophotometrically at 760 nm and 30°C by appearance of the vanadium(IV), as vanadyl. The reaction rate was determined under pseudo-first-order conditions with an excess of hydroxyacid over the oxidant concentration. The oxidation showed a first-order dependence with respect to vanadium(V) concentration and fractional orders with respect to tartaric acid and sulfuric acid concentrations, with no control and with constant ionic strength. The reaction rate is enhanced by an increase of ionic strength, and slightly reduced by a decrease of the dielectric constant of the medium. The activation parameters were calculated based on the rate constants determined in the 293 to 313 K interval. The proposed oxidation mechanisms and the derived rate laws are consistent with the experimental rate laws. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 55-61, 1998.
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  • 43
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    International Journal of Chemical Kinetics 30 (1998), S. 99-110 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of silane thermal decomposition is investigated in a flow reactor. The time dependencies of silane consumption and disilane formation were compared with those parameters of solid product (aerosol particles) such as concentration, total hydrogen content in solid product, and fraction of hydrogen contained in solid product as polyhydride groups (SiH2)n. Silane loss and gaseous product formation were analyzed using a mass spectrometer. The hydrogen content in solid product was analyzed by the methods of IR-spectroscopy and hydrogen evolution. Based on a simple kinetic scheme we qualitatively explained the experimental dependencies of silane conversion and disilane formation, the effective activation energy of the decomposition process, and the amount of polyhydride groups in the solid product on reaction time and initial silane concentration. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 99-110, 1998.
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  • 44
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    International Journal of Chemical Kinetics 30 (1998), S. 137-143 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of tert-amyl methyl ether (TAME) from methanol (MeOH) and tert-amyl alcohol (TAA) in the liquid phase was studied by using an ion exchange resin, Amberlyst15 (A15) in the H+ form. Experiments were carried out in a stirred batch reactor under atmospheric pressure. The effects of catalyst size, agitation speed, temperatures, feed ratio and water on the reaction rate were investigated. Both of intraparticle and external diffusion effects could be neglected in this system. The dehydration of TAA could be decreased by increasing the ratio of MeOH/TAA and the reaction rates were greatly inhibited by water.A kinetic model which considered the inhibition of water was proposed. The experimental results agreed well with the model. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 137-143, 1998.
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  • 45
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of proton transfer between poly(A - AH) (partially protonated double-stranded polyadenylic acid) and CPR (chlorophenol red), and between poly(C - H - C) (partially protonated double-stranded polycytidylic acid) and the indicators CPR, BCP (bromocresol purple), and BCG (bromocresol green) have been investigated at 25°C and ionic strength 0.1 M (NaClO4) by the temperature-jump method. The acidic proton of poly(C - H - C) is engaged in a hydrogen bond (N3H+----N3) which is believed to contribute to stabilizing the double-strand conformation, whereas the acidic proton of poly(A - A - H) does not form hydrogen bonds. The analysis of the dependence of the relaxation times on the concentrations of the reactants has enabled the evaluation of the rate constants for the direct proton transfer and for the protolysis paths. The rate constants for proton recombination with the deprotonated forms of the polynucleotides and the indicators are of the order of magnitude expected for diffusion controlled processes involving oppositely charged ions (k2=(0.2-1.6)×1010 M-1s-1). The direct proton transfer from poly(C - H - C) to BCG is thermodynamically disfavored and its rate constant, k1, is lower than k2 by about three orders of magnitude. The (thermodynamically favored) proton transfers from poly(A - A - H) to CPR and from poly(C - H - C) to CPR and BCP are characterized by similar values of k1. This result indicates that the hydrogen bonds in poly(C - H - C) are very weak and suggests that the stabilization of the double-stranded conformation of this polynucleotide could be ascribed to the large number of hydrogen bonds rather than to their specific strength. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 161-169, 1998.
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  • 46
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    International Journal of Chemical Kinetics 30 (1998), S. 201-206 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dual-phase oscillations are observed in Belousov-Zhabotinsky system with 4-hydroxy-3-methoxybenzaldehyde (vanillin) as the substrate and manganous sulphate or ammonium Ce(IV) sulphate as the catalyst. The nonoscillatory period of time between the two phases decreases with increase in the concentration of the catalyst and the substrate. Under uncatalyzed and ferroin catalyzed conditions the system exhibits single-phase oscillations. The first-phase oscillations are due to vanillin whereas the second-phase oscillations are brought about by 4-hydroxy-3-methoxybenzoic acid (vanillic acid) formed during the course of the first-phase reactions. The reactions are explained with relevant steps of the FKN mechanism. © 1998 John Wiley & Sons, Inc. Int J. Chem. Kinet 30: 201-206, 1998.
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  • 47
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    International Journal of Chemical Kinetics 30 (1998), S. 215-221 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The lifetime of the ferryl ion FeO2+, (minutes at pH below 1) is reduced by a factor of 50 at pH above 3. This is rationalized in terms of an acid-base equilibrium between two different hydrolytic forms of this species (Fe(OH)++2 and Fe(OH)+3) with a pKa=2.0. The rate constants for reactions between FeO2+ and selected compounds found in cloud water were measured in acid solutions by stopped-flow technique. For inorganic reactants: kHNO2=1.1×104 M-1 s-1, kNO2-≤105 M-1 s-1, kCl-=1.0×102 M-1 s-1, kHSO3-=2.5×105 M-1 s-1, kSO2=4.5×105 M-1 s-1, and kMn(II)=1.0×104 M-1 s-1 were obtained and for the organic reactants: kHCOOH=160 M-1 s-1, kHCOO-=3×105 M-1, kCH3COOH=3.1 M-1 s-1, kCH2(OH)2=400 M-1 s-1, kCH3COCH3=16 M-1 s-1, kCH3CH20H=2.5×103 M-1 s-1, kC6H5OH=4.0×103 M-1 s-1, and kC6H5COOH=80 M-1 s-1 were obtained. A good correlation between log(k) and the standard one electron reduction potential (E°) indicates that the reactions of inorganic compounds proceed by electron transfer. The reaction mechanisms in case of organic compounds are very similar to the reactions of the OH radical, i.e., H-abstraction, and a fairly good correlation between log(k) and the bond dissociation energy BDE was obtained. Activation parameters were measured for the reaction of FeO2+ with HNO2 (Ea=34.5 kJ/mol); Mn2+ (Ea=21.3 kJ/mol); HCOOH (Ea=22.3 kJ/mol); CH2(OH)2 (Ea=44.5 kJ/mol); and C6H5OH (Ea=28.1 kJ/mol). © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 215-221, 1998.
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  • 48
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    International Journal of Chemical Kinetics 30 (1998), S. 249-255 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A discharge flow reactor coupled to a laser-induced fluorescence (LIF) detector and a mass spectrometer was used to study the kinetics of the reactions CH3O+Br→products (1) and CH3O+BrO→products (2). From the kinetic analysis of CH3O by LIF in the presence of an excess of Br or BrO, the following rate constants were obtained at 298 K: k1=(7.0±0.4)×10-11 cm3 molecule-1 s-1 and k2=(3.8±0.4)×10-11 cm3 molecule-1 s-1. The data obtained are useful for the interpretation of other laboratory studies of the reactions of CH3O2 with Br and BrO. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 249-255, 1998.
