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971.
Papousková B Bednár P Frysová I Stýskala J Hlavác J Barták P Ulrichová J Jirkovský J Lemr K 《Journal of mass spectrometry : JMS》2007,42(12):1550-1561
Selected precursors and degradation products of chemical warfare agents namely N,N-dialkylaminoethane-2-ols, N,N-dialkylaminoethyl-2-chlorides and some of related N-quaternary salts were studied by means of electrospray ionization-multiple tandem mass spectrometry (ESI-MS(n)). Proposed structures were confirmed with accurate mass measurement. General fragmentation patterns of these compounds are discussed in detail and suggested processes are confirmed using deuterated standards. The typical processes are elimination of alkene, hydrogen chloride, or water, respectively. Besides, elimination of ethene from propyl chain under specific conditions was observed and unambiguously confirmed using exact mass measurement and labelled standard. The potential of mass spectrometry to distinguish the positional isomers occurring among the studied compounds is reviewed in detail using two different MS instruments (i.e. ion trap and hybrid quadrupole-time of flight (Q-TOF) analyzer). A new microcolumn liquid chromatography (microLC)/MS(n) method was designed for the cases where the resolution based solely on differences in fragmentation is not sufficient. Low retention of the derivatives on reversed phase (RP) was overcome by using addition of less typical ion pairing agent (1 mM/l, 3,5-dinitrobenzoic acid) to the mobile phase (mixture water : acetonitrile). 相似文献
972.
In this work, we present molecular dynamics simulations of comb-like polyelectrolytes in selective solvent. The studied polymers have a neutral backbone and polyelectrolyte side chains. The solvent is poor for the backbone and the theta solvent for the side chains. The polymers are modeled on a coarse-grained level with implicit solvent. The simulations show that the comb-like polyelectrolytes tend to form intramolecular self-organized structures of the pearl necklace type. This type of conformational behavior has been predicted by Borisov and Zhulina (Borisov, O. V.; Zhulina, E. B. Macromolecules 2005, 38, 2506) for neutral comb-like copolymers in selective solvent. The present study shows that comb-like polyelectrolytes in selective solvent exhibit the same type of behavior; however, it can be controlled by one additional parameter, the degree of dissociation of the grafts. The local conformational characteristics are studied using the ensemble-averaged bond angle cosines as functions of monomer position in the chain, which reveal structural details invisible by other means. 相似文献
973.
iBodies: Modular Synthetic Antibody Mimetics Based on Hydrophilic Polymers Decorated with Functional Moieties 下载免费PDF全文
Dr. Pavel Šácha Tomáš Knedlík Dr. Jiří Schimer Dr. Jan Tykvart Jan Parolek Václav Navrátil Petra Dvořáková Dr. František Sedlák Prof. Karel Ulbrich Dr. Jiří Strohalm Dr. Pavel Majer Dr. Vladimír Šubr Dr. Jan Konvalinka 《Angewandte Chemie (International ed. in English)》2016,55(7):2356-2360
Antibodies are indispensable tools for biomedicine and anticancer therapy. Nevertheless, their use is compromised by high production costs, limited stability, and difficulty of chemical modification. The design and preparation of synthetic polymer conjugates capable of replacing antibodies in biomedical applications such as ELISA, flow cytometry, immunocytochemistry, and immunoprecipitation is reported. The conjugates, named “iBodies”, consist of an HPMA copolymer decorated with low‐molecular‐weight compounds that function as targeting ligands, affinity anchors, and imaging probes. We prepared specific conjugates targeting several proteins with known ligands and used these iBodies for enzyme inhibition, protein isolation, immobilization, quantification, and live‐cell imaging. Our data indicate that this highly modular and versatile polymer system can be used to produce inexpensive and stable antibody substitutes directed toward virtually any protein of interest with a known ligand. 相似文献
974.
