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21.
An enantioselective gas chromatography (GC) method has been developed and validated for determination of the enantiomers of citronellol in kinetic resolution experiments. S-(-)-beta-Citronellol is a precursor of rose oxide. After solid-phase extraction (SPE) with ethyl acetate, the enantiomers of R-(+)-beta-citronellol and S-(-)-beta-citronellol and their corresponding acetate- and butyrate esters were separated through enantioselective GC respectively. The method was validated and found to be reproducible, specific, accurate, and precise. Analyte recoveries and detection limits were also determined. The applicability of this method was shown in a kinetic resolution experiment using lipase A of Bacillus subtilis. 相似文献
22.
René Grouls Wim van de Laar Henk M. J. Goldschmidt Frits G. van Merode 《Accreditation and quality assurance》2004,10(1-2):41-46
Many medical professionals are involved in patient care processes. For pharmaceutical care this results in many information transfer moments. To provide optimal care, communication and information the transfer should be conducted in a timely manner, fully transparent, complete and relevant. The TRANSFORM project is directed towards the development of a reference information model of the pharmaceutical care chain with the aim to improve the availability (time, place, completeness) and access of pharmaceutical information regarding patients, thereby resulting in continuity and quality of pharmaceutical care, reduction in medical errors and improvement in patient safety through the design of a safer healthcare system. TRANSFORM leads to improved insight into the processes and data transfer points in the pharmaceutical chain of care. Focussed on laboratory medicine and pharmacy, the implementation of the integration of laboratory test and pharmacy information may result in major improvements in drug therapy monitoring and guidance (i.e. drug impact monitoring). Because of the overwhelming amount of data generated by this integration of drugs, drug effects and laboratory test results, an online decision support system is warranted.Presented at the 9th Conference on Quality in the Spotlight, 18–19 March 2004, Antwerp, Belgium.The following paper may appear at first sight not to be specifically within the realm of ACQUAL. It has been accepted for publication anyway as it is about reliable handling of data, incl. measurement results, which lead to important decisions (in this case related to a patient). The reliability of handling (a large amount of) measurement results towards a basis for important decisions, is a very important feature of the use of such results.Paul De Bièvre, Editor in Chief 相似文献
23.
Klopper W 《The Journal of chemical physics》2004,120(23):10890-10895
In the framework of second-order M?ller-Plesset linear-r(12) (MP2-R12) perturbation theory, a method is developed and implemented that uses an auxiliary basis set for the resolution-of-the-identity (RI) approximation for the three- and four-electron integrals. In contrast to previous work, the two-electron integrals that must be evaluated never involve more than one auxiliary basis function. The new method therefore scales linearly with the number of auxiliary basis functions and is much more efficient than the previous one, which scaled quadratically. A general formulation of MP2-R12 theory is presented for various ansatze, approximations, and orbitals (canonical or localized). The new method is assessed by computations of the valence-shell second-order M?ller-Plesset correlation energy of a few small closed-shell systems. The preliminary calculations indicate that the difference between the new and previous methods is about one order of magnitude smaller than the errors that occur due to basis-set truncations and RI approximations and under the assumptions of generalized and extended Brillouin conditions. 相似文献
24.
Kaval N Ermolat'ev D Appukkuttan P Dehaen W Kappe CO Van der Eycken E 《Journal of combinatorial chemistry》2005,7(3):490-502
The "click chemistry" approach has been explored on the 2-(1H)-pyrazinone scaffold for the generation of pharmacologically interesting heterocyclic moieties. Huisgen 1,3-dipolar cycloaddition has been evaluated as the key step for the construction of the 1,2,3-triazole ring at the C-3 position of 2-(1H)-pyrazinones. Two different pathways have been successfully evaluated: (1) via C-C or C-O linkage of the acetylenic part to the C-3 position of the 2-(1H)-pyrazinone scaffold or (2) via azide introduction in the C-3 position. The subsequent application of "click chemistry" resulted in the formation of hitherto unknown skeletons. Microwave irradiation has successfully been applied in different steps of the sequence. 相似文献
25.
