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  • 2000-2004  (222)
  • MRI  (121)
  • Analytical Chemistry and Spectroscopy  (101)
  • Industrial Chemistry
  • Nuclear reactions
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  • 101
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Liquordynamik ; Aquädukt ; Quantifizierung ; MRT ; Phasenkontrast ; Normalwerte ; Key Words: CSF dynamics ; Aqueduct ; Quantification ; MRI ; Phase contrast ; Normal values
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: With the 2D-phase-contrast technique the volume flow of the CSF via the cerebral aqueduct can be quantified by MRI-means. In this study the stroke volume of CSF via the aqueduct per cardiac cycle (SVcc) is used to measure the extent of the volume flow. Normative values for the SVcc are not yet defined, however, they are indispensable for the clinical utility of this non-invasive method. The aim of the presented investigation is to evaluate, if the interthalamic width of the third ventricle is useful as a reference system for the extent of the SVcc via the aqueduct and if a normal CSF-flow can be defined. Hundred and seven patients (56 female, 51 male; age distribution 8 to 89 years) without clinical or imaging findings of a CSF-flow disturbance were examined on a standard 0.5 T MRI-scanner (Gyroscan, Philips). The measurements of the SVcc via the aqueduct were performed in a single slice perpendicular to the aqueduct in the level of its median third with a retrospective cardial-gated quantitative 2D-phase-contrast sequence. The interthalamic width of the third ventricle was measured in a transversal slice (bicommissural orientation, standard T1-weighted spin-echo sequence) in the level of the upper margin of the tectorial membrane. In 83 patients with a normal heart rate and without any further abnormalities in their imaging studies the SVcc is essentially dependent (r = 0.822) on the interthalamic width of the third ventricle (between 1 and 16 mm). Eleven patients with either a subcortical atrophy without leucencephalopathy, megacisterna magna, Dandy-Walker variant or bradycardia showed a significant increase of the SVcc (p 〈 0.05). On the other hand a significant decrease of the SVcc (p 〈 0.05) is seen in 13 patients with either tachycardia, Arnold-Chiari Type-1 malformation, relative aqueductal stenosis and/or severe periventricular leucencephalopathy. These results are in good agreement with the current conceptions on the physiology of the CSF-flow. As the above mentioned criterias of influence have ho pathological significance concerning a CSF-flow disturbance requiring therapy, we used the linear regression with y = B1*× +b0 (b1 = 22.2 ± 2.9; b0 = 43,5 ± 21.1) in all 107 patients to evaluate the extent of the SVcc (y) versus the interthalamic width of the third ventricle (x). This correlation offers the possibility to differentiate a hyperdynamic (above +3 standard error SE), a hypodynamic (below −3 SE) and a normodynamic (between ± 3 SE) CSF-flow via the cerebral aqueduct for the first time. Additional imaging findings and the heart rate must find their influence in the evaluation.
    Notes: Zusammenfassung: Mit Hilfe der 2D-Phasenkontrasttechik kann der Volumenfluss des Liquors über dem Aquädukt magnetresonanztomographisch quantifiziert werden. Als Maß für die Höhe des Volumenflusses dient in vorgestellter Untersuchung das Schlagvolumen pro Herzzyklus (SVcc). Normwerte für die Höhe des SVcc konnten bislang nicht definiert werden. Sie sind jedoch für eine klinische Nutzung dieses nichtinvasiven Verfahrens unerläßlich. Ziel vorliegender Untersuchung ist es zu prüfen, ob die interthalamische Weite des dritten Ventrikels als Bezugssystem für die Höhe des SVcc über dem Aquädukt geeignet ist und sich ein normaler Liquorfluss definieren läßt. Die Untersuchungen erfolgten bei 107 Patienten (56 Frauen, 51 Männer im Alter von acht bis 89 Jahren) ohne klinische und bildmorphologische Hinweise auf eine Liquorzirkulationsstörung an einem Standardsystem 0,5 T (Gyroscan, Fa. Philips). Die Messung des SVcc über dem Aquädukt wurde in einer Eizelschicht senkrecht zum Aquädukt in Höhe des mittleren Drittels mit einer retrospektiv kardial getriggerten 2D-quantitativen Phasenkontrastsequenz durchgeführt. Die Messung der interthalamischen Weite des dritten Ventrikels erfolgte im Transversalschnitt (Bikommissuralebene, Standard-T1-gewichtete SE-Sequenz) in Höhe des Oberrandes der Lamina tecti. Für 83 kardial normofrequente Patienten ohne zusätzliche bildmorphologische Auffälligkeiten wird die Höhe des SVcc maßgeblich von der interthalamischen Weite des dritten Ventrikels (1 bi 16 mm) bestimmt (r = 0,822). Bei elf Patienten mit einer subkortikal betonten Atrophie ohne Leukenzephalopathie, Megacisterna magna, Dandy-Walker-Variante oder Bradykardie ist das SVcc signifikant erhöht (p 〈 0,05). Dagegen ist das SVcc für 13 Patienten mit Tachykardie, Arnold-Chiari-Malformation Typ 1, relativer Aquäduktestenose und/oder fortgeschrittener periventrikulärer Leukenzephalopathie signifikant erniedrigt (p 〈 0,05). Diese Ergebnisse lassen sich gut mit den geltenden Vorstellungen über die Physiologie des Liquorflusses in Einklang bringen. Da den vorgenannten Einflusskriterien keine pathologische Bedeutung hinsichtlich einer therapiebedürftigen Liquorzirkulationsstörung beigemessen werden kann, nutzen wir zur Bewertung der Höhe des SVcc (y) gegenüber der interthalamischen Weite des dritten Ventrikels (x) die lineare Regression mit y = b1*× + b0 (b1 = 22,2 ± 2,9; b0 = 43,5 ± 21,1) für alle 107 Patienten. Diese Beziehung gibt erstmals die Möglichkeit, einen hyperdynamen (〉 +3 SE), hypodynamen (〈 −3 SE) und normodynamen (in den Grenzen ± 3SE) Liquorfluss über dem Aquädukt zu differenzieren. In die Bewertung müssen das Vorliegen zusätzlicher bildmorphologischer Einflussfaktoren und die Höhe der Herzfrequenz einfließen.
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  • 102
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Medulloblastom ; Pubertas praecox ; MRT ; Kontrastmittel ; Key Words: Medulloblastoma ; Subarachnoid metastases ; Precocious puberty ; MRI ; Contrast enhancement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: Medulloblastoma, the most frequent pediatric brain tumor, has known propensity for subarachnoid dissemination. Spinal metastases indicate a poor prognosis. Intraventricular spread is much less common. We report a case of primary intraventricular dissemination with precocious puberty as the first clinical symptom due to a metastasis at the infundibulary stalk. This has not been reported so far as initial symptom of a medulloblastoma. Furthermore, we encountered an unusually mild contrast enhancement of the spinal and intraventricular metastases. Delayed scanning after contrast administration and FLAIR sequences proved to be particularly valuable in this case.
    Notes: Zusammenfassung: Medulloblastome des Kleinhirns sind die häfigsten malignen Hirntumoren im Kindesalter. Ihre Neigung zur Ausbreitung im Subarachnoidalraum ist bekannt und Prognose bestimmend. Wir berichten über den ungewöhnlichen Fall eines Medulloblastoms mit ausgeprägter intraventrikulärer Aussaat. Eine Metastase im Reccessus infundibularis führte hierbei zum Auftreten einer Pubertas praecox als initiales Krankheitssymptom, eine Beobachtung, die bisher nicht beschrieben wurde. Bemerkenswert war zudem die ungewöhnlich schwache Kontrastmittelaufnahme der intraventrikulären und spinalen Metastasen. Für die Diagnostik erwiesen sich FLAIR-Sequenzen und Spätaufnahmen nach Kontrastmittelgabe als besonders wertvoll.
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  • 103
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Vena ophthalmica superior ; Thrombose ; Sinus caverosus ; Computertomographie ; Kernspintomographie ; Key Words: Superior ophthalmic vein ; Thrombosis ; Sinus cavernosus ; CT ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: A 65-year-old woman with persistant headache since a few weeks is presented. The day before hospitalization there was a sudden onset of protrusio bulbi and progredient swelling of the soft-tissue of the left eye. In the clinical examination left side protrusio bulbi, double-vision, chemosis and swelling of the eye-lid were found. Blood sample showed an elevation of inflammation indicators. MRI and CT revealed a thrombosis of the left superior ophthalmic vein with partial thrombosis of the left cavernous sinus.
    Notes: Zusammenfassung: Eine 65-jährige Patientin stellt sich mit seit Wochen bestehenden Kopfschmerzen vor. Am Tag vor der Aufnahme war morgens akut eine Protrusio bulbi mit einem periorbitalen Ödem aufgetreten. Klinisch fanden sich eine Protrusio bulbi mit Chemosis und Oberlidschwellung links, Doppelbildern sowie einer Erhöhung der Entzündungsparameter. Kernspintomographisch und computertomographisch ließ sich eine Thrombose der Vena ophthalmica superior links mit Teilthrombose des linken Sinus cavernosus nachweisen.
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  • 104
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 83 (2000), S. 363-369 
    ISSN: 1439-6327
    Keywords: Key words Achilles tendon moment arm ; MRI ; Maximum voluntary contraction ; In vivo ; Tendon excursion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of the present study was to estimate and compare in vivo measurement-based Achilles tendon moment arm lengths at rest and during isometric plantarflexion maximum voluntary contraction (MVC) using the centre-of-rotation (COR) and the tendon-excursion (TE) methods. Both methods were based on morphometric analysis of sagittal-plane magnetic resonance images of the foot. Using the COR method, moment arms were obtained at ankle angles from 15° of dorsiflexion to 30° of plantarflexion in steps of 15°, digitizing the perpendicular distance from a moving centre of rotation in the tibio-talar joint to the Achilles tendon action line. The TE method was based on measurement of calcaneal displacement along the tibial axis during 15° rotations of the ankle joint, from 30° of dorsiflexion to 45° of plantarflexion. The two methods gave similar estimations at rest varying from 4.3 to 5.6 cm. Using the COR method, the Achilles tendon moment arm during MVC was larger by 1–1.5 cm (22–27%, P 〈 0.01) than the respective resting value. In contrast, no difference (P 〉 0.05) was found between the resting and MVC moment arm estimations of the TE method. The disagreement in moment arms during MVC may be attributed to differences in the assumptions made between the two methods. The TE method has more limitations than the COR method and its estimations during MVC should be treated with caution. Resting Achilles tendon moment arm estimations of the COR method should be multiplied by 1.22–1.27 when maximal isometric plantarflexion joint moments, musculotendon forces and stresses are predicted using modelling.
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  • 105
    ISSN: 1573-7373
    Keywords: SCLC ; brain matastases ; neurologic asympotomatic ; MRI ; prophylactic radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose. In this study we evaluated the usefulness of MR-imaging in the detection of asymptomatic brain metastases (BM) at the initial diagnosis in patients with small cell lung cancer (SCLC) and studied the follow-up of these patients. Patients and methods. One-hundred and twenty-five patients with SCLC were investigated with MR-imaging. Results. In 112 patients with normal neurological findings, MR-imaging of the brain demonstrated BM in 17 patients (15%). Six of these 17 patients were therefore upgraded to extensive disease (ED). Two of these 17 patients died during chemotherapy because of progressive disease and 3 patients became neurologic symptomatic with progressive disease on MR-imaging of the brain. After completion of chemotherapy a repeated MR-imaging of the brain in the remaining 12 patients showed 1 complete remission, 4 partial remission and 7 progressive disease of the BM. Conclusion. This study showed that at presentation an unexpectedly high percentage of SCLC patients had asymptomatic BM on MR-imaging. We propose that MR-imaging of the brain should be included in the staging of SCLC patients as well for staging, prognosis and therapy.
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  • 106
    ISSN: 1573-7373
    Keywords: astrocytoma ; 201thallium SPECT ; MRI ; MR spectroscopy ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose To compare chemotherapy treatment monitoring in astrocytoma by 201thallium single photon emission computed tomography (SPECT) and photon magnetic resonance spectroscopy (1H-MRS) with magnetic resonance imaging (MRI), and to evaluate the influence of morphological tumor changes on cerebral 201thallium uptake and metabolic changes in 1H-MRS. Materials and methods Six patients with highly malignant astrocytomas were followed with quantitative 201thallium SPECT, MRI, and 1H-MRS during chemotherapy. Maximum follow-up included six examinations per patient by either method during 18 months. Criteria were set for: (1) regression (≥ 25% tumor reduction), (2) status quo (〈 25% reduction and 〈 25% increase), and (3) progression of disease (≥ 25% tumor increase). Results were compared with the clinical state of disease. Changes of tumor volume, contrast enhancement, necrosis, hemorrhage and edema on MRI were compared to changes in 201thallium uptake volumes and 1H-MRS metabolite ratios. Results Six patients were followed with a total of twenty-four examinations with 201thallium SPECT, MRI and 1H-MRS, respectively, between February 1997 and October 1998. Five patients developed clinical progression of disease, 4 out of 5 cases showed SPECT progression, 4 out of 5 cases MRI progression, and 1 out of 2 interpretable cases 1H-MRS progression at final assessment before clinical deterioration. During the phase of clinically stable disease; (A) the criterion for regression or status quo was met in 10 out of 13 assessments with SPECT, 11 out of 13 with MRI, and 8 out of 9 interpretable 1H-MRS; (B) the criterion for progression was met in 3 out of 13 with SPECT, 2 out of 13 with MRI, and 1 out of 9 interpretable 1H-MRS. The accuracy of SPECT, MRI, and 1H-MRS in identifying changes of tumor burden concordant with patients' clinical course was 78%, 83%, and 82%, respectively. SPECT regression was associated with MRI decrease of tumor size, contrast enhancement, edema and hemorrhage. SPECT progression was associated with MRI increase of the same parameters and the increase of necrosis. 1H-MRS regression was associated with decrease of edema. 1H-MRS progression was associated with increase of tumor size, hemorrhage, and increase or decrease of contrast enhancement. Conclusions Both 201thallium SPECT and 1H-MRS evaluation showed sensitivity for detection of astrocytoma progression. We did not find a higher accuracy of SPECT or MRS than of MRI in astrocytoma chemotherapy monitoring. Treatment induced MRI changes were associated with 201thallium uptake variations. 1H-MRS was difficult to apply for astrocytoma treatment monitoring. Improvements regarding size of measurement area such as multivoxel MRS and fat suppression pulses appeared desirable, and also the use of functional techniques with superior resolution such as dual isotope SPECT. However, our results suggest that 201thallium SPECT and 1H-MRS can provide additional information to MRI for chemotherapy efficacy evaluation in selected cases.
