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  • 2000-2004
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  • Electronic Resource  (261)
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  • 2000-2004
  • 1990-1994  (261)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Neurosurgical review 15 (1992), S. 125-133 
    ISSN: 1437-2320
    Keywords: Angiography ; cavernous angioma ; CT ; epilepsy ; hemorrhage ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We report 14 cases of intracranial cavernous angioma, analyzing the clinical features, with special reference to the risk of bleeding, radiological images and treatment in these and in 153 published cases, 167 in all. Cerebral hemorrhage occurred in 44%: typical (intraparenchymal or subarachnoid) in 24.6%, and masked by epilepsy, headache or neurological deficits in 19.2%. In patients with the typical hemorrhagic pattern posthemorrhagic mortality was 12.2%. Of the patients who had a hemorrhage 42.5% were left with more or less disabling neurological deficits, and 16.4% had a rebleed. In discussing treatment we consider four groups of intracranial cavernous angioma: A) symptomatic in a zone of low surgical risk; B) asymptomatic with low surgical risk; C) symptomatic with high surgical risk; D) asymptomatic with high surgical risk. The treatment is surgical, except in the high risk asymptomatic variety, best followed initially with sequential CT scan and MRI and then considered for surgery if the lesion becomes symptomatic, increases in size or presents neuroradiological signs of bleeding.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    The international journal of cardiovascular imaging 8 (1992), S. 249-254 
    ISSN: 1573-0743
    Keywords: Marfan ; MRI ; aortic dilatation ; dissection ; symptomatic ; asymptomatic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Marfan's syndrome is a connective tissue disorder, which mainly affects the cardiovascular system, together with ocular, skeletal and connective tissue. The cardiovascular manifestations in particular determine the mortality of this disorder. We studied 13 patients, suffering of Marfan's syndrome, with suspected aortic dilatation by means of magnetic resonance imaging (MRI). Aneurysmal dilatation of the aortic root and dissection were the two major findings in our study. Two of the five patients with dissections presented without relevant symptoms in the medical history nor at the time of the MRI examination.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 116 (1992), S. 44-48 
    ISSN: 0942-0940
    Keywords: Cervical discectomy ; cervical radiculopathy ; cervical myelopathy ; disc herniation ; myelography ; magnetic resonance imaging ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In a prospective study of 63 surgical patients cervical myelography was compared with MRI to establish the relative value of the 2 diagnostic procedures in patient selection for surgery of ruptured cervical discs and bony nerve root compression. While MRI in the T1-weighted and gradient echo modes matched the diagnostic accuracy of invasive myelography (95%), T1 and T2-weighted MRI images alone were associated with an error rate of 10%. In patients with medial protrusion myelography did not always show the true extent of compression, whereas MRI tended to miss small laterally protruding disc fragments. Cervical myelography continues to have a place in the diagnosis of cervical disc disease, whenever clinical signs and symptoms do not agree with MRI data.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 116 (1992), S. 119-127 
    ISSN: 0942-0940
    Keywords: Arteriovenous malformation ; cavernous angioma ; MRI ; surgery
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary AVMs of the posterior fossa are reviewed on the basis of personal experience of 47 cases including 2 venous angiomas, 7 cavernous angiomas, 5 arteriovenous fistulas and 33 true arteriovenous malformations and of the few series reported in the literature. MRI is now an indispensable tool to define the exact localization of any malformation. Combined with angiography, it permits one to choose the most adequate therapeutic strategy and the best surgical approach. Radical cure is to be contemplated in most cases considering the often dramatic consequences of bleeding at the infratentorial level. Deep AVMs and moreover cavernous angiomas, even those located in highly functional structures such as the brain stem, can now be discussed for treatment. Encouraging results have already been obtained using, alone or in association, the recently advanced modalities of treatment: interventional neuroradiology, radiosurgery, and microsurgery.
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  • 5
    ISSN: 0942-0940
    Keywords: Intraparenchymal brain tumour ; malignancy ; Gd-DTPA ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The feasibility of diagnosing the malignancy and viability of intraparenchymal brain tumours using Gd-DTPA, enhanced and unenhanced T1-weighted MRIs was investigated. The relationship between the Gd-DTPA enhancement pattern, the growth fraction (GF) determined by using the anti-bromode-oxyuridine (BrdU) monoclonal antibody, the clinical condition, the proliferative potential and the change of Gd-DTPA enhancement over time was studied. Forty-five patients with intracranial tumours were studied with the static method of Gd-DTPA MRI. The enhanced effect in Gd-DTPA MRIs was dependent on tumour-cell density, vascularization, necrosis, and dilatation of vascular lumen. Tumour-cells were observed in eighty-seven of eighty-nine specimens taken from areas with Gd-DTPA enhanced MRIs. Seventy-four percent of these specimens (64 of 87) showed a malignancy of more than 5% growth fraction. On the other hand, tumour cells were observed in twentyseven of fifty-six specimens taken from areas with Gd-DTPA unenhanced MRIs. Eighty-five percent of these specimens (23 of 27) showed a malignancy value of less than 5% GF. However, fifteen percent of these specimens showed values between 5 and 15% GF. In the kinetic study of Gd-MRIs five patients who were in a clinically stable condition and one patient who had radionecrosis showed a constant pattern of enhancement or slightly increased enhancement 30 min after injection compared to 4 min after injection. Therefore, GD-DTPA MRI can be used effectively in the diagnosis of tumour viability and malignancy after treatment.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1432-1084
    Keywords: Urinary bladder carcinoma ; Pelvis ; MRI ; Gadolinium-DTPA ; T-Staging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Forty-nine patients with urinary bladder carcinomas underwent pre-operative examinations using magnetic resonance (MR) imaging. The results of the MR examinations were correlated with the clinical-pathological findings following transurethral resection (TUR) and bimanual palpation (n = 47) or radical cystectomy (n = 2). The results of pre-contrast MR tumor staging (T1, T2), viewing stages Tis-T2 collectively, and subsequent to separate assessments of stages T3b-T4b, were correct 76.6% of the time. Gadolinium-DTPA (Gd-DTPA) contrast-enhanced examinations (pre-contrast T1 and after Gd-DTPA) showed a staging accuracy rate of 85.7%. T2-weighted images did not indicate any advantage when compared to T1-weigthed images follwing Gd-DTPA. The signal intensity ratios of tumor/fat and tumor/muscle tissue were measured on T1-weighted pre-contrast images and following Gd-DTPA and then evaluated statistically, whereby the increased tumor signal intensity was statistically significant (Wilcoxon test, P 〈 0.01). Due to the relatively short examination time needed for T1-weighted images and the specific tumor enhancement, the administration of Gd-DTPA proves valuable in the diagnosis of bladder carcinomas. T2-weighted images are not necessary.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-1084
    Keywords: MRI ; Shoulder ; Fat saturation ; Gradient-echo sequences ; Soft-tissue contrast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Although the signs of complete rotator cuff tears on MRI are well established, tendinitis and partial rotator cuff tears cannot always be readily depicted. In order to optimize the soft-tissue contrast of shoulder imaging without increasing imaging time for routine applications, we compared spin-echo and gradient-echo sequences with and without fat saturation and studied the soft-tissue contrast of spoiled gradient-echo sequences with several different parameters. We conclude, that fat-saturation is not necessary in order to improve the soft-tissue contrast. Successful fat suppression was only achieved in 50% of cases. We found a gradient-echo sequence with a double echo acquisition (echo times TE: 11 and 34 ms) with a long repetition time (TR: 600 ms) and a moderate flip angle (20°) very helpful in diagnosing rotator cuff pathology.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1432-1084
    Keywords: Induratio penis plastica (IPP) ; Peyroni'es Disease ; Ultrasound ; MRI ; Gadolinium-enhanced
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Penile induration, a disease of connective tissue, requires the precise delineation and differentiation of inflammatory changes (plaques) for accurate therapy. Seventy two patients with clinically suspected Induratio penis plastica (IPP) underwent ultrasound examination between 1984 and 1991. In 37 patients (aged 18 to 80) the diagnosis was proven by ultrasound. Out of this group 27 patients were examined with magnetic resonance imaging (MRI), 15 of them with additional intravenous application of adolinium DTPA (Gd-DTPA). All examinations were performed within four weeks. The results showed, that ultrasound was able to detect plaques and changes of the tunica albuginea in all 37 cases, but MRI was more sensitive in the detection of possible inflammatory change (T2-prolongation and moderate Gd-DTPA enhancement in gradient-echo sequences. MRI revealed inflammatory changes in 22 of 27 examined patients while ultrasound detected only nine such cases out of 37. Ultrasound is the method of choice in diagnosing IPP, due to the overall sensitivity to plaques and changes in the tunica. On the other hand MRI offers valuable additional information with respect to inflammatory changes particularly after Gd-DTPA. Therefore MRI has the potential to improve therapeutic planning and should be used in monitoring therapeutic effects.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 2 (1992), S. 508-510 
    ISSN: 1432-1084
    Keywords: MRI ; Knee joint ; Three-dimensional reconstruction: preprocessing, segmentation, shading, surface rendering, volume rendering, hybrid rendering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We tried to improve the basic three-dimensional reconstruction technique by comparing preprocessing, segmentation, shading and rendering techniques in 15 examples of MR investigations of the knee joint. We conclude that signal-normalising, combined threshold and tracking segmentation, grey-level-gradient shading, and combined surface and volume rendering (i. e. hybrid rendering) are the methods of choice for the three-dimensional reconstruction process.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1432-1084
    Keywords: Diffuse liver disease ; MRI ; CT ; Ultrasound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Twenty-nine patients with diffuse liver disease were examined by ultrasound, CT and MRI. MRI was performed using T1- and T2-weighted spin-echo sequences as well as fast gradient-echo-sequences. The paramagnetic contrast agent Gd-DTPA was applied intravenously (0.1 mmol/kg). in patients with hepatitis, MRI could be used in guiding liver biopsies as inflammatory changes were clearly delineated. CT and ultrasound were superior to MRI in the detection of focal or diffuse fatty degeneration. On the other hand MRI was more helpful in differentiating fatty changes and neoplasm. In liver cirrhosis, fibrotic changes were most clearly demonstrated by MRI. In patients suffering from hemochromatosis MRI offers advantages over CT and ultrasound in the diagnosis and follow up due to the paramagnetic properties of iron, resulting in a reduction in signal intensity. In patients with Wilson's disease a characteristic pattern of parenchymal changes was seen. Administration of Gd- DTPA contributes additional information about perfusion conditions in the liver parenchyma, however this information was not of diagnostic relevance in the cases we studied.