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  • 49
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    International Journal of Chemical Kinetics 30 (1998), S. 471-474 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate method, rate constants have been measured for the gas-phase reactions of the OH radical with the dibasic esters dimethyl succinate [CH3OC(O)CH2CH2C(O)OCH3], dimethyl glutarate [CH3OC(O)CH2CH2CH2C(O)OCH3], and dimethyl adipate [CH3OC(O)CH2CH2CH2CH2C(O)OCH3] at 298±3 K. The rate constants obtained were (in units of 10-12 cm3 molecule-1 s-1): dimethyl succinate, 1.4±0.6; dimethyl glutarate, 3.3±1.1; and dimethyl adipate, 8.4±2.5, where the indicated errors include the estimated overall uncertainty of ±25% in the rate constant for cyclohexane, the reference compound. The calculated tropospheric lifetimes of these dibasic esters due to gas-phase reaction with the OH radical range from 1.4 days for dimethyl adipate to 8.3 days for dimethyl succinate for a 24 h average OH radical concentration of 1.0×106 molecule cm-3. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 471-474, 1998
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  • 50
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of mixed CH3CN(SINGLEBOND)H2O solvents on rates of aminolysis of ionized phenyl salicylate, PS-, reveal a nonlinear decrease in the nucleophilic second-order rate constants, knms, (for aminolysis) with increase in the content of CH3CN until it becomes ∼50%, v/v. The values of knms remain almost unchanged with change in the CH3CN content within 50 to 70 or 80%, v/v. The effects of mixed CH3CN(SINGLEBOND)H2O solvents on pKa of leaving group, phenol, and protonated amine nucleophile have been concluded to be the major source for the observed mixed solvent effects on knms. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 301-307, 1998.
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  • 51
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    International Journal of Chemical Kinetics 30 (1998), S. 629-640 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes an experimental and modeling study of the oxidation of isobutene. The low-temperature oxidation was studied in a continuous-flow stirred-tank reactor operated at constant temperature (from 833 to 913 K) and pressure (1 atm), with fuel equivalence ratios from 3 to 6 and space times ranging from 1 to 10 s corresponding to isobutene conversion yields from 1 to 50%. The main carbon containing products were analyzed by gas chromatography. The ignition delays of isobutene-oxygen-argon mixtures with fuel equivalence ratios from 1 to 3 were measured behind shock waves. Reflected shock waves permitted to obtain temperatures from 1230 to 1930 K and pressures from 9.5 to 10.5 atm.A mechanism has been proposed to reproduce the profiles obtained for the reactants consumption and the products formation during the slow oxidation and to compute the ignition delays in the shock tube. Simulations were performed using CHEMKIN II. A correct agreement between the simulated values and the experimental data has been obtained in both apparatuses. The main reaction paths have been determined for both series of measurements by a sensitivity and rate of production analysis. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 629-640, 1998
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  • 52
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    International Journal of Chemical Kinetics 30 (1998), S. 589-594 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate method, rate constants for the gas-phase reactions of 2-methyl-3-buten-2-ol (MBO) with OH radicals, ozone, NO3 radicals, and Cl atoms have been investigated using FTIR. The measured values for MBO at 298±2 K and 740±5 torr total pressure are: kOH=(3.9±1.2)×10-11 cm3 molecule-1 s-1, kO3=(8.6±2.9)×10-18 cm3 molecule-1 s-1, kNO3=(8.6±2.9)×10-15 cm3 molecule-1 s-1, and kCl=(4.7±1.0)×10-10 cm3 molecule-1 s-1. Atmospheric lifetimes have been estimated with respect to the reactions with OH, O3, NO3, and Cl. The atmospheric relevance of this compound as a precursor for acetone is, also, briefly discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 589-594, 1998
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  • 53
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    International Journal of Chemical Kinetics 30 (1998), S. 621-628 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1,1-Trifluoroethane has been decomposed in comparative rate single-pulse shock-tube experiments. The rate expression for elimination at ca. 2.5 bar and in the temperature range of 1050 to 1200 K has been found to be\documentclass{article}\pagestyle{empty}\begin{document}$ \it k\rm (CF_{3}\joinrel{\relbar\!\!\relbar}CH_{3}\relbar\!\!\rightarrow HF+CF_{2}=CH_{2})=7.0\times 10^{14}\ exp(-37260/T)s^{-1} $\end{document}The experimental conditions appear to be such that the unimolecular reaction is at the beginning of the fall-off region and we find that for step sizes down between 500 and 1000 cm-1 the high-pressure rate expression is in the range\documentclass{article}\pagestyle{empty}\begin{document}$ \it k\rm (CF_{3}\joinrel{\relbar\!\!\relbar}CH_{3}\relbar\!\!\rightarrow HF+CF_{2}=CH_{2})=2.0\times 10^{15}\ exp(-38300/T)\ to\ 4\ \times\ 10^{15}\ exp(-39000/T)s^{-1} $\end{document}where the smaller rate parameters refer to the larger step size down. The results are compared with those from an earlier study and the anomalously high A-factor is noted. It is suggested that the existing rate expressions for the fluorinated ethanes may need to be reevaluated. © 1998 John Wiley & Sons, Inc., Int J Chem Kinet: 30: 621-628, 1998
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  • 54
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    International Journal of Chemical Kinetics 30 (1998), S. 673-681 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The authors present a critical analysis of the use of an overall single reaction rate equation instead of the true rate equations corresponding to the decomposition of a substance according to two parallel reactions. Isothermal as well as nonisothermal decomposition are considered. An apparent compensation effect has been evidenced in both cases. It has been assigned to the dependence of the kinetic parameters on temperature (for the isothermal case), conversion, and heating rate (for nonisothermal one). © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 673-681, 1998
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  • 55
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    International Journal of Chemical Kinetics 30 (1998), S. 785-797 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reduction of iodine by hydroxylamine within the [H+] range 3×10-1-3×10-4 mol.L-1 was first studied until completion of the reaction. In most cases, the concentration of iodine decreased monotonically. However, within a narrow range of reagent concentrations ([NH3OH+]0/[I2]0 ratio below 15, [H+] around 0.1 mol.L-1, and ionic strength around 0.1 mol.L-1), the [I2] and [I3-] vs. time curves showed 2 and 3 extrema, respectively. This peculiar phenomenon is discussed using a 4 reaction scheme (I2+I-⇔I3-, 2 I2+NH3OH++H2O→HNO2+4 I-+5 H+, NH3OH++HNO2→N2O+2 H2O+H+, and 2 HNO2+2 I-+2 H+→2 NO+I2+2 H2O). In a flow reactor, sustained oscillations in redox potential were recorded with an extremely long period (around 24 h).The kinetics of the reaction was then investigated in the starting conditions. The proposed rate equation points out a reinforcement of the inhibition by hydrogen ions when [H+] is above 4×10-2 mol.L-1 at 25°C. A mechanism based on ion-transfer reactions is postulated. It involves both NH2OH and NH3OH+ as the reducing reactive species. The additional rate suppression by H+ at low pH would be connected to the existence of H2OI+ in the reactive medium. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 785-797, 1998