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  • 107
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 47 (2000), S. 195-210 
    ISSN: 1573-7373
    Keywords: MRI ; spinal cord ; tumor ; intramedullary
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The advent of MRI has significantly changed the diagnosis of spinal cord tumors. Standard imaging provides excellent localization and characterization of the tumor in a noninvasive fashion. Exact histologic diagnosis of the two most common tumors, ependymoma and astrocytoma, remains elusive but there are some suggestive imaging characteristics. It is hoped that some of the newer MR imaging sequences will improve characterization of the tumor and thereby influence therapy. Several of these pulse sequences are already used routinely in brain imaging. Evaluation of new imaging sequences in the spine has lagged behind brain MR imaging, mainly due to technical factors. Work on animal spine models and extrapolation from brain imaging studies suggest that it is only a matter of time before some of these techniques become clinically relevant.
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  • 108
    ISSN: 1573-7373
    Keywords: brain ; brain tumors ; MRI ; MR spectroscopy ; diffusion imaging ; glioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This study sought to correlate quantitative presurgical proton magnetic resonance spectroscopic imaging (1H- MRSI) and diffusion imaging (DI) results with quantitative histopathological features of resected glioma tissue. The primary hypotheses were (1) glioma choline signal correlates with cell density, (2) glioma apparent diffusion coefficient (ADC) correlates inversely with cell density, (3) glioma choline signal correlates with cell proliferative index. Eighteen adult glioma patients were preoperatively imaged with 1H-MRSI and DI as part of clinically-indicated MRI evaluations. Cell density and proliferative index readings were made on surgical specimens obtained at surgery performed within 12 days of the radiologic scans. The resected tissue location was identified by comparing preoperative and postoperative MRI. The tumor to contralateral normalized choline signal ratio (nCho) and the ADC from resected tumor regions were measured from the preoperative imaging data. Counts of nuclei per high power field in 5–10 fields provided a quantitative measure of cell density. MIB-1 immunohistochemistry provided an index of the proportion of proliferating cells. There was a statistically significant inverse linear correlation between glioma ADC and cell density. There was also a statistically significant linear correlation between the glioma nCho and the cell density. The nCho measure did not significantly correlate with proliferative index. The results indicate that both ADC and spectroscopic choline measures are related to glioma cell density. Therefore they may prove useful for differentiating dense cellular neoplastic lesions from those that contain large proportions of acellular necrotic space.
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  • 109
    ISSN: 1615-6692
    Keywords: Key Words Cardiac imaging ; MRI ; Heart ; Ventricular function ; Schlüsselwörter Kardiale Bildgebung ; Magnetresonanztomographie ; Herz ; Ventrikelfunktion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die kardiale Dysfunktion ist eine der Hauptursachen kardiovaskulärer Morbidität und Mortalität. Eine genaue und reproduzierbare Bestimmung der Herzfunktion ist essentiell für die Diagnosestellung, Prognoseabschätzung und Beurteilung des Therapieeffekts beim einzelnen Patienten. Die kardiovaskuläre Magnetresonanztomographie (CMR) bietet eine Messmethode für die globale und regionale Herzfunktion, die nicht nur genau und reproduzierbar, sondern auch nichtinvasiv, ohne ionisierende Strahlung und unabhängig von geometrischen Annahmen und einem akustischen Fenster ist, das den Einsatz der Echokardiographie limitiert. Mit der Verfügbarkeit schnellerer MR-Scanner und automatisierter Analysesysteme sowie mit zunehmender Verbreitung und reduzierten Kosten wird CMR bald den Referenzstandard für die Messung der Herzfunktion darstellen.
    Notes: Abstract Cardiac dysfunction is a major cause of cardiovascular morbidity and mortality. Accurate and reproducible assessment of cardiac function is essential for the diagnosis, the assessment of prognosis and evaluation of a patient's response to therapy. Cardiovascular Magnetic Resonance (CMR) provides a measure of global and regional function that is not only accurate and reproducible but is noninvasive, free of ionising radiation, and independent of the geometric assumptions and acoustic windows that limit echocardiography. With the advent of faster scanners, automated analysis, increasing availability and reducing costs, CMR is fast becoming a clinically tenable reference standard for the measurement of cardiac function.
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  • 110
    Electronic Resource
    Electronic Resource
    Springer
    Herz 25 (2000), S. 365-383 
    ISSN: 1615-6692
    Keywords: Key Words Congenital heart disease ; MRI ; Blood flow ; MRA ; Postoperative ; Pulmonary arteries ; Schlüsselwörter Kongenitale Herzerkrankung ; MRT ; Blutfluss ; MR-Angiographie ; Postoperativ ; Pulmonalarterien
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Weltweit werden jährlich etwa 1,5 Millionen Kinder mit kongenitalen Herzerkrankungen (CHD, congenital heart disease) geboren. Durch Verbesserung der verschiedenen chirurgischen und interventionellen Techniken ist die Überlebensrate von CHD-Patienten drastisch gestiegen. Immer mehr Patienten mit postoperativen Residuen, Folgezuständen und Komplikationen benötigen eine umfassende Nachsorge. Die Darstellung und Quantifizierung morphologischer und funktioneller kardiovaskulärer Anomalien erfordern zuverlässige und vorzugsweise nichtinvasive bildgebende Verfahren. Die Röntgenkontrastangiokardiographie, der bisherige Goldstandard, eignet sich nicht zur wiederholten Anwendung. Die transthorakale Echokardiographie (TTE) ist die meistverwendete nichtinvasive Methode, doch bei älteren Patienten, insbesondere mit komplexen oder operativ behandelten Malformationen, sind die damit gewonnenen Informationen unter Umständen unbefriedigend. Narben-, Knochen- und Lungengewebe sowie Thoraxdeformitäten können mit dem Schallfenster interferieren. Die transösophageale Echokardiographie (TEE) liefert bei Erwachsenen mit verschiedenen CHD-Formen eindeutig einen weitaus besseren Bildausschnitt, ist jedoch als semiinvasiv einzustufen. Bei Kleinkindern ist die TEE für die auf Intensivstationen und in Operationssälen erforderliche unmittelbare prä- und postoperative Überwachung inzwischen unentbehrlich. Die Kernspintomographie (Magnetresonanztomographie, MRT) hat sich zu einem klinischen nützlichen Verfahren zur Untersuchung des Herzens entwickelt, vor allem bei angeborenen Fehlbildungen. Sie gilt heute als etablierte nichtinvasive Methode, mit der sich die Anatomie des Herzens in jeder gewünschten Ebene mit hoher Auflösung und naturgetreuen Kontrast zwischen kardialen Strukturen und strömendem Blut darstellen läßt. Das konventionelle Spin-Echo eignet sich hervorragend zur morphologischen Beurteilung, liefert jedoch nicht unbedingt funktionelle Informationen. Die durch neuere Impulssequenzen mögliche funktionelle Analyse verleiht der MRT ihren besonderen Wert. Mehrere dieser neuen MRT-Verfahren werden gegenwärtig klinisch eingesetzt. Die Gradienten-Echo-MRT liefert ein Bild des Blutflusses. Mit ihr können Stenosen, Regurgitation oder Shunts aufgrund der durch diese hämodynamischen Läsionen verursachten Strömungsturbulenzen entdeckt werden. Außerdem ermöglicht die Gradienten-Echo-MRT eine fortlaufende Schleifendarstellung der Ventrikelwandbewegung und eine Quantifizierung der Kammerfunktion. Mit der quantitativen Phasenkontrast-MR-Angiographie lassen sich Blutströmungsgeschwindigkeit und Volumendurchfluss in den mittleren und großen Gefäßen messen. Diese Besonderheit der MRT läßt sich zur Quantifizierung von Stenosen, Regurgitation, intrakardialen Shunts und des differentiellen pulmonalen Blutstroms nutzen. Vor allem ihre Fähigheit zur Messung des Volumendurchflusses ist ein klarer Vorteil der MRT. Die kontrastverstärkte MR-Angiographie ist besonders nützlich zur Darstellung der Pulmonalarterienäste und des Aortenbogens. Pulmonaler Blutfluss, rechtsventrikuläre Funktion, pathologische Aortenbefunde und Fontan-Umgehungskreislauf sind u. a. hochinteressante Fragestellungen, die mit multifunktioneller MRT untersucht wurden. Bei Patienten mit Pulmonalstenose oder Fallot-Tetralogie lassen sich mittels MRT Morphologie und Schwere jeder pulmonalen (Rest-)Stenose beurteilen, die rechtsventrikuläre Hypertrophie bewerten sowie eine postoperative Insuffizienz der Pulmonalklappe oder ventrikuläre Dysfunktion quantifizieren. Bei Patienten, die wegen Koarktation operiert wurden, kann die Morphologie von Rest- oder Restenosen MR-tomographisch mit Hilfe von Spin-Echo-Bildern und der kontrastverstärkten MR-Angiographie des Aortenbogens beurteilt werden. Die quantitative Phasenkontrastangiographie erlaubt zusätzlich, den Druckgradienten über der Stenose und das Ausmaß des Kollateralflusses zu bestimmen. Patienten mit Transposition der großen Arterien werden in der Regel mit Umkehroperationen auf Vorhofebene behandelt. Eine Dysfunktion des rechten systemischen Ventrikels ist bei diesen Patienten eine wesentliche Frage, die mit funktionellen MRT-Verfahren untersucht wurde. Andere Komplikationen nach Vorhofumkehroperation wie Obstruktionen im pulmonalen oder systemisch-venösen Kreislauf lassen sich mit der Gradienten-Echo-MRT mühelos aufdecken. Der Fongan-Umgehungskreislauf bleibt nach wie vor ein faszinierendes, in vielerlei Hinsicht noch nicht völlig verstandenes Thema. Zahlreiche Modifikationen der ursprünglichen Fontan-Operation wurden eingeführt, mit jeweils eigenen hämodynamischen Charakteristika. Zweifellos kann die kombinierte morphologisch-funktionelle MRT zur Entwicklung weiterer Verbesserungen des Fontan-Verfahrens beitragen. Trotz aller technischen Verbesserungen, insbesondere der Einführung des Atemanhalteverfahrens, bleibt die MRT nach wie vor eine Ergänzung zu Echokardiographie und Angiokardiographie. Verfügbarkeit, Ortsgebundenheit und die bei Säuglingen und Kindern erforderliche Sedierung sind bekannte Hindernisse. Nicht zuletzt gilt es, gegen die relativ begrenzte Einbeziehung von Kardiologen in die MRT-Abteilung und die eingeschränkte Verfügbarkeit von Radiologen mit Erfahrung in CHD anzugehen, um die MRT zu einem “vollwertigen Mitglied im Klub” der bildgebenden Verfahren bei CHD zu machen.
    Notes: Abstract With the increasing number of patients surviving after therapeutic intervention for congenital heart disease (CHD), accurate and frequent follow-up of their morphologic and functional cardiovascular status is required, preferably with a noninvasive imaging technique. Echocardiography, either transthoracic or transesophageal, has been the first choice for this purpose, and will probably keep that status, at least in a large segment of the CHD spectrum. Magnetic resonance imaging (MRI) is an established method for high-resolution visualization of cardiovascular morphology. In the past decade, newer MRI techniques have been developed that allow functional evaluation of CHD patients. Particularly the introduction of breath-hold imaging, contrast-enhanced MRA and user-friendly computer software for image analysis may move functional MRI of CHD from the science laboratory to clinical use. It is already evident that MRI is superior to echocardiography in certain areas of limited echocardiographic access, such as the pulmonary artery branches and the aortic arch in adult patients. But MRI has also a unique potential for accurate volumetric analysis of ventricular function and cardiovascular blood flow, without any geometric assumptions. If supported by increased cooperation between cardiologists and radiologists, MRI will grow into a useful noninvasive imaging tool that, together with echocardiography, will obviate the need for invasive catheter studies for diagnostic purposes.
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  • 111
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Arthroskopie ; Klinische Untersuchung ; Kniegelenk ; MRT ; Key words Arthroscopy ; Clinical examination ; Knee ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Magnetic resonance imaging (MRI) is used frequently in the diagnosis of knee injuries. The aim of this study was to compare the accruracy of MRI and clinical examination in diagnosing meniscal and cruciate ligament tears. Between January 1997 and June 1998, a total of 883 patients had undergone knee joint arthroscopy, operated on by one orthopedic surgeon. Of these, 144 patients had a preoperative MRI (group 1). This group was compared with 309 patients who had undergone arthroscopy without MRI between January 1997 and June 1997 (group 2). Sensitivity, specificity and accuracy for tears of the medial meniscus were 80.6%/58.8%/72.9% in group 1 and 83.3%/78.5%/80.3% in group 2, respectively, for tears of the lateral meniscus 44.4%/88.9%/83.3% in group 1 and 60.6%/98.8%/92.5% in group 2 and for tears of the anterior cruciate ligament 58.1%/92.0%/¶84.7% in group 1 and 80.1%/96.6%/¶89.6% in group 2. This study demonstrates that an experienced orthopedic surgeon can rely on the clinical diagnosis and decide whether arthroscopy is necessary in most cases without MRI. He will find intraarticular pathology in almost all cases if arthroscopy is performed. MRI should be reserved for special cases and should not be performed without first conducting a thorough clinical examination. The orthopedic surgeon should decide whether MRI is needed.
