Proline-tryptophan complexes derived from experimental structures are investigated by quantum chemical procedures known to properly describe the London dispersion energy. We study two geometrical arrangements: the "L-shaped", stabilized by an H-bond, and the "stacked-like", where the two residues are in parallel orientation without any H-bond. Interestingly, the interaction energies in both cases are comparable and very large ( approximately 7 kcal mol(-1)). The strength of stabilization in the stacked arrangement is rather surprising considering the fact that only one partner has an aromatic character. The interaction energy decomposition using the SAPT method further demonstrates the very important role of dispersion energy in such arrangement. To elucidate the structural features responsible for this unexpectedly large stabilization we examined the role of the nitrogen heteroatom and the importance of the cyclicity of the proline residue. We show that the electrostatic interaction due to the presence of the dipole, caused by the nitrogen heteroatom, contributes largely to the strength of the interaction. Nevertheless, the cyclic arrangement of proline, which allows for the largest amount of dispersive contact with the aromatic partner, also has a notable-effect. Geometry optimizations carried out for the "stacked-like" complexes show that the arrangements derived from protein structure are close to their gas phase optimum geometry, suggesting that the environment has only a minor effect on the geometry of the interaction. We conclude that the strength of proline non-covalent interactions, combined with this residue's rigidity, might be the explanation for its prominent role in protein stabilization and recognition processes. 相似文献
Vesicles bearing either cationic (amino) groups or zwitterionic (amino acid) groups on the surface were coated with a reactive multivalent hydrophilic N-(2-hydroxypropyl)methacrylamide polymer (PHPMA) and its positively charged analogue (3 mol % quaternary ammonium groups), both having reactive thiazolidine-2-thione (TT) groups randomly distributed along the polymer chain. The vesicles were dispersed in water at a concentration of 1 mg/mL. The effect of surface charges of model vesicles on the surface coating efficiency was evaluated. The changes in the weight-average molecular weight, in the hydrodynamic size, and in the zeta-potential of model vesicles were tested using light scattering methods. The most effective coating of vesicles was observed for the zwitterionic vesicles coated with the positively charged hydrophilic PHPMA-TT copolymer at a concentration of reactive polymer cp = 2 mg/mL. The coating efficiency was more than 1 order of magnitude higher than that obtained for positively charged vesicles coated by the uncharged hydrophilic polymer at the same cp. 相似文献
Electron ionization (EI), methane chemical ionization (CI), and collision-induced dissociation (CID) mass spectra of complete series of positional monochloro-isomers of 3-hydroxy-2-phenyl-4(1H)-quinolinone are evaluated and discussed. It is shown that in the CI experiments, in addition to the protonated precursor molecules, odd-electron molecular ions are formed and this affects the appearance of the CID spectra. The influence of different direct probes and other experimental parameters such as the pressure of the reagent gas, isolation width, or collision energy was studied. EI, CI and CID spectra of the positional isomers show essentially the same fragmentation pathways but comparisons of the relative signal intensities of various product ions reveal some positional effects. Different isomers are also distinguished. The compounds can be divided into two groups using diagnostic ions (chloro substitution of the quinolinone moiety or the phenyl ring) or identified using a created spectral database. It was demonstrated that the reproducibility of the CID spectra is fully satisfactory for isomer identification, and that the created database can be applied for comparison of spectra measured over an extended time period (1 month) or spectra obtained during the direct analysis of a reaction mixture extract. Explanation of the fragmentation of the isomers is supported by exploratory density functional theory (DFT) calculations, e.g. rationalization of the relatively higher importance of the M(+.)-H(.)-Cl(.)-CO fragmentation pathway during EI than during CID, and vice versa for the pathway M(+.)-Cl(.)-CO. Copyright (c) 2008 John Wiley & Sons, Ltd. 相似文献
The development of a rapid, simple and accurate analytical method aimed at the detection and quantification of bovine milk in either ovine or caprine milk samples by means of CE-MS analyses of whey proteins with high-ionic strength and presence of acidic running buffer is described. The high-ionic strength buffer was used in order to minimize the problems with the adsorption of the proteins onto the fused-silica capillary wall. The acidic running electrolyte, pH 1.9, was used to support the production of positive ions in electrospray. Highly linear dependences of the ratio of the sum of non-bovine beta-lactoglobulins (ovine or caprine) to the total beta-lactoglobulins in milk mixture (bovine plus ovine or bovine plus caprine) vs. the volume percentage of added bovine milk in ovine (or caprine) milk were obtained. This technique allowed the fast and reliable evaluation of milk adulteration. The amount of bovine milk added into the "non-bovine" ones can be well within the concentration range of 5-95%. 相似文献
