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101.
Many biological processes are characterized by an essentially quantum dynamical event, such as electron or proton transfer, in a complex classical environment. To treat such processes properly by computer simulation, allowing nonadiabatic transitions involving excited states, we recently developed a density matrix evolution (DME ) method [H. J. C. Berendsen and J. Mavri, J. Phys. Chem, 97 , 13464 (1993)] which simulates the dynamics of quantum systems embedded in a classical environment. The formalism of the method is presented and an overview of the applications ranging from collisions of a quantum harmonic oscillator with noble gas atoms to proton tunneling in a double-well hydrogen bond is given. The methodology for treatment of proton-transfer processes with inclusion of excited states is presented. Future application of the method on biologically interesting processes, such as proton transfer in enzymatic reactions, is discussed. © 1996 John Wiley & Sons, Inc. 相似文献
102.
Polymers containing substituted 2-phenyl-benzoxazole side-chain groups: Synthesis and phase behavior
Roberto Centore Barbara Panunzi Antonio Roviello Augusto Sirigu Paola Villano 《Journal of polymer science. Part A, Polymer chemistry》1996,34(15):3203-3211
The synthesis of substituted 2-phenyl-benzoxazoles has been accomplished by ring closure of Schiff bases. The compounds have been used as precursors of acrylic derivatives displaying LC properties: Four comb-like homopolymers have been obtained by radical catalysis from the acrylic monomers. The polymers have been characterized by 1H-NMR, DSC, x-ray diffraction, viscometry, and polarizing microscopy. Three of the polymers exhibit liquid crystalline properties of smectic type. © 1996 John Wiley & Sons, Inc. 相似文献
103.
104.
Magdalena
widro Klaudia Ordon Magorzata Herman Dominika Dudek Renata Wietecha-Posuszny 《Molecules (Basel, Switzerland)》2022,27(1)
The diagnosis of affective disorders has been the subject of constant research by clinicians from all over the world for many years. Making an appropriate diagnosis among patients suffering from mood disorders is sometimes problematic due to the personality-changing nature of patients and the similarity in the clinical picture of episodes in affective disorders. For this reason, there is a need to develop rapid and effective methods of determining biological markers that differentiate these diseases. The research was carried out with blood taken from 15 patients and 15 volunteers. The analysis of biological material for trace concentrations of zinc and copper was carried out with the use of ultrasensitive triple-quadrupole inductively coupled plasma mass spectrometry (TQ ICP-MS). The obtained results prove that the concentration of copper in the test group was lower than in the control group. For the zinc concentrations, the inverse relationship was observed. The group of patients was characterized by a higher concentration of this element than the group of healthy volunteers. Summarizing the obtained results and comparing them with the results of studies by other authors, it was found that zinc and copper may be potential biomarkers of affective disorders and pandemic syndrome. 相似文献
105.
106.
A Multivalent Ligand for the Mannose‐6‐Phosphate Receptor for Endolysosomal Targeting of an Activity‐Based Probe 下载免费PDF全文
Dr. Sascha Hoogendoorn Dr. Gijs H. M. van Puijvelde Prof. Dr. Johan Kuiper Prof. Dr. Gijs A. van der Marel Prof. Dr. Herman S. Overkleeft 《Angewandte Chemie (International ed. in English)》2014,53(41):10975-10978
The ubiquitously expressed mannose‐6‐phosphate receptors (MPRs) are a promising class of receptors for targeted compound delivery into the endolysosomal compartments of a variety of cell types. The development of a synthetic, multivalent, mannose‐6‐phosphate (M6P) glycopeptide‐based MPR ligand is described. The conjugation of this ligand to fluorescent DCG‐04, an activity‐based probe for cysteine cathepsins, enabled fluorescent readout of its receptor‐targeting properties. The resulting M6P‐cluster–BODIPY–DCG‐04 probe was shown to efficiently label cathepsins in cell lysates as well as in live cells. Furthermore, the introduction of the 6‐O‐phosphates leads to a completely altered uptake profile in COS and dendritic cells compared to a mannose‐containing ligand. Competition with mannose‐6‐phosphate abolished all uptake of the probe in COS cells, and we conclude that the mannose‐6‐phosphate cluster targets the MPR and ensures the targeted delivery of cargo bound to the cluster into the endolysosomal pathway. 相似文献
107.
108.