    Notes: Zusammenfassung Mit zunehmender Häufigkeit wird beim Verdacht auf einen Kniebinnenschaden die Magnetresonanztomographie (MRT) eingesetzt. Ziel der vorliegenden Arbeit war es, die Treffsicherheit von MRT und klinischer Untersuchung bei der Diagnose von Meniskusläsionen und Kreuzbandverletzungen zu vergleichen und daraus zu schlussfolgern, wann ein MRT am Kniegelenk indiziert ist. Vom 1.1.1997 bis zum 30.6.1998 wurden 883 Kniegelenkarthroskopien durchgeführt. Bei 144 Kniegelenken lag präoperativ ein MRT vor (Gruppe 1). Dieser Gruppe wurde eine Vergleichsgruppe, bestehend aus allen vom 1.1.1997 bis zum 30.6.1997 arthroskopierten Kniegelenken ohne präoperatives MRT (n = 309) gegenübergestellt (Gruppe 2). Sensitivität, Spezifität und Präzision betrugen für den medialen Meniskus 80,6%, 58,8% bzw. 72,9% in Gruppe 1 und 83,3%, 78,5% bzw. 80,3% in Gruppe 2, für den lateralen Meniskus 44,4%, 88,9% bzw. 83,3% in Gruppe 1 und 60,6%, 98,8% bzw. 92,5% in Gruppe 2 und für das vordere Kreuzband 58,1%, 92,0% bzw. 84,7% in Gruppe 1 und 80,1%, 96,6% bzw.89,6% in Gruppe 2. Mit einer sorgfältigen klinischen Untersuchung können in Verbindung mit Standardröntgenaufnahmen in den meisten Fällen die Diagnose und damit die Indikation zur Arthroskopie mit ausreichender Sicherheit gestellt werden. Die Magnetresonanztomographie sollte Spezialindikationen vorbehalten bleiben und durch den Operateur veranlasst werden.
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  • 112
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    Arthroskopie 13 (2000), S. 132-137 
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Qualitätssicherung ; Knorpeldefekte ; MRT ; Scores ; Keywords Quality control ; Cartilage repair ; MRI ; Clinical scores
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Most procedures currently in use for the treatment of full thickness cartilage defects lack solid data as a proof of quality. Various techniques for quality control are advisable. Meticulous documentation of adverse events and treatment failures is crucial. Patient self-assessment and clinical scores are often biased but focussed on the basis of medical efforts: the well-being of the patient. Second-look arthroscopies produce fewer facts for quality control than expected but enable therapeutical intervention. Magnetic resonance imaging will be essential for cartilage assessment in the future. To date, the evaluation of tissue quality is experimental. Histology and immunohistochemistry are widely accepted as precise tools to characterize cartilaginous tissue. Ethical reasons prohibit daily use. Quality control following the repair of cartilage defects is complicated, expensive, and of variable outcome, but dangerous if neglected. Multiple insignificant results can lead to a sharp image of the postoperative condition and may enable quality control of treatment and surgery.
    Notes: Die meisten Verfahren zur Behandlung von Gelenkknorpeldefekten werden angewendet, ohne dass ihre Qualität zweifelsfrei nachgewiesen ist. Verschiedene Möglichkeiten der Qualitätssicherung können derzeit mit vertretbarem Aufwand routinemäßig eingesetzt werden. Die Beurteilung der Sicherheit einer Behandlung hinsichtlich Komplikationen und Therapieversagern ist von eminenter Bedeutung. Patientenfragebögen und klinische Scores sind subjektiv, orientieren sich aber am eigentlichen Ziel einer Therapie: der Wiederherstellung des Wohlbefindens des Patienten. Noch in den Anfängen, aber mit hervorragenden Perspektiven für die Zukunft steht die Magnetresonanztomographie. Knorpelqualität und -aktivität können heute noch nicht beurteilt werden. Die Kontrollarthroskopie nach der Behandlung von Gelenkknorpeldefekten liefert weniger harte Daten für die Qualitätssicherung als erwünscht, ermöglicht aber therapeutische Maßnahmen. Histologische Untersuchungen stehen im Ruf der unbestechlichen Präzision. Dem breiten Einsatz stehen jedoch fehlende Standards und berechtigte ethische Bedenken entgegen. Qualitätssicherung nach der operativen Behandlung von Gelenkknorpeldefekten ist schwierig, teuer und häufig ungenau – keine Qualitätssicherung ist oft gefährlich. Aus vielen, isoliert gesehen ungenauen Befunden werden die Bewertung eines Zustands immer sicherer und die Beurteilung der Qualität einer Behandlung möglich.
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  • 113
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    Cancer and metastasis reviews 19 (2000), S. 39-43 
    ISSN: 1573-7233
    Keywords: angiogenesis ; MRI ; permeability ; in vivo imaging ; hypoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Magnetic resonance imaging (MRI) provides a range of non-invasive measures for visualization of tumor angiogenesis in the clinic as well as in experimental tumor models. MRI methods were developed for assessment of spatial and temporal changes in perfusion, blood volume fraction, vascular permeability, vascular function, vascular maturation, vessel diameter and tortuosity. Molecular targeted contrast agents were used for mapping specific markers of neovasculature. These approaches were applied for analysis of a number of regulatory mechanisms controlling tumor angiogenesis and for preclinical evaluation of tumor response to antiangiogenic agents.
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  • 114
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    Journal of neural transmission 107 (2000), S. 1427-1436 
    ISSN: 1435-1463
    Keywords: Keywords: Brain ; MRI ; PSP ; MSA ; parkinsonism.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary. To establish diagnostic magnetic resonance imaging (MRI) criteria for differentiating progressive supranuclear palsy (PSP) from multiple system atrophy (MSA), magnetic resonance images from eight patients with probable PSP, 30 with probable MSA {nine striatonigral degeneration (MSA-P) and 21 olivopontocerebellar atrophy (MSA-C)}, and ten age-matched controls were retrospectively studied. Anteroposterior diameters in the midline sagittal T1-weighted image of the rostral (RMT) and caudal midbrain tegmentum (CMT), caudal pons and medulla were measured. Divergence of the red nuclei (RN) in the axial T2-weighted image was judged. All PSP images had a smaller RMT diameter than the lower limit of the normal range, showed RN divergence, and had a pontine diameter within the normal range. All MSA images had a CMT diameter within the normal range; no MSA images showed divergence of RN. Forty-four percent (4/9) of MSA-P and 76% (16/21) of MSA-C images had a pontine diameter smaller than the lower limit of the normal range. On basis of the results, we propose MRI diagnostic criteria for differentiating PSP from MSA.
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  • 115
    ISSN: 1436-2023
    Keywords: Key words Osteonecrosis ; Femoral head ; Bone marrow edema ; MRI ; Histology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Sequential magnetic resonance imaging (MRI) was performed on a 38-year-old woman with systemic lupus erythematosus who had received corticosteroid and had developed non-traumatic osteonecrosis of the femoral head. The initial MR finding was a band lesion on the T1-weighted image, which had been present before the onset of symptoms. At the onset of symptoms, a diffuse bone marrow edema pattern, with a low signal intensity on T1 and high signal intensity on T2-weighted images, was noted around the band lesion, extending to the femoral neck. Histopathologically, this region was found to consist of serous exudate, focal interstitial hemorrhage, and mild fibrosis, without any evidence of extension of osteonecrosis. It should be noted that extension of a low signal intensity area on MRI after the onset of hip pain may not be the result of the extension of osteonecrosis, but may represent concomitant edema due to collapse.
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  • 116
    ISSN: 1573-6792
    Keywords: EEG ; MRI ; Co-registration ; Spline ; Source localization ; Head model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two classes of functional neuroimaging methods exist: hemodynamic techniques such as PET and fMRI, and electromagnetic techniques such as EEG/ERP and MEG. In order to fusion these images with anatomical information, co-registration with volumetric MRI is needed. While such co-registration techniques are well established for hemodynamic images, additional steps are needed for electromagnetic recordings, because the activity is only recorded on the scalp surface and inverse solutions based on specific head models have to be used to estimate the 3-dimensional current distribution. To date most of the experimental and clinical studies use multi-shell concentric sphere models of the head, solve the inverse problem on this simplistic model, and then co-register the solution with the MRI using homogeneous transform operations. Contrary to this standard method, we here propose to map the MRI to the spherical system by defining transformation operations that transform the MRI to a best-fitting sphere. Once done so, the solution points are defined in the cerebral tissue of this deformed MRI and the lead field for the distributed linear inverse solutions is calculated for this solution space. The method, that we call SMAC (Spherical Model with Anatomical Constrains) is tested with simulations, as well as with the following real data: 1) estimation of the sources of visual evoked potentials to unilateral stimulation from data averaged over subjects, and 2) localization of interictal discharges of two epileptic patients, one with a temporal, the other with an occipital focus, both confirmed by seizure freedom after resection of the epileptogenic region.
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  • 117
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    Neurological sciences 21 (2000), S. 53-55 
    ISSN: 1590-3478
    Keywords: Key words Genetic Creutzfeldt-Jakob disease ; Deafness ; MRI ; 14-3-3 protein
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We describe a case of genetic Creutzfeldt-Jakob disease (CJD) with deafness at the onset. We report clinical features, 14-3-3 protein positivity, electroencephalography and brain stem auditory evoked potential abnormalities, and high signal on magnetic resonance imaging in basal ganglia and temporal cortex. Similarities with CJD Heidenhain variant are discussed.
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  • 118
    ISSN: 1590-9999
    Keywords: Key words Disc herniation ; Lumbar spine ; Migration ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The majority of symptomatic lumbar disc herniations are located in a posterolateral position with resultant nerve root compression. Although caudal, rostral and lateral migrations of disc fragments are common, posterior epidural migration of an extruded free fragment from a lumbar disc herniation is a rare occurrence and sometimes may cause a dural sac compression with cauda equina syndrome. This retrospective case report describes a 63-year-old man with intractable lower back pain and cauda equina syndrome. Emergency magnetic resonance imaging (MRI) revealed a posterior epidural soft tissue compressing the dural sac. The lesion was hypointense on T1-weighted images, hyperintense on T2-weighted images and showed rim enhancement after intravenous injection of gadolinium. A laminectomy at L3 was performed and the extruded disc fragment was removed with dural sac decompression. Postoperatively the patient's radicular symptoms completely resolved. At the 2-year follow-up visit, the patient had recovered full motor, sensory and urinary functions. MRI is the modality of choice in the evaluation of an extruded free disc fragment and a cauda equina compression. In such cases a wide decompressive laminectomy is recommended.
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  • 119
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    Neurological sciences 21 (2000), S. 151-155 
    ISSN: 1590-3478
    Keywords: Key words Epilepsy ; Venous angioma ; MRI ; Vascular malformations ; Focal cortical dysplasia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of this study was to evaluate the frequency and characteristics of epilepsy associated with cerebral venous angiomas (VA). We examined epileptic patients in which magnetic resonance imaging (MRI) showed VA. The characteristics of epilepsy and its relationships to VA were studied. Out of 1020 epileptic patients submitted to MRI in a 10-year period, 4 presented with VA. All had partial seizures, most frequently complex partial, with secondary generalizations in 3. Drug resistance was observed in 2. One patient had a small area of cortical dysplasia near the VA; another had a cutaneous angioma. In 2 patients, there was no topographic concordance between the VA and the focus on electroencephalography. Our study reveals that VA are rarely found in epileptic patients, differently from other vascular malformations, in particular cavernomas. Topographic and/or etiological relationships between VA and epilepsy are still undefined.
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  • 120
    ISSN: 1573-3297
    Keywords: Extended twin study ; methodology ; structural equation modeling ; intermediate phenotype ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Psychology
    Notes: Abstract The hunt for genes influencing behavior may be aided by the study of intermediate phenotypes for several reasons. First, intermediate phenotypes may be influenced by only a few genes, which facilitates their detection. Second, many intermediate phenotypes can be measured on a continuous quantitative scale and thus can be assessed in affected and unaffected individuals. Continuous measures increase the statistical power to detect genetic effects (Neale et al., 1994), and allow studies to be designed to collect data from informative subjects such as extreme concordant or discordant pairs. Intermediate phenotypes for discrete traits, such as psychiatric disorders, can be neurotransmitter levels, brain function, or structure. In this paper we conduct a multivariate analysis of data from 111 twin pairs and 34 additional siblings on cerebellar volume, intracranial space, and body height. The analysis is carried out on the raw data and specifies a model for the mean and the covariance structure. Results suggest that cerebellar volume and intracranial space vary with age and sex. Brain volumes tend to decrease slightly with age, and males generally have a larger brain volume than females. The remaining phenotypic variance of cerebellar volume is largely genetic (88%). These genetic factors partly overlap with the genetic factors that explain variance in intracranial space and body height. The applied method is presented as a general approach for the analysis of intermediate phenotypes in which the effects of correlated variables on the observed scores are modeled through multivariate analysis.
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  • 121
    ISSN: 0935-6304
    Keywords: Capillary HPLC ; gradient elution ; temperature programming ; phenolic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper describes a liquid chromatographic method using a reversed phase capillary column coupled to an UV detector for the quantitation of thirteen pollutant phenols. Chromatographic separation was carried out with gradient elution at 25.0 ± 0.1°C. The two major anisocratic elution modes (gradient elution and temperature programming) were evaluated. The detection limit range was 10-81 pg (100 nL injected). The chromatographic method combined with liquid-liquid extraction was applied to analysis of these compounds in river water. Recoveries of 75-103% were achieved for most of them.
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  • 122
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    Journal of High Resolution Chromatography 23 (2000), S. 389-392 
    ISSN: 0935-6304
    Keywords: Capillary SFC ; zinc dialkyldithiophosphates ; lubricating oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 5 Ill.
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  • 123
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    Journal of High Resolution Chromatography 23 (2000), S. 393-396 
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography (SFC) ; micropacked capillary columns ; waxes ; restoring ; objects of art ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 2 Ill.
