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1.
Coupling of side chain dynamics over long distances is an important component of allostery. Methionine side chains show the largest intrinsic flexibility among methyl-containing residues but the actual degree of conformational averaging depends on the proximity and mobility of neighboring residues. The 13C NMR chemical shifts of the methyl groups of methionine residues located at long distances in the same protein show a similar scaling with respect to the values predicted from the static X-ray structure by quantum methods. This results in a good linear correlation between calculated and observed chemical shifts. The slope is protein dependent and ranges from zero for the highly flexible calmodulin to 0.7 for the much more rigid calcineurin catalytic domain. The linear correlation is indicative of a similar level of side-chain conformational averaging over long distances, and the slope of the correlation line can be interpreted as an order parameter of the global side-chain flexibility.  相似文献   
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This study observed the activities of bromelain in the presence of various cationic surfactants at different temperatures and the conformational changes in bromelain by 1H NMR spectroscopy. We found that the bromelain activity was enhanced by tens to hundreds of micromoles per liter of the surfactant. In the presence of the surfactants, bromelain exhibited good tolerance to a range of substrate temperatures and its thermal stability was also increased. The 1H NMR experiments indicated that when the temperature was increased from 25.0 to 45.0 °C, the protons of bromelain having chemical shifts (δ) between 3.7 and 5.2 ppm moved upfield, while those having δ values between 3.2 and 3.7 ppm moved downfield. In the bromelain/cationic surfactant mixture, the values of δ for the protons in both bromelain and the cationic surfactants decreased, accompanied by the broadening of the half-peak width of the surfactant protons. These results indicated that both increasing temperature and adding a cationic surfactant made the bromelain chain more flexible and hence, increased the bromelain activity. To the best of our knowledge, this was the first time that the relationship between the protein activity and the 1H NMR data was expounded.  相似文献   
4.
The interactions of amino acids and peptides at model membrane interfaces have considerable implications for biological functions, with the ability to act as chemical messengers, hormones, neurotransmitters, and even as antibiotics and anticancer agents. In this study, glycine and the short glycine peptides diglycine, triglycine, and tetraglycine are studied with regards to their interactions at the model membrane interface of Aerosol-OT (AOT) reverse micelles via 1H NMR spectroscopy, dynamic light scattering (DLS), and Langmuir trough measurements. It was found that with the exception of monomeric glycine, the peptides prefer to associate between the interface and bulk water pool of the reverse micelle. Monomeric glycine, however, resides with the N-terminus in the ordered interstitial water (stern layer) and the C-terminus located in the bulk water pool of the reverse micelle.  相似文献   
5.
Lipopolysaccharide (LPS), the major component of the outer membrane of Gram-negative bacteria, is important for bacterial viability in general and host–pathogen interactions in particular. Negative charges at its core oligosaccharide (core-OS) contribute to membrane integrity through bridging interactions with divalent cations. The molecular structure and synthesis of the core-OS have been resolved in various bacteria including the mammalian pathogen Pseudomonas aeruginosa. A few core-OS structures of plant-associated Pseudomonas strains have been solved to date, but the genetic components of the underlying biosynthesis remained unclear. We conducted a comparative genome analysis of the core-OS gene cluster in Pseudomonas syringae pv. tomato (Pst) DC3000, a widely used model pathogen in plant–microbe interactions, within the P. syringae species complex and to other plant-associated Pseudomonas strains. Our results suggest a genetic and structural conservation of the inner core-OS but variation in outer core-OS composition within the P. syringae species complex. Structural analysis of the core-OS of Pst DC3000 shows an uncommonly high phosphorylation and presence of an O-acetylated sugar. Finally, we combined the results of our genomic survey with available structure information to estimate the core-OS composition of other Pseudomonas species.  相似文献   
6.
Precision oncology is an emerging approach in cancer care. It aims at selecting the optimal therapy for the right patient by considering each patient’s unique disease and individual health status. In the last years, it has become evident that breast cancer is an extremely heterogeneous disease, and therefore, patients need to be appropriately stratified to maximize survival and quality of life. Gene-expression tools have already positively assisted clinical decision making by estimating the risk of recurrence and the potential benefit from adjuvant chemotherapy. However, these approaches need refinement to further reduce the proportion of patients potentially exposed to unnecessary chemotherapy. Nuclear magnetic resonance (NMR) metabolomics has demonstrated to be an optimal approach for cancer research and has provided significant results in BC, in particular for prognostic and stratification purposes. In this review, we give an update on the status of NMR-based metabolomic studies for the biochemical characterization and stratification of breast cancer patients using different biospecimens (breast tissue, blood serum/plasma, and urine).  相似文献   
7.