Oudhoff KA Macka M Haddad PR Schoenmakers PJ Kok WT 《Journal of chromatography. A》2005,1068(1):183-187
A capacitively coupled contactless conductivity detection (CCD) system has been applied for the detection of neutral synthetic polymers in capillary size-exclusion electrokinetic chromatography (SEEC). Polystyrene standards, that were used as a model compounds, were separated on a capillary column packed with porous 10 microm silica particles with an electrokinetically driven mobile phase, and detected by CCD and UV detection simultaneously. Mass-calibration curves for polystyrene were constructed. Satisfactory results were obtained for the linearity, the run-to-run repeatability (<0.2% for the relative retention and <4% for the peak area) and the robustness of the detector. One of the major issues in this preliminary study was to investigate the origin of the peaks observed for the polystyrene standards. The effect of the molar mass of the polystyrenes on the sensitivity was small. Therefore, the signals obtained could not be explained as the result of an increased viscosity and a decreased solution conductivity of the solute zone. An alternative hypothesis is suggested, and recommendations for further research are given. 相似文献
26.
27.
Carstens MG van Nostrum CF Ramzi A Meeldijk JD Verrijk R de Leede LL Crommelin DJ Hennink WE 《Langmuir : the ACS journal of surfaces and colloids》2005,21(24):11446-11454
Methoxypoly(ethylene glycol)-b-oligo-L-lactate (mPEG-b-OLA) diblock oligomers with monodisperse OLA blocks were obtained by fractionation of polydisperse block oligomers using preparative HPLC. The fractionated oligomers were composed of an mPEG block with a molecular weight of 350, 550, or 750 and an OLA block with a degree of polymerization of 4, 6, 8, or 10. The diblock oligomers with a low PEG content were fully amorphous, with glass transition temperatures ranging from -60 to -20 degrees C, indicating that the blocks were miscible. Upon heating aqueous dispersions of the block oligomers, cloud points, depending on the PEG/OLA ratio of the block oligomer, were observed at temperatures above 40 degrees C. The monodispersity of the hydrophobic block enabled the amphiphilic molecules to form nanoparticles in water with a hydrodynamic radius of 130-300 nm, at concentrations above the critical aggregation concentration (0.4-1 mg/mL), whereas polydisperse mPEG-b-OLAs gave formation of large aggregates. Static light scattering measurements showed that the nanoparticles have a low density (0.6-25 mg/mL), indicating that the particles are highly hydrated. In agreement herewith, the (1)H NMR spectra of nanoparticles in D2O closely resembled spectra in a good solvent for both blocks (CDCl3). It is therefore suggested that the nanoparticles contain a hydrated core of mPEG-b-OLA block oligomers, stabilized by a thin outer PEG layer. The particles were stable for two weeks, except for the mPEG350 series and mPEG750-b-OLA4, indicating that both the PEG block size and the PEG weight fraction of the oligomers determine their stability. The evident self-emulsifying properties of mPEG-b-oligo-l-lactates with monodisperse hydrophobic blocks as demonstrated in this study, together with their expected biocompatibility and biodegradability, make these systems well suitable for pharmaceutical applications. 相似文献
28.
Petrignani A van der Zande WJ Cosby PC Hellberg F Thomas RD Larsson M 《The Journal of chemical physics》2005,122(1):14302
We have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.4 eV for five different vibrational populations of the ion beam, as well as the partial (vibrationally resolved) rate coefficients and the branching fractions near 0 eV collision energy for the vibrational levels v=0, 1, and 2. The vibrational populations used were produced in a modified electron impact ion source, which has been calibrated using Cs-O(2)(+) dissociative charge transfer reactions. The measurements indicate that at low collision energies, the total rate coefficient is weakly dependent on the vibrational excitation. The calculated thermal rate coefficient at 300 K decreases upon vibrational excitation. The partial rate coefficients as well as the partial branching fractions are found to be strongly dependent on the vibrational level. The partial rate coefficient is the fastest for v=0 and goes down by a factor of two or more for v=1 and 2. The O((1)S) quantum yield, linked to the green airglow, increases strongly upon increasing vibrational level. The effects of the dissociative recombination reactions and super elastic collisions on the vibrational populations are discussed. 相似文献
29.