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  • 124
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    Journal of High Resolution Chromatography 23 (2000), S. 379-385 
    ISSN: 0935-6304
    Keywords: Aroma ; “lulo del Chocó” ; Solanum topiro ; volatiles ; glycosidically bound volatiles ; glycoside TFA derivatives ; enantioselective gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The volatile constituents of lulo del Chocó (Solanum topiro) fruit pulp obtained by liquid-liquid extraction were analyzed by capillary GC and capillary GC-MS. In total, 30 components were identified with methyl salicylate, hexadecanoic acid, hexanal, guaiacol, ethyl butanoate, and ethyl acetate being the major components. Chirospecific MDGC analysis revealed the predominance of (R)-ethyl-3-hydroxybutanoate (ee 40%) and the presence of racemic mixtures both of δ-octalactone and of δ-decalactone. For γ-hexalactone, γ-octalactone, and γ-decalactone enantiomeric distributions of 22.4 : 77.6, 22.9 : 77.1, and 20.0 : 80.0, (R) : (S), respectively, were determined. Glycosidically bound aroma compounds were identified by capillary GC and capillary GC-MS after isolation of the glycosidic fraction obtained by Amberlite XAD-2 adsorption and methanol elution followed by hydrolysis with a commercial pectinase enzyme. In total 13 bound aroma compounds (aglycones) were identified. These aglycones mainly consisted of compounds exhibiting aromatic structures. Additionally, with the aid of capillary GC and capillary GC-MS (EI and NCI) of trifluoroacetylated derivatives we identified eight glucosides: the novel 3,6-epoxy-7-megastigmen-5,9-diol β-D-glucopyranoside and the hexyl, benzyl, linalyl oxide (furanic), 2-phenylethyl, vomifolyl (isomer 1), (6S,9R)-vomifolyl, and scopoletin β-D-glucopyranosides.
    Additional Material: 1 Ill.
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  • 125
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    Journal of High Resolution Chromatography 23 (2000), S. 409-412 
    ISSN: 0935-6304
    Keywords: Cyclodextrin ; capillary electrophoresis ; system peak ; CHES 1 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a running buffer containing cyclodextrins (CDs) and 2-[N-cyclohexylamino]-ethanesulfonic acid (CHES), positive system peaks were observed in the analysis of a ganglioside mixture by CE-UV. These system peaks were related to CDs in the running buffer because these peaks were also detected when a plug of solution devoid of CDs but having the same CHES concentration and pH as the running buffer was injected. Neutral CDs were separated owing to the formation of inclusion complexes with the anionic CHES ion. One possible explanation for the positive system peaks is that the anionic CD-CHES inclusion complex is displaced by co-ions with higher UV absorptivity.
    Additional Material: 3 Ill.
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  • 126
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    Journal of High Resolution Chromatography 23 (2000), S. 565-566 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; zinc dithiocarbamate ; vulcanization accelerator ; rubber gloves ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 2 Ill.
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  • 127
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    Journal of High Resolution Chromatography 23 (2000), S. 603-608 
    ISSN: 0935-6304
    Keywords: Solvation parameter model ; ystem constants for poly(dimethyldiphenylsiloxane) HP-5 and poly(ethylene glycol) HP-INNOWax stationary phases ; temperature ; molecular interaction ; retention models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 128
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    Journal of High Resolution Chromatography 23 (2000), S. 561-564 
    ISSN: 0935-6304
    Keywords: Retention factors ; Cinnamomi ramulus ; high-performance liquid chromatography ; capillary electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 3 Ill.
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  • 129
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    Journal of High Resolution Chromatography 23 (2000), S. 590-594 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; graphitic carbon stationary phases ; anions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Inorganic anions could be separated on porous graphitic carbon stationary phases in ion chromatography. Ion exchange between eluent anions and sample anions on the stationary phase was confirmed by the retention behavior and the possibility of indirect photometric detection. The elution order of anions was different from that observed for commercially available anion exchangers. Chloride, nitrate, and sulfate contained in tap water could be determined in 7 min.
    Additional Material: 6 Ill.
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  • 130
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    Journal of High Resolution Chromatography 23 (2000), S. 485-488 
    ISSN: 0935-6304
    Keywords: Pyrethroids ; solid-phase microextraction ; water analysis ; temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Synthetic pyrethroids are increasingly being used for insect control on field crops because of their advantageous environmental properties such as short field life, broad spectrum of insecticide activity, and relatively low mammalian toxicity. In the present work, experimental conditions were optimized for trace analysis of pyrethroids in water by using solid-phase microextraction followed by capillary gas chromatography. Effects of temperature, SPME-fiber diameter, and matrix were studied. SPME used off-line with a gas chromatograph electron-capture detection (GC-ECD) showed a linear response over a wide concentration range. Our results showed a strong temperature effect on pyrethroid extraction yield. The detection limit after 5 min of SPME-fiber exposure to the samples changed from 1 ppb (at 30°C) to 0.1 ppt (at 90°C), which is a 10000 increase in pyrethroid detection. The standard deviations of the analyte peak area ratios were typically in the range of 1-7% at 30°C and of 3 to 15% at 90°C. Best conditions for pyrethroids analysis were achieved using high temperature solution and a 100 μm polydimethylsiloxane fiber. No matrix (river water) influence was observed on detection of the investigated pyrethroids.
    Additional Material: 6 Ill.
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  • 131
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    Journal of High Resolution Chromatography 23 (2000), S. 19-26 
    ISSN: 0935-6304
    Keywords: Microfabrication ; monolith ; electrochromatography ; peptides ; reactive ion etching ; reversed phase ; nanocolumns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolith columns are generally fabricated by polymerization of monomers within a column. This paper reviews an alternative strategy in which the bed is microfabricated in an inorganic material by ablation. Channels of 1.5 μm width and 10 μm depth were sculpted in quartz by deep reaction ion etching. Using this approach chromatographic beds were constructed in which cubic support structures were created and arranged in rows to mimic particles in a conventional column. Beds ranging from hundreds of thousands to millions of “particles” with volumes of 15 nL to 15 μL were produced. Columns that had been derivatized with an octadecyl silane stationary phase were used to separate both low molecular weight analytes and peptides in the CEC mode. Plate height in the CEC mode was 1.2 μm at maximum efficiency.
    Additional Material: 9 Ill.
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  • 132
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    Journal of High Resolution Chromatography 23 (2000), S. 39-43 
    ISSN: 0935-6304
    Keywords: Monoliths ; CIM® monolithic column ; dynamic binding capacity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characterization of CIM® DEAE monolithic columns in terms of dynamic binding capacity is presented in this paper. Breakthrough experiments were performed for capacity determination. Bovine serum albumin (BSA) was used as a model protein. It is shown that CIM® monolithic columns have good batch-to-batch reproducibility as well as long-term stability. The experiments performed under different linear velocities demonstrated that the dynamic capacity is unaffected at least up to a linear velocity of 2450 cm/h. Furthermore, the breakthrough curve slope is constant, indicating that the capacity would remain constant at even higher linear velocities. The adsorption isotherm of BSA dissolved in 20 mM Tris-HCl buffer shows a constant capacity of around 30 mg/mL of support down to a concentration of 20 μg/mL. The capacity is substantially influenced by the ionic strength; however, 20% of the maximal capacity is still preserved at 0.3 M NaCl.
    Additional Material: 5 Ill.
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  • 133
    ISSN: 0935-6304
    Keywords: Monolith ; factor VIII ; affinity chromatography ; combinatorial peptide library ; peptide synthesis ; recombinant proteins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: FVIII is a very complex molecule of great therapeutic significance. It is purified by a sequence of chromatographic steps including immunoaffinity chromatography. A peptide affinity chromatography method has been developed using peptides derived from a combinatorial library. Spot technology using cellulose sheets has been applied for this purpose. The dual positional scanning strategy was used for identification of the amino acids in random positions. Approximately 5000 possible candidates found in the first screening round were reduced to a panel of 36. Six candidates have been selected empirically. Five peptides seem to be directed against the light chain of FVIII, one peptide seems to be directed against the heavy chain. The peptides have been immobilized on conventional beaded material and CIM polymethacrylate monoliths. Much better performance with respect to capacity and selectivity has been observed with the monolithic material. Exposure of the ligand and its ensuing accessibility are responsible for these properties.
    Additional Material: 8 Ill.
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  • 134
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    Journal of High Resolution Chromatography 23 (2000), S. 67-72 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic column ; electroosmotic flow ; retention mechanism ; aromatic compound ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically. The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.
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  • 135
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    Journal of High Resolution Chromatography 23 (2000), S. 73-80 
    ISSN: 0935-6304
    Keywords: Continuous-bed ; sol-gel ; octadecylsilica ; mixed-mode stationary phase ; large-pore ; column technology ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Sol-gel bonded packing materials in continuous-bed columns have been prepared for capillary electrochromatography (CEC). Three packing materials were investigated: small-pore Spherisorb ODS1 (3 μm, 80 Å) with octadecyl as stationary phase, small-pore mixed-mode Spherisorb ODS/SCX (3 μm, 80 Å) with octadecyl and propyl sulfonic acid as stationary phases, and large-pore Nucleosil ODS (7 μm, 1 400 Å) with octadecyl as stationary phase. The characteristics of these columns were compared in terms of electroosmotic flow, efficiency, inertness, and retention factors. In contrast to columns containing sol-gel bonded ODS, columns containing sol-gel bonded mixed-mode ODS/SCX generated nearly pH independent electroosmotic flow (EOF) over pH 2-9. Columns containing sol-gel bonded large-pore ODS produced nearly three times lower reduced plate height than those containing small-pore ODS. Efficiencies of 220,000 plates per meter and 175,000 plates per meter were obtained from columns containing sol-gel bonded 7 μm, 1 400 Å ODS and columns containing sol-gel bonded 3 μm, 80 Å ODS, respectively, which are among the highest reported efficiencies for continuous-bed columns. In CEC, over one million plates per meter and pH independent EOF are expected from continuous-bed columns containing sol-gel bonded 1.5 μm particles with large pores and mixed-mode stationary phases.
    Additional Material: 11 Ill.
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  • 136
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    Journal of High Resolution Chromatography 23 (2000), S. 81-88 
    ISSN: 0935-6304
    Keywords: Monolithic chromatography columns ; capillary electrochromatography (CEC) ; micro high performance liquid chromatography ; sol-gel based columns for chromatography ; fritless capillary chromatography columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Particle-loaded (3 μm, octadecylsilica) monolithic sol-gel columns have been prepared and selected characteristics measured. Several electrical properties may be calculated from simple current measurements in the column as a whole. Resistivity in the packed segment is approximately three times that in open segments, resulting in a 60% increase in field strength in the packed regions compared to the capillary with no packing. The surprisingly high specific permeability of these sol-gel columns is characteristic of 8-μm particles, which allows their operation in the microLC mode at pressures as low as 69 kPa where their efficiency is about 50,000 plates per meter and in the CEC mode where efficiency is about 106,000 plates per meter at 5 kV. There is a relatively rapid loss of efficiency with increasing linear velocity beyond 0.2 mm/s in microLC mode, which may be due to additional diffusion processes in the inter-particulate voids. A rapid loss of efficiency above 0.5 mm/s is also observed in the CEC mode, for the same reasons. Chromatographic retention behavior in either separation mode is characteristic of conventional octadecylsilica particles, indicating that analytes have significant access to the surface within the pores of the immobilized bonded phase.
    Additional Material: 6 Ill.
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  • 137
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    Journal of High Resolution Chromatography 23 (2000), S. 89-92 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; packed columns ; fritless columns ; stationary phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Fritless packed silica gel columns were prepared using sol-gel technology. A part of a 75 μm i.d. fused silica capillary was filled with a mixture of tetramethoxysilane and poly(ethylene glycol). After gelling at 40°C and heating at 300°C, the resultant silica gel was derivatized with dimethyloctadecylchlorosilane. A scanning electron micrograph of a cross-section of the capillary column showed that the gel took the form of a spherical particle aggregate and adhered to the column inner wall. The column performance was evaluated for electrochromatography using acetonitrile-50 mM HEPES buffer (pH 6.6) (60/40 or 40/60, v/v) as the mobile phase. An electroosmotic flow of 1.0 mm/s was generated with (60/40, v/v) acetonitrile/HEPES buffer at a field strength of 546 V/cm. Using a sol-gel-derived packed column at an electroosmotic flow of 0.5 mm/s, efficiencies of up to 1.1×105 plates/m were obtained for retained solutes.
    Additional Material: 4 Ill.
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  • 138
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    Journal of High Resolution Chromatography 23 (2000), S. 93-99 
    ISSN: 0935-6304
    Keywords: HPLC ; monolithic column ; silica rod column ; fast separations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The application of a new silica-based, monolithic-type HPLC-column for fast separations is presented. The column is prepared according to a new sol-gel process, which is based on the hydrolysis and polycondensation of alkoxysilanes in the presence of water soluble polymers. The method leads to “rods” made of a single piece of porous silica with a defined pore structure, i. e. macro- and mesopores. The main feature of silica rod columns is a higher total porosity, about 15% higher than of conventional particulate HPLC columns. The resulting column pressure drop is therefore much lower, allowing operation at higher flow rates including flow gradients. Consequently, HPLC analysis can be performed much faster, as it is demonstrated by various applications.
    Additional Material: 9 Ill.
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  • 139
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    Journal of High Resolution Chromatography 23 (2000), S. 3-18 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic columns ; synthetic polymers ; stationary phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithic materials have quickly become a well-established stationary phase format in the field of capillary electrochromatography (CEC). Both the simplicity of their in situ preparation method and the large variety of readily available chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. This review summarizes the contributions of numerous groups working in this rapidly growing area, with a focus on monolithic capillary columns prepared from synthetic polymers. Various approaches employed for the preparation of the monoliths are detailed, and where available, the material properties of the resulting monolithic capillary columns are shown. Their chromatographic performance is demonstrated by numerous separations of different analyte mixtures in variety of modes. Although detailed studies of the effect of polymer properties on the analytical performance of monolithic capillaries remain scarce at this early stage of their development, this review also discusses some important relationships such as the effect of pore size on the separation performance in more detail.
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  • 140
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    Journal of High Resolution Chromatography 23 (2000), S. 100-105 
    ISSN: 0935-6304
    Keywords: Preparative chromatography ; silica monoliths ; PrepROD™ ; productivity ; SMB-chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The use of monolithic silica sorbents for the isolation of substances by preparative liquid chromatography is demonstrated. Preparative liquid chromatography is recognized as a valuable technique for the isolation and purification of substances in the pharmaceutical and fine chemicals industry. The system technology has meanwhile reached a high standard, and the greatest future improvements are expected to arise from new and improved adsorbents. Monolithic silica sorbents offer some unique features for preparative liquid chromatography. They exhibit high efficiencies even at high flow rates due to their fast convective mass transfer and can therefore be used at very high mobile phase velocities, leading to high productivity and hence to maximum process economy. The benefits of this new type of adsorbent are illustrated for an example in batch-chromatographic mode and an example using the continuous simulated moving bed (SMB) technology.