    Type of Medium: Electronic Resource
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  • 11
    ISSN: 1432-1084
    Keywords: MRI ; Psychiatry ; white matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract T2-weighted MRI scans of psychiatric patients with at least one white matter lesion (WML) were compared to 83 non-psychiatric controls with respect to WML number and distribution. MANOVA results in significant effects for sex, age and patient group with respect to WML number. In the psychiatric patients, infratentorial WML prevailed in organic psychoses. WML number was positively correlated with age with the exception of rith temporal lobe WML. Based on WML spatial distribution, four patient clusters were found. Clusters with widely distributed WML comprised older patients with late onset of illness; right frontal and temporal WML were associated with mania, euphoria and unstable mood.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 1432-1920
    Keywords: Multiple sclerosis ; MRI ; Mass lesions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Six patients presenting with new neurological deficits underwent magnetic resonance imaging (MRI) that displayed mass lesions leading to diagnoses of tumor or abscess. Biopsy revealed demyelinating lesions.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Neuroradiology 34 (1992), S. 105-106 
    ISSN: 1432-1920
    Keywords: syphilis ; spinal cord ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary MR imaging was performed on a patient with syphilitic myelitis. T2-weighted images showed high intensity areas in the thoracic spinal cord. On T1-weighted images after gadolinium-DTPA injection, heterogeneous enhancement was observed in the superficial portion of the spinal cord. The intramedullary high intensity areas on T2-weighted images disappeared after antibiotic therapy.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1432-1920
    Keywords: Angioma ; Central nervous system, angioma ; MRI, spinal cord ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report a patient with multiple angiographically occult vascular malformations in the brain and spine. Magnetic resonance imaging showed multiple lesions in brain and spine with hypointense areas on both T1 and T2-weighted images. These hypointense areas are usually secondary to hemosiderin deposits consistent with remote bleeding in the lesions. We conclude that when magnetic resonance reveals an intraspinal lesion with signal intensity characteristics consistent with a vascular malformation, an examination of the brain should be performed to rule out associated intracranial lesions. The finding of multiple lesions in the brain with identical signal intensity characteristics reinforces the diagnosis of vascular malformation.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Neuroradiology 34 (1992), S. 117-121 
    ISSN: 1432-1920
    Keywords: Cockayne's syndrome ; Ataxia telangiectasia ; Fanconis anaemia ; Central nervous system ; MRI ; CT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The CT and MRI appearances of 5 patients with Cockayne's syndrome, 5 with ataxia telangiectasia and 1 with Fanconi's anaemia are reported. These conditions, together with Bloom's syndrome and xeroderma pigmentosum are regarded as disorders of DNA repair. Characteristic CT and MRI features of Cockayne's syndrome include generalised atrophy, calcification in basal ganglia and dentate nuclei and white matter low density. Neuroradiological findings in the other DNA repair disorders are nonspecific.
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  • 16
    ISSN: 1432-1920
    Keywords: Granuloma paranasal sinuses ; Computed tomography ; MRI ; Lethal midline granuloma ; Lymphoma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In 13 patients presenting as lethal midline granuloma (LMG), computed tomography proved essential for determining the extent of the disease, guiding biopsy and planning radiotherapy. Magnetic resonance imaging (MRI) was also helpful for the latter, because it could distinguish fluid retained within the paranasal sinuses from solid masses and tumour from granulation tissue; it was of little value for detecting bone lysis. Eight of the 13 patients proved to have T-cell lymphoma, two had Crohn's disease, in one the lesion was factitious and two had granulomas without diagnostic histological features.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 2 (1992), S. 2-13 
    ISSN: 1432-1084
    Keywords: Contrast media ; MRI ; Ultrasound ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 151 (1992), S. 38-41 
    ISSN: 1432-1076
    Keywords: Mediastinal cysts ; MRI ; Children
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The signals obtained from mediastinal cystic lesions in children by magnetic resonance imaging (MRI) have been analysed. The advantages and pitfalls in establishing the final diagnosis by MRI are compared to the conventional radiographic technique and to computed tomography.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    European archives of psychiatry and clinical neuroscience 242 (1992), S. 69-71 
    ISSN: 1433-8491
    Keywords: Marchiafava-Bignami disease ; CT ; MRI ; SPECT ; Corpus callosum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Marchiafava-Bignami disease (MBD) is a rare complication of chronic alcoholism. The clinical features, X-ray, CT and MRI findings are well documented. However, functional brain imaging has not been used in cases of MBD. We used single-photon emission computed tomography (SPECT) to monitor the regional cerebral blood flow in a patient suffering from a acute form of MBD, from which he subsequently recovered. Several abnormalities were found. A more frequent use of functional brain imaging in MBD could improve our knowledge of pathogenesis and prognosis for MBD.
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Neurological sciences 13 (1992), S. 517-519 
    ISSN: 1590-3478
    Keywords: MRI ; cerebellum ; anoxic ; ischemic encephalopathy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Un indagine di RM rivelò un quadro di alterazioni simmetriche nel putamen e negli emisferi cerebellari in una paziente sopravvissuta ad un arresto cardiorespiratorio dovuto a polineurite acuta idiopatica. Dal momento che alterazioni simili possono far seguito ad intossicazione da cianuro o da metanolo, la diagnosi differenziale di queste condizioni deve tener conto sia degli elementi clinico-anamnestici sia degli elementi della diagnostica per immagini.
    Notes: Abstract MRI demonstrated symmetric putaminal and cerebellar changes in a patient who survived a cardiorespiratory arrest due to acute idiopathic polyneuritis. Since similar aspects can be observed following cyanide or methanl poisoning differential diagnosis from these conditions has to rely on the combination of clinical and imaging findings.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Oral radiology 8 (1992), S. 37-43 
    ISSN: 1613-9674
    Keywords: Chondrosarcoma ; Mandibular condyle ; CT ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A rare case of chondrosarcoma of the mandibular condyle is reported. CT and MRI were available in the diagnosis of chondrosarcoma, but plain radiograms were nearly non-contributory. Microscopically, the malignant chondroid tissue and malignant chondrocytes were observed.
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Oral radiology 8 (1992), S. 33-39 
    ISSN: 1613-9674
    Keywords: MRI ; Gd-DTPA ; Cystic lesion ; Odontogenic tumor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The authors present examples of the significantly improved diagnostic imaging for cystic lesions in the jaw bone, floor of the mouth and maxillary sinus with Gadolinium-DTPA (Gd-DTPA) enhanced MRI. Twelve cases of cystic lesions, which were 6 cases of intra-osseous odontogenic cysts and cystic tumors, 2 cases of epidermoid cysts in the floor of the mouth and 4 cases of cystic polyp of the maxillary sinus. Improved MR images provided useful information delineating the thickness of circumscribed soft tissue wall (cystic wall), the location of the intra-cystic substance and the configuration of the tumor masses.
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 65 (1992), S. 438-444 
    ISSN: 1439-6327
    Keywords: Force/CSA ; Muscle stress ; Specific tension ; Skeletal muscle strength ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The physiological cross-sectional areas (CSAp) of the vastus lateralis (VL), vastus intermedius (VI), vastus medialis (VM) and rectus femoris (RF) were obtained, in vivo, from the reconstructed muscle volumes, angles of pennation and distance between tendons of six healthy male volunteers by nuclear magnetic resonance imaging (MRI). In all subjects, the isometric maximum voluntary contraction strength (MVC) was measured at the optimum angle at which peak force occurred. The MVC developed at the ankle was 746.0 (SD 141.8) N and its tendon component (F t) given by a mechanical advantage of 0.117 (SD 0.010), was 6.367 (SD 1.113) kN. To calculate the force acting along the fibres (F f) of each muscle, F t was divided by the cosine of the angle of pennation and multiplied for (CSAp · ΣCSAp−1), where ΣCSAp was the sum of CSAp of the four muscles. The resulting F f values of VL, VI, VM and RF were: 1.452 (SD 0.531) kN, 1.997 (SD 0.187) kN, 1.914 (SD 0.827) kN, and 1.601 (SD 0.306) kN, respectively. The stress of each muscle was obtained by dividing these forces for the respective CSAp which was: 6.24 × 10−3 (SD 2.54 × 10−3) m2 for VL, 8.35 × 10−3 (SD 1.17 × 10−3) m2 for VI, 6.80 × 10−3 (SD 2.66 × 10−3) m2 for VM and 6.62 × 10−3 (SD 1.21 × 10−3) m2 for RE The mean value of stress of VL, VI, VM and RF was 250 (SD 19) kN m2; this value is in good agreement with data on animal muscle and those on human parallel-fibred muscle.
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  • 24
    ISSN: 1573-7373
    Keywords: metastatic disease ; spinal cord ; MRI ; myelography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Comparison between myelography (MY) and magnetic resonance imaging (MRI) was carried out in 36 patients with clinical suspicion of spinal cord or root compression due to metastatic disease in the spinal canal. In 3 patients metastatic lesions were visualized on MY but not on MRI, while there were no cases with a negative MY and a positive MRI. In 44% of the cases MY alone or combined with postmyelographic CT (pm-CT) showed a larger tumor extension than did MRI, while the opposite occurred in 25%. As for detection of bony metastases and tumor masses localized outside the spine there was no difference between MRI and MY + pm-CT. The results indicate that the choice between MRI and MY + pm-CT still can be based on the availability and quality of the procedure at a given institution.