A novel europium complex of fluoroquinolone ciprofloxacin (cfqH) with formula [Eu(cfqH)(cfq)(H2O)4]Cl2 · 4.55H2O (1) was synthesized and its crystal structure determined by X-ray crystallography. The coordination number of europium is eight and in this structure two bidentate, O,O-bonded quinolone molecules and four aqua ligands are coordinated to the metal. One molecule of quinolone is anionic whereas the other is zwitterionic. Additionally, two chloride ions are also present in the structure to compensate the charge of the europium(III) whilst disordered solvent water molecules too are present. The spectral properties (IR, Raman, luminescence) of compound 1 were studied. Analysis of the Stark structure of the luminescence spectra was carried out and the scheme of the electronically excited states and photophysical processes of compound 1 was arranged. The spectral properties show that europium–ciprofloxacin complexes could be suitable for various applications based on their solution-state stability as measured by 1H and 19F NMR. 相似文献
Pheochromocytomas and paragangliomas (PPGLs) are rare neuroendocrine tumors arising from chromaffin cells of adrenal medulla or sympathetic or parasympathetic paraganglia, respectively. To identify new therapeutic targets, we performed a detailed membrane-focused proteomic analysis of five human paraganglioma (PGL) samples. Using the Pitchfork strategy, which combines specific enrichments of glycopeptides, hydrophobic transmembrane segments, and non-glycosylated extra-membrane peptides, we identified over 1800 integral membrane proteins (IMPs). We found 45 “tumor enriched” proteins, i.e., proteins identified in all five PGLs but not found in control chromaffin tissue. Among them, 18 IMPs were predicted to be localized on the cell surface, a preferred drug targeting site, including prostate-specific membrane antigen (PSMA), a well-established target for nuclear imaging and therapy of advanced prostate cancer. Using specific antibodies, we verified PSMA expression in 22 well-characterized human PPGL samples. Compared to control chromaffin tissue, PSMA was markedly overexpressed in high-risk PPGLs belonging to the established Cluster 1, which is characterized by worse clinical outcomes, pseudohypoxia, multiplicity, recurrence, and metastasis, specifically including SDHB, VHL, and EPAS1 mutations. Using immunohistochemistry, we localized PSMA expression to tumor vasculature. Our study provides the first direct evidence of PSMA overexpression in PPGLs which could translate to therapeutic and diagnostic applications of anti-PSMA radio-conjugates in high-risk PPGLs. 相似文献
In a project environment, a manufacturer is confronted with two types of demand: regular demand from many small orders and very irregular, lumpy demand from infrequent, large orders. Manufacturers who build to stock must carry large safety stocks to meet the lumpy demand. As part of the project engineering process, however, project engineers and implementers (e.g. installers) typically have developed information about material requirements well in advance of placement of orders. We analyze the inventory reduction that could be achieved if the installer were to communicate advance demand information (ADI) to the manufacturer. We look at it in particular when the bid is placed. We focus on the following characteristics of available ADI in project environments: First, ADI information is uncertain, because decisions on installer and manufacturer selection have not yet been finalized. Second, information is detailed, available at the item level. We show that ADI is particularly valuable when potential demand for large projects is irregular and when proposals for potential projects have a high probability of leading to orders. 相似文献
Summary: A novel method for the tailoring of unique three‐phase crystalline systems in isotactic poly(propylene) has been proven. It is based on a synergistic application of a specific β‐nucleating agent and high pressure during crystallization. The formation of a γ phase was supported by elevated pressure and high temperature during crystallization; under these conditions the growth of both β and α phases was significantly suppressed. Nevertheless, during the course of crystallization at lower pressure and/or lower temperatures, strong β‐nucleation efficiency favored the formation of a β phase.
It is reported on the measuring of the synchronic mechanoluminescent (ML) and acoustical emission (AE). The source of both ML and AE was the mechanical deformation of organic glass, of steel and copper plates. The results confirmed the connection between MA and AE stimulated by the same deformation source. 相似文献