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  • 141
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    Journal of High Resolution Chromatography 23 (2000), S. 106-110 
    ISSN: 0935-6304
    Keywords: Silica ; monolithic column ; aging ; mesopores ; pore size distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Mesopore formation in silica gels having continuous macropores has been investigated. The macroporous wet silica gel prepared by the sol-gel process including phase separation was aged in a basic solvent making use of hydrolysis of urea in a closed condition. The mesopore structure was finally obtained by subsequent evaporation drying of solvent and heat-treatment at 600°C for 2 h. The dissolution-reprecipitation kinetics at the interfaces between wet gel skeletons and an external solvent affected the size and volume of pores formed within the skeletons. Below 120°C, mesopores suitable for various chromatographic applications have been formed typically within 24 h. On the other hand, at 200°C, the pore size attained the macropore dimensions (〉50 nm), and the whole macroporous morphology was significantly modified.
    Additional Material: 7 Ill.
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  • 142
    ISSN: 0935-6304
    Keywords: Monolithic column ; silica monolith ; HPLC ; capillary liquid chromatography ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two types of monolithic silica columns derivatized to form an ODS phase, one prepared in a fused silica capillary (SR-FS) and the other prepared in a mold and clad with an engineering plastic (poly-ether-ether-ketone) (SR-PEEK), were evaluated. The column efficiency and pressure drop were compared with those of a column packed with 5-μm ODS-silica particles and of an ODS-silica monolith prepared in a mold and wrapped with PTFE tubing (SR-PTFE). SR-FS gave a lower pressure drop than a column packed with 5-μm particles by a factor of 20, and a plate height of 20 μm at a linear velocity below 1 mm/s. SR-PEEK showed higher flow-resistance than the other monolithic silica columns, but they still showed a minimum plate height of 8-10 μm and a lower pressure drop than popular commercial columns packed with 5-μm particles. The evaluation of SR-FS columns in a CEC mode showed much higher efficiency than in a pressure-driven mode.
    Additional Material: 6 Ill.
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  • 143
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    Journal of High Resolution Chromatography 23 (2000), S. 119-126 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; retention volume ; real gas carrier ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the calculation and interpretation of the net retention volume with a real gas as carrier is revisited. The properties of the carrier are described by a first order virial equation of state. The net retention volume of a solute is related to the mean flow rate of the carrier, therefore determination of the mean flow rate of a real gas carrier is reviewed. It is shown that the mean flow rate cannot be calculated from the mean column pressure. With a real gas carrier the local capacity factor depends on the local pressure of the real gas. The basic relationship between the net retention volume and the function describing this pressure dependence is also reviewed. Precise formulae as well as practical approximations are presented for the calculation of the mean flow rate, of the mean column pressure, and of a representative pressure related to the mean capacity factor.
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  • 144
    ISSN: 0935-6304
    Keywords: Chemiluminescence ; diol compound ; oxalate ; post-column reaction ; ruthenium complex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this paper we propose a new post-column detection method for polyols containing 1,2-diol, 1,3-diol, and saccharides. The polyols are oxidized in a photochemical reactor to yield oxalate with subsequent chemiluminescence detection using [Ru(III)(bpy)3]3+. A mixing solution of eluate and oxidizing reagent is delivered to a reaction coil, which is then irradiated with ultraviolet light to promote the oxidation reaction. The detection limits for 1,2-ethanediol (ethylene glycol) and 1,3-propanediol were 38 pmol and 23 pmol, respectively.
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  • 145
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    Journal of High Resolution Chromatography 23 (2000), S. 131-137 
    ISSN: 0935-6304
    Keywords: On-line coupled LC-GC ; nitrogen selective detection ; NPD ; carbazoles ; PANH ; personal exposure measurement ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A coupled LC-GC method for the analysis of carbazole-type PANH has been developed and evaluated. Group separation and isolation of carbazoles from interfering acridines in a complex sample matrix was accomplished by using a back-flush technique and an in situ end-capped dimethylaminopropyl silica column in the HPLC part of the system. On-line injection of the carbazole fraction into the GC column was performed with a loop-type interface utilizing concurrent solvent evaporation technique. An LOD of 1-3 pg of individual carbazole compounds was achieved by nitrogen selective detection using an NPD. The method is shown to be robust and is demonstrated by application to personal exposure measurement in an aluminum reduction plant.
    Additional Material: 4 Ill.
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  • 146
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    Journal of High Resolution Chromatography 23 (2000), S. 138-142 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; nucleosides ; short-end injection ; phenyl-bonded silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The influence of several experimental parameters (pH, ionic strength, organic modifier content of hydro-organic buffer) upon EOF, migration time, and retention factor has been studied in CEC with a phenyl-bonded silica column on a model mixture of five nucleosides. This paper illustrates the current interest in CEC as a method of resolving complex mixtures of neutral and ionic solutes and demonstrates the potential of the short-end injection method as a means of reducing analysis time.
    Additional Material: 4 Ill.
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  • 147
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    Journal of High Resolution Chromatography 23 (2000), S. 143-148 
    ISSN: 0935-6304
    Keywords: Analysis of anthraquinones ; capillary electrophoresis ; high-performance liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The separation and determination of twelve anthraquinones, viz. anthraquinone 1, chrysphanol 2, aloe-emodin 3, alizarin 4, anthraquinone-2-carboxylic acid 5, purpurin 6, sennoside B 7, sennoside A 8, emodin 9, quinalizarin 10, rhein 11, and anthraflavic acid 12, were achieved by capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC). Detection at 260 nm with a buffer solution containing 30 mM sodium borate (adjusted to pH = 10.56 with 0.05N NaOH) and acetonitrile (9 : 1) in CE or with a linear gradient elution containing 20 mM KH2PO4 with 0.05% phosphoric acid (pH = 2.91) and methanol in HPLC was found to be the most suitable approach for this separation. Contents of six components (2, 3, 7, 8, 9, 11) in crude Rhei Rhizoma extract could easily be determined within 39 min by CE or 63 min by HPLC. The effects of buffers on this separation and the validation of the two methods were studied.
    Additional Material: 5 Ill.
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  • 148
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    Journal of High Resolution Chromatography 23 (2000), S. 156-157 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; trichlorophenols ; ammonia ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 1 Tab.
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  • 149
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    Journal of High Resolution Chromatography 23 (2000), S. 149-155 
    ISSN: 0935-6304
    Keywords: Capillary GC ; fast GC ; on-column injection ; narrow-bore column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this work a fast gas chromatography set-up with on-column injection was optimized and evaluated with a model mixture of C8-C28 n-alkanes. Usual injection volumes when using narrow-bore (e. g., 0.1 mm i.d.) analytical columns are ca. 0.1 μL. The presented configuration allows introduction of 10-30-fold larger sample volumes without any distortion of peak shapes. In the set-up a normal-bore retention gap (1 m×0.32 mm i. d.) was coupled to a narrow-bore (4.8 m×0.1 mm i. d.×0.4 μm film thickness) analytical column using a low dead volume column connector. The effects of the experimental conditions such as inlet pressure, sample volume, initial injection temperature, and oven temperature on a peak focusing are discussed. H-u curves for helium and hydrogen are used to compare their suitability for high speed gas chromatography and to show the dependence of separation efficiency on the carrier gas velocity at high inlet pressures. In the fast gas chromatography system a baseline separation of C10-C28 n-alkanes was achieved in less than 3 minutes.
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  • 150
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    Journal of High Resolution Chromatography 23 (2000), S. 182-188 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; GC×GC ; thermal modulation ; oil analysis ; petroleum analysis ; analysis of middle-distillate oil fractions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) is an utterly suitable separation technique for the analysis of complex samples, such as oil fractions. Once the two columns and the operating conditions are properly tuned, the technique is able to provide a detailed characterization of such materials. Some considerations applying to the tuning of a GC×GC system for a specific separation are presented and discussed. The authors present a number of different column sets and conditions which allow the separation of a non-aromatic hydrocarbon solvent, a kerosene, the light end of a crude oil, and an olefinic fraction, respectively. The highly structured GC×GC chromatograms, together with chemical knowledge about the samples, provide a much more comprehensive characterization of the samples than hitherto possible.
    Additional Material: 7 Ill.
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  • 151
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; thermal desorption modulator ; temperature programming ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In comprehensive two-dimensional gas chromatography, two individual separations are coupled by means of a rotating thermal desorption modulator interface. The injection pulse introduced via the interface onto the second column should be as short as possible. Parameters affecting the modulator operation are studied. In the set-up used in this study, the temperature of the second column can be programmed independently from that of the first column. Optimization of the second-dimension separation to minimize peak broadening and maximize resolution is discussed and an elegant approach to determine second-dimension retention times using a non-constant modulation frequency is demonstrated. The high separation power of the comprehensive system is demonstrated by the analysis of technical and biota samples containing chlorinated biphenyls and toxaphene.
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  • 152
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    Journal of High Resolution Chromatography 23 (2000), S. 197-201 
    ISSN: 0935-6304
    Keywords: Multidimensional gas chromatography ; comprehensive two-dimensional gas chromatography ; GC×GC ; oxygenates ; MTBE ; reformulated gasoline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) has been applied to the quantitation of oxygenates in reformulated gasoline. Target oxygenates were C1-C4 alcohols, tert-pentanol, methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). These were separated from the gasoline matrix using a volatility-based selectivity in the first chromatographic dimension, followed by a mixed-phase polarity/shape selectivity in the second dimension. The high resolving power of this stationary phase combination completely separated all oxygenates except DIPE, ETBE, and TAME, which exhibited coelution with other nonpolar gasoline components. Oxygenates quantitation was achieved with the use of an internal standard, an FID detector, and calibration curves. Quantitation results are in good agreement with ASTM and EPA standard methods. When coupled with our previous method for BTEX and aromatics, a single GC×GC method can now quantitate MTBE, alcohols, BTEX, and aromatics in a one-hour analysis.
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  • 153
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    Journal of High Resolution Chromatography 23 (2000), S. 474-478 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Solid-phase extraction, on-line derivatization, and measurement by ion trap mass spectrometry (ITD-MS) were used to investigate the biological degradation of pharmaceutical residues (clofibric acid, ibuprofen, diclofenac). The results of the single steps of sample pretreatment and analytical determination are reported. MS/MS measurements were performed on an ITD-MS by selecting collision induced dissociation of the molecular ions (M+) as parent ions to defined daughter ions. A pilot sewage plant and biofilm reactors operating under oxic and anoxic conditions were run as model systems with synthetic sewage water containing 10 to 50 mg/L dissolved organic carbon (DOC) and pharmaceuticals in concentrations of 10 μg/L. Clofibric acid displayed its persistent character in all cases. The pilot sewage plant and the oxic biofilm reactor showed comparable results for diclofenac and ibuprofen, which both were partly degraded. These results can explain the occurrence of these substances in sewage effluents and in the aquatic environment. A high degree of degradation was found especially for ibuprofen in the oxic biofilm reactor, which was attributed to adaptation of the biofilm to the residue. Two metabolites of ibuprofen could be identified on the basis of their mass spectra and comparison with literature data, viz. hydroxyibuprofen and carboxyibuprofen.
    Additional Material: 8 Ill.
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  • 154
    ISSN: 0935-6304
    Keywords: Silicone oil ; supercritical fluid chromatography (SFC) ; micropacked columns ; MALDI-TOF ; GC/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 4 Ill.
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  • 155
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    Journal of High Resolution Chromatography 23 (2000), S. 511-514 
    ISSN: 0935-6304
    Keywords: CZE ; indirect UV detection ; metal ions ; ecological samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 5 Ill.
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  • 156
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    Journal of High Resolution Chromatography 23 (2000), S. 297-303 
    ISSN: 0935-6304
    Keywords: Sample preparation ; gas extraction techniques ; membrane-type techniques ; water analysis ; soil analysis ; gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This review focuses on the role of so-called solventless methods of sample preparation in contemporary environmental analysis. The basic classification of this group of methods as well as the principal features and advantages of the techniques in current use are discussed.
    Additional Material: 2 Ill.
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  • 157
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    Journal of High Resolution Chromatography 23 (2000), S. 253-258 
    ISSN: 0935-6304
    Keywords: Comprehensive gas chromatography ; cryogenic modulation ; semi-volatile aromatics ; thermal sweeper ; peak widths ; peak asymmetries ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The two current technologies for achieving comprehensive gas chromatography (GC×GC) - the thermal sweeper and the cryogenic modulator - are compared in an interlaboratory study using a multicomponent semi-volatile aromatic compound sample. The same column set (phases, film thickness, dimensions of columns) and conditions of oven temperature program were used. Carrier gas flow settings however were different for the data reported here. The thermal sweeper has a longer overall length due to the extra ca. 30 cm length of narrow bore tubing used for the modulator/accumulator section. Data reveal that the two methods behave in an analogous manner in respect of delivering GC×GC results, with key peak parameters of peak widths and symmetry measures showing good correlation. Retention time dissimilarity on the first dimension columns in the two systems arises from different flow rates used, however the second column retention is similar, and this is due to the resulting different elution temperatures that peaks elute on the first dimension in each system. Overall, the two approaches to GC×GC appear to produce equivalent results within the scope of the application studied. Each system does have its experimental limitations; the thermal sweeper has what may be called a ‘thick film effect’, where at high temperature it can be difficult to sufficiently trap the migrating bands in the accumulator column, and the pulsing of solutes in the cryogenic system may suffer from a ‘thick wall effect’ if a column with too thick a wall dimension is used at low oven temperature.
    Additional Material: 4 Ill.
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  • 158
    ISSN: 0935-6304
    Keywords: Proteomics ; protein analysis ; multidimensional HPLC ; ion-exchange chromatography ; reversed phase chromatography ; comprehensive HPLC ; two-dimensional HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The interactive modes of High Performance Liquid Chromatography (HPLC) of proteins provide a platform for the construction of a multidimensional HPLC system coupled to mass spectrometry. We present a system composed of both anion and cation exchanger columns, in the first dimension, and n-octadecyl bonded 1.5 μm nonporous silica columns in the second dimension. Both columns are operated under gradient conditions. A system suitability test with standard proteins showed that the total analysis can be performed within about 20 minutes. The fractions taken from the ion exchanger column are directly analyzed within one minute on the reversed phase column at a high flow rate. Two reversed phase columns are applied and operated alternatively: while the first column performs the separation within one minute, the analytes leaving the first dimension are enriched in an on-column focusing mode on top of the second column. The sample clean-up and enrichment is performed on a novel type of restricted access cation exchanger column with internal sulfonic acid groups and external diol groups. The columns exhibit a molecular weight exclusion limit for globular proteins of about 15 kDa. Our next studies will be directed towards the analysis of proteins and peptides from extracts of fibroblasts.