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  • 56
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some relative rate experiments have been carried out at room temperature and at atmospheric pressure. This concerns the OH-oxidation of some oxygenated volatile organic compounds including methanol (k1), ethanol (k2), MTBE (k3), ethyl acetate (k4), n-propyl acetate (k5), isopropyl acetate (k6), n-butyl acetate (k7), isobutyl acetate (k8), and t-butyl acetate (k9). The experiments were performed in a Teflon-film bag smog chamber. The rate constants obtained are (in cm3 molecule-1 s-1): k1=(0.90±0.08)×10-12; k2=(3.88±0.11)×10-12; k3=(2.98±0.06)×10-12; k4=(1.73±0.20)×10-12; k5=(3.56±0.15)×10-12; k6=(3.97±0.18)×10-12; k7=(5.78±0.15)×10-12; k8=(6.77±0.30)×10-12; and k9=(0.56±0.11)×10-12. The agreement between the obtained rate constants and some previously published data has allowed for most of the studied compounds to point out a coherent group of values and to suggest recommended values. Atmospheric implications are also discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 839-847, 1998
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  • 57
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic studies of the oxidation of the bis[1-hydroxy-2-(salicylideneamino)ethane]manganese(II) complex by hydrogen peroxide in acetonitrile solutions, at (30.0±0.2)°C, are described. A first-order dependence on the total manganese and the peroxide concentrations was verified, leading to the rapid formation of a Mn(III) intermediate, monitored by stopped-flow measurements, at 394 nm, with a rate constant kf=(1.15±0.03)×105 mol-1 dm3 s-1. The participation of hydroxyl radicals in the process was detected by spin-trapping EPR spectra. The final product was monitored both by EPR spectra, and spectrophotometrically by the slow decay of the intermediary Mn(III) species, with a rate constant kd=(2.60±0.09) s-1. It was identified as the corresponding mononuclear Mn(IV) complex, and characterized by different spectroscopic techniques. Comparative results of the reactivity of the starting complex versus molecular oxygen, leading to the same final product, were also discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 889-897, 1998
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  • 58
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    International Journal of Chemical Kinetics 30 (1998), S. 923-932 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 1-butanethiol with hydrogen atoms was investigated at room temperature under pressures of 133, 266, 532, 2660, and 5320 Pa, using two types of fast-flow discharge reactors; the main products were n-butane and 1-butene with total yields of more than 90%. In the reaction of 1-butanethiol and deuterium atoms, monodeuterated 1-butanethiol was observed by a photo-ionizing mass spectrometer. The relative rate of the two initial reactions of 1-butanethiol with hydrogen atoms was 0.272 (k1/k2). The n-butane and 1-butene are considered to be produced via chemically activated 1-butanethiol on the basis of the pressure dependence of the two main products.\scriptfont4=\seveni \scriptscriptfont4=\fivei \halign{\hfill $#$&$#$\hfill &$#$\hfill &\hfill\qquad\qquad #\cr\rm 1\hbox{-}C_{4}H_{9}S&\rm H&\rm +H\longrightarrow 1\hbox{-}C_{4}H_{9}\cdot +H_{2}S& (1)\cr \rm 1\hbox{-}C_{4}H_{9}S&\rm H&\rm +H\longrightarrow 1\hbox{-}C_{4}H_{9}S\cdot +H_{2}& (2)\cr\rm 1\hbox{-}C_{4}H_{9}S&\rm \cdot &\rm +H\longrightarrow 1\hbox{-}C_{4}H_{9}SH\ast & (3)\cr } \bigskip\rm{}Relative rates of molecular elimination of hydrogen sulfide and C—S bond fission for the chemically activated 1-butanethiol, k5/k4 and k6/k4, were 0.114 and 0.0552 under 532 Pa of pressure at room temperature. Activation energies of the two reactions were calculated to be 228 [kJ/mol] and 297 [kJ/mol], respectively, by use of RRKM on the base of estimated A factors.\scriptfont4=\seveni \scriptscriptfont4=\fivei \halign{\hfill $#$&$#$\hfill &$#$\hfill &\hfill\qquad\qquad #\cr\rm 1\hbox{-}C_{4}H_{9}SH\ast +M&\rm \longrightarrow &\rm 1\hbox{-}C_{4}H_{9}SH& (4)\cr \rm 1\hbox{-}C_{4}H_{9}SH\ast &\rm \longrightarrow &\rm 1\hbox{-}C_{4}H_{8}+H_{2}S& (5)\cr\rm 1\hbox{-}C_{4}H_{9}SH\ast &\rm \longrightarrow &\rm 1\hbox{-}C_{4}H_{9}\cdot +HS\cdot & (6)\cr } \bigskip\rm{}© 1998 John Wiley & Sons, Inc. Int. J. Chem Kinet 30: 923-932, 1998
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  • 59
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    International Journal of Chemical Kinetics 30 (1998), S. 849-857 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aminolyses of the title substrates with anilines and benzylamines are investigated in acetonitrile. A clean second-order kinetics is obtained with a first-order rate law in the amine concentration, which is uncomplicated by the fast proton transfer step. The large magnitude of ρZ (ρ1g) as well as ρX (ρnuc) together with relatively large positive ρXZ values is consistent with a stepwise mechanism in which thiophenolate ion expulsion from the intermediate is rate limiting. For the reactions of aryl dithio-2-thiophenates with benzylamines the magnitude of ρX and ρZ values is relatively smaller suggesting that both the addition and expulsion of thiophenolate are partially rate determining. Relatively large secondary kinetic isotope effects, kH/kD≥1.7, with deuterated nucleophiles, support involvement a concurrent proton transfer to the departing thiophenolate ion in the transition state. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 849-857, 1998
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  • 60
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    International Journal of Chemical Kinetics 30 (1998), S. 899-902 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stoichiometry of CO2 production during the ceric oxidation of various organic acids is measured under conditions with organic acid excess. Measurements utilize a photometric methodology. For anaerobic conditions stoichiometries [CO2]produced:[Ce(IV)]reduced of about 0 (malonic acid), 0.5 (e.g., glyoxylic acid), and 1.0 (oxalic acid) are found. Oxalic acid showed an oxygen-induced decrease of CO2 production, while other compounds such as malonic acid increased the amount of produced CO2 or showed no changes (e.g., tartronic acid). In the case of mesoxalic acid the stoichiometry is increased from about 0.5 to 2.0 due to the presence of molecular oxygen. The results are discussed on the basis of simple reaction mechanisms demonstrating that useful information on reaction pathways and intermediates can be extracted from these simple measurements. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 899-902, 1998
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  • 61
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    International Journal of Chemical Kinetics 30 (1998), S. 7-19 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Manganese(III) solutions were prepared by known electrochemical methods in sulfuric acid, acetic acid, and pyrophosphate media. The nature of the oxidizing species present in manganese(III) solutions was characterized by spectrophotometric and redox potential measurements. Kinetics of oxidation of L-glutamine by manganese(III) in sulfuric acid (1.5 M), acetic acid (60% v/v), and pyrophosphate (pH=1.3) media at 313 K, 323 K, and 328 K, respectively, have been studied. Three different rate laws have been obtained for the three media. Effects of varying ionic strength, solvent composition, and added anions, such as fluoride, chloride, perchlorate, pyrophosphate, and bisulfate, have been investigated. There is evidence for the existence of free radicals as transient species. Activation parameters have been evaluated using Arrhenius and Eyring plots. Mechanisms consistent with the observed kinetic data have been proposed and discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 7-19, 1998.