四川盆地川中地区须家河组致密砂岩气藏含水饱和度普遍较高。基于天然气地球化学分析测试数据和核磁共振高压充注模拟实验,研究了天然气运聚特征及气藏高含水机制。结果表明:①须家河组烃源岩—储层大面积交替叠置发育奠定了油气近距离聚集的基础,随烃源岩成熟度增高,天然气湿度系数变小、δ13C1值增高,为近源成藏;②须家河组气藏含气饱和度主体分布在50%~65%之间,储集空间的主要孔隙半径为0.1~10 μm,相对大孔径占比越大,含气饱和度越高;③随充注压力增大,天然气在致密砂岩中由大孔径向小孔径空间“渐进式”聚集,并呈现出快速增加、缓慢增加和基本稳定的“三段式”充注特点,小压力驱动与相对大孔隙储集的耦合是川中地区须家河组天然气可以形成大中型气藏但含水饱和度高的主要原因。研究成果将为致密砂岩领域的拓展勘探提供理论技术支撑。  相似文献   
8.
The oxidation behavior and mechanism of aluminum oxynitride (AlON) powder exposed to air at elevated temperatures between 800°C and 1300°C was investigated by X-ray diffractometry (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), nuclear magnetic resonance (NMR), and simultaneous thermogravimetry, differential thermal analysis, and mass spectrometry techniques (TG-DTA-MS). The weight of AlON gradually increases to a maximum value at 1150°C and then decreases with further heating. Meanwhile, AlON powder undergoes chemical changes, as evidenced by lattice expansion, and turns eventually into alumina. ESR spectra reveal the occurrence of lone pair electrons in the oxidized products and the intensity of corresponding resonance signal increases before disappearing with the increase in temperature. Combined with the results of NMR and TG-DTA-MS, the measured data suggest that Al-N in [AlO3N] tetrahedron and [AlO5N] octahedron are gradually oxidized into Al-O-N group with lone pair electrons, which causes continuous weight gain and lattice expansion. Further oxidation at higher temperatures results in alumina and N2.  相似文献   
9.
The substitution of coal blending with sawdust had been widely investigated for metallurgical coke production. In this paper, the physiochemical structures of the semicoke derived from sawdust/coals blends co-coking were characterized by several analytical techniques including FTIR-ATR, XPS, NMR, OM, and SEM. Meanwhile, the influence of the sawdust on the physicochemical properties of the sawdust/coals blends were also investigated. Results indicated that partial substitution of coal blending with sawdust benefited from the formation of colloid and optical anisotropy due to the positive synergetic effect, whereas high proportion of sawdust (>10 wt%) inhibited the agglomeration of semi-coke. On the other hand, the semicoke consisted primarily of aromatic carbons replaced by the oxygen linked to carbons and aliphatic carbons when the coal blending was replaced by high proportion of sawdust, causing a less polyaromatic graphite-like structure formation in the semicoke.  相似文献   
10.
王民  李明  李进步  徐亮  邵好明  余昌琦  李婷婷 《石油学报》2022,43(12):1758-1769
页岩含油率是页岩油资源评价的基本参数,但其测定方法尚无统一认识,制约了页岩油资源潜力的评估准确率。选取松辽盆地页岩油井的密闭取心页岩样品,依次开展二维核磁共振(T1T2 NMR)、有机溶剂蒸馏萃取(Dean Stark)、热解气相色谱(PY-GC)和岩石热解(Rock-Eval)4种页岩含油率测定实验。对比分析表明,T1T2 NMR法与Dean Stark法的页岩含油率测试结果相近,均高于PY-GC法,Rock-Eval法测试结果最低。样品处理方式对页岩含油率的测试结果具有重要影响,块状样品的测试含油率明显高于粉碎样品。综合分析认为,T1T2 NMR法测试页岩含油率结果的可靠性高,具有时间短、样品无损、样品非均质性影响小等特点,是分析页岩含油率的最优手段,具有良好的推广应用前景。建立了不同热演化成熟度页岩的含油率恢复系数、轻烃恢复系数及校正图版,对于湖相I型有机质页岩发育区开展页岩含油率分析具有重要参考价值。  相似文献   
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