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21.
A procedure has been developed for estimating the information content of retrieval systems with binary-coded mass spectra, as well as mass spectra coded by other methods, from the statistical properties of a reference file. For a reference file, binary-coded with a threshold of 1% of the intensity of the base peak, this results typically in an estimated information content of about 50 bits for 200 selected values. It is shown that, because of errors occurring in the binary-coded spectra, the actual information content is only about 12 bits. This explains the poor performance observed for retrieval systems with binary-coded mass spectra. 相似文献
22.
N. C. van de Merbel M. Stenberg R. Öste G. Marko-Varga L. Gorton H. Lingeman U. A. Th. Brinkman 《Chromatographia》1995,41(1-2):6-14
Summary A two-dimensional, column liquid chromatographic system is used for the determination of the D- and L-enantiomers of amino acids in biological samples. Separation of the amino acids is first on ion-exchange column by gradient elution with a sodium citratesodium chloride buffer. Enantioseparation is by subsequent injection of 3 l heart-cuts of the individual amino acids onto a second column with a chiral crown ether stationary phase. Finally, fluorescence detection is after post-column labelling of the amino acids using ano-phthalaldehyde-2-mercaptoethanol reagent solution. The high separation power and selectivity of the system allow processing of complex samples with hardly any additional treatment and the determination of small quantities of D-amino acids in the presence of excess L-form. Applicability of the system is illustrated by the determination of D- and L-aspartate, serine, glutamate and alanine in various complex biological samples, such as protein hydrolysates, urine and biotechnological and food samples. Data are given on detectability, repeatability and linearity. 相似文献
23.
Peter C. Burgers Henk Hommes Johan K. Terlouw 《Journal of mass spectrometry : JMS》1979,14(10):571-573
Loss of an alkyl group X? from acetylenic alcohols HC?C? CX(OH)(CH3) and gas phase protonation of HC?C? CO? CH3 are both shown to yield stable HC?C? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}(OH)(CH3) ions. Ions of this structure are unique among all other [C4H5O]+ isomers by having m/z 43 [C2H3O]+ as base peak in both the metastable ion and collisional activation spectra. It is concluded that the composite metastable peak for formation of m/z 43 corresponds to two distinct reaction profiles which lead to the same product ion, CH3\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O, and neutral, HC?CH. It is further shown that the [C4H5O]+ ions from related alcohols (like HC?C? CH(OH)(CH3)) which have an α-H atom available for isomerization into energy rich allenyl type molecular ions, consist of a second stable structure, H2C?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? C(OH)?CH2. 相似文献
24.
Monserrat García Gerhard van Vliet Mattijs G. J. ten Cate Francisco Chvez Ben Norder Bart Kooi Werner E. van Zyl Henk Verweij Dave H. A. Blank 《先进技术聚合物》2004,15(4):164-172
Solution impregnations, pulltrusion and film stacking are widely used methods to prepare thermoplastic composite materials. Extruders are used to melt the polymer and to incorporate fibers into the polymer in order to modify physical properties. In this article, the compounding of colloidal silica nanoparticles filled polyamide‐6 (PA‐6) is achieved using a twin‐screw extruder, which has a significant market share due to its low cost and easy maintenance. The experiments were performed at 250 rpm and the bulk throughput was 6 kg h?1 with a pump pressure of 30 bars. The composites were characterized with nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). As determined by WAXD, the PA‐6 showed higher amounts of γ‐phase when compared to other synthesis methods such as in situ polymerization. TEM pictures showed that the silica particles aggregated nevertheless, upon addition of 14% (w/w) silica the E‐modulus increased from 2.7 to 3.9 GPa indicating that an effective mechanical coupling with the polymer was achieved. The behavior, illustrated with dynamic mechanical analysis (DMA) curves, indicated that in general when a filled system is compared to unfilled material, the values of the moduli (E′ and E″) increased and tan δ decreased. Determination of molecular mass distribution of the samples by means of size exclusion chromatography (SEC) coupled to a refractive index (RI), viscosity (DV) and light scattering (LS) detector revealed that the addition of silica did not decrease the average molecular weight of the polymer matrix, which is of importance for composite applications. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
25.
M Ozcimder A J Louter H Lingeman W H Voogt R W Frei M Bloemendal 《Journal of chromatography. A》1991,570(1):19-28
A method for the detection of oxidized, reduced and protein-bound glutathione in eye lenses has been developed. Homogenized lens samples are deproteinated with acetonitrile and perchloric acid. Protein-bound glutathione is reduced by 1,4-dithiothreitol. Separation of the different forms of glutathione and dithiothreitol is performed by ion-pair reversed-phase high-performance liquid chromatography with sodium octylsulphate as the ion-pairing agent. The compounds are detected amperometrically using on-line-generated bromine, which oxidizes thiols and disulphides. In this way two samples can be analysed in triplicate in a single day. The lower detection limits are 80 and 48 nmol per gram wet lens for reduced and oxidized glutathione, respectively. The amounts of free reduced and protein-bound glutathione in calf lenses, determined with this method, are 6.8 +/- 0.4 and 0.96 +/- 0.03 mumol per gram wet lens, respectively. That of oxidized glutathione is less than 0.048 mumol per gram wet lens. 相似文献
26.