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  • 62
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    International Journal of Chemical Kinetics 30 (1998), S. 63-67 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of reagent concentration and the pH in the kinetic behavior of the dissociation of Fe(II)-fulvic acid complexes were studied using a spectrophotometric technique. The results show that this behavior is not strongly affected by the concentration of fulvic acid, the concentration of the metal cation on the ratio of these concentrations and that variations in pH are more important in the dissociation process. A possible explanation based in the relative influence of proton concentration on the stability of the complexes is proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 63-67,1998.
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  • 63
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    International Journal of Chemical Kinetics 30 (1998), S. 111-120 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The detailed kinetics of the reaction of toluidine blue {phenothiazine-5-ium, 3-amino-7(dimethylamino)-2-methyl chloride, tolonium chloride, TB+Cl-} with potassium bromate and with aqueous bromine reaction were studied. In most of the experiments, the kinetics were monitored by following the rate of consumption of TB+ at 590 nm with excess acid and bromate. The reaction exhibited complex kinetic behavior. Initial reaction was slow and after an induction time, the TB+ concentration decreased fast. It had first-order dependence on both TB+ and bromate, and second-order dependence on H+. Under excess bromate conditions, the stoichiometric ratio of TB+ to bromate was 1:1. Demethylated sulfoxides were found at the reaction products. Sharp increase in the overall potential synchronized with the increase in bromine levels and the fast depletion of [TB+]. The role of bromide ion and bromine in the reaction was established. A multi-step reaction mechanism is proposed consistent with the experimental results. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 111-120, 1998.
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  • 64
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    International Journal of Chemical Kinetics 30 (1998), S. 145-150 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants were determined for the nitrosation reactions of the following substrates: Methyl (MU), Ethyl (EU),Propyl (PU)Butyl (BU), and Allylurea (AU). The rate equation found at a constant pH was: v=k[HNO2] [Urea]. The reactions were carried out in predominantly organic media(dioxane-acetic acid-water) with differing polarities. The proposed reaction mechanism involves the proton transfer from the protonated N-alkyl-N-nitrosourea to the acetate anion. As the polarity of the medium decreased, an approximation of the rate constants of the nitrosation of the different substrates was observed. This approximation can be interpreted as a function of the impediment generated by the R alkyl radical in the rate controlling step. Accordingly, the substrate reactivity will be associated with the ease in which the protonated N-alkyl-N nitrosurea can transfer the proton to the acetate anion. The results achieved in this study are in accordance with there activities observed in the nitrosation of these substrates in aqueous media MU≫(EU≈PU≈BU)〉AU. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 145-150, 1998.
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  • 65
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    International Journal of Chemical Kinetics 30 (1998), S. 185-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decomposition of azetidine {(CH2)3N(SINGLEBOND)H)} was measured using single-pulse shock-tube techniques, over the temperature range 855-1100 K, in high argon dilution. These data confirm and extend an earlier investigation that utilized the very low-pressure pyrolysis method. A brief survey of many reports regarding the interesting features of azetidine is presented. In two appendices the thermodynamic and kinetic data on trimethylene sulfide, oxide, and immine are intercompared. New ab-initio calculations are cited for the parent species and their fragmentation products. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 185-191, 1998.
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  • 66
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    International Journal of Chemical Kinetics 30 (1998), S. 207-214 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Manganese(II) is oxidized by ozone in acid solution, k=(1.5±0.2)×103 M-1 s-1 in HClO4 and k=(1.8±0.2)×103M-1 s-1 in H2SO4. The plausible mechanism is an oxygen atom transfer from O3 to Mn2+ producing the manganyl ion MnO2+, which subsequently reacts rapidly with Mn2+ to form Mn(III). No free OH radicals are involved in the mechanism. The spectrum of Mn(III) was obtained in the wave length range 200-310 nm. The activation energy for the initial reaction is 39.5 kJ/mol. Manganese(III) is reduced by hydrogen peroxide to Mn(II) with k(Mn(III)+H2O2)=2.8×103M-1 s-1 at pH 0-2. The mechanism of the reaction involving formation of the manganese(II)-superoxide complex and reaction of H2O2 with Mn(IV) species formed due to reversible disproportionation of Mn(III), is suggested. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 207-214, 1998.
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  • 67
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    International Journal of Chemical Kinetics 30 (1998), S. 243-247 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nine amino acids, aspartic acid, glycine, serine, tyrosine, alanine, glutamic acid, threonine, cystine, phenylalanine, and two peptides, and two peptides, glycine-glycine peptide, glutamic acid-cystine-glycine peptide, give rise to damped oscillations of the Belousov-Zhabotinskii(BZ) type in a batch reactor. Both Mn2+ and Fe(phen)32 are essential for most of those oscillations; and the oscillations in [Mn3+] and [Fe(phen)33+] are also observed. The role of two metallic ions played in the oscillations are analyzed, showing that Mn2+ catalyzes the oxidation of the amino acids or peptides by BrO3- to produce some intermediates which effectively reduce Br2 to Br- catalyzed by Fe(phen)32+. © 1998 John Wiley & Sons, Inc. Int. J. Chem Kinet 30: 243-247, 1998.
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  • 68
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    International Journal of Chemical Kinetics 30 (1998), S. 267-272 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions are subjected to a kinetic analysis in 44 wt% ethanol-water, at 25.0°C, ionic strength 0.2 (KCl). With a large excess of amine over the substrate, pseudo-first-order rate coefficients (kobs) are obtained, which are linearly dependent on the amine concentration. The nucleophilic rate constants (kN) are determined from plots of kobs vs. amine concentration. The Brönsted-type plot obtained with the kN values is linear, with slope β=0.63. The magnitude of this slope suggests that the mechanism is concerted, as opposed to a stepwise process with rate-determining breakdown of a zwitterionic tetrahedral intermediate (T±), in which the value of β is usually 0.8-1.0. The pyridinolysis of the same substrate in the same solvent is stepwise with the breakdown of T± as the rate-determining step. The change to a concerted mechanism for the title reactions is attributed to the superior nucleofugality of the alicyclic amines, compared to the isobasic pyridines, which destabilizes kinetically the “intermediate” T± in such a way that it does not exist, and the mechanism becomes enforced concerted. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 267-272, 1998.
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  • 69
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    International Journal of Chemical Kinetics 30 (1998), S. 309-310 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 70
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    International Journal of Chemical Kinetics 30 (1998), S. 313-327 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By surveying the most used methods for evaluating the kinetic parameters from nonisothermal experiments, a new classification scheme of the methods is proposed. For each method the number of principles and theoretical approximations required to derive the equation which grounds it, is considered as a comparison criterion. The methods are, finally, classified into classes of equivalence.As a result of the analysis it is also suggested that the activation energy, as calculated from nonisothermal data, should be given as a range of values instead of a unique value. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 313-327, 1998.