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  • 25
    ISSN: 1573-7373
    Keywords: CT ; irradiation ; leukoencephalopathy ; methotrexate ; MRI ; PET
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A case of treatment-related leukoencephalopathy is presented. A patient with medulloblastoma was postoperatively treated with craniospinal axis irradiation. One month after irradiation, weekly intrathecal administration of methotrexate was performed 4 times to treat cerebrospinal fluid dissemination of the tumor. Two months after the initiation of intrathecal chemotherapy, the patient became somnolent and developed decerebrate posturing. Magnetic resonance imaging showed diffuse leukoencephalopathy. Positron emission tomography revealed a diffuse decrease in glucose uptake in the deep white matter. Auditory evoked potential also showed diffuse abnormalities, not only in the cerebrum, but also in the brain stem. High dose intravenous leucovorin rescue was attempted without any neurologic improvement.
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  • 26
    Electronic Resource
    Electronic Resource
    Springer
    Brain topography 5 (1992), S. 129-133 
    ISSN: 1573-6792
    Keywords: NMR ; MRI ; MRS ; Nuclear magnetic resonance ; Brain metabolism ; Imaging ; Functional brain imaging ; Spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The first successful demonstrations of nuclear magnetic resonance (NMR) in bulk matter were reported in 1946 (Bloch, Hansen and Packard 1946; Purcell, Torrey and Pound 1946). Since then NMR has become a widespread technique for investigating matter of all kinds. In the 1970's NMR was applied to living systems, including man, in 2 distinct approaches. One application was in the production of images (Lauterbur 1973), called Magnetic Resonance Imaging or MRI, and the other in the production of NMR spectra (Moon and Richards 1973; Hoult et al. 1974), called Magnetic Resonance Spectroscopy or MRS. By appropriate manipulation of the NMR signal an NMR image may be generated. This can be a 2D image of a single slice, or a set of 2D images of parallel slices, or a 3D image. 2D images may be obtained directly in any orientation, axial, coronal, sagittal. The method uses no ionizing radiation and is inherently safe. It is non-invasive, although paramagnetic solutions may be injected intravenously to improve contrast. MRI images observed in normal clinical practice are maps of the NMR signals from water and fat in the tissues; they depend on proton density, but also significantly on the relaxation times T1 and T2. Images can be provided of flow (MR angiography) and diffusion (free, restricted or anistropic). Images are typically 512×512 pixels with spatial resolution of about 0.5mm. The images can be correlated with anatomical structures and indeed MRI is a primary source of such structures with localization precision of 0.5mm as in CT. Normal imaging times are about 5mins, but fast images of lower resolution can be obtained in 50ms, enabling real time movie images to be generated. Recording sessions are typically 1hr. The NMR spectrum from living tissue gives a non-invasive measure of the concentration of each molecular species. Such spectra (MRS) provide information concerning the biochemistry of the body's metabolism and associated pathology.31P spectra report concentrations of ATP, ADP, phosphocreatine, inorganic phosphate, other metabolites and also local pH.1H spectra (with suppression of water and lipid responses) give spectra from lactate, NAA, choline, creatine and other components. Spectroscopic Imaging (SI) combines MRI and MRS to provide spectra simultaneously from an array of pixels or voxels, each usually several cm3 in size in an overall time of order 20 mins. This procedure provides a spatial map of the whole spectrum or individual maps of each molecular species. Two recent developments have demonstrated that NMR can provide functional mapping of the normal human brain, and map the response of the human cerebral cortex to physiological stimulation.
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  • 27
    Electronic Resource
    Electronic Resource
    Springer
    Brain topography 5 (1992), S. 153-157 
    ISSN: 1573-6792
    Keywords: Brain Imaging ; CT ; Geometrical Features ; Image Matching ; Image Processing ; Image Registration ; MRI ; SPECT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Clinical diagnosis, as well as therapy planning and evaluation, are increasingly supported by multimodal images. There are many instances desiring integration of the information obtained by various imaging devices. This paper describes a new approach to match images of different modalities. Differential operators are used in combination with Gaussian blurring to extract geometric features from the images that correspond to similar structures. The resulting ‘feature’ images may be used with existing matching techniques that minimize the distance between the features in the images to be matched. Our first application of this new approach concerns matching of MRI and CT brain images. The so-called Lυυ operator produces a ridge-like feature image from which in CT and MRI the center curve of the cranium is easily extracted. First results of this operator's performance in matching tasks are shown. Another promising operator is the ‘umbilicity’ operator, which is presented in combination with SPECT images.
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  • 28
    Electronic Resource
    Electronic Resource
    Springer
    Medical & biological engineering & computing 40 (1992), S. 145-152 
    ISSN: 1741-0444
    Keywords: Brain glioma ; Classification ; Fuzzy rule extraction ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The current pre-operative assessment of the degree of malignancy in brain glioma is based on magnetic resonance imaging (MRI) findings and clinical data. 280 cases were studied, of which 111 were high-grade malignancies and 169 were low-grade, so that regular and interpretable patterns of the relationships between glioma MRI features and the degree of malignancy could be acquired. However, as uncertainties in the data and missing values existed, a fuzzy rule extraction algorithm based on a fuzzy min-max neural network (FMMNN) was used. The performance of a multi-layer perceptron network (MLP) trained with the error back-propagation algorithm (BP), the decision tree algorithm ID3, nearest neighbour and the original fuzzy min-max neural network were also evaluated. The results showed that two fuzzy decision rules on only six features achieved an accuracy of 84.6% (89.9% for low-grade and 76.6% for high-grade cases). Investigations with the proposed algorithm revealed that age, mass effect, oedema, post-contrast enhancement, blood supply, calcification, haemorrhage and the signal intensity of the T1-weighted image were important diagnostic factors.
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  • 29
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    Neurological sciences 13 (1992), S. 603-605 
    ISSN: 1590-3478
    Keywords: Cervical radiculopathy ; vertebral A-V fistula ; CT ; MRI ; angiography ; embolization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Descriviamo il caso di una donna di 28 anni, che soffrì di una radicolopatia acuta prevalente motoria C5-C6 destra da fistola congenita artero-venosa vertebrale. Il reperto di un soffio latero-cervicale fece valorizzare i quadri T.A.C. e R.M. Lo studio arteriografico fu diagnostico, la fistola venne embolizzata con successo.
    Notes: Abstract We report the case of a 28 year old woman with acute, mainly motor, radiculopathy at C5-C6 on the right side secondary to a congenital vertebral arteriovenous fistula. The finding of a bruit at the side of the neck lent weight to the CT and MRI findings. Angiography was diagnostic. The fistula was embolized successfully.
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  • 30
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    Neurological sciences 13 (1992), S. 611-616 
    ISSN: 1590-3478
    Keywords: Mills syndrome ; chronic spastic atrophic hemiparesis (CSAH) ; MRI ; CT scan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Vengono presentati i dati clinici e neuroradiologici relativi a quattro pazienti (età media 62 anni, range 54–67; follow-up medio 19,5 anni, range 26 mesi-29 anni) affetti da emiparesi cronica spastica ed atrofica (CSAH). La TAC e la RMN cerebrale hanno evidenziato la presenza di lesioni localizzate nel centro semiovale in due casi, in regione parieto-occipitale e a livello del ponte in un caso ciascuno. Questo studio sottolinea il fatto che i pazienti con CSAH possono presentare una prognosi favorevole a lunggo termine. Lo studio con RMN cerebrale può evidenziare lesioni a livello della sostanza bianca emisferica o del tronco cerebrale ed è pertanto indicato in tutti i soggetti con CSAH. Tuttavia, ulteriori studi sono necessari al fine di chiarire la natura delle lesioni osservate.
    Notes: Abstract We present the clinical and neuroimaging data of 4 patients (mean age: 62 years, range 54–67; mean follow-up: 19.5 years, range: 26 months-29 years) with chronic spastic atrophic hemiparesis (CSAH). Neuroimaging findings were non specific, CT scan and MRI showing white matter lesions located within the centrum semiovale in two cases, parieto-occipital lobe and pons in one case each. This study underlines that patients with CSAH may have a good long-term prognosis. MRI studies may demonstrate associated lesions within the white matter or brainstem and are advisable in all subjects with CSAH, but further studies are necessary to clarify the nature of the observed lesions.
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  • 31
    ISSN: 1590-3478
    Keywords: Demyelinating diseases ; multiple sclerosis ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Descriviamo le caratteristiche cliniche e i riscontri laboratoristici-strumentali di due pazienti con malattia demielinizzante acuta monofasica ad espressione clinica focale: un caso di mielite trasversa cervicale incompleta ed uno di encefalite sopratentoriale focale. Sono illustrati il decorso clinico e l'evoluzione dei reperti neuroradiologici (TAC e RMN), discutendone il significato patologico e l'utilità diagnostica.
    Notes: Abstract We report the clinical features and laboratory-instrumental findings in two patients with acute monophasic demyelinating disease with focal clinical expression: one case of incomplete cervical transverse myelitis and one of focal supratentorial encephalitis. We describe the clinical course and evolution of the neuroradiological findings (CT and MRI) and discuss their pathological meaning and diagnostic value.
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  • 32
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    Neurological sciences 13 (1992), S. 151-156 
    ISSN: 1590-3478
    Keywords: Olivopontocerebellar atrophy ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Sotto il termine di atrofia olivo-pontocerebellare si raggruppano quadri nosografici di verosimile diversa origine, caratterizzati tutti dalla presenza di segni clinici deficitari pontini e cerebellari. La diagnosi è stata sino ad ora solo clinica con conferma autoptica del danno pontocerebellare. Sono descritti tre casi di atrofia olivo-pontocerebellare, appartenenti, a tre distinti sottogruppi ed in fasi diverse della malattia. In tutti e tre i casi la MRI ha evidenziato un quadro di atrofia pontina e cerebellare ed una riduzione dimensionale delle olive bulbari che risultava in un allargamento dell'angolo pontobulbare normalmente rilevabile sulla faccia anteriore del tronco in proiezione laterale. L'esame si conferma di importanza diagnostica essenziale nella malattia sin dalle sue fasi iniziali.
