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61.
The total interaction parameter at infinitely high polymer concentration. χt∞, and the effective exchange energy parameter, X̄12, of poly(dimethyl siloxane) with n-pentane, n-hexane, n-heptane and n-nonane were determined around room temperature using the inverse gas chromatography technique. The values of χt∞ are in agreement with corresponding literature values. The exchange enthalpy X12 and entropy, Q12, parameters were determined at the same temperature. The X12 parameters increase with the carbon number of the n-alkanes, while their temperature dependence is almost negligible. The Q12 parameters are approximately independent of temperature and carbon number of the n-alkanes. 相似文献
62.
Asghar Azizi Seid Ziaoddin Shafaei Mohammad Noaparast Mohammad Karamoozian 《Frontiers of Chemical Science and Engineering》2013,7(4):464
The role of pH, solid content, water chemistry and ore mineralogy on the galvanic interactions between chalcopyrite and pyrite and low alloy steel balls were investigated in the grinding of Sarcheshmeh porphyry copper sulfide ore. All these factors strongly affect the galvanic current between the minerals and the steel during the grinding process. The galvanic current density decreased as the solution pH and percent solids increased. In addition, changing the water in the ball mill from tap to distilled water reduced the galvanic current between the minerals and the balls. Potentiodynamic polarization curves showed that pyrite and chalcopyrite demonstrated typical active-passive-transpassive anodic behavior in the grinding of copper ore. However, the nature of their transitions from the active to the passive state differed. This behavior was not seen in the grinding of pure minerals. In addition, an EDTA extraction technique was employed to quantify the amount of oxidized iron in the mill discharge. The amount of extractable iron was influenced by the same experimental factors and in the same way as the galvanic current. 相似文献
63.
Dr. Kenichiro Ito Dr. Yoshihiko Matsuda Ayako Mine Kyohei Miyairi Dr. Yoshimi Kikuchi Dr. Atsushi Konishi 《Chembiochem : a European journal of chemical biology》2023,24(2):e202200599
The inhibition of protein-protein interactions (PPIs) is an effective approach for therapy. Owing to their large binding surface areas to target proteins, macrocyclic peptides are suitable molecules for PPI inhibition. In this study, we developed single-chain tandem macrocyclic peptides (STaMPtides) that inhibits the vascular endothelial growth factor (VEGF) receptor 2 (VEGFR2). They were artificially designed to comprise two different VEGFR2-binding macrocyclic peptides linked in tandem by peptide linkers and secreted by Corynebacterium glutamicum. Most potent VEGFR2-inhibitory STaMPtides with length-optimized linkers exhibited >1000 times stronger inhibitory activity than their parental monomeric peptides, possibly due to the avidity effect of heterodimerization. Our approach of using STaMPtides for PPI inhibition may be used to inhibit other extracellular factors, such as growth factors and cytokines. 相似文献
64.
Dr. Joshua A. Visser Dr. Deborah Yager Dr. Schuyler A. Chambers Dr. Ji Youn Lim Xujun Cao Prof. Lynette Cegelski 《Chembiochem : a European journal of chemical biology》2023,24(18):e202300266
Escherichia coli and other Enterobacteriaceae thrive in robust biofilm communities through the coproduction of curli amyloid fibers and phosphoethanolamine cellulose. Curli promote adhesion to abiotic surfaces and plant and human host tissues and are associated with pathogenesis in urinary tract infection and food-borne illness. The production of curli in the host has also been implicated in the pathogenesis of neurodegenerative diseases. We report that the natural product nordihydroguaiaretic acid (NDGA) is effective as a curlicide in E. coli. NDGA prevents CsgA polymerization in vitro in a dose-dependent manner. NDGA selectively inhibits cell-associated curli assembly and inhibits uropathogenic E. coli biofilm formation. More broadly, this work emphasizes the ability to evaluate and identify bioactive amyloid assembly inhibitors by using the powerful gene-directed amyloid biogenesis machinery in E. coli. 相似文献
65.
The less polar π‐surface of protein amide groups is exposed in many receptor binding sites, either as part of the backbone or in Gln/Asn side chains. Using quantum chemical calculations and Protein Data Bank (PDB) searches on model systems, we investigate the energetics and geometric preferences for the stacking on amide groups of a large number of heteroarenes that are relevant to medicinal chemistry. From this study, we discern that the stacking energy of an aromatic ligand substituent can be improved by: 1) orienting the fragment dipole vector such that it is aligned in an antiparallel fashion with the dipole of the interacting protein amide group, 2) increasing its dipole moment, and 3) decreasing its π‐electron density. These guidelines should be helpful to more rationally exploit this interaction type in future structure‐based drug design. 相似文献
66.