Martin Pavlačka Petra Bajerová Kateřina Kortánková Jiří Bláha Michal Zástěra Roman Mázl Karel Ventura 《International Journal for Ion Mobility Spectrometry》2016,19(1):31-39
Characterization of ions from eight explosives (2,4,6-trinitrotoluene, pentaerythritol tetranitrate, 2,4,6-trinitrophenol, 2,4-dinitrotoluene, erythritol tetranitrate, hexamethylene triperoxide diamine, 2,4,6-trinitrophenylmethylnitramine and 1,3,5-trinitro-perhydro-1,3,5-triazine) using differential mobility spectrometry (DMS) with 63Ni as an ionization source was performed. Presented results of explosive analysis have been evaluated by use of special software tool which communicates with DMS in real time. This tool was developed for visualization, identification and comparison of measured data. Each explosive provides characteristic signal at a specific compensation voltage under a fixed dispersion field. Peaks in DMS spectra for these ions were confined to a range of compensation voltages between ?1.61 to +1.71 V at RF = 1060 V. We calculated specific alpha coefficients (α2 and α4) to obtain a nonlinear function of explosives, based on their DMS spectra. Dependence of mobility for measured explosives ions in electric field at E/N values between 0 to 120 Td were used to inspectional graphical differentiation of explosives. 相似文献
975.
Sachl R Uchman M Matĕjícek P Procházka K Stĕpánek M Spírková M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(6):3395-3400
Aqueous solutions of self-assembled nanoparticles formed by biocompatible diblock copolymers of poly(epsilon-caprolactone)-block-poly(ethylene oxide) (PCL-PEO) with the same molar mass of the PEO block (5000 g mol-1) and three different molar masses of the PCL block (5000, 13 000, and 32 000 g mol-1) have been prepared by a fast mixing the copolymer solution in a mild selective solvent, tetrahydrofuran (THF)/water, with an excess of water, that is, by quenching the reversible micellization equilibrium, and a subsequent removal of THF by dialysis of the water-rich solution against water. The prepared nanoparticles have been characterized by static and dynamic light scattering and atomic force microscopy imaging. It was found that stable monodisperse nanoparticles are formed only if the initial mixed solvent contained 90 vol % THF. The results show that the prepared nanoparticles are spherical vesicles with relatively thick hydrophobic walls, that is, spherical core/shell nanoparticles with the hollow core filled with the solvent. 相似文献
976.
Yadolah Ganjkhanlou Zdeněk Tišler José Miguel Hidalgo Karel Frolich Jiří Kotera Pavel Čičmanec Roman Bulánek 《Chemical Papers》2018,72(4):937-946
Effect of zirconium presence in the silica framework and content and speciation of vanadium surface oxo-complexes on the catalytic behavior of VOx/Zr–SBA-15 catalysts in oxidative dehydrogenation of ethanol was investigated. Experimental results bring evidence of successful incorporation of zirconium into ordered mesoporous silica framework with the preservation of ordered mesoporosity by hydrothermal template base synthesis method. The presence of zirconium in the SBA-15 framework increases reducibility of vanadium species and acidity of the catalysts. It is reflected in higher activity of vanadium species expressed as turn-over frequency (e.g., TOF of 20 h?1 for 5%VOx/Zr–SBA-15 sample in comparison with TOF of 12 h?1 for 5%VOx/SBA-15 sample) and also in significant decrease of selectivity to acetaldehyde (65% in comparison with 90% for mentioned samples) followed by increase in selectivity to ethylene (25% in comparison with 5%). This change in distribution of reaction products is related to stronger acidity character of surface OH groups and inhibition effect of formed water vapours on the oxidative dehydrogenation products (acetaldehyde). Catalytic data also reveal that oligomeric/polymeric tetrahedrally coordinated vanadium species exhibit higher activity in ethanol oxidative dehydrogenation than monomeric complexes. In addition, comparison of the catalytic performance of VOx/Zr–SBA-15 catalysts with VOx/SBA-15 catalysts showed that catalytic properties of VOx/Zr–SBA-15 catalysts can be tuned by incorporation of controlled amount of zirconium into silica framework. 相似文献
977.