    Notes: Abstract Under the term of olivopontocerebellar atrophy different nosological pictures are grouped, all characterized by showing clinical signs of deficiency of the structures of the pons and of the cerebellum. The diagnosis of olivopontocerebellar atrophy has been made, until now, by clinical criteria while typical anatomopathological changes are found at the autoptic studies. We describe three patients affected by olivopontocerebellar atrophy, of different types and at different stages of disease. In all cases MRI showed a similar and typical picture of atrophy of the olivary eminences of the medulla oblongata resulting in straightening of the angle usually present on the ventral frontier between pons and medulla oblongata. This diagnostic tool demonstrated thus to be of primary relevance yet in the early phases of the disease.
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  • 33
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    Neurological sciences 13 (1992), S. 165-168 
    ISSN: 1590-3478
    Keywords: Bickerstaff brainstem encephalitis ; Miller Fisher syndrome ; SOAA ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Sommario Viene descritto il caso di una paziente che, tre settimane dopo aver sofferto una sindrome influenzale, presentò un quadro clinico caratterizzato da oftalmoplegia, atassia ed are flessia osteotendinea il quale, come è noto, caratterizza sia la sindrome di Bickerstaff che quella di Miller Fisher. La normalità degli esami neurofisiologici (SEPs, VEPs, BAEPs, studio della VCM, VCS), il reperto liquorale e, soprattutto, l'esame di risonanza magnetica encefalica hanno permesso di ricondurre il quadro sindromico osservato and una compromissione del mesencefalo.
    Notes: Abstract A 33-year-old woman three weeks after a febrile illness presented with a syndrome of ophthalmoplegia, ataxia and areflexia (SOAA) that characterizes clinically both Bickerstaff and Miller Fisher syndromes. The normality of the electrophysiological tests performed, the CSF findings and the magnetic resonance images proved that the syndrome stemmed from brainstem pathology.
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  • 34
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    Journal of Physical Organic Chemistry 5 (1992), S. 244-252 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The protonation of diphenyl sulfoxide and several substituted diphenyl sulfoxides was probed by the MNDO-PM3 method to gain a theoretical insight into the experimentally observed preference for stable diphenyl sulfoxonium ion formation (O-protonation) in 1:1 FSO3H - SbF5 (Magic Acid) - SO2. In agreement with solution studies, O- protonation is uniformly favored (by ca 17 kcal mol -1) over S-protonation. The differences in the heats of formation of protonated and unprotonated diphenyl sulfoxides are increased by electron-withdrawing substituents (F, CF3) and decreased by electron-donating groups (Me, OMe). Variations in the SO bond length and bond order in the onium ions are compatible with simple resonance arguments and the oxonium/sulfonium character of both the O- and S-protonated onium ions. Surprisingly, the O- and S-protonated dibenzothiophene S-oxides are predicted to have identical energetics as compared with the corresponding protonated diphenyl sulfoxides. On structure optimization dibenzothiophene S-oxide itself, if the initial geometry is somewhat twisted, rearranges by ring expansion to give a new heterocycle with lower energy. A rotational barrier study on the parent O-protonated diphenyl sulfoxide showed two minima, separated by 1.3 kcal mol-1, at HOSC dihedral angles of 60° and 240°. The two conformations correspond to syn and anti orientations of the OH proton relative to the aromatic rings, and support the lowtemperature solution observations of the presence of two distinct sulfoxonium ions in solution. The rotational barriers for diphenyl sulfoxonium cation are compared with those of O-protonated dimethyl sulfoxide.
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  • 35
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The base-promoted nitrile-forming elimination reactions of YCH=CHCβH=NOCH=CHZ (Y=OCH3, H or Cl and Z=H or NO2) were studied by the AM1 MO theoretical method with Cl- as a base. The reaction is found to proceed by an E1cB-like E2 mechanism in which Cβ - H bond cleavage is more advanced than N - O bond breaking. The syn-elimination has a more E1cB-like transition state (TS) than the anti elimination, which is attributed to the structurally favourable nN - ó * (Cβ - H) charge-transfer interaction. An electron-withdrawing Y substituent lowers the activation barrier by stabilizing negative charge developed on Cβ in the TS. An electron-withdrawing substituent in the leaving group (Z = NO2) tends to enhance the anti relative to the syn elimination process by depressing the δ*(N - O) level, which in turn makes the nć - δ*(N - O) interaction more effective. The YCH=CH -  and  - CβH=N fragments are perpendicular in the TS, which is stabilized by delocalization of negative charge developed on the Cβ atom.
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  • 36
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    Journal of Physical Organic Chemistry 5 (1992), S. 253-258 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An AM1/PM3 study of several tetrahalomethane-arene molecular complexes is presented. The results indicate the existence of weak attractive non-dispersion interactions in some of these complexes, which can be rationalized in terms of multipole - multipole and multipole - induced dipole interactions. No evidence was found for the occurrence of charge transfer in the ground states of these complexes.
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  • 37
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    Journal of Physical Organic Chemistry 5 (1992) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 38
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    Journal of Physical Organic Chemistry 5 (1992), S. 285-286 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The first direct determination of a 1,2-chlorine atom shift in a chlorobenzylcarbene was achieved by nanosecond laser flash photolysis. Arrhenius activation parameters of Eact = 3.39 ± 0.14 kcal mol-1 and log [A(s-1)] = 10.98 ± 0.14 were obtained for 1,2-chlorine migration in α-methyl-α-chlorobenzyl(ch1oro)carbene. The lifetime of this carbene is considerably longer than previously estimated and the measured Eact, is in excellent agreement with that determined by product analysis.
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  • 39
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    Journal of Physical Organic Chemistry 5 (1992), S. 275-284 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate constants of the pseudo-first-order methylation reaction of seven substituted pyridinium-N-phenoxide betaine dyes by iodomethane, were determined by UV-visible spectrophotometry in nine different solvents. The influence of substituents on the position of the long-wavelength, intramolecular charge-transfer absorption band of the unsubstituted betaine dye can be described by a modified Hammett equation. The solvent-dependent absorption constant ρA correlates satisfactorily with the acceptor properties of the nine solvents used. The substituent-dependent alkylation rate constants (In k) correlate linearly with the Hammett substituent constants, whereas the solventdependence of in k follows a more complicated pattern. Temperature-dependent measurements of the rate of alkylation exhibit an isoenthalpic behaviour for all the betaines in all the solvents investigated, i.e. the Arrhenius activation energy is almost constant for all differently substituted betaines in a given solvent. Temperature-dependent measurements of the alkylation rate of the unsubstituted betaine in different solvents led to an isosolvent relationship, i.e. the corresponding Arrhenius plots show a common point of intersection. According to the theory of isokinetic relationships, this isosolvent behaviour is interpreted in terms of a resonant energy exchange between the reacting species and the surrounding heat-bath system, which in this particular case seems to be the betaine molecule itself.
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  • 40
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    Journal of Physical Organic Chemistry 5 (1992), S. 295-298 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To study molecular features connected with chirality, a procedure for the quantitative estimation of the chirality level of compounds of different classes is needed. A procedure for estimating the molecular asymmetry level relative to mirror-reflection axes of symmetry, S1, S2, S4 and S6, has been developed. The geometrical mean of these parameters is the disymmetry function (DF). To calculate the DF, the molecule must be fixed in the coordinate system, transferred to the main axes of inertia.
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  • 41
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The efficiency of the developed method of dissymmetry functions was studied using various model systems. The alteration of the dissymmetry function was analysed with systematic variations of the bond lengths, valence angles and masses of atoms in model tetrahedra. The behaviour of the dissymmetry function was studied for conformationally labile systems and chiral polyhedra. In general, it was found that in all cases the alteration of the dissymmetry function is in agreement with the speculative representations of the changes in degree of chirality.
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  • 42
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    Journal of Physical Organic Chemistry 5 (1992), S. 287-294 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on analysis of recently reported measurements, it is suggested that, provided a sufficiently large set of specific rate measurements in a wide variety of solvent types is available, the negligible to moderate improvements in the correlations of other types of benzylic chlorides, which are gained by use of a benzylic chloride (in place of 1-adamantyl chloride) as the standard substrate, do not justify the development of new specialized scales of solvent ionizing power. A similar conclusion is reached concerning solvent ionizing power scales developed for use with benzylic p-nitrobenzoates. However, such scales could be helpful when specific rates of solvolysis in only a limited variety of solvents are available, e.g. when a change in mechanism severely limits the range of operation of one of the pathways. Contrary to a previous claim, variations in ion-pair return could be the cause of deviations from Grunwald-Winstein plots for solvolyses of benzhydryl chloride in fluorinated alcohol solvents; such effects could be coupled, at least in part, with variations in aromatic ring solvation.
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  • 43
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    Journal of Physical Organic Chemistry 5 (1992), S. 317-321 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The differences between charge-transfer transition energies calculated for donor-acceptor pairs at infinite separation and values determined experimentally for the charge-transfer complex geometry vary according to the charge type of the pairs and within a group of fixed charge type. It is argued that these differences provide a guide to the slope of the state-correlation curves for the product configuration in electrophile-nucleophile reactions of the corresponding charge type and that the observed variation invalidates the use of the simple expression ΔE=fΛ-β with constant f, derived from the curve-crossing model, to estimate energy barriers to reaction.
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  • 44
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For a number of chiral α,β-unsaturated carbonyl compounds, cyclohexanone and cyclohexenone derivatives, existing essentially in the form of single molecular conformation, the correlation dependences were established between the values of the calculated dissymmetry functions (DF) with respect to atomic masses and atom refractions, and the induction effectiveness of helical ordering in the nematic mesophase (twisting power). Such correlative dependencies, as the examples show, allow one to predict safely enough the twisting power of new substances with the ‘fixed’ molecular conformation. Types of dissymmetry functions and kinds of correlative dependences, the most acceptable for these reasons, were revealed. Dissymmetry functions formed on the basis of atom refractions (polarizabilities) describe the influence of the molecular structures of chiral compounds on the twisting power with higher accuracy than those that characterize the dissymmetry of the atomic masses distribution, according to the important role of the dispersion forces in the formation of helical ordering in liquid crystalline systems. The components characterizing the distribution dissymmetry of atomic refractions and masses with respect to the long and two shorter axes as the peculiar characteristics of biaxiality of chiral molecules describe the influence of the molecular structure on the twisting power with the same accuracy as the general DF do. Thus influence of chiral dopant molecules on the interactions between molecules in the uniaxial mesophases is negligible within the limits of the DF method. Based on the calculations for model systems it is established that the presence of the non-linear cinnamoyl fragment has a decisive influence on the molecular dissymmetry of the chiral α,β-unsaturated ketones. The alkyl groups influence the molecular dissymmetry only slightly, but it is important that their presence ensures the stabilization of the chiral conformer with the defined helicity of the cinnamoyl fragment.