Soga O van Nostrum CF Ramzi A Visser T Soulimani F Frederik PM Bomans PH Hennink WE 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9388-9395
Amphiphilic AB block copolymers consisting of thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) and poly(ethylene glycol), pHPMAmDL-b-PEG, were synthesized via a macroinitiator route. Dynamic light scattering measurements showed that these block copolymers form polymeric micelles in water with a size of around 50 nm by heating of an aqueous polymer solution from below to above the critical micelle temperature (cmt). The critical micelle concentration as well as the cmt decreased with increasing pHPMAmDL block lengths, which can be attributed to the greater hydrophobicity of the thermosensitive block with increasing molecular weight. Cryogenic transmission electron microscopy analysis revealed that the micelles have a spherical shape with a narrow size distribution. 1H NMR measurements in D2O showed that the intensity of the peaks of the protons from the pHPMAmDL block significantly decreased above the cmt, indicating that the thermosensitive blocks indeed form the solidlike core of the micelles. Static light scattering measurements demonstrated that pHPMAmDL-b-PEG micelles with relatively large pHPMAmDL blocks possess a highly packed core that is stabilized by a dense layer of swollen PEG chains. FT-IR analysis indicated that dehydration of amide bonds in the pHPMAmDL block occurs when the polymer dissolved in water is heated from below to above its cmt. The micelles were stable when an aqueous solution of micelles was incubated at 37 degrees C and at pH 5.0, where the hydrolysis rate of lactate side groups is minimized. On the other hand, at pH 9.0, where hydrolysis of the lactic acid side groups occurs, the micelles started to swell after 1.5 h of incubation and complete dissolution of micelles was observed after 4 h as a result of hydrophilization of the thermosensitive block. Fluorescence spectroscopy measurements with pyrene loaded in the hydrophobic core of the micelles showed that when these micelles were incubated at pH 8.6 and at 37 degrees C the microenvironment of pyrene became increasingly hydrated in time during this swelling phase. The results demonstrate the potential applicability of pHPMAmDL-b-PEG block copolymer micelles for the controlled delivery of hydrophobic drugs. 相似文献
30.
Zhou C Friedt JM Angelova A Choi KH Laureyn W Frederix F Francis LA Campitelli A Engelborghs Y Borghs G 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5870-5878
Time-resolved adsorption behavior of a human immunoglobin G (hIgG) protein on a hydrophobized gold surface is investigated using multitechniques: quartz crystal microbalance/dissipation (QCM-D) technique; combined surface plasmon resonance (SPR) and Love mode surface acoustic wave (SAW) technique; combined QCM-D and atomic force microscopy (AFM) technique. The adsorbed hIgG forms interfacial structures varying in organization from a submonolayer to a multilayer. An "end-on" IgG orientation in the monolayer film, associated with the surface coverage results, does not corroborate with the effective protein thickness determined from SPR/SAW measurements. This inconsistence is interpreted by a deformation effect induced by conformation change. This conformation change is confirmed by QCM-D measurement. Combined SPR/SAW measurements suggest that the adsorbed protein barely contains water after extended contact with the hydrophobic surface. This limited interfacial hydration also contributed to a continuous conformation change in the adsorbed protein layer. The viscoelastic variation associated with interfacial conformation changes induces about 1.5 times overestimation of the mass uptake in the QCM-D measurements. The merit of combined multitechnique measurements is demonstrated. 相似文献