Dr. Els Pardon Dr. Cecilia Betti Dr. Toon Laeremans Dr. Florent Chevillard Dr. Karel Guillemyn Prof. Dr. Peter Kolb Prof. Dr. Steven Ballet Prof. Dr. Jan Steyaert 《Angewandte Chemie (International ed. in English)》2018,57(19):5292-5295
The conformational complexity of transmembrane signaling of G‐protein‐coupled receptors (GPCRs) is a central hurdle for the design of screens for receptor agonists. In their basal states, GPCRs have lower affinities for agonists compared to their G‐protein‐bound active state conformations. Moreover, different agonists can stabilize distinct active receptor conformations and do not uniformly activate all cellular signaling pathways linked to a given receptor (agonist bias). Comparative fragment screens were performed on a β2‐adrenoreceptor–nanobody fusion locked in its active‐state conformation by a G‐protein‐mimicking nanobody, and the same receptor in its basal‐state conformation. This simple biophysical assay allowed the identification and ranking of multiple novel agonists and permitted classification of the efficacy of each hit in agonist, antagonist, or inverse agonist categories, thereby opening doors to nanobody‐enabled reverse pharmacology. 相似文献
978.
Due to their low polarities and dielectric constants, analytes in solvents such as hexane, chloroform, and ethyl acetate exhibit poor electrospray ionization (ESI) efficiency. These are deemed to be “non-ESI-friendly” solvents. Continuous flow extractive desorption electrospray ionization (CF-EDESI) is a novel ambient ionization technique that was recently developed in our group to manipulate protein charge distributions. Here we demonstrate its potential for ionizing analytes from non-ESI-friendly solvents. This feature makes CF-EDESI attractive to the general analytical community due to its apparent potential in lipidomics, normal phase separations, and hyphenation of mass spectrometry with HPLC-NMR systems. In this context, interest was subsequently initiated to discern mechanistic aspects of CF-EDESI. To achieve this, mechanistic experiments associated with a seemingly similar ambient ionization technique, extractive electrospray ionization (EESI), were emulated to compare CF-EDESI and EESI. Analysis of a series of fatty acids in multiple solvents in the negative ionization mode revealed differences between the two techniques. Whereas EESI has been previously shown to operate via extraction of analytes into the spray solvent, data presented here for CF-EDESI point toward a liquid-liquid mixing process to facilitate ionization. Further, a partial factorial design experiment was performed to evaluate the effects of different experimental variables on signal intensity. Sample flow rate was confirmed to be among the most significant factors to affect sensitivity. As a whole, the work presented provides greater insight into a new ambient ionization process, which exhibits expanded capabilities over conventional ESI; in this case, for direct analysis from non-ESI-friendly solvents. 相似文献
979.
Pyrenebutanoate, a fluorescent amphiphilic probe, is suggested here as a capillary zone electrophoresis (CZE) buffer additive for dynamic modification and analysis of microbial cells. Mixed cultures of microorganisms Escherichia coli, Candida albicans, Enterococcus faecalis and Staphylococcus epidermidis were concentrated, resolved by CZE and detected. Using UV excitation for on-column fluorometric detection, a detection sensitivity for the microorganisms on the order of from one to tens of injected cells was achieved. 相似文献
980.
A divergent-flow isoelectric focusing (DF IEF) technique has been applied for the separation and preparative analysis of peptides. The parameters of the developed DF IEF device such as dimension and shape of the separation bed, selection of nonwoven material of the channel, and separation conditions were optimized. The DF IEF device was tested by the separation of a peptide mixture originating from the tryptic digestion of BSA, cytochrome c, and myoglobin. The pH gradient of DF IEF was created by the autofocusing of tryptic peptides themselves without any addition of carrier ampholytes. The focusing process was monitored visually using colored pI markers, and the obtained fractions were analyzed by RP-HPLC and ESI/TOF-MS. DF IEF operating in the autofocusing mode provides an efficient preseparation of peptides, which is comparable with a commercially available MicroRotofor multicompartment electrolyzer and significantly improves sequence coverage of analyzed proteins. The potential of the DF IEF device as an efficient tool for the preparative scale separations was demonstrated by the isolation of caseinomacropeptide (CMP) from a crude whey solution. 相似文献