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  • 71
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    International Journal of Chemical Kinetics 30 (1998), S. 329-333 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the reactions CHFO+F, CFO+F and the self-reaction of CFO were determined over the temperature range of 222-298 K. A computer controlled discharge-flow system with mass spectrometric detection was used. The results are expressed in the Arrhenius form (with energies in J):CHFO+F→CFO+HF:k1(T)=(9.7±0.7)·10-12 exp[-(5940±150)/RT] cm3 molecule-1 s-1CFO+F+M→CF2O+M:FORMULA DISC=“MATH”〉k2(T)=(2.60±1.17)·10-10 exp[-(10110±1250)/RT cm3 molecule-1 s-1FORMULACFO+CFO→CF2O+CO:k3(T)=(3.77±2.7)·10-10 exp[-(8350±2800)/RT] cm3 molecule-1 s-1© 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 329-333, 1998
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  • 72
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    International Journal of Chemical Kinetics 30 (1998), S. 359-366 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal dehydrochlorination CF2ClCH3→CF2(DOUBLEBOND)CH2+HCl has been studied in a static system between 597 and 664 K in the presence of CCl4, C2Cl6, CF2(DOUBLEBOND)CH2, HCl, and CF3CH3. A kinetic radical and molecular reaction model has been developed. In addition to describing earlier results on the acceleration of the pyrolysis by CCl4 and the further acceleration by HCl, this model describes quantitatively up to conversions of 20% (i) the dependence of the catalytic effect of CCl4 at low concentrations, (ii) the stronger catalytic effect of C2Cl6, and (iii) the inhibitory effect of added CF2CH2 and CF3CH3 when CCl4 is used as a catalyst. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 359-366, 1998
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  • 73
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    International Journal of Chemical Kinetics 30 (1998), S. 407-414 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of aspirin (ASP) by bromamine-T (BAT), N-bromosuccinimide (NBS), and N-bromophthalimide (NBP) has been studied in aqueous perchloric acid at 303 K. The oxidation reaction follows identical kinetics with first-order in [oxidant], fractional-order in [ASP], and inverse fractional-order in [H+]. Under identical experimental conditions the extent of oxidation with different oxidizing agents is in the order: NBS 〉 BAT 〉 NBP. The rate decreased with decreasing dielectric constant of the medium. The variation of ionic strength and the addition of the reaction products and halide ions had no significant effect on the reaction rate. The solvent isotope effect was studied using D2O. Kinetic parameters were evaluated by studying the reaction at different temperatures. The reaction products were identified by GC-MS. The proposed reaction mechanism and the derived rate law are consistent with the observed kinetic data. Formation and decomposition constants for ASP-oxidant complexes have been evaluated. Decarboxylation, bromination, and loss of acetic acid gave 2,4,6-tribromophenol. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 407-414, 1998
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  • 74
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    International Journal of Chemical Kinetics 30 (1998), S. 425-437 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isobutane pyrolysis is studied in an unpacked Pyrex reactor at 20-100 torr initial pressures and 750-793 K. Results are interpreted in terms of a long chain radical mechanism and the reaction is modeled. The reaction selectivity or ratio of the initial production rate of isobutene (or hydrogen) to that of propene (or methane) is practically given by the ratio of the rate constant of abstraction of a tertiary hydrogen atom of isobutane to that of a primary one. A sensitivity analysis clearly shows that self-inhibition is essentially due to methylallyl radicals produced by hydrogen abstraction from isobutene. The model has been manually adjusted to experimental results and most of the adjusted rate constants are in agreement with literature data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 425-437, 1998
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  • 75
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    International Journal of Chemical Kinetics 30 (1998), S. 463-469 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent effects on the kinetics of hydrolysis of isatin by sodium hydroxide have been investigated within the temperature range (30-55°C) in methanol-water and acetonitrile-water media of varying solvent compositions up to 70% (v/v) of the organic solvent component. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. The determined isokinetic temperatures, in both systems, revealed the existence of compensation effect arising from strong solute-solvent interactions; log k was correlated with both log [H2O] and the reciprocal of the dielectric constant. The first correlation was observed to be linear while the second was nonlinear. Finally a mechanism for the isatin ring opening was proposed, which accounts for the role and the effect of the solvent on the reaction rate. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 463-469, 1998
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  • 76
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    International Journal of Chemical Kinetics 30 (1998), S. 565-570 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tert-Butyl hydroperoxide and hydrogen peroxide readily react with the radical cation derived from 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). The reaction is inhibited by ABTS and protons, and can be interpreted in terms of a mechanism comprising a partially reversible electron transferROOH+ABTS•+↔ ROO · + ABTS + H+ (1)followed by the self-reactions of the hydroperoxide derived radicals and reactions between them and another ABTS derived radical. A complete kinetic analysis allows an evaluation of the rate constant for reaction (1). A value of 0.2 M-1 s-1 was obtained for both compounds. The back reaction of process (1) is more relevant when tert-butyl hydroperoxide is employed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 565-570, 1998
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  • 77
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    International Journal of Chemical Kinetics 30 (1998), S. 595-604 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a stirred batch reactor, the Ce(III)- or Mn(II)-catalyzed Belousov-Zhabotinsky reaction with mixed organic acid/ketone substrates exhibits oscillatory behavior. The organic acids studied here are: dl-mandelic acid (MDA), dl-4-bromomandelic acid (BMDA), and dl-4-hydroxymandelic acid (HMDA), and the ketones are: acetone (Me2CO), methyl ethyl ketone (MeCOEt), diethyl ketone (Et2CO), acetophenone (MeCOPh), and cyclohexanone ((CH2)5CO). The effects of bromate ion, organic acid, ketone, metal-ion catalyst, and sulfuric acid concentrations on the oscillatory patterns are investigated. Both conventional and stopped-flow methods are applied to study the kinetics of the oxidation reactions of the above organic acids by Ce(IV) or Mn(III) ion. The order of relative reactivities of the oxidation reactions of organic acids in 1 M H2SO4 is Mn(III)(SINGLEBOND)HMDA reaction 〉 Ce(IV)(SINGLEBOND)HMDA reaction 〉 Mn(III)(SINGLEBOND)BMDA, reaction 〉 Mn(III)(SINGLEBOND)MDA reaction 〉 Ce(IV)(SINGLEBOND)BMDA reaction 〉 Ce(IV)(SINGLEBOND)MDA reaction. Spectrophotometric study of the bromination reactions of the above ketones shows that these reactions are zero-order with respect to bromine and first-order with respect to ketone and that ketone enolization is the rate-determining step. The order of relative rates of bromination or enolization reactions of ketones in 1 M H2SO4 is (CH2)5CO≫(MeCOEt, Et2CO, Me2CO)〉MeCOPh. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet:30: 595-604, 1998
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  • 78
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    International Journal of Chemical Kinetics 30 (1998), S. 641-646 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of bromide ions to the component solutions of the Briggs- Rauscher oscillating system produces a variety of phenomena, depending on the sequence of the addition and on the initial bromide concentration. If the addition is made some minutes after the mixing of H2O2 and acidic IO3- and before adding malonic acid and Mn2+ ions, the oscillations last for five or six cycles, then suddenly ceases. If the addition is made immediately after the mixing of H2O2 and acidic IO3- and before adding malonic acid and Mn2+ ions, the oscillations do not start at all. The addition of bromide ions to an actively oscillating BR reaction causes a rapid suppression of the oscillations. Our observations may be accounted for by a mechanism involving the IBr species. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 641-646, 1998
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  • 79
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    International Journal of Chemical Kinetics 30 (1998), S. 683-697 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental and theoretical study of the pyrolysis and oxidation of parabenzoquinone has been performed. The experiments were conducted in an isothermal quartz flow reactor at atmospheric pressure in the temperature range 600-1500 K. The main variables considered are temperature, oxygen concentration, and presence of CO. A detailed reaction mechanism for the pyrolysis and oxidation chemistry of parabenzoquinone is proposed, which provides a good description of the experimental results. Both the experimental work and the kinetic mechanism proposed for the pyrolysis and oxidation of parabenzoquinone represent the first systematic study carried out for this important aromatic compound.Our pyrolysis results confirm that the primary dissociation channel for p-benzoquinone leads to CO and a C5H4O isomer, presumably cyclopentadienone. However, significant formation of CO2 during the pyrolysis may indicate the existence of a secondary dissociation channel leading to CO2 and a C5H4 isomer. Under oxidizing conditions, consumption of p-benzoquinone occurs mainly by dissociation at lower temperatures. As the temperature increases interaction of OC6H4O with the radical pool becomes more significant, occurring primarily through hydrogen abstraction reactions followed by ring opening reactions of the OC6H3O radical. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 683-697, 1998