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  • 45
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    Journal of Physical Organic Chemistry 5 (1992), S. 322-326 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enol of acetophenone was generated flash photolytically in aqueous solution by photosolvolysis of PhCBr=CH2 and photohydration of PhC≡CH and PhC≡CD, and rates of its ketonization were measured in dilute perchloric acid solutions in H2O and D2O at 25°C. The rate constants so obtained provide the solvent isotope effects, kH+/kD+ = 5.02 ± 0.08, and the secondary isotope effect for deuterium substitution at the β-position of the enol double bond, (kH/kD)β = 0.999 ± 0.014. Arguments are presented which show that these isotope effects requre a stepwise rather than a concerted mechanism for the ketonization reaction.
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  • 46
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    Journal of Physical Organic Chemistry 5 (1992), S. 334-340 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of an assistant reagent to monitor spectroscopically the concentration of compounds that lack chromophores is described. It is demonstrated, for example, that the concentration of an aliphatic alcohol (present during acidcatalyzed hydrolysis or esterification reactions) can be monitored continuously by addition of a small amount of chromium trioxide. From a knowledge of the rate law and the rate constants for chromic acid oxidations, - d [CrO3]/dt = k [alcohol] [CrO3], the concentration of alcohol can be determined at any time by monitoring the absorbance of chromic acid at 363 nm. The rate at which the concentration of the alcohol is changing can then be used to calculate rate constants for the corresponding esterification or hydrolysis reactions. Rate constants obtained in this way are compared with those previously obtained by use of direct methods, and the application of this approach to the study of kinetics under conditions not accessible by other methods is illustrated.
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  • 47
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    Journal of Physical Organic Chemistry 5 (1992), S. 349-354 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ionization constants of sixteen 5-furylmethylenehydantoins and 5-thienylmethylenehydantoins were measured in 80% (w/w) dimethyl sulphoxide-water solvent at 25°C. The effects of the 2-/3-furyl and 2-/-3-thienyl rings and the effects of configuration and conformation on acidity are discussed. The very low acidity of (Z)-5-(2-furyl)methylene-3-methylhydantoin suggests the possibility of some weak intramolecular interaction between the proton at N-1 and the 2-furyl oxygen in the s-cis conformation.
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  • 48
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The substitution reactions of Br(CH2)nBr(1, n = 3-5) with KCN in methanol were studied in detail. Second-order rate constants k1 [formation of the mononitrile (2) from 1] and k2 (formation of the dinitrile (3) from 2) were determined, as were the rates for the reaction of H(CH2)nBr (4, n = 3-5) with KCN under the same conditions. The ratios k2/k1 ( = x) of the three homologs of 1 were found to be 1.15, 0.77 and 0.61 for n = 3, 4 and 5, respectively; a x value of 0.5 indicates that the functional groups behave independently. The second-order rate constants k1 (statistically corrected) and k2 exhibit modest enhancements compared with model compound 4 when any of the following substituents are present: δ or ∊-bromo, γ-, δ-, or ∊-cyano. By contrast, a γ-bromo substituent slightly retards the rate. These results indicate that the functional groups do influence each other to a modest degree by field effects which accelerate the reactions. Steric effects do not appear to play a significant role.
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  • 49
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    Journal of Physical Organic Chemistry 5 (1992), S. 429-434 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between 1-fluoro-2,4-dinitrobenzene and n-butylamine in toluene shows a two-step plot of kobs, values vs the initial values of the concentration of the amine. The usual base-catalysis mechanism for HF elimination from the zwitterionic intermediate hardly explains this kinetic behaviour and the kinetic effect of addition of salts (and of 2-hydroxypyridine) to the reaction mixtures at different initial values of the concentration of n-butylamine. In contrast, the kinetic behaviours are easily explained by the presence of substrate-amine (or catalyst) interactions on the pathway of the substitution reaction.
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  • 50
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    Journal of Physical Organic Chemistry 5 (1992), S. 74-82 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Owing to the importance of the concept of aromaticity, different indices have been developed to try to quantify this property. The possible π delocalization through an X—SOn—X group (X = C, N; n = 0, 1 or 2) could explain heteroaromaticity in rings containing the moiety. For that reason, the aromaticity of five-membered sulphurcontaining rings with different oxidation numbers (S, SO and SO2) and including no (thiophene), one (isothiazole) or two (1,2,5-thiadiazole) adjacent atoms was investigated. Ab initio calculations were carried out to determine geometrical parameters (planarity of the ring, bond length and bond order), electronic structure (charge distribution and dipolar moment) and the participation of d-orbitals of sulphur. According to these calculations, only compounds with S(II) can be considered to be aromatic, whereas compounds bearing S(IV) or S(VI) are better described as ylides.
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  • 51
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    Journal of Physical Organic Chemistry 5 (1992), S. 83-92 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrolysis of geranyl diphosphate (GPP) at pH 7 in water gives largely linalool (LOH) + geraniol (GOH) in the ratio of 3:1. Added N-3 generates mixed acylic allylic azides and increases the LOH GOH ratio to 15:1 in 2 M NaN3, but does not speed up the overall reaction. Hydrolysis of neryl diphosphate (NPP) gives largely α-terpineol (TOH) +p LOH, but their ratio is not very sensitive to NaN3 concentration although acyclic azide and small amounts of α-terpinyl azide (TN3) are formed. Hydrolysis of α-terpinyl diphosphate (TPP) gives large amounts of the cyclic alkenes, limonene and terpinolene. Added N-3 does not change the amount of elimination, but increases the ratio of limonene to terpinolene, and diverts some substitution product to TN3. Trapping of carbocationic species from GPP by N-3 is sharply increased by addition of Mn2+, which also catalyzes the overall reaction. Products of reaction of GPP are derived from acyclic intermediates and of NPP from acyclic and cyclic intermediates, and ionizations of the three substrates do not generate common carbocationic species.
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  • 52
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    Journal of Physical Organic Chemistry 5 (1992), S. 104-107 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclopropylmethoxycarbene undergoes ambiphilic-nucleophilic intermolecular reaction with alkenes and methanol, but its intramolecular chemistry (1,2-carbon migration) is suppressed (k 〈 3 × 103 s-1) by the α-methoxy substituent.
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  • 53
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    Journal of Physical Organic Chemistry 5 (1992) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 54
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    Journal of Physical Organic Chemistry 5 (1992), S. 101-103 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dewar-anthraquinone (1a) and 1,2,3-tri-tert-butyl-5,8-Dewar-anthraquinone (1b) were synthesized. Thermodynamic parameters for their cycloreversion to the corresponding anthraquinones indicate that thermal population of the excited states of the products via non-adiabatic valence isomerization is energetically feasible. On thermolysis of 1b, the formation of a detectable amount of 1,2,3-tri-tert-butyl-1,4-Dewar-anthraquinone (3) was observed. The excited singlet state of 1,2,3-tri-tert-butylanthraquinone (2b) produced via the non-adiabatic process is responsible for the formation of 3.
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  • 55
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    Journal of Physical Organic Chemistry 5 (1992), S. 109-118 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular mechanics study on some organophosphorus podands, with both rigid and flexible terminal groups, and on their complexes with Li+ and Na+ was carried out. Na+ causes smaller deformations of the ligands than Li+, but its complexes are less stable, as the interaction energy with the podands is weaker. The ligands with rigid terminal groups are, in general, more pre-organized for complex formation. The cation-ligand interaction energies, including also the changes in steric energies, are always higher in complexes of flexible molecules than in those containing rigid ligands. The lower entropy losses which accompany the formation of complexes of rigid molecules with alkali metal cations probably account for the observed higher stabilities of the complexes.
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  • 56
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    Journal of Physical Organic Chemistry 5 (1992), S. 119-122 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarographic half-wave potentials for the electrochemical reduction of a series of para-substituted iodobenzenes in acetonitrile, acetone, benzonitrile, dimethylformamide, dimethyl sulphoxide and methanol obey Hammett equations and the reaction constant found, ρ = 0·36 ± 0·02, is independent of the solvent used. The results obtained are discussed on the basis of a mechanism of the electrode process.
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  • 57
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of cavity theories of solution and linear solvation energy relationships to the interpretation of enthalpy of solution values of tert-butyl halides in hydroxylic media, measured at 25 °C and infinite dilution, is deserted, in order to define the intermolecular forces acting between solutes and solvents. It is concluded that solvent dipolarity and solvent HBD acidity effects dominate the solution process. An empirical equation relating the enthalpies of solution with selected properties of both solvents and solutes is proposed. New experimental Δ Hs∞ values for tert-butyl iodide in 13 alcohols are reported.
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  • 58
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    Journal of Physical Organic Chemistry 5 (1992), S. 123-128 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 10, 10-Dimethyl-9-anthrylidene (DMA) was studied by laser flash photolysis (LFP) techniques. LFP of the requisite diazo precursor in pentane or carbon tetrachioride produced transient spectra attributed to the hydrocarbon and monochlorinated diarylmethyl radicals, respectively. In the presence of pyridine and oxygen, ylides were formed upon LFP of 10, 10-dimethyl-9-diazoanthrone. However, ylides are not formed in acetonifrile or acetone. The carbene itself was not detected by transient absorption spectroscopy. The absolute rate constants for reaction of DMA with pyridine, methanol and triethylsilane are 1·96 × 109, 1·8 × 1010, and 1·0 × 108 I mol-1 s-1, respectively. It is concluded that the singlet and triplet states of DMA are essentially degenerate.