    Additional Material: 4 Ill.
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  • 159
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    Journal of High Resolution Chromatography 23 (2000), S. 343-347 
    ISSN: 0935-6304
    Keywords: SPME ; desorption ; fiber conditioning ; field sampling ; sample preparation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 3 Ill.
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  • 160
    ISSN: 0935-6304
    Keywords: Silver ion high-performance liquid chromatography (Ag-HPLC) ; conjugated linoleic acid (CLA) ; p-methoxyphenacyl derivatives ; single-column Ag-HPLC ; fatty acid analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 5 Ill.
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  • 161
    ISSN: 0935-6304
    Keywords: Artemisia palustris ; Asterothamnus centrali-asiaticus ; capillary gas liquid chromatography ; Compositae (Asteraceae) ; Heteropappus hispidus ; seed oil ; silver ion thin layer chromatography ; trans-fatty acids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Seed oils from the Compositae plant family are known to contain a variety of unusual fatty acids. Subsequent to the recent discovery of γ-linolenic acid in Saussurea and Youngia, further Mongolian Compositae species were investigated for their seed oil fatty acid composition. A number of δ3trans-fatty acids (16 : 1δ3t, 18 : 1δ3t and 18 : 3δ3t, 9c, 12c) were found in the seed oils of Heteropappus hispidus and Asterothamnus centrali-asiaticus. The latter fatty acid, but not the trans-monoenes, was also found in one species of Artemisia. These unusual fatty acid isomers were characterized by capillary gas-liquid chromatographic (GLC) separations in combination with other chromatographic techniques (analytical thin layer chromatography, TLC and preparative argentation TLC), and infrared spectrocsopy (IR). Their identity was further confirmed by co-chromatography with other seed oils known to contain these trans-fatty acids. The fact that within the Compositae plant family there are apparently two or three distinct groups of genera containing δ3trans-fatty acids is discussed.
    Additional Material: 5 Ill.
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  • 162
    ISSN: 0935-6304
    Keywords: 2H/1H ratio analysis ; HRGC-P-IRMS ; stable isotopes ; benzaldehyde ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Isotope ratio monitoring gas chromatography-mass spectrometry of the 2H/1H ratio by pyrolysis isotope ratio mass spectrometry (P-IRMS) was used to analyze benzaldehyde originating from various sources. Based on the δ2HSMOW value of an authentic reference sample determined with an elemental analyzer (EA), the range of reproducibility and linearity was checked. Correct (EA related) and reproducible data were obtained for sample amounts 〉0.6 μg benzaldehyde (on column). In another series of experiments, the influence of sample preparation, i. e. simultaneous distillation-extraction (SDE) was found to be negligible. The following ranges of δ2HSMOW values were determined for benzaldehyde using five types of samples, i. e. (i) synthetic (δ2HSMOW -78 to -85‰, ex benzal chloride; +420 to +668‰, ex toluene) and ‘natural’ (including ‘ex-cassia’) references (δ2HSMOW -83 to -144‰); (ii) bitter almond oils (δ2HSMOW -113 to -148‰); (iii) fruits (δ2HSMOW -111 to -146‰); (iv) kernels (δ2HSMOW -115 to -188‰); and (v) leaves (δ2HSMOW -165 to -189‰).
    Additional Material: 1 Ill.
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  • 163
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    Journal of High Resolution Chromatography 23 (2000), S. 373-378 
    ISSN: 0935-6304
    Keywords: Open tubular columns ; capillary electrochromatography ; column efficiency ; injected volume ; applied voltage ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of some instrumental parameters on column efficiency in open tubular capillary electrochromatography (OTCEC) has been evaluated. First, it was investigated whether band broadening due to the sample injection process is within a tolerable range when an open tubular column (OTC) of about 10 μm i. d. is used. As a result of the small injection profile factor (K2 = 1.3), injected volumes must be sufficiently small (less than 10 pL) to avoid a significant efficiency loss (〉5%) when hydrodynamic injection by siphoning is employed. Secondly, the kinetic performance of OTCs in a CEC system was estimated from the variation of the reduced plate height (h) with the reduced linear velocity (ν) which was controlled by the voltage applied. Reasonable agreement was obtained between the theoretical h versus ν curve and the experimental values for a group of polycyclic aromatic hydrocarbons used as test compounds. Values of 0.25 for minimum h at an optimum ν of 16 are estimated, which permit separations with around 400,000 plates per meter to be obtained in less than 5 min. Finally, the possibility of estimating the diffusion coefficients of the solutes in the mobile phase from the plot of the height of a theoretical plate versus electroosmotic flow velocity is shown.
    Additional Material: 5 Ill.
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  • 164
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    Journal of High Resolution Chromatography 23 (2000), S. 413-429 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; enantiomer separation ; chiral drugs ; TM-γ-cyclodextrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---High-throughput screening is a promising new approach in analytical chemistry. Within the framework of an extended screening program (The German-Chinese Drug Screening Program), the enantioseparation of 86 drugs was investigated by capillary zone electrophoresis in the presence of the chiral solvating agent (CSA) octakis-(2,3,6-tri-O-methyl)-γ-cyclodextrin (TM-γ-CD). By this means, 15 drugs could be separated into enantiomeric pairs. Approximate measures for the degree of interaction (migration retardation factor, Rm) and for the degree of enantiomer recognition (migration separation factors, αm) revealed intriguing patterns that were compared with those found for native γ-cyclodextrin (γ-CD). Although there is a distinct influence of the analyte structure on the electrophoretic data, interpretation remains difficult. Most remarkably, permethylation of γ-CD leads neither to a higher affinity nor to better chiral recognition, in contrast to the findings with α-CD.
    Additional Material: 10 Ill.
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  • 165
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    Journal of High Resolution Chromatography 23 (2000), S. 445-448 
    ISSN: 0935-6304
    Keywords: O-Aryl,O-(1-methylthioethylideneamino)phosphates ; retention prediction ; quantitative structure-retention relationship (QSRR) ; reversed-phase HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Using factor analysis and stepwise linear regression methods, two parameters - CMR and ECCR - were selected from eight solute-related structure parameters as the most retention-influencing parameters. The relationships between the retention data (k ´) and the two structure parameters were established for 13 O-aryl,O-(1-methylthioethylideneamino)phosphate compounds under a wide range of experimental conditions. The retention data (k ´) of another seven compounds with similar structures were predicted using these QSRR equations. Good agreement was obtained between the experimental k ´ values and predicted ones.
    Additional Material: 1 Ill.
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  • 166
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    Journal of High Resolution Chromatography 23 (2000), S. 525-530 
    ISSN: 0935-6304
    Keywords: Packed capillary liquid chromatography ; temperature programming ; Fourier-transform infrared spectroscopy ; polymer additives ; pneumatic nebulization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Temperature-programmed packed capillary liquid chromatography has been coupled off-line to Fourier-transform infrared spectroscopy, utilizing a commercially available interface with a pneumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to non-aqueous reversed phase separations of polymer additives, resulting in constructed Gram-Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in-house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature-programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P-EPQ.
    Additional Material: 5 Ill.
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  • 167
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    Journal of High Resolution Chromatography 23 (2000), S. 531-538 
    ISSN: 0935-6304
    Keywords: Capillary isotachophoresis ; capillary electrophoresis ; column-coupling electrophoresis ; enantiomers ; chiral ; amino acids ; tryptophan ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The ability of capillary zone electrophoresis (CZE) coupled on-line with capillary isotachophoresis (ITP) sample pretreatment in the column-coupling capillary electrophoresis equipment to separate trace enantiomers present in samples of complex ionic matrices and enantiomers present in their mixtures at significantly differing concentrations has been studied. Enantiomers of 2,4-dinitrophenyl labeled norleucine (DNP-Nleu) and tryptophan enantiomers were employed as model analytes in this work while urine and mixtures of tryptophan enantiomers of differing concentrations served as model samples. Experiments performed with urine samples spiked with the DNP-Nleu racemate at sub-μmol/L concentrations demonstrated excellent sample pretreatment capabilities of ITP (concentration of the analytes, in-column and post-column sample clean up) when coupled on-line with chiral CZE separations. In the CZE separations of enantiomers present in the samples at trace concentrations the sample pretreatment could be performed in both achiral and chiral ITP electrolyte systems. The use of a chiral electrolyte system was found to be essential in the ITP pretreatment of the samples containing the enantiomers at very differing concentrations. For example, a 2×10-7 mol/L concentration of L-tryptophan could be detected in the CZE separation stage of the ITP-CZE combination in samples containing about a 104 excess of D-tryptophan only when the ITP pretreatment was carried out in the electrolyte system providing the resolution of enantiomers (α-cyclodextrin served for this purpose in the present work). A post-column ITP sample clean up was found effective in enhancing the destacking rate of the trace enantiomer in the CZE stage when the migration configuration of the enantiomers was less favorable (the trace constituent migrating behind the major enantiomer).
    Additional Material: 8 Ill.
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  • 168
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    Journal of High Resolution Chromatography 23 (2000), S. 554-560 
    ISSN: 0935-6304
    Keywords: Comprehensive gas chromatography ; multidimensional gas chromatography ; essential oils ; coupled column analysis ; high resolution analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The essential oils from French lavender (Lavandula angustifolia) and tea tree (Melaleuca alternifolia) were separated by the two-dimensional GC technique of comprehensive gas chromatography. A coupled column combination of non-polar (5% phenyl equivalent) and polyethylene glycol phase columns was used to provide the desired resolution performance. By using a range of known standards, some of the peaks in lavender oil can be assigned. Some of these also occur in tea tree oil; however, from our knowledge of the major constituents in this oil and their relative retention behaviour, most of the major peaks may be tentatively assigned within the 2-dimensional separation space. There appear to be elution patterns within the 2-D space which should be useful in correlating retention with chemical and structural properties of the components, although this will require further evaluation. A range of coeluting peaks, which may not be so readily separated by using a single column capillary GC analysis, are resolved in the experiment described.
    Additional Material: 10 Ill.
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  • 169
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    Journal of High Resolution Chromatography 23 (2000), S. 619-627 
    ISSN: 0935-6304
    Keywords: Enantiomer separation ; mixed chiral selectors ; modified cyclodextrins ; gas chromatography ; PCB ; o,p´-DDD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Columns containing different types of cyclodextrin derivatives have been evaluated for chiral gas chromatographic separation of atropisomeric PCBs, o,p´-DDT and o,p´-DDD. Separation was attempted on columns containing mixed chiral selectors, and the performance of two closely related selectors was also examined. The cyclodextrins were: permethylated-β-CD (PM-β-CD), heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-CD (2,3-M-6-TBDMS-β-CD), heptakis(2,3-di-O-methyl-6-O-tert-hexyldimethylsilyl)-β-CD (2,3-M-6-THDMS-β-CD), and heptakis(2,3-di-O-ethyl-6-O-tert-hexyldimethylsilyl)-β-cyclodextrin (2,3-E-6-THDMS-β-CD). The cyclodextrins were dissolved in OV-1701 or in a dimethylsiloxane/silarylene copolymer containing 5% phenyl in the backbone. The application of mixed chiral selectors led to improved separations, however; at most eleven PCB congeners were separated on a single column. Chiral resolution of o,p´-DDD was achieved. The use of a dimethylsiloxane/silarylene copolymer as a matrix for the cyclodextrins is a promising approach. With such a matrix, blocking of the CD cavities by silicone substituent groups can be avoided, and a reasonable CD solubility can be provided. The selectivity of heptakis(2,3-di-O-ethyl-6-O-tert-hexyldimethylsilyl)-β-CD and heptakis(2,3-di-O-methyl-6-O-tert-hexyldimethylsilyl)-β-CD was quite different, the former selector could separate four congeners, while the latter separated ten congeners.
    Additional Material: 5 Ill.
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  • 170
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    Journal of High Resolution Chromatography 23 (2000), S. 576-582 
    ISSN: 0935-6304
    Keywords: Gas chromatography-mass spectrometry ; amino acid enantiomers ; D-amino acids ; physiological fluids ; mammals ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quantities of D-amino acids were determined in body fluids (urine, blood plasma and blood serum, milk) of mammals (hamster, horse, bovine, sheep, pig, and dog). Amino acids were isolated using a cation exchanger and converted into their N(O)-pentafluoropropionyl (or trifluoroacetyl) amino acid 2-propyl esters. Enantiomers were separated and quantified on a Chirasil-L-Val capillary column with mass spectrometric detection using selected ion monitoring. D-Enantiomers of most protein L-amino acids were detected. Largest absolute and relative amounts in most cases were determined for D-Ser and D-Ala in urine. Stereoisomers of 2,6-diaminopimelic acid were also measured in bovine, ovine, and porcine urine. Since D-amino acids were detected in all representative classes of the major orders of Mammalia, namely Artiodactyla, Perissodactyla, Rodentia, and Carnivora, and taking reports in the literature into account, it is postulated that D-amino acids occur in all mammals.
    Additional Material: 5 Ill.
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  • 171
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    Journal of High Resolution Chromatography 23 (2000), S. 595-599 
    ISSN: 0935-6304
    Keywords: GC-MS/MS ; PCDDs ; PCDFs ; human tissue ; fish tissue ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper outlines the possibilities of selectivity and sensitivity enhancement in measuring PCDD/F congeners using an ion trap GC-MS/MS. The pressure of the collision gas and the collision energy were optimized. The modified GC-MS/MS method was applied to the determination of PCDDs and PCDFs in human and fish tissues. Limits of quantification were about 1 pg/g of fat for all seventeen 2378 PCDD/Fs tested (starting amount of fat, 2 g).
    Additional Material: 2 Ill.
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  • 172
    ISSN: 0935-6304
    Keywords: On-line coupling HPLC/NMR ; HPLC/ESI-MS ; (2E,4Z)-decadienoic acid ; Agromyces spec ; isolation ; structure elucidation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 4 Ill.