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  • 80
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    International Journal of Chemical Kinetics 30 (1998), S. 721-727 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the reactions of hydrogen atoms with n-C3H7Br, s-C3H7Br, n-C4H9Br, and s-C4H9Br were determined in a discharge flow-reactor at 298 K and a pressure of 4 mbar. Molecular-beam sampling and subsequent mass-spectrometric detection with electron-impact ionisation was used for the measurement of the bromo-hydrocarbon concentration. The rate coefficients obtained are (in 1010 cm3 mol-1 s-1): 2.3±1.2 for n-C3H7Br, 2.3±1.2 for s-C3H7Br, 2.4±1.2 for n-C4H9Br, and 2.8±1.4 for s-C4H9Br. The results are compared with predictions from bond-energy bond-order (BEBO) calculations, where a reasonable agreement is found. Furthermore, also by BEBO calculations, the relative importance of bromine abstraction as compared to hydrogen abstraction is estimated. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 721-727, 1998
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  • 81
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    International Journal of Chemical Kinetics 30 (1998), S. 769-776 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reaction of ozone with methylvinyl ketone (H2C(DOUBLEBOND)CHC(O)CH3), methacrolein (H2C(DOUBLEBOND)C(CH3)CHO), methacrylic acid (H2C(DOUBLEBOND)C(CH3)C(O)OH), and acrylic acid (H2C(DOUBLEBOND)CHC(O)OH) were measured at room temperature (296±2 K) in the presence of a sufficient amount of cyclohexane to scavenge OH-radicals. Results from pseudo-first-order experiments in the presence of excess ozone were found not to be consistent with relative rate measurements. It appeared that the formation of the so-called Criegee-intermediates leads to an enhanced decrease in the concentration of the two organic acids investigated. It is shown that the presence of formic acid, which is known to react efficiently with Criegee-intermediates, diminishes the observed removal rate of the organic acids. The rate constant for the reaction of ozone with the unsaturated carbonyl compounds methylvinyl ketone and methacrolein was found not to be influenced by the addition of formic acid. Rate constants for the reaction of ozone determined in the presence of excess formic acid are (in cm3 molecule-1 s-1): methylvinyl ketone (5.4±0.6)×10-18; methacrolein (1.3±0.14)×10-18; methacrylic acid (4.1±0.4)×10-18; and acrylic acid (0.65±0.13)×10-18. Results are found to be consistent with the Criegee mechanism of the gas-phase ozonolysis. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 769-776, 1998
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  • 82
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extension to the rotating-sector method, which is usually applied to determine propagation and termination rate constants, is presented. The analytical treatment developed accounts for the simultaneous presence of a thermal initiation and of a first-order termination process. The applicability of the rotating-sector method is thus extended to situations where the rate in dark is higher than 5% of the rate in the presence of light, and more accurate estimates of the rate constants are obtained than before for any values of the “dark” rate. A previously published experiment on the application of the rotating-sector method to the autoxidation of styrene was reanalyzed. The estimates obtained for the propagation and the termination rate constants were 11% and 19% higher than the previous estimates, respectively. Finally, the improved rotating-sector method was also applied to the experimental determination of propagation (kp) and termination rate constants (2×kt) for both 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine (PLPC) and 1,2-dilinoleoyl-sn-glycero-3-phosphocholine (DLPC) liposomes. The following results were obtained at 37°C: for PLPC kp =16.6 M-1s-1, and 2×kt=1.27×105 M-1s-1; for DLPC kp(intermolecular)=(13.3-13.9) M-1s-1, kp(intramolecular)=(4.7-5.4) s-1, and 2×kt=(0.99-1.05)×105 M-1s-1. The separation of the intermolecular and intramolecular propagation rate constants for DLPC was made possible both by a special adaptation of the rotating-sector equations to substrates with two oxidizable moieties, and by the experimental determination of the ratio between partially oxidized DLPC molecules (only one acyl is oxidized) and fully oxidized DLPC molecules (both acyls are oxidized). © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 753-767, 1998
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  • 83
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    International Journal of Chemical Kinetics 30 (1998), S. 805-830 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comprehensive detailed chemical kinetic mechanism for methanol oxidation has been developed and validated against multiple experimental data sets. The data are from static-reactor, flow-reactor, shock-tube, and laminar-flame experiments, and cover conditions of temperature from 633-2050 K, pressure from 0.26-20 atm, and equivalence ratio from 0.05-2.6. Methanol oxidation is found to be highly sensitive to the kinetics of the hydroperoxyl radical through a chain-branching reaction sequence involving hydrogen peroxide at low temperatures, and a chain-terminating path at high temperatures. The sensitivity persists at unusually high temperatures due to the fast reaction of CH2OH+O2=CH2O+HO2 compared to CH2OH+M=CH2O+H+M. The branching ratio of CH3OH+OH=CH2OH/CH3O+H2O was found to be a more important parameter under the higher temperature conditions, due to the rate-controlling nature of the branching reaction of the H-atom formed through CH3O thermal decomposition. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 805-830, 1998
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  • 84
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    International Journal of Chemical Kinetics 30 (1998), S. 869-874 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between BrO3- and sulfite was studied by measuring the concentrations of [Br-] and [H+] both in buffered and in unbuffered solutions. A mechanism was applied for simulation of the experimental observations. Rate constants k1=(0.027±0.004) M-1s-1 and k2=(85±5) M-1s-1 were determined for the following reactions:\halign{\hfill $#$\hfill &\hfill\qquad\qquad #\cr 3\ \rm HSO_{3}\!^{-}+BrO_{3}\!^{-}\longrightarrow 3\ SO_{4}\!^{2-}+Br^{-}+3\ H^{+}& (1)\cr 3\ \rm H_{2}SO_{3}(\hbox{or}\ SO_{2.}\hbox{aq})+BrO_{3}\!^{-}\longrightarrow 3\ SO_{4}\!^{2-}+Br^{-}+6\ H^{+}& (2)\cr }Rate constant k1 was obtained directly from the experimental results on unbuffered reactions, where Reaction (1) was predominant. Rate constant k2 was obtained by computer fitting of [Br-] to the experimental values for buffered reactions, where the rate of Reaction (2) was about four times higher than that of Reaction (1). © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 869-874, 1998
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  • 85
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    International Journal of Chemical Kinetics 30 (1998), S. 859-867 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Br-atom atomic resonance absorption spectrometry (ARAS) has been developed and applied to measure thermal decomposition rate constants for CF3Br (+ Kr)→CF3+Br (+ Kr) over the temperature range, 1222-1624 K. The Br-atom curve-of-growth (145〈λ〈163 nm) was determined using this reaction. For [Br]≤1×1012 molecules cm-3, absorbance, (ABS)=1.410×10-13 [Br], yielding σ=1.419×10-14 cm2. The curve-of-growth was then used to convert (ABS) to Br-atom profiles which were then analyzed to give measured rate constants. These can be expressed in second-order by k1=8.147×10-9 exp(-24488 K/T) cm3 molecule-1 s-1 (±33%, 1222≤T≤1624 K). A unimolecular theoretical approach was used to rationalize the data. Theory indicates that the dissociation rates are closer to second- than to first-order, i.e., the magnitudes are 30-53% of the low-pressure-limit rate constants over 1222-1624 K and 123-757 torr. With the known, E0=ΔH00=70.1 kcal mole-1, the optimized theoretical fit to the ARAS data requires 〈ΔE〉down=550 cm-1. These conclusions are consistent with recently published data and theory from Kiefer and Sathyanarayana. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 859-867, 1998
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  • 86
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    International Journal of Chemical Kinetics 30 (1998), S. 47-54 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new linear regression method is applied to determine the rate constants from time-dependent profiles. The method is effective for obtaining the rate constants of such consecutive processes as vibrational relaxation. The ambiguity of ordinary nonlinear analysis is eliminated by the linearization of regression equations. Because the new method also determines relative detectivity, the nascent vibrational distributions immediately following reactions or photolysis can be obtained simultaneously. In order to demonstrate the reliability of the new method under practical conditions, several examples of analysis of the data with noise are shown in detail. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 47-54, 1998.