Dr. Duncan E. Scott Dr. Matthias T. Ehebauer Dr. Tara Pukala Dr. May Marsh Prof. Sir Tom L. Blundell Prof. Ashok R. Venkitaraman Prof. Chris Abell Dr. Marko Hyvönen 《Chembiochem : a European journal of chemical biology》2013,14(3):332-342
The ability to identify inhibitors of protein–protein interactions represents a major challenge in modern drug discovery and in the development of tools for chemical biology. In recent years, fragment‐based approaches have emerged as a new methodology in drug discovery; however, few examples of small molecules that are active against chemotherapeutic targets have been published. Herein, we describe the fragment‐based approach of targeting the interaction between the tumour suppressor BRCA2 and the recombination enzyme RAD51; it makes use of a screening pipeline of biophysical techniques that we expect to be more generally applicable to similar targets. Disruption of this interaction in vivo is hypothesised to give rise to cellular hypersensitivity to radiation and genotoxic drugs. We have used protein engineering to create a monomeric form of RAD51 by humanising a thermostable archaeal orthologue, RadA, and used this protein for fragment screening. The initial fragment hits were thoroughly validated biophysically by isothermal titration calorimetry (ITC) and NMR techniques and observed by X‐ray crystallography to bind in a shallow surface pocket that is occupied in the native complex by the side chain of a phenylalanine from the conserved FxxA interaction motif found in BRCA2. This represents the first report of fragments or any small molecule binding at this protein–protein interaction site. 相似文献
67.
Dr. Madina Mansurova Julian Simon Dr. Susanne Salzmann Prof. Dr. Christel M. Marian Prof. Dr. Wolfgang Gärtner 《Chembiochem : a European journal of chemical biology》2013,14(5):645-654
Two chemically synthesized flavin derivatives, 8‐trifluoromethyl‐ and 8‐bromoriboflavin (8‐CF3RF and 8‐BrRF), were photochemically characterized in H2O and studied spectroscopically after incorporation into the LOV domain of the blue light photoreceptor YtvA from Bacillus subtilis. The spectroscopic studies were paralleled by high‐level quantum chemical calculations. In solution, 8‐BrRF showed a remarkably high triplet quantum yield (0.97, parent compound riboflavin, RF: 0.6) and a small fluorescence quantum yield (0.07, RF: 0.27). For 8‐CF3RF, the triplet yield was 0.12, and the fluorescence quantum yield was 0.7. The high triplet yield of 8‐BrRF is due to the bromine heavy atom effect causing a stronger spin–orbit coupling. Theoretical calculations reveal that the decreased triplet yield of 8‐CF3RF is due to a smaller charge transfer and a less favorable energetic position of T2, required for intersystem crossing from S1 to T1, as an effect of the electron‐withdrawing CF3 group. The reconstitution of the LOV domain with the new flavins resulted in the typical LOV photochemistry, consisting of triplet state formation and covalent binding of the chromophore, followed by a thermal recovery of the parent state, albeit with different kinetics and photophysical properties. 相似文献
68.
Dr. Simeon S. Andrews Dr. Zachary B. Hill Dr. B. Gayani K. Perera Prof. Dustin J. Maly 《Chembiochem : a European journal of chemical biology》2013,14(2):209-216
Protein kinases are essential enzymes for cellular signaling, and are often regulated by participation in protein complexes. The mitogen‐activated protein kinase (MAPK) p38 is involved in multiple pathways, and its regulation depends on its interactions with other signaling proteins. However, the identification of p38‐interacting proteins is challenging. For this reason, we have developed label transfer reagents (LTRs) that allow labeling of p38 signaling complexes. These LTRs leverage the potency and selectivity of known p38 inhibitors to place a photo‐crosslinker and tag in the vicinity of p38 and its binding partners. Upon UV irradiation, proteins that are in close proximity to p38 are covalently crosslinked, and labeled proteins are detected and/or purified with an orthogonal chemical handle. Here we demonstrate that p38‐selective LTRs selectively label a diversity of p38 binding partners, including substrates, activators, and inactivators. Furthermore, these LTRs can be used in immunoprecipitations to provide low‐resolution structural information on p38‐containing complexes. 相似文献
69.
Dr. Andrew T. Krueger Prof. Dr. Barbara Imperiali 《Chembiochem : a European journal of chemical biology》2013,14(7):788-799
Fluorescence spectroscopy is a powerful tool for probing complex biological processes. The ubiquity of peptide–protein and protein–protein interactions in these processes has made them important targets for fluorescence labeling, and to allow sensitive readout of information concerning location, interactions with other biomolecules, and macromolecular dynamics. This review describes recent advances in design, properties and applications in the area of fluorescent amino acids (FlAAs). The ability to site‐selectively incorporate fluorescent amino acid building blocks into a protein or peptide of interest provides the advantage of closely retaining native function and appearance. The development of an array of fluorescent amino acids with a variety of properties, such as environment sensitivity, chelation‐enhanced fluorescence, and profluorescence, has allowed researchers to gain insights into biological processes, including protein conformational changes, binding events, enzyme activities, and protein trafficking and localization. 相似文献
70.
Application of Acoustic Emission Measurements to Investigate Adhesion in Filled Polymeric Composites
Adhesion in filled polymeric composites is characterized by an acoustic technique in which specimens of the composites are subjected to a ramped uni-axial tensile stress while particle-matrix debonding events are detected acoustically. The maximum in a fitted distribution of debonding events as a function of applied stress is related to the interfacial strength using elasticity theory. Results are reported for different silanetreated and untreated glass and aluminum spheres embedded in a poly(vinyl butyral) matrix. Silane treatment profoundly affects the adhesive strength, with the strongest bonds being formed when acid-base interactions between the particle surface and the matrix polymer are promoted. Significant differences are also found between the aluminum-particle and glass-particle cases, attributable in part to differences in mechanical interlocking. 相似文献