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  • 59
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    Journal of Physical Organic Chemistry 5 (1992), S. 142-154 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some transimination processes were studied using an intermolecular model formed by pyridoxal-5′ -phosphate (PLP) an amino acid and dodecylamine (DOD) in an aqueous medium. All the kinetic constants for the reversible reaction were determined. The results show that in these cases transimination proceeds through an addition-elimination by forming a diamine geminal intermediate. Equilibria are always shifted to dodecylamine-PLP Schiff base formation. Differences between the stability of this Schiff base and the ∊-aminocaproic Schiff base cannot be explained only on the basis of the different nucleophicities of amine groups and therefore differences in the imine double bond environment must be taken into account to explain this behaviour.
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  • 60
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cycloaddition reactions of 4-methylphenylthio-, methoxy-, 4-methoxyphenyl-, phenyl-, chloro- and cyanoallene with tert-butylthioacrylonitrile (BTA) in toluene-d8 solution were investigated. The relative reactivity sequence of these substituted allenes is 4-methylphenylthio ∼ methoxy- 〉 4-methoxyphenyl- 〉 phenyl- 〉 chloro- 〉 cyanoallene. Activation parameters were measured for diradical intermediate formation of BTA with 4-methylphenylthio-, methoxy- and 4-methoxyphenylallene, giving average values of Ea and ΔS± of 14.2-16.8 kcal mol-1 and ca. -33 eu, respectively. The relative reactivity sequence is consistent with a FMO allene-HOMO, BTA-LUMO dominant interaction for diradical intermediate formation. However, the regioselectivity of attack on the substituted allene appears to be thermodynamically controlled. The formation of the diradical intermediates in these cycloaddition processes appears to be irreversible. However, the ring closure of the diradical intermediates formed from 4-methylphenylthio-, methoxy- and 4-methoxyphenylallene is reversible under the conditions of the kinetic experiments. The kinetically controlled ring closure of the diradical intermediates is allyl radical SOMO controlled, while the final cycloadduct distribution is thermodynamically controlled.
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  • 61
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    Journal of Physical Organic Chemistry 5 (1992) 
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 62
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    Journal of Physical Organic Chemistry 5 (1992), S. 201-208 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative stabilities of gaseous protonated propylene oxide and its isomers, protonated propanal, oxetane and acetone, were reinvestigated in a Fourier transform ion cyclotron resonance mass spectrometer by using multiple-stage tandem mass spectrometri experiments. The dependence of ion structure on internal energy was examined by generating the ions in proton transfer reactions with different exothermicities and then probing their structures by using energy-resolved mass spectrometry (collision-activated dissociation as a function of collision energy). In contrast to results obtained in several recent investigations, protonated propylene oxide was found to be distinct from its more stable isomers when generated with only a small amount of internal energy. When the exothermicity of the proton transfer reaction was higher than 6 kcal mol-1 (1 kcal = 4·184 kJ) or when the epoxide ion was subjected to multiple activating collisions, rapid isomerization to protonated propanal occurred. The energy required for opening of the epoxide ring estimated to be similar to that measured earlier for protonated cyclohexene oxide (5-10 kcal mol-1).
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  • 63
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    Journal of Physical Organic Chemistry 5 (1992), S. 218-224 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ESR spectra of 2-arylindan-1,3-dionyl radicals in various solvents at 343 K were obtained and assignments of the hyperfine structures were made. The hyperfine coupling constant (hfcc) of the dimethylamino nitrogen increases whereas the 2',6'-hydrogen hfcc decreases as the ET value, a solvent polarity parameter, increases. MO calculations were made according to the semi-empirical procedure of Rieger and Fraenkel; the nitrogen and oxygen Coulomb integrals were adjusted so that the calculated spin density on the nitrogen atom agrees with that estimated from its hfcc. It is found that the π-moment of the radicals increases from 9·13 D in toluene to 9·85 D in acetic acid. The solvent dependence of the equilibrium between the radicals and its dimer has been explained in terms of the solventinduced π-moment in polar solvents.
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  • 64
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    Journal of Physical Organic Chemistry 5 (1992), S. 225-229 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A bond and group equivalent scheme that allows the calculation of heats of formation for aldehydes and ketones from ab initio 6-31G* energies has been developed. For a group of 24 aldehydes and ketones, the RMS error for the calculated heat of formation was 0 · 46 kcal mol-1. Heats of formation have been predicted for an additional seven compounds for which the experimental values are believed to be either in error or unknown. There are some problems with the norbornanones.
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  • 65
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    Journal of Physical Organic Chemistry 5 (1992), S. 239-243 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pK values of some arylthiomethylbenzoic acids and the corresponding sulphones were determined spectrophotometerically. The role of substituent and the position of the carboxylic group are discussed.
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  • 66
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    Keywords: Organic Chemistry ; Physical Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate, endo/exo and diastereofacial selectivities of the Diels-Alder reaction between cyclopentadiene and ( - )-menthyl acrylate were measured in a series of organic solvents and organic-aqueous mixtures. Regression analyses show that a model with the α empirical solvent parameter accounts for most of the changes in rates and diastereofacial selectivities, whereas in the case of the endo/exo selectivity, inclusion of the π* and δ parameters is needed. Theoretical calculations carried out on the model reaction between methyl acrylate and cyclopentadiene using dielectric continuum and supermolecule models do not clearly show the effect of the different solvation mechanisms on rate. However, they agree with the above-mentioned influence of α and π* on the endo/exo and diastereofacial selectivities.
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  • 67
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enhancement factors of the 1H polarization induced in radical pairs generated by α-cleavage of 12C=O- and C=O-labelled ketones deviate from the ratios expected on the basis of the relative abundances of the respective carbon isotopomers. For dibenzyl ketone, the ratio of absolute CIDNP intensities of the 1H(13C) doublet (90% 13C=O) to the 1H(12C) singlet (10% 12C=O) was found to be 〉9:1 at 58·3 kG and 〈9:1 at 21 kG. Similar deviations were observed for other 13C labelled ketones, viz. deoxybenzoin (13C=O) and acetophenone (13C=O or 13CH3). This novel enhancement or suppression effect on the CIDNP enhancement can be ascribed to the presence of a second hyperfine coupled nucleus in the intermediate radical pair. The individual contributions of the g factor difference (Δg), the external magnetic field strength (Ho), and the hfc constants of the observed (aA) and the interacting nucleus (ax) in the enhancement-suppression are exemplified. The experimental results are consistent with theoretical calculations of the mutual effect of Δg, H0, aA and ax on the CIDNP enhancement factor of the observed nucleus.
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  • 68
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    Journal of Physical Organic Chemistry 5 (1992), S. 269-274 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants (k2) were determined for the reduction of 1-benzyl-3-cyanoquinolinium ion by phosphonate dianion in mixed solvents consisting of propan-2-ol and water. The reduction product was mostly 1-benzyl-3-cyano-1,4-dihydroquinoline with a trace of the 1,2-isomer. The solvent properties were varied by increasing the fraction of water in the mixed solvent, which increases the polarity of the solvent. Increasing the proportion of alcohol makes the solvent a better electron pair donor. The higher fraction of propan-2-ol in the mixed solvent gives rise to a substantial increase in k2. A quantitative comparison of the solvent effect on this reaction with the solvent effects on related reactions suggests a solvent Brønsted α value of 0·45. This suggests that the PO3- unit of the transition state interacts only weakly with the solvent although the final oxidized product is phosphate.
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  • 69
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    Journal of Physical Organic Chemistry 5 (1992), S. 609-613 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The visible spectrum of di-tert-butylstilbazolium betaine (DTBSB) was recorded in eight simple amides. The appearance of a ‘coarse’ structure in the main absorption band is due to the shielding effect of the tert-butyl groups, which hinder the approach of the solvent. Since this structure disappears in formamide, it is concluded that this solvent associates through its NH to the carbonyl group of DTBSB. For the other amides, there is a clear relationship between the steric effect, for both the N- and C-substituents, of the solvent-solute hydrogen bond association and the structure of the visible band.
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  • 70
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title compounds (1 and 3, respectively) were studied by X-ray crystal structure analysis. Both are trigonal, space group R3, with lattice parameters a = 27.718(6), c = 8.161(2) Å, Z = 3 and a = 31.267(7), c = 6.560(2), Z = 18, respectively. The dodecamethyl compound 1 is isomorphous with its parent hexakis(4-benzylphenoxy)benzene (2), a known host. However, ‘collapse’ along the c-axial direction has occurred such that the appreciable clathrate cavity of 2 has been replaced by only a very small residual void for 1. Phenol 3 does not pack in discrete [OH]6 hydrogenbonded hexamers; instead, molecules are assembled in infinite chains, linked by OH…O hydrogen bonds of length 2.735(3) Å, which are propagated along threefold screw axes. A variable-temperature CPMAS NMR study of sidechain aryl group rotation in 1 gives a value ΔG≠ of 14.0 ± 0.7 kcal mol-1 (at 42 °C) for the (crystallographically unique) para -disubstituted ring, a similar 14 kcal mol-1 free energy barrier being found hindering rotation of this ring, and of the outer phenyl ring of 1, at 9°C.
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  • 71
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A transition structure for the syn and anti attack of formonitrile oxide on both cis-3,4-dichlorocyclobutene and norbornene was obtained using HF/3-21G method. These calculations correctly predict dominance of the syn attack in the reaction of dichlorocyclobutene and 100% syn selectivity, with respect to the methano bridge, in the reaction of norbornene. Analysis of the activation energy shows that the inherent facial bias of dichlorocyclobutene is reflected, at the transition state, in a complex way in the deformation energy of both dichlorocyclobutene and formonitrile oxide and in the interaction energy between them. With norbornene the out-of-plane deformation energy of the olefinic hydrogens clearly emerges as the major factor in controlling facial selectivity.