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  • 87
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined the kinetics and mechanism of the dediazoniation reaction of p-methylbenzenediazonium tetrafluoroborate in the presence and absence of CuCl2 using a methodology developed by us that allows, simultaneously, and within the same experiment to identify, to quantify, and to obtain the rate constants for the formation of all dediazoniation products, and, indirectly, the rate constant for the diazonium salt decomposition. The methodology developed combines the use of coupling reactions, to form a stable azo dye, followed by analysis by HPLC. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 31-39, 1998.
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  • 88
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    International Journal of Chemical Kinetics 30 (1998), S. 41-45 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heats of formation of BrONO2, BrONO, BrOOH, FOOH, FOOCl, CF3C(O)OOH, HC(O)OOH, CH3C(O)OOH, and [CH3C(O)O]2 are estimated from bond contributions taken from J. Phys. Chem.,100, 10150 (1996). They agree within ±2 kcal/mol with recent experimental or ab initio data. The resulting BDE(O(SINGLEBOND)O)=36 kcal/mol value in diacetyl peroxide requires the concerted assistance of exothermic C(SINGLEBOND)C(O) weakening in the transition state of its decomposition into free radicals. It also implies the existence of a previously unrecognized 12 kcal/mol nonbonded repulsion in acyl anhydrides. The formation of chloryl chlorate with ΔHf(O2ClOClO2)=50 kcal/mol, a marginally stable species toward dissociation into (ClO3+OClO), may account for observations made in the [O(3P+OClO] system at low temperatures. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 41-45, 1998.
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  • 89
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    International Journal of Chemical Kinetics 30 (1998), S. 89-97 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data relative to methane trapping of SiCl2 and a rate constant for the SiCl2 into C(SINGLEBOND)H bond insertion process of k-1=13.4 M-1s-1 at 921 K are reported. Results on the decomposition of the trapping product, methyldichlorosilane, are also reported. This decomposition follows first-order kinetics with a rate constant of k=1.5±0.2×10-3 s-1 at 905 K and produces methane, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane. It is argued that the decomposition involves silylene intermediates, is nonchain, and is initiated primarily by the molecular methane elimination process MeSiHCl2(SINGLEBOND)1→ CH4+SiCl2. Free radicals and Si(SINGLEBOND)C bond fission may also contribute to the decomposition but are not dominant. The kinetics of MeSiHCl2 decomposition are shown to be consistent with the kinetics of the reverse SiCl2/CH4 trapping reaction and with the overall reaction thermochemistry. Reaction modeling gives product yields, reactant conversions, and rates in reasonable agreement with the data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 89-97, 1998.
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  • 90
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    International Journal of Chemical Kinetics 30 (1998), S. 121-127 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From a study of the complexation of FeIII with 2,6-dimethyl-3,5-heptanedione in aqueous solution, thermodynamic and kinetic parameters have been obtained. Results obtained for this system and a series of structurally similar iron(III) diketonates at different temperatures, establishes isokinetic behaviors of these kinds of reactions.Analytical correlations obtained may be useful to predict, for analogous ligands in similar experimental conditions, an essential mechanism, that pathways involving reaction of metal-hydrolyzed species with the enol tautomer are faster than pathways involving hexa-aqua species. Additionally, thermodynamic parameters associated with the monochelated complexations may be predicted. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 121-127, 1998.
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  • 91
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    International Journal of Chemical Kinetics 30 (1998), S. 151-159 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article is concerned with the application of a new method to recover the rate constants in chemical reactions. The method is based on treating the unknown parameters as time dependent. With appropriate experimental data the unknown rate constants are guided from an arbitrary initial condition to their true value at a final time. An explicit equation describing the time evolution of the parameters is obtained by minimizing the error along the trajectory. The method leads to an iterative algorithm which is described in detail. Numerical results with the method indicate that accurate estimates of the rate constants can be obtained directly from experimental data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 151-159, 1998.
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  • 92
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    International Journal of Chemical Kinetics 30 (1998), S. 179-184 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio calculations have been used to characterize the transition states for halogen abstraction by CH3 in reactions with CF4, CF3Cl, CF3Br, and CF3I (1-4). Geometries and frequencies were obtained at the HF/6-31G(d) and MP2=full/6-31G(d) levels of theory. Energy barriers were computed via the Gaussian-2 methodology, and the results were employed in transition state theory analyses to obtain the rate constants over 298-2500 K. There is good accord with literature measurements in the approximate temperature range 360-500 K for reactions (2-4), and the computed activation energies are accurate to within ±6 kJ mol-1. Recommended rate constant expressions for use in combustion modeling are k;1=1.6×10-19 (T/K)2.41 exp(-13150 K/T), k2=8.4×10-20(T/K)2.34 exp(-5000 K/T), k3=4.6×10-19 (T/K)2.05 exp(-3990 K/T), and k4=8.3×10-19 (T/K)2.18 exp(-1870 K/T) cm3 molecule-1 s-1. The results are discussed in the context of flame suppression chemistry. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 179-184, 1998.