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  • 173
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    Journal of High Resolution Chromatography 23 (2000), S. 497-501 
    ISSN: 0935-6304
    Keywords: Historical remarks ; modern separation methods ; gas chromatography ; selective sorbents ; selectors ; discovery process ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The research conducted and the discoveries during the development of chromatography are briefly surveyed, with emphasis being placed on gas chromatography. Some actors are presented who played major roles en route from Tswett's original discovery to modern separation methods. The article is based mainly on personal memories and encounters. A few examples of the participation of our country in the development of chromatography are mentioned as well as international contacts. Some remarks are made on the use of selective sorbents or selectors in modern analytical separations. The paper closes with a few comments on the “philosophy” of the discovery process.
    Additional Material: 1 Tab.
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  • 174
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional GC ; time-of-flight ; oil analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this work a comprehensive two-dimensional system (GC×GC) was coupled to a time-of-flight mass spectrometer (TOF/MS) for the analysis of oil samples. Group-types like the alkanes and saturated cyclic compounds (naphthenes), which are present in oil, are shown separately by selecting their unique masses. On selecting appropriate ion fragments, this method also permits the determination of sulfur- and oxygen-containing species in oil. Former results obtained by FID detection could be confirmed. After proper selection of unique ions in GC×GC-TOF both selectivity and sensitivity increase.
    Additional Material: 6 Ill.
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  • 175
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    Journal of High Resolution Chromatography 23 (2000), S. 515-518 
    ISSN: 0935-6304
    Keywords: Capillary supercritical fluid chromatography (c-SFC) ; coal analysis ; SFE ; instrumentation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This work describes the construction and evaluation of a simple and versatile capillary supercritical fluid chromatographic (SFC) system and its application to the analysis of liquid fuels obtained by SFE. The modular supercritical fluid chromatography (SFC) system uses a syringe pump, a fused silica capillary column (100 μm i.d., coated with a 0.2-μm thick film of 5% phenylpolymethylsiloxane), a FID detector, and a high pressure injection valve with a 60-nL internal loop. Coal-derived samples were obtained by supercritical fluid extraction (SFE) of a Brazilian high-inertinite coal from Amando Simões mine, located in Paraná state (Brazil) using toluene as solvent and operating in the static mode. SFE was followed by preparative liquid chromatography fractionation into eight discrete fractions (PLC-8 method). Two of those fractions (F-2 and F-8) were used to evaluate the proposed set-up. The system described proved to be simple, easy-to-use, and versatile when used in the analysis of a range of samples from low molecular weight-low volatility (F-2) to higher molecular weight-high polarity asphaltols (F-8).
    Additional Material: 3 Ill.
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  • 176
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    Journal of High Resolution Chromatography 23 (2000), S. 27-38 
    ISSN: 0935-6304
    Keywords: Monolith ; continuous bed column ; convective interaction media ; membrane chromatography ; membrane adsorber ; HPMDC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithic stationary phases have revolutionized protein chromatography because they combine speed, capacity, and resolution in a unique manner. Since such stationary phases contain no particles but only flow-through pores, the usual mass transfer restrictions to the chromatography of large molecules are not observed and extremely fast separations become possible. Recently the area of application of monolith chromatography has been extended to the separation and analysis of small molecules and plasmid DNA. This review summarizes the state of art in high performance monolith and especially high performance monolithic disk chromatography (HPMDC). The current understanding of the theory of protein HPMDC is summarized, while an introduction to the evolving field of small molecule HPMDC is attempted. The basic differences between the monolithic disks and columns packed with conventional stationary phases (including perfusion and micropellicular particles) but also monolithic columns (porous rods) are outlined. Finally, the potential of HPMDC to analytical and preparative biochromatography is demonstrated by a discussion of recent applications of chromatographic disks for protein isolation and bioprocess analysis.
    Additional Material: 14 Ill.
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  • 177
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    Journal of High Resolution Chromatography 23 (2000), S. 44-46 
    ISSN: 0935-6304
    Keywords: In situ molecular imprinting ; continuous polymer rod ; miniaturized column ; chiral recognition ; diastereoselectivity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Molecularly imprinted continuous polymer rods are prepared inside PEEK tubes of 1 mm i. d. by an in situ preparation technique; and chiral separations on such media have been demonstrated. The miniaturized column filled with (-)-cinchonidine-imprinted or (+)-cinchonine-imprinted polymer rods based on a copolymer of 2-(trifluoromethyl)acrylic acid and ethylene glycol dimethacrylate permitted diastereoseparation of (-)-cinchonidine and (+)-cinchonine; the template molecule is retained to a greater extent than the corresponding antipode. Increasing the amount of cyclohexanol in the polymerization mixture decreased the backpressure of the resultant rod and the addition of latex beads suspended in water to the prepolymerization mixture affected the selectivity and affinity of the imprinted polymer rods. The column length is adjusted easily by cutting, thus allowing easy control of retention behavior and analysis time.
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  • 178
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    Journal of High Resolution Chromatography 23 (2000), S. 59-66 
    ISSN: 0935-6304
    Keywords: Enantiomeric separation ; capillary electrochromatography ; positively charged polyacrylamide gel ; allyl carbamoylated β-cyclodextrin derivatives ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The novel enantiomeric separation of acidic and neutral compounds by capillary electrochromatography with β-cyclodextrin-bonded positively charged polyacrylamide gels was examined. The columns used are capillaries filled with a positively charged polyacrylamide gel, a so-called monolithic stationary phase, to which allyl carbamoylated β-CD derivatives covalently bind. The capillary wall was activated first by bifunctional reagent to make the resulting gel bind covalently inside the fused-silica tubing. Enantiomeric separations of sixteen acidic and two neutral compounds were achieved using the above-mentioned columns and 200 mmol dm-3 Tris-300 mmol dm-3 boric acid buffer (pH 8.1) as a mobile phase. High efficiencies of up to 150 000 plates m-1 were obtained for dansyl-DL-amino acids. The within-run and between-run reproducibilities of retention time and separation factor were examined for three dansyl-DL-amino acids and warfarin. The relative standard deviations of the within-run and between-run reproducibilities of retention time were less than 1.2 and 1.3% over the six injections, respectively. Those of the separation factor were less than 0.3 and 0.2%, respectively. The gel-filled capillaries were stable for at least four months with intermittent use.
    Additional Material: 6 Ill.
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  • 179
    ISSN: 0935-6304
    Keywords: Enantioselective gas chromatography ; cyclodextrins ; heptakis(2,6-di-O-tert-butyldimethylsilyl)-β-cyclodextrin ; heptakis(2,6-di-O-tert-butyldimethylsilyl-3-O-methyl)-β-cyclodextrin ; heptakis(3,6-di-O-tert-butyldimethylsilyl-2-O-methyl)-β-cyclodextrin ; octakis(2,6-di-O-tert-butyldimethylsilyl-3-O-methyl)-γ-cyclodextrin ; thermodynamic parameters ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Separation factors and thermodynamic data for the separation of various chiral analytes on different di-O-tert-butyldimethyl-silylated cyclodextrin derivatives are collected and described. Modifying the substitution pattern of the tert-butyldimethylsilyl group in position 2 and 3 or changing from β- to γ-cyclodextrin significantly affects the separation properties of the cyclodextrin derivatives.
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  • 180
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    Journal of High Resolution Chromatography 23 (2000), S. 583-589 
    ISSN: 0935-6304
    Keywords: Monofunctionalized cyclodextrins ; enantioselective capillary-HPLC ; immobilized chiral stationary phases ; separation of chiral drugs ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Heptakis(2,6-di-O-methyl-3-O-pentyl)-β-cyclodextrin was monofunctionalized by the regioselective introduction of exactly one ω-epoxyoctyl group at the primary site of the cyclodextrin. The site-specifically substituted cyclodextrin was immobilized to commercially available aminopropyl silica by nucleophilic opening of the epoxy function of the spacer substituent resulting in a lipophilic chiral stationary phase with broad applicability for enantiomer separations in capillary-HPLC under reversed-phase conditions.
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  • 181
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    Journal of High Resolution Chromatography 23 (2000), S. 600-602 
    ISSN: 0935-6304
    Keywords: HPLC separation ; lucidin ; Rubia tinctorum ; anthraquinones ; isocratic elution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---An HPLC method has been developed for the separation of anthraquinones with particular attention to the determination of lucidin in commercially available sources of Rubia tinctorum aglycones. Variations of chromatographic conditions have been studied in order to provide suitable resolution of anthraquinones under isocratic conditions on an end-capped RP C18-column.
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  • 182
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    Journal of High Resolution Chromatography 23 (2000), S. 644-646 
    ISSN: 0935-6304
    Keywords: Stir Bar Sorptive Extraction (SBSE) ; thermal desorption (TD) ; capillary GC-MS ; benzoic acid ; beverages ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Stir Bar Sorptive Extraction (SBSE), a recently introduced solventless extraction technique, was applied for the enrichment of benzoic acid in lemon flavored beverages. The stir bar is covered with 50 mg polydimethylsiloxane (PDMS) and the extraction mechanism is similar to that of solid phase micro extraction (SPME) but the enrichment factor is ca. 100 times higher. SBSE is followed by thermal desorption (TD)-capillary gas chromatography (CGC)-mass spectroscopy (MS). Calibration graphs for benzoic acid were linear from 1 to 1000 ppm for water and diluted soft drinks and the repeatability (n = 6) was less than 5% RSD.
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  • 183
    ISSN: 0935-6304
    Keywords: Packed capillary LC ; large volume injection ; temperature programming ; ceramides ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 1 Ill.
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  • 184
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    Journal of High Resolution Chromatography 23 (2000), S. 677-680 
    ISSN: 0935-6304
    Keywords: Capillary ; fast separations ; mass spectrometry ; vacuum ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---There is a constant drive to speed up GC separations. Shorter analysis times provide more analyses per day, which reduces cost. One approach is to reduce column length and column diameter and columns of 0.15 mm i.d. have indeed grown in popularity. However, the majority of applications are still done with 0.25 mm and 0.32 mm columns.
    Additional Material: 10 Ill.
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  • 185
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    Journal of High Resolution Chromatography 23 (2000), S. 681-687 
    ISSN: 0935-6304
    Keywords: Focused microwave assisted extraction ; close microwave-assisted extraction ; DDT ; soil samples ; experimental design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Optimization of focused microwave (FMW)-assisted extraction of 4,4′-DDE, 4,4′-DDD, and 4,4′-DDT from soil samples was carried out using central composite designs. All the extracts were analyzed with GC/MS and some of them also with GC/AED using columns of different polarities for each of the techniques. The extraction of the analytes was carried out in two ways: with acetic acid as microwave radiation absorbent solvent and n-decane to concentrate the analytes and with reagent water and iso-octane as solvents. In the first case, the influence of the extraction temperature, the extraction time, and the addition of sodium chloride were studied and the optimum conditions for the extraction of 1 g of soil with 5 mL of acetic acid and 2 mL of n-decane were 1.30 mol L-1 sodium chloride at 98°C for 9.3 min. In the second case, the temperature was kept constant (94°C) and the influence of the concentration of sodium chloride and the extraction time were studied. The optimum conditions were 5 mL of a 2.0 mol L-1 sodium chloride together with 2 mL of iso-octane for 15 min. The recoveries obtained by water-FMW extraction were significantly lower than those obtained by the acetic acid-FMW procedure. These last recoveries were in good agreement with those obtained by closed microwave assisted-extraction with acetone-n-hexane as solvent.
    Additional Material: 3 Ill.
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  • 186
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    Journal of High Resolution Chromatography 23 (2000), S. 699-701 
    ISSN: 0935-6304
    Keywords: Phenol derivatives ; RP-HPLC separation ; short RP column ; gradient elution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 1 Ill.
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  • 187
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    Journal of High Resolution Chromatography 23 (2000), S. 167-181 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional GC ; GC×GC ; orthogonal chromatography ; GC/MS ; group type separations ; PCBs ; petroleum ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The writer of this review published in 1978 a three-part article on two-dimensional gas chromatography in the first three issues of this journal [1]. The review was written at a time when capillary column GC was still in its infancy. Commercial columns were (essentially) unavailable and sample introduction into capillary columns was done exclusively in the split mode. Two-dimensional separations were explored in only a few laboratories. The limitations of capillary column technology made this exercise rather difficult. The introduction of fused silica capillary columns in the early eighties drastically changed the landscape in which gas chromatography was practiced. It took the chromatographic community just a few years to convert from packed columns to capillary columns. Instrumentation and accessories specifically designed for capillary column use came onto the market. This writer had great hopes that the revolution in capillary column GC would be mirrored in the development of instrumentation for Two-Dimensional Gas Chromatography. This never materialized. On the contrary, tentative steps taken by a few manufacturers and suppliers of chromatographic equipment fizzled out. It was perhaps the introduction of relatively inexpensive and user friendly GC/MS instrumentation, in combination with nearly indestructible fused silica capillary columns that took away the incentive to develop commercially viable Two-Dimensional Gas Chromatography. Much of the thinking went like this: why insist on good chromatography if mass spectrometry can do the job without the need of complete separation. Some progress in the further development of conventional Two-Dimensional Gas Chromatography has certainly been made over the last 20 years but there has not been a great deal of excitement. Applications have also been relatively sparse and they are limited to just a few areas. Science does not remain static and chromatography is no exception. Progress in gas chromatography is driven by new technology and ideas. Substantial improvements in two-dimensional GC were not forthcoming until Phillips and his research group introduced and implemented an entirely new form of Two-Dimensional Gas Chromatography, called comprehensive GC×GC. This breakthrough occurred only in 1991 [2]. It does take some time before scientists change attitudes and habits. There is always a time lag between the introduction of new technology and its general acceptance. The public's attitude toward comprehensive Two-Dimensional Gas Chromatography is probably no exception. The number of scientists who are actively pursuing this new branch of gas chromatography is still very small. It is often a single individual who carries the torch. J.B. Phillips' name is synonymous with comprehensive Two-Dimensional Gas Chromatography. He is not only its inventor and proponent but his fertile mind has initiated research in other related areas. Sadly, he passed aware shortly before this review was written. This contribution is dedicated to his memory.
    Additional Material: 9 Ill.