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  • 72
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 73
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    Journal of Physical Organic Chemistry 5 (1992), S. 341-348 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two amphiphilic oximes, 10-phenyl-10-hydroxyiminodecanoic acid (oxime II) and 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroxyimino nonanyl)benzene (oxime III) were synthesized. The pKa values of oximes II and III and acetophenoxime (oxime I) and the rates of oximolysis of p-nitrophenyl acetate (NPA) and p-nitrophenyl octanoate (NPO) were determined in the presence and absence of micellar hexadecyltrimethylammonium bromide (CTAB). The rates of oximolysis increased by up to 3 × 104-fold in the presence of CTAB. Quantitative analysis of micellar effects, using an ion-exchange pseudo-phase model, allowed the determination of the second-order rate constants for the reactions of oximes I-III with NPA and NPO in the micellar pseudo-phase. The calculated rate constants in the micellar pseudo-phase were lower than those in water, demonstrating that the rate enhancements were due to substrate concentration in the micelles. Comparison of the rate constants in micelles and water suggests that the sites of reaction of oximes I-III with NPO and NPA are similar to those in bulk aqueous solution. Micellar incorporation of the hydrophobic oximes II and III does not lead to a major change in the nucleophilicity of the oximate anion.
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  • 74
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    Journal of Physical Organic Chemistry 5 (1992), S. 355-360 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,2′-Furil (di-2-furyl diketone) undergoes photoreduction to give furoin on irradiation at 366 nm in triethylamine-containing benzene and ethers. On the other hand, in ethanol the photoirradiation leads to the formation of an enediol type of compound, 1,2-di(2-furan)ethene-1,2-diol. The results of quenching and sensitization both for the photoreactions and the phosphorescence demonstrate that furoin and the enediol are formed via the lowest excited singlet and the triplet states of 2,2′-furil, respectively.
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  • 75
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    Journal of Physical Organic Chemistry 5 (1992) 
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 76
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    Journal of Physical Organic Chemistry 5 (1992), S. 361-366 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis reaction of methyl nitrate was simulated by quantum mechanical and molecular mechanical methods. The gas-phase reaction was calculated to proceed with no barrier when ab initio calculations at the STO-3G level were utilized, and with a very small barrier (5.70 kJ mol-1) when the MINDO/3 method was applied. In solution, the solvation energy was estimated to be 70.33 kJ mol-1 by molecular mechanical calculations. Thus the activation energy (76.03 kJ mol-1) of alkaline hydrolysis of methyl nitrate was found to be in good agreement with the available experimental value (82.42 kJ mol-1). The results indicated that the substantial activation barrier in alkaline hydrolysis was essentially solvent-induced.
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  • 77
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolysis of 1,1-diphenyl-1-X-ethane (1-X) [X = 4-nitrobenzoate (PNB), 3,5-dinitrobenzoate (DNB), AcO, MeOH+, EtOH+ or H2O+] was studied in 20 vol% dimethyl sulphoxide in water, in which specific salt effects are very small, and in 25 vol% acetonitrile in water. Substrates with negatively charged leaving groups yield more elimination product 1,1-diphenylethene (3) than those with uncharged groups, indicating the intermedicacy of ion pairs. Thus, three times more alkene is formed in the reactions of the substrates 1-OAc and 1-PNB than in the acid-catalysed hydrolysis of 1-OMe and 1-OAc. The substitution products may be formed via the solvent-equilibrated carbocation since the measured nucleophilic selectivities are very similar with different leaving groups.
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  • 78
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    Journal of Physical Organic Chemistry 5 (1992), S. 373-381 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of oxidation of indole (In) and 5-substituted indoles (OCH3, Br and Cl) by chloramine-B (CAB) were studied in alkaline medium with Os(VIII) as catalyst at 303 K. At low [In]0 the rate law rate = k [CAB] [Os(VIII)] [In]0 is obeyed, which changes to rate = k [CAB] [Os(VIII)] [OH-]-1 at higher substrate concentrations. Variation of ionic strength has no effect on the rate and the dielectric effect is negative. The reaction was studied at different temperatures and activation parameters were evaluated. Hammett correlation of substituent effects indicated a linear free energy relationship with ρ+ = - 1.0, showing the formation of an electrondeficient transition state. From enthalpy-entropy relationships and Exner correlations, the isokinetic temperature β was found to be 330 K, indicating enthalpy as a controlling factor. The mechanism assumes the formation of a complex between oxidant and Os(VIII) at high and low [In]0. Proton inventory studies in H2O-D2O mixtures showed the involvement of a single exchangeable proton of OH- ion in the transition state.
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    Journal of Physical Organic Chemistry 5 (1992), S. 382-394 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular mechanical model is presented which allows computational interpretation of stereodynamics in ferrocenophanes by using a simple form of bending potential for angles involving the central iron atom and extended to carbon atoms of different cyclopentadienyl rings. Potential energy surfaces of [3] -, [4] - and [45] ferrocenophanes were studied in detail. For [3] ferrocenophane, the calculated energy barrier of the bridge reversal process agrees well with the experimental value. The previous interpretation of a rigid bridge in [4] ferrocenophane is questioned on the basis of the calculated low barriers. The predominance of experimentally indistinguishable enantiomeric pairs may be responsible for the misinterpretation. [45] Ferrocenophane is estimated to interconvert into D5-symmetric global energy minima over barriers of 13-15 kcal mol-1 through one-by-one flipping of five tetramethylene bridges.
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  • 80
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    Journal of Physical Organic Chemistry 5 (1992), S. 395-408 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of computational techniques to biology, chemistry and physics is growing rapidly. Quantitative structure-activity relationships (QSAR) have been used widely to relate biological activities and physicochemical properties to molecular structural features. A difficulty in this approach has been non-uniformity of parameter sets resulting in the inability to examine contributions across properties and data sets. Linear solvation energy relationships (LSER) developed by Kamlet and Taft successfully utilize a single set of parameters to correlate a wide range of biological, chemical and physical properties. The empirical LSER solvatochromic parameters have been replaced with theoretically determined parameters to permit greater ease in a priori property prediction. These TLSER descriptors have given good correlations and interpretations for some biological activities. This paper discusses the application of these descriptors to six physicochemical properties involving equilibria, kinetics and spectra. The results show good correlation and physical interpretation.
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  • 81
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    Journal of Physical Organic Chemistry 5 (1992), S. 424-428 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The O-17 NMR spectra of 13 α′-alkyl- and aryl-substituted α-diazoketones were measured. The results obtained show a clear discrimination between them. A good correlation in a series of para-substituted α-diazoacetophenones between O-17 chemical shifts and both α+p and dual substituent parameters indicated a greater contribution of resonance than inductive effects.
    Additional Material: 2 Ill.
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  • 82
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants (kB1 and kBH-1) for the reversible deprotonation of triphenyl(2-Z-9-fluorenyl)phosphonium ions (Z = H, Br, NO2) by piperidine, morpholine, n-butylamine, 2-methoxyethylamine, glycine ethyl ester, cyanomethylamine, OH- and water were determined in 50% Me2SO-50% (v/v) water at 20°C. Brønsted αCH (variation of carbon acid) and β values (variation of amine), and intrinsic rate constants [log k0 = log kB1/q when pKBHa - pKCHa + log(p/q) = 0] were obtained. αCH decreases with increasing basicity of the amine whereas βB decreases with increasing acidity of the carbon acid. These trends, which imply changes in the transition-state structure with reactivity, can be described by the interaction coefficient pxy = ∂βB/∂pKCHa = ∂αCH/ - ∂pKBHa = 0.03 (primary amines) and 0.01 (piperidine/morpholine). αCH is smaller than βB, indicating an imbalance due to a lag in the delocalization of the negative charge into the fluorenyl moiety at the transition state. The influence of the Ph3P+ group on the intrinsic rate constant is analyzed in terms of possible contributions by inductive/field (I), resonance (R), polarizability (P) and steric (S) effects. Using 9-carbomethoxyfluorene as a reference, it is shown that the stronger electron-withdrawing I effect of the Ph3P+ group relative to the COOMe group enhances log k0 substantially; the fact that the R effect of Ph3P+ is weaker than that of COOMe also contributes to an increase in k0, and so does the P effect of the phosphorus. All these increases are virtually completely offset by the rate-retarding S effect of the bulky Ph3P+ group. A similar analysis for the Me2S+ derivative studied by Murray and Jencks [J. Am. Chem. Soc. 112, 1880 (1990)] leads to similar conclusions except that the still smaller R effect is probably one of the main reasons why k0 for the Me2S+ derivative is more than ten times higher than for the Ph3P+ derivative; another potential reason is a difference in the steric effect.
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  • 83
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    Journal of Physical Organic Chemistry 5 (1992) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 84
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    Journal of Physical Organic Chemistry 5 (1992), S. 435-435 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 85
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    Journal of Physical Organic Chemistry 5 (1992), S. 443-450 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acid dissociation and anion complexation properties of 3+ and 4+ forms of 1,4,7,10,13-pentaazacyclopentadecane were investigated by pH potentiometry, conductometric titration and 13C NMR experiments. The 3+ and 4+ species form complexes with a variety of mono- and divalent anions, and their complexation constants can be determined by pH potentiometric methods. However, no iodide complexes are detected and neither is a pentaprotonated species. Enthalpy and entropy changes for the acid dissociation of the 3+ ligand and for its complexation with chloride are estimated. The complexation and acid dissociation properties of the ligand are discussed in terms of internal hydrogen bonding interactions and solvation effects.
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  • 86
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    Journal of Physical Organic Chemistry 5 (1992), S. 437-442 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl chloride) (PVC) membranes impregnated with 2-borono-1,3-xylyl crown ethers were evaluated in ion-selective electrodes. The response pattern obtained with these crown ethers appears to be essentially independent of ring size but there is a linear correlation between selectivity and hydration enthalpy of the cation which is similar to that obtained for electrodes prepared only with the lipophilic anionic site KTCIPB. The similarities in correlation and mechanism between these two types of electrodes has been attributed to the presence of anionic sites in both cases dominating the observed selectivity. For the four ionophores considered the pH-dependent ionization of the boronate group to the boronate anion is proposed to be responsible for the domination of anionic sites on the properties of the ionophores. The ionophores proved to be good K+ neutral carriers, showing responses to this ion in the range 10-1-10-4 M. The compounds tested showed a fast response to changes in K+ concentration which was stable to within 〈 0.2 mV h-1.