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  • 93
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    International Journal of Chemical Kinetics 30 (1998), S. 707-709 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Upper limits of 4×10-20 and 7×10-20 cm3 molecule-1 s-1 were established for the gas-phase reactions of H2O2 with O3 and NO, respectively. These reactions are too slow to explain features observed in the atmospheric vertical profile of H2O2. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 707-709, 1998
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  • 94
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    International Journal of Chemical Kinetics 30 (1998), S. 737-744 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the mass transfer phenomena on the thermal decomposition of calcium carbonate powders under vacuum was investigated through a detailed kinetic analysis by the constant transformation rate thermal analysis (CRTA). Reliable kinetic curves, free from the mass transfer problems, can be obtained by CRTA under vacuum, but within a restricted range of small sample sizes, 〈10 mg. The influence of mass transfer phenomena on the apparent kinetic parameters is discussed in relation to the distribution of fractional reaction α of the individual particles in a sample assemblage. Only when the distribution of α is maintained constant among a series of experimental kinetic curves, can a reliable activation energy, E, be obtained by one of the isoconversion methods. In this respect, a single cyclic CRTA permits the α distribution to be maintained constant between the two adjacent data points with different decomposition rates. In the present study, an apparent E value of about 223 kJ mol-1 was obtained by the Friedman method from a series of CRTA curves with sample sizes less than 10 mg and by the rate jump method from a single cyclic CRTA curve with sample size of about 40 mg. The first-order (F1) law was determined to be the most appropriate kinetic model function, from a series of CRTA curves, instead of the ideal contracting geometry (R3) law formalized for the three-dimensional shrinkage of the reaction interface in the respective particles. The particle size distribution of the sample particles is suggested to be one possible reason for the apparent agreement with the F1 law. A kinetic exponent n of the nth-order law that deviated from unity was obtained from the CRTA curves with sample sizes larger than 10 mg, due to an additional distribution of α produced by mass transfer phenomena. Because the α distribution due to the mass and heat transfer phenomena cannot be expressed practically in an analytical function, a meaningful kinetic model and preexponential factor are difficult to estimate from kinetic data that are influenced by the transfer phenomena. © 1998 John Wiley & Sons, Inc. Int. J Chem Kinet: 30: 737-744, 1998
    Additional Material: 9 Ill.
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  • 95
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 777-783 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 2-phenoxyquinoxaline (1) with hydroxide ion is accelerated by reactive counter-ion micelles of cetyltrialkylammonium hydroxides (alkyl=Me, Et, n-Pr, and n-Bu), cetylmethylpiperidinium hydroxide, and cetylquinuclidinium hydroxide containing bulky head groups. First-order rate constants for reaction of (1) with OH- increase with increasing bulk of the head group and are associated with an increase in nucleophile reactivity as water is squeezed away from the micelle surface. Micellar effects upon the alkaline hydrolysis of compound (1) were analyzed by using a model that describes micelle-ion interactions in terms of Langmuir isotherms. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 777-783, 1998
    Additional Material: 6 Ill.
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  • 96
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 831-837 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-resolved total emission of SO2 (B1B1→X1A1) at 354.9 nm were monitored following the direct excitation by a 266 nm laser pulse. A three-level model was proposed to deal with SO2 (X1A1, A1A2, B1B1) system. From a kinetic treatment of these measurements, the coupling coefficient, ξ, and the relaxation time, τ, relating to the high vibronic levels of A1A2 and B1B1 states were first obtained. It is found that ξ and τ values keep basically constant, reflecting the characteristics of the studied system. In addition, the quenching rate constants of SO2 (A1A2, B1B1) by some alkane and chloromethane molecules were measured at room temperature. The formation cross sections of complexes of SO2 (A1A2, B1B1) and quenchers were calculated by means of a collision complex model. It is shown that the dependence of the formation cross section of complex on the number of C(SINGLEBOND)H or C(SINGLEBOND)Cl bonds is generally in agreement with that of the measured quenching cross section. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 831-837, 1998
    Additional Material: 3 Ill.
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  • 97
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 577-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products of the gas-phase reaction of the OH radical with 3-methyl-1-butene in the presence of NO have been investigated at room temperature and 740 torr total pressure of air by gas chromatography with flame ionization detection, in situ Fourier transform infrared absorption spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry. The products identified and quantified by GC-FID and in situ FT-IR absorption spectroscopy were HCHO, 2-methylpropanal, acetone, glycolaldehyde, and methacrolein, with formation yields of 0.70±0.06, 0.58±0.08, 0.17±0.02, 0.18±0.03, and 0.033±0.007, respectively. In addition, IR absorption bands due to organic nitrates were observed, consistent with API-MS observations of product ion peaks attributed to the β-hydroxynitrates (CH3)2CHCH(ONO2)CH2OH and/or (CH3)2CHCH(OH)CH2ONO2 formed from the reactions of the corresponding β-hydroxyalkyl peroxy radicals with NO. A formation yield of ca. 0.15 for these nitrates was estimated using IR absorption band intensities for known organic nitrates. These products account for essentially all of the reacted 3-methyl-1-butene. Analysis of the potential reaction pathways involved shows that H-atom abstraction from the allylic C(SINGLEBOND)H bond in 3-methyl-1-butene is a minor pathway which accounts for 5-10% of the overall OH radical reaction. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 577-587, 1998
    Additional Material: 9 Ill.
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  • 98
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 613-619 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between glycolaldehyde (GA) and tetrachloroaurate(III) in acetic acid-sodium acetate buffer has been studied. The reaction is first-order with respect to [AuIII] as well as [GA]. Both H+ and Cl- ions retard the rate of reaction. AuCl4-, AuCl3(OH2), and AuCl3(OH)- are the reactive species of gold(III) with gradually increasing reactivity. A reaction mechanism involving two-electron transfer rate determining steps has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 613-619, 1998
    Additional Material: 3 Ill.
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  • 99
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 949-959 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Detailed modeling of the oxidation of n-octane and n-decane in the gas phase was performed by using mechanisms written by means of a software recently developed in our laboratory. This computer-aided design of mechanisms permits the automatic generation of detailed oxidation and combustion kinetic models in the case of paraffins and isoparaffins [1]. For n-octane, the predictions of the model were compared with experimental results obtained by Dryer and Brezinsky by means of a turbulent plug flow reactor (1080 K, 1 atm) [2]. The experimental study of Balès-Guéret et al., performed in a perfectly stirred reactor (922-1033 K, 1 atm) [3], was used as a basis of comparison for the modeling of the oxidation of n-decane. Considering that no fitting of any kinetic parameter was done, the agreement between the computed and the experimental values is satisfactory both for conversions and for the distribution of the products formed. This modeling has required improvement in the generation of the secondary reactions of alkenes, which are the main primary products obtained during the oxidation of these two alkanes in the range of temperature studied and for which reaction paths are detailed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 949-959, 1998
    Additional Material: 6 Ill.
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  • 100
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 69-88 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Decomposition studies of trichlorosilane, dichlorosilane, and monochlorosilane at 921 K, 872 K, and 806 K, respectively, are reported. The studies were made at fixed reactant pressures over a range of total pressures in a wall conditioned, quartz reactor connected to a quadrupole mass-spectrometer. Products were monitored sequentially and continuously in time. The dichlorosilane decomposition was also studied by the comparative-rate single-pulse shock-tube method at temperatures around 1250 K. Two mechanisms of decomposition are considered: a silylene based mechanism initiated by molecular elimination reactions (Scheme I), and a free radical based mechanism initiated by bond fission reactions (Scheme V). Modeling tests of these mechanisms show that only the former is consistent with the experimental data. The decompositions are shown to be essentially nonchain processes initiated by the following pressure dependent reactions: HSiCl3(SINGLEBOND)4→ SiCl2+HCl, H2SiCl2(SINGLEBOND)1→ SiCl2+H2 and H3SiCl(SINGLEBOND)5→ HSiCl+H2. High pressure Arrhenius parameters recommended for these reactions are A4,∞=A1,∞=A5,∞=1014.5±0.5 s-1, E4,∞=71.9±2.1 kcal/mol, E1,∞=69.2±2.0 kcal/mol, and E5,∞=60.6±1.8 kcal/mol. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 69-88, 1998.
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