Jan Claereboudt Magda Claeys Herman Geise Renaat Gijbels Akos Vertes 《Journal of the American Society for Mass Spectrometry》1993,4(10):798-812
The use of laser microprobe mass spectrometry (LMMS) for the structural characterization of thermolabile quaternary phosphonium salts has been evaluated. A comparison has been made between LM mass spectra obtained by direct analysis of “neat” organic salts and the corresponding “matrix-assisted” LM mass spectra. Main limitations of LMMS for the direct analysis of neat organic salts (i.e., no matrix) result from (1) formation of artifact ions that originate from thermal degradation and surface recombination reactions and (2) poor shot-to-shot reproducibility of the spectra. Dilution of the organic salts in a suitable, UV-absorbing matrix (e.g., nicotinic acid) significantly enhances the quality of the LM mass spectra. Improvements are: (1) an increase of the ion yield of preformed cations, (2) reduction or elimination of thermal decomposition and other deleterious surface reactions, and (3) a much better shot-to-shot spectral reproducibility. An interesting analytical feature is that these LM mass spectra, which contain only a few matrix peaks, can be obtained for subnanogram amounts of sample. The results also show that triphenylphosphonium salts with polycyclic aromatic substituents can be used as “molecular thermometers” to probe both the temperatures experienced by the sample molecules during the laser-induced desorption ionization process and the internal energies of the desorbed ion species. In this way, quaternary phosphonium salts can be used for evaluating whether improvements have been achieved by applying different sample treatments. Comparison of four different matrices (i.e., nicotinic acid, ammonium chloride, glycerol, and 3-nitrobenzylalcohol) indicates that the effectiveness of a matrix to reduce thermal degradation and to decrease the internal energies of the ions depends on the UV-absorption characteristics and the volatilization/sublimation temperature of the matrix material. 相似文献
109.
Jan A. Herman Kazimiera Herman Terry B. McMahon 《Journal of the American Society for Mass Spectrometry》1991,2(3):220-225
Fourier transform ion cyclotron resonance mass spectrometry has been used to measure the reaction rates for ions derived from methylamine with dimethylamine or trimethylamine. The use of the selective ion ejection technique greatly simplifies the elucidation of the ion-molecule reaction channels. The rate constants for proton transfer from protonated metwlamine, CH3NH 3 + (m/z 32), to dimethylamine and trimethylamine are 16.1 ± 1.6 × 10?10 and 9.3 ± 0.9 × 10?10 cm3 molec?1s?1, respectively. The rate constants for charge transfer from methylamine molecular ion, CH3NH 2 + (m/z 31), to dimethylamine and trimethylamine are 9.3 ± 1.8 x 10?10 and 15.0 ± 5 × 10?10 cm3molec?1s?1, respectively. 相似文献
110.
Herman Bachelard Peter Morris Andrew Taylor Nicola Thatcher 《Magnetic resonance imaging》1995,13(8):1223-1226
We are applying multi-nuclear high-field (500 MHz) MR spectroscopy of metabolising whole tissue preparations of the mammalian brain to studies on individual components of convulsions, which include prolonged depolarization, metabolic deprivation, and the effects of excitotoxins. The responses of glial cells and neurones can be partially distinguished by following labelling patterns of metabolic intermediates from 13C-labelled glucose or acetate (which enters only glial cells). This approach clearly confirmed our earlier indications that the metabolic response to depolarization (40 mM extracellular K+) occurs essentially in glial cells. Some evidence for metabolic shuttling between glia and neurones was obtained from the changes in C3/C4 ratios of glutamate and glutamine, and the C2/C3 of GABA. Mechanisms for metabolic support of neurones by glia may be of importance in neuronal protection under such metabolic stress as occurs in epilepsy. Changes in free intracellular divalent cations ([Ca2+]i and [Zn2+]i) were monitored using the 19F-MRS indicator, 5FBAPTA. Large increases in [Ca2+]i and decreases in PCr were produced by excitotoxins (glutamate and NMDA), depolarization or ischaemia, but intracellular Zn2+ appeared only after exposure to the excitotoxins. The NMDA receptor blocker, MK801, removed all of the responses to NMDA, but only prevented the appearance of Zn2+ observed with glutamate. These results indicate that the damage caused to neurones by such insults as convulsions is not due simply to the presence of excessive excitotoxic glutamate. 相似文献