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  • 87
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    Journal of Physical Organic Chemistry 5 (1992), S. 457-460 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of alkali metal ions (Li+, Na+, K+, Cs+) on the reactivity of toluenethiolate anion in the demethylation of 2-methoxy-1,3-xylyl-18-crown-5, 2-methoxy-1,3-xylyl-24-crown-7 and the model compounds anisole and 2,6-dimethylanisole was investigated in dimethylformamide (+3.3 M water) at 60°C. It was found that the metal ion effects are markedly influenced by the presence of the polyether chain in the reaction system. Whereas reactions of the model compounds are slightly inhibited by the presence of alkali metal ions, the latter strongly enhance rate of demethylation of the crown ether derivatives, the observed catalytic factors ranging over nearly three orders of magnitude. These remarkable rate-enhancing effects are ascribed to a strong transition-state stabilization by metal ions through cooperation of electrostatic binding with the negative charge developing on the oxygen atom of the methoxy group undergoing nucleophilic attack and coordinative interaction with the polyether chain.
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  • 88
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    Journal of Physical Organic Chemistry 5 (1992), S. 451-456 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper describes a fluorescence depolarization and 31P NMR spectroscopic study of the phase transition behaviour of a series of identical and mixed-chain di-n-alkyl phosphate vesicles in the presence of different counterions (Na+,K+,Me4N+,Ca2+). Using trans, trans, trans-1, 6-diphenyl-1, 3, 5-hexatriene (DPH) as a fluorescent probe, the fluorescence polarization (P) was measured for the identical-chain vesicles (Na+, K+, Me4N+) as a function of temperature. The temperature for the main phase transition (Tm) only responded to variation of the counterion in the case of the longer-chain di-n-alkyl phosphates, with Tm decreasing in the sequence Na+ 〉 K+ 〉 Me4N+. This result is rationalized in terms of a decreasing counterion binding, which affects chain ordening in the core of the bilayer. Peak intensities and line widths of the 31P NMR resonances for the bilayer vesicles suggest a more complex phase behaviour, but the overall results are reconcilable with the picture emerging from the fluorescence depolarization experiments. Fluorescence depolarization measurements were also carried out with vesicles formed from the sodium di-n-alkyl phosphates and in the presence of various concentrations of Ca2+ (0-6 mM) at temperatures above Tm. For both the identical-chain and mixed-chain di-n-alkyl phosphate vesicles, a steep increase in P was found between ca 1.0 and 1.4 mM Ca2+, indicative of a strong Ca2+-induced ordening of the alkyl chains.
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  • 89
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    Journal of Physical Organic Chemistry 5 (1992), S. 461-466 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using a flourescence-detected ethidium displacement assay, the calf thymus DNA complexation properties of 27 mono-, di-, tri-, tetra- and hexacationic polyamines were determined. The DNA-binding affinity of these polyamine compounds increased with increasing cationic charge on the polyamine. Although most of the compounds exhibited no base pair binding selectivity, two of the tricationic polyamines possessing additional neutral amine groups exhibited approximately tenfold GC binding selectivities.
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  • 90
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    Journal of Physical Organic Chemistry 5 (1992), S. 496-501 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of chemical modifications on the lower rim of calix [n] arenes is analysed with respect to the cation binding ability of the receptor. Extraction data and stability constants of the complexes are discussed. Three main factors are investigated: the size of the calixarene, the conformation of the calixarene and the nature of the ligating group attached to the phenolic oxygen. The work concentrates on esters, ketones, amides, thioamides and carboxylic acids. Some data concern chemically modified tetrahomodioxacalix [4] arene esters.
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  • 91
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    Journal of Physical Organic Chemistry 5 (1992), S. 529-532 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectroscopic and potentiometric studies of Ag(I) binding by tris-bipyridine strands indicate that the formation of trinuclear silver trihelicates is a process displaying positive cooperativity.
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  • 92
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    Journal of Physical Organic Chemistry 5 (1992), S. 533-539 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crown ether complexation of 1:1 alkali metal TCNQ salts, MTCNQ (M=K, Rb, Tl) leads to structures containing isolated TCNQ dimers. These materials provide valuable models for investigating the spectroscopic and electronic behaviour of TCNQ-. dimer components which are key structural fragments of, for example, organic metals and semiconductors.
    Additional Material: 6 Ill.
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  • 93
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    Journal of Physical Organic Chemistry 5 (1992) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 94
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    Journal of Physical Organic Chemistry 5 (1992), S. 581-589 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The partial rate factors of the four modes of meta photocycloaddition of methyl-substituted benzenes to cyclopentene have been determined by measuring quantum yields of formation of the most important meta photocycloadducts of benzene, toluene and the three xylenes. It is demonstrated that the results can be applied to predict quantum yields of any meta photocycloadduct of methylbenzenes to cyclopentene. The predicted yields agree very well with those determined experimentally, and it is shown that the effects of two or more methyl groups are fully additive. The method is promising for the investigation of mechanisms of photochemical reactions and can be used to predict regioselectivities.
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  • 95
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    Journal of Physical Organic Chemistry 5 (1992), S. 595-599 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The participation of the carboxylate group in the ionization of Rhodamine B leucocyanide was studied in an aqueous solution of poly(vinylbenzyltrimethylammonium chloride) (PVBTA) or cetyltrimethylammonium bromide (CTAB) at constant temperature and pH 8. The experimental rate constant (kexp) decreases with increasing PVBTA concentration. The results are interpreted in terms of the binding of the ionized form of Rhodamine B leucocyanide (RBCN-) to a single class of completely independent binding sites on the PVBTA. From this model, a value of 1.09 × 106 l mol-1 was obtained for the binding constant. The effect of CTAB is different from that obtained with PVBTA. After a region in which there are large changes in kexp with the CTAB concentration, this constant reaches a zone where its value is independent of the surfactant concentration. The decrease in kexp in the first zone was explained in terms of an ionic association between RBCN- and the cationic heads. In the second zone, it was assumed that a micellar effect operates on the ionization kinetics. In a similar form, the esterification of the carboxylate group leads to a slower ionization rate.
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  • 96
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    Journal of Physical Organic Chemistry 5 (1992), S. 617-618 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational analysis of dimethyl [2] metacyclo [2] (3,4)thiophenophane (1), which is the thiophene analogue of [2.2] orthometacyclophane, is described. The comparison between the dynamic NMR spectra of 1 and the computer-simulated spectra led to the energy barrier between syn and anti conformers of 1. This is the first conformational analysis of a [2,2] orthometa-type cyclophane.
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  • 97
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    Journal of Physical Organic Chemistry 5 (1992), S. 619-627 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition metal ions are effective catalysts of the hydrolytic cleavage of amino acid esters and their effects can be enhanced and properly directed when they are chelated to functionalized ligands. The resulting metallocatalysts are attracting increasing attention and the systems so far investigated are briefly reviewed. Particular emphasis is given to supramolecular systems which may add to the metallocatalysts the benefits of the cooperativity, set upon convergent non-covalent interactions of their components, needed for substrate recognition. The results obtained with metallomicellar aggregates and molecular metalloreceptors, with particular reference to those studied in the authors' laboratory, are reported in more detail. In the case of loosely structured metallomicelles, remarkable accelerations and, generally, modest selectivities have been observed; less spectacular kinetic effects, but promising substrate selectivity, have been obtained with structurally well defined metalloreceptors.
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  • 98
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    Journal of Physical Organic Chemistry 5 (1992), S. 644-648 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoreduction, but not the corresponding photooxidation, of cytosine can be sensitized by a covalently appended pyrene molecule in a process that may have some importance for understanding the known carcinogenic activity of polynuclear aromatic hydrocarbons.
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  • 99
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hybrid molecular assemblies were prepared in combinations of a synthetic peptide lipid, involving an L-alanine residue interposed between an anionic head group and a hydrophobic double-chain segment, with cationic macrocyclic hosts, a steroid cyclophane bearing four rigid steroid moieties and octopus cyclophanes having eight flexible hydrocarbon branches. On addition of the cyclophanes to multi-walled bilayer membranes composed of the anionic lipid, thermodynamic parameters (ΔH and ΔS) associated with the phase transition between the gel and liquidcrystalline states were subjected to changes that are consistent with the formation of the hybrid assemblies. Anionic fluorescent guests, 8-anilinonaphthalene-1-sulphonate and 6-p-toluidinonaphthalene-2-sulphonate, were effectively incorporated into the hydrophobic cavities provided by the cationic cyclophanes embedded in the bilayer membrane through hydrophobic and electrostatic interactions. The guest-binding modes of the hybrid assemblies are classified into two types; a guest is included in the proximity of the hydrogen-belt domain of the bilayer membrane in one mode, and a guest is incorporated into the hydrophobic bilayer domain composed of double hydrocarbon chains of the lipid in another.
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  • 100
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    Journal of Physical Organic Chemistry 5 (1992), S. 663-669 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of strontium and barium ions on the acyl transfer reaction to ethoxide ion from 2-acetoxy-1,3-xylyl-15-crown-4, 2-acetoxy-1,3-xylyl-18-crwon-5, 2-acetoxy-1,3-xylyl-21-crown-6 and the model compound phenyl acetate was investigated in ethanol at 25°C. Significant catalytic effects were observed in all of the studied reactions as a result of stronger metal ion associations with the transition states than with reactants. The rate enhancements observed with the crown ether substrates are much larger than those observed with phenyl acetate, the largest acceleration being displayed by 2-acetoxy-1,3-xylyl-21-crown-6, which reacts with EtOBaBr 5 × 105 times faster than with EtONMe4. These findings provide strong evidence that cooperation of electrostatic binding to the negative charge developing at the carbonyl oxygen and coordinative binding to the polyether chain is highly efficient in the metal-bound transition state. Comparison of rate data reported here with analogous data obtained in methanol solution clearly shows that both modes of interaction contributing to the stability of the metal-bound transition state are much more efficient in ethanol than in methanol solution.
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