Henk C. van der Plas 《Chemistry of Heterocyclic Compounds》1994,30(11-12):1427-1443
In this review attention is paid to two topics, which were of great interest to us during 30 years of studies in pyrimidine chemistry in our laboratory: first, the development of our concepts of the AIYRORC processes, which occur in ring transformation reactions; second, the intra- and intermolecular inverse Diels-Alder reactions in which the pyrimidine ring acts as the electron poor diazadiene system. Their use in synthetic chemistry is illustrated and evidence is presented, based on experiments and molecular mechanics calculations, that in intermolecular Diels-Alder reactions the geometry of the side-chain plays a vital role. 相似文献
27.
Henk Van Der Poel Gerard Van Koten Kees Vrieze 《Journal of organometallic chemistry》1977,135(3):C63-C65
Complexes of di(t-butyl)diimine with PdCl2(PhCN)2 and with (CO)2RhCl dimer have been synthesized and characterized. The diimine ligand is monodentate bonded in PdCl2(t-butyldiimine)2, while in (t-butyldiimine)-[Rh(CO)2Cl]2 it bridges two Cl(CO)2Rh units. 相似文献
28.
Maria Grzegozek Marian Wo
niak Andrzej Baraski Henk C. Van Der Plas 《Journal of heterocyclic chemistry》1991,28(4):1075-1077
A number of 2-X-3-nitro-1,8-naphthyridines (X= H,D,OH,Cl,NH2, OEt) react with the anion of chloromethyl phenyl sulfone exclusively into 2-X-3-nitro-4-(phenylsulfonylmethyl)-1,8-naphthyridines in high yield. The reaction is found by quantum chemical calculations to be controlled by the interactions of the HOMO of the nucleophile with the LUMO of the substrate, and not by charge. 相似文献
29.
Henk de Vries Peter J. Hemelaar Alice C. M. Gevers Gerard M. J. Beyersbergen van Henegouwen 《Photochemistry and photobiology》1994,60(3):249-252
Abstract The negative side effects of chlorarnphenicol (CAP) mostly involve blood dyscrasias (e.g. irreversible nondose-dependent aplastic anemia), allergic skin reactions and eye damage. To learn the cause of these side effects, most research focuses on metabolically formed nitroso- and hydroxylamino derivatives in the predisposed patient. In previous investigations it was demonstrated that photochemical decomposition of CAP in vitro by UV-A leads to formation of p-nitrobenzaldehyde (pNB), p-nitrobenzoic acid (pNBA) and p-nitrosobenzoic acid (pNOBA); the latter comprises up to 45 mol% of the starting amount of CAP. Incubation of these photoproducts in rat blood showed that pNB and pNOBA rapidly react and that PNBA is stable under these conditions. Reaction products from pNB (half-life 1.7 min) proved to be pNBA and p-nitrobenzyl alcohol (pNBOH) while pNOBA (half-life 3.7 min) was converted into p-aminobenzoic acid (pABA). Exposure of CAP in rat blood to UV-A yielded the same end products: pNBA, PABA and pNBOH. To estimate the amount of oxidative stress generated in vivo by these compounds, the ability to form methemoglobin (MetHb) in erythrocytes was tested; only pNOBA and p-hydroxylaminobenzoic acid (pHABA), a possible intermediate in the decomposition of pNOBA, proved to be reactive. Ultraviolet-A exposure of rats, after intraperitoneal injection of CAP, led to 3.6 times the basic level of MetHb. In addition, covalent binding of 3H-labeled CAP photoproducts to the skin of the back and to the ears was found, which was 9.1 and 3.2 times higher, respectively, than the dark values. Toxicity toward bone marrow cells of all photoproducts was established in vitro. p-Nitrobenzaldehyde, pNOBA andpHABA were 20, 6 and 6 times more toxic than CAP, respectively. These results show that photodecomposition of CAP in vivo does occur. Its reactive photoproducts are able to cause damage that may lead to (systemic) side effects. The latter is supported by the fact that the nature of the reactive products, nitroso- and hydroxylamino derivatives, is the same as the expected metabolites. 相似文献
30.
Wim Goettsch Johan Garssen Arja de Klerk Tineke M. P. T. Herremans Paul Dortant Frank R. de Gruijl Henk Van Loveren 《Photochemistry and photobiology》1996,63(5):672-679
A rat infection model using the bacterial pathogen Listeria monocytogenes was employed to analyze the im-munosuppressive activity of UVB radiation. Rats were exposed to suberythemal doses of UVB radiation for 5 or 7 consecutive days, using Kromayer or FS40 lamps respectively. Subsequently, the rats were infected subcuta-neously or intravenously with Listeria . Exposure to UVB resulted in an increased number of bacteria in the spleen 4 days after infection. Listeria -specific lymphocyte proliferation assays as well as delayed-type hypersensitivity reactions demonstrated that T cell-mediated immunity to Listeria was impaired by UVB as measured 4 and 8 days after infection. In addition, UVB exposure decreased phagocytotic activity of peripheral blood macrophages. This study demonstrated that suberythemal doses of UVB radiation caused a delay in the clearance of Listeria bacteria from the spleen of the rats and that this was probably caused by impaired nonspecific phagocytosis of Listeria by macrophages in addition to an impaired activity of Listeria -specific T cells. 相似文献