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  • 188
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    Journal of High Resolution Chromatography 23 (2000), S. 202-204 
    ISSN: 0935-6304
    Keywords: GC×GC ; comprehensive two-dimensional GC ; thermal modulation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A jet of cool gas is used to locally cool a section of modulator tube in the presence of the stirred oven bath of a GC×GC instrument. Local cooling decouples the temperature of the modulator tube from that of the first dimension column, which was 100 meters long. Overall resolution of the GC×GC experiment was improved as a result. Another consequence of the jet-cooled thermal modulation structure is the elimination of moving parts in the GC oven. By pulsing cold and hot jets of gas onto a modulator tube with solenoid valves, two stage thermal modulation can be obtained without the complexity of moving parts in the vicinity of the capillary columns.
    Additional Material: 1 Ill.
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  • 189
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    Journal of High Resolution Chromatography 23 (2000), S. 205-207 
    ISSN: 0935-6304
    Keywords: GC×GC ; thermal modulation ; comprehensive three-dimensional GC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive three-dimensional gas chromatography (GC3) is demonstrated using modified GC×GC apparatus. A new thermal modulation scheme employing a single moving heater to operate two thermal modulators is introduced. Considerations of the bandwidth/resolution tradeoff of GC3 show that high-speed tertiary columns would make GC3 practical, with modest loss of underlying GC×GC peak capacity.
    Additional Material: 3 Ill.
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  • 190
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    Journal of High Resolution Chromatography 23 (2000), S. 208-214 
    ISSN: 0935-6304
    Keywords: Spearmint ; peppermint ; GC×GC ; essential oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper investigates the separation of moderately complex samples by comprehensive two-dimensional gas chromatography (GC×GC). The analysis of peppermint (Mentha piperita) and spearmint (Mentha spicata) essential oil components, including acetates, alcohols, furans, ketones, sesquiterpenes, and terpenes, was achieved by one-dimensional gas chromatography with quadrupole mass spectrometry detection (GC/MSD) and GC×GC with flame ionization detection. Peppermint essential oil was found to contain 89 identifiable peaks by GC×GC compared to 30 peaks in the GC/MSD chromatogram. Likewise, 68 peaks were found in the GC×GC chromatogram of spearmint (compared to 28 in GC/MSD). Plots of the first dimension versus second dimension retention times provided a fingerprint of the two essential oils, which revealed 52 similar compounds between the two essential oils as opposed to 18 matches by 1D GC.
    Additional Material: 6 Ill.
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  • 191
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    Journal of High Resolution Chromatography 23 (2000), S. 225-234 
    ISSN: 0935-6304
    Keywords: Tunable column ensembles ; high speed GC ; comprehensive two-dimensional GC ; time of flight ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A series-coupled ensemble of two capillary GC columns of different selectivity with an adjustable pressure at the column junction point is used to obtain tunable selectivity for high-speed GC and GC/TOFMS. An electronic pressure controller with a 0.1-psi step size is used to obtain numerous computer-selected unique selectivities. System configurations for conventional, atmospheric-pressure outlet operation with flame ionization detection and for vacuum-outlet operation with photoionization detection are described for GC-only experiments. Polydimethylsiloxane is used as the non-polar column and polyethylene glycol (atmospheric outlet) or triflouropropylpolysiloxane (vacuum outlet) is used as the polar column. For GC/TOFMS experiments, 5% phenyl polydimethylsiloxane was used as the non-polar column, and polyethylene glycol was used as the polar column. The time-of-flight mass spectrometer can acquire up to 500 complete mass spectra per second. Since spectral continuity is achieved across the entire chromatographic peak profile, severely overlapping peaks can be spectrally deconvoluted for high-speed characterization of completely unknown mixtures. For mixture components with significantly different fragmentation patterns, spectral deconvolution can be achieved for chromatographic peak separations of as little as 6.0 ms. This can result is very large peak capacity for time compressed (not completely resolved) chromatograms. The use of columns with tunable selectivity allows for precise peak-position control, which can result in more efficient utilization of available peak capacity and thus further time compression of chromatograms. The limits of tunability and deconvolution are tested for near co-elutions of different classes of hydrocarbon compounds as well as for more multi-functional mixtures.
    Additional Material: 9 Ill.
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  • 192
    ISSN: 1434-1948
    Keywords: NMRD ; MRI ; Contrast agents ; Carbonic anhydrase ; Sulfonamides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel Gd-DTPA derivative with a built-in sulfonamide (SA) was synthesized as a contrast agent for MRI. The complex was designed to selectively target the enzyme carbonic anhydrase. It is shown that the longitudinal relaxation rates of aqueous solutions of Gd-DTPA-SA in the presence of carbonic anhydrase increase significantly. The binding constant is determined to be 15,000 ± 5,000 M-1. This value ensures substantial formation of the carbonic anhydrase adduct at imaging concentrations of Gd-DTPA-SA. The complex interacts with erythrocytes, presumably due to a high affinity for the carbonic anhydrase present on the outer surface of the latter. This takes place even though the enzyme has a low abundance and is easily saturated by small amounts of Gd-DTPA-SA. The interaction of Gd-DTPA-SA with serum proteins is negligibly small. Therefore, the complex could potentially be tested as a selective contrast agent for compartments outside the blood pool.
    Additional Material: 4 Ill.
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  • 193
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    Journal of High Resolution Chromatography 23 (2000), S. 235-244 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional GC ; peak overlap ; statistical-overlap theory ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The need for two-dimensional gas chromatography is justified by the extent of peak overlap in one-dimensional gas chromatograms (GCs) of complex mixtures. Such overlap was predicted long ago by statistical-overlap theory (SOT). In this paper, SOT is conceptually reviewed and its predictions are shown to be quantitatively accurate. GCs of complex mixtures of polychlorinated biphenyls, pyridine- and nitrogen-containing polynuclear aromatic hydrocarbons, tetrachlorodibenzo-p-dioxins and dibenzofurans, fatty acid methyl esters, flavors and fragrances, and naphtha were simulated by commercial GC software on DB-1, DB-5, and Stabilwax stationary phases. The numbers of peak maxima in the GCs agreed with predictions of SOT, when the interval of time between successive peaks of pure compounds was described by Poisson statistics. This agreement was realized even though the time intervals actually are deterministic, not statistical. In addition, the numbers of mixture components were predicted with accuracy by regression of peak numbers against SOT. Similar regressions have been reported before, but the theory used here is more sophisticated and its predictions consequently are more accurate. Future directions for finalizing SOT are suggested.
    Additional Material: 4 Ill.
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  • 194
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    Journal of High Resolution Chromatography 23 (2000), S. 304-308 
    ISSN: 0935-6304
    Keywords: Enantioselectivity ; gas chromatography ; ethylated γ-cyclodextrin ; toxaphene ; enantiomers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The enantioselectivity of three batches of octakis-(2,3,6-tri-O-ethyl)-γ-cyclodextrin (TEG-CD), which differed significantly in their degree of ethylation, is reported for toxaphene congeners. The cyclodextrin composition was determined by high performance liquid chromatography-mass spectrometry. Columns prepared with almost fully ethylated cyclodextrin showed no enantiomer separation. Increasing the average number of free OH groups up to an optimum of 3.8 allowed to resolve the following toxaphene congeners into enantiomers: Parlar no. 11, 12, 15, 21, 25, 32, 38, 42.1, 42.2, 50, 51, 56, 58, 59, 62, 69 as well as B8-1412. More free OH groups did not improve the enantiomer resolution. The structure of the polysiloxane used for dilution of TEG-CD also had an influence on the enantiomer separations achieved. Compared to OV 1701-OH, the use of PS 086 significantly improved the enantiomer resolutions of the separated congeners. However, neither increasing the column length nor the cyclodextrin amount in the stationary phase led to better separation results.
    Additional Material: 2 Ill.
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  • 195
    ISSN: 0935-6304
    Keywords: HPLC ; industrial wastewater ; process development ; 4-amino-azobenzene-4′,5-disulfonic acid (AABDS) ; 4-amino-azobenzene (AAB) ; 4-amino-azobenzene-4′-sulfonic acid (AABS) ; 4-amino-azobenzene-4′,3,5-trisulfonic acid (AABTS) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A simple and rapid reversed-phase high-performance liquid chromatographic method for the separation and determination of 4-amino-azobenzene-4′,5-disulfonic acid (AABDS) and its process-related impurities was developed. The separation was achieved on a μ-Bondapak C18 column using 0.15 M ammonium sulfate-acetonitrile (55:45) (v/v) as eluent. A UV-visible spectrophotometric detector fixed at 386 nm was used both for detection and quantitation. The method was used not only for quality assurance but also for process development and wastewater management of AABDS.
    Additional Material: 4 Ill.
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  • 196
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    Journal of High Resolution Chromatography 23 (2000), S. 317-323 
    ISSN: 0935-6304
    Keywords: Conjugated linoleic acids ; underivatized ; Ag+-HPLC ; resolution ; mixed mode retention ; hydrogen bonding ; competing acid ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Fatty acids (FAs) and fatty acid residues are generally methylated and analyzed by GC. The reasons for this are partly historic and partly because of the sensitivity advantage of flame ionization detection over UV absorption by the carboxylic acid functionality in saturated FAs. However, for strongly absorbing unsaturated acids such as the conjugated linoleic acids (CLAs), the sensitivity advantage is greatly reduced. Hence there seems little reason to waste time and introduce errors associated with methylation. Remarkably, this appears not to have been recognized. In this paper we describe our method development for the analysis of underivatized CLAs by silver ion HPLC separation on the ChromSpher Lipids column. Using mobile phases previously optimized for the analysis of the methylated CLAs, retention is excessive and a competing acid is required. Various combinations of small concentrations of acetic acid (3.0-2.5%) with acetonitrile (0.0-0.025%), respectively, yield similar resolution and run times. As well as its role as a competing acid, acetic acid acts as a general strong solvent and thus can be used alone as a modifier (without acetonitrile). However, for slightly shorter run times a mobile phase of 2.5% acetic acid and 0.025% acetonitrile was chosen as the optimum mobile phase for analysis. The separation of the free CLAs is clearly superior to those previously published and obtained in this study for the methylated CLAs. The additional specific strong interactions of the underivatized CLAs seem certain to be due to hydrogen bonding between the CLA carboxylic acid functionality and the large number of residual silanols on the surface of the silica support of the stationary phase.
    Additional Material: 6 Ill.
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  • 197
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    Journal of High Resolution Chromatography 23 (2000), S. 333-337 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; chiral separation ; chiral stationary phase ; separation of enantiomers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new reciprocal π-basic chiral stationary phase (CSP) was designed based on the reciprocity conception of chiral recognition and prepared starting from (S)-leucine. The CSP thus prepared was applied in resolving various π-acidic N-(3,5-dinitrobenzoyl)-α-amino amides and esters and found to be very effective. Especially, N-(3,5-dinitrobenzoyl)-α-amino N,N-dialkyl amides were resolved very well on the new reciprocal CSP. From the chromatographic resolution results and based on the reciprocity conception of chiral recognition with the aid of Corey/Pauling/Koltan (CPK) molecular model studies, a chiral recognition mechanism which utilizes π-π interaction and simultaneously two hydrogen bonding interactions between the CSP and the analyte has been proposed. The CSP prepared in this study was also successful in resolving 3,5-dinitrophenylcarbamate derivatives of 2-hydroxycarboxylic acid esters.
    Additional Material: 4 Ill.
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  • 198
    ISSN: 0935-6304
    Keywords: μLC ; FID ; LC-FID ; carbohydrates ; amino acids ; alcohols ; phosphonic acids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The potential of the on-line coupling of microcolumn liquid chromatography (μLC) using aqueous eluents with a flame ionization detector (FID) was evaluated. An eluent-jet interface was modified to allow the efficient introduction of the eluent into the FID. The potential of the method is demonstrated by the μLC-FID determination of lower alcohols and bis(2-hydroxyethylthio)alkanes on porous and non-porous stationary phases, respectively. Flow injection analysis (FIA)-FID experiments with highly polar, thermolabile, semi-volatile and non-volatile compounds like amino acids, organic acids, alkylphosphonic acids, and carbohydrates showed the developed configuration to be a promising approach for the detection of a wide range of analytes. Compared with a nebulization interface, the eluent-jet interface showed 4-10 times higher peaks for citric acid. Detection limits by FIA for all compounds were in the range of 0.2-5 ng injected. With ribose as test compound, plots of peak height vs. amount injected showed good linearity (r2 〉 0.999) in the range of 75-12,000 μg/mL. The repeatability showed relative standard deviations of less than 5%.
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  • 199
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    Journal of High Resolution Chromatography 23 (2000), S. 324-328 
    ISSN: 0935-6304
    Keywords: Antioxidants ; propyl gallate ; octyl gallate ; dodecyl gallate ; butylated hydroxyanisole ; butylated hydroxytoluene ; reverse-phase liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The influence of cationic and anionic surfactants and short-chain alcohols in the mobile phase on the retention of five antioxidants has been studied. The solutes chosen were butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and propyl, octyl, and dodecyl gallates (PG, OG, DG).The surfactants were hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS), and n-propanol (PrOH) was the selected alcohol. A simple isocratic reversed-phase method for the antioxidant determination is proposed. Separation of five primary antioxidants takes 18 min with the mobile phase SDS 0.10 M/H3PO4 0.01 M/PrOH 30%. Variation of the percentage of alcohol in the mobile phase permits optimization of the retention times of the antioxidants. Detection limits in the pg range were obtained for the all solutes. The method was used to determine the antioxidants in olive oil at three different levels, giving mean recoveries close to 100% for all the solutes (BHA 102%, PG 99%, OG 99%, DG 99%) except BHT (84%).
    Additional Material: 3 Ill.
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  • 200
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    Journal of High Resolution Chromatography 23 (2000), S. 338-342 
    ISSN: 0935-6304
    Keywords: Polyunsaturated fatty acids (PUFA) ; high performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-MS with APCI) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analysis of polyunsaturated fatty acids using high performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry is described. The standard fatty acid methyl esters from 16 to 22 carbons were analyzed by LC-MS with APCI. The effect of orifice voltage and total carbon atoms versus number of double bonds in each homologue on the mass spectra is discussed. The correction coefficients for homologues from saturated fatty acids to hexaenoic acid are also mentioned.
    Additional Material: 4 Ill.
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