Chemical-Shift Perturbations Reflect Bile Acid Binding to Norovirus Coat Protein: Recognition Comes in Different Flavors

Bile acids have been reported as important cofactors promoting human and murine norovirus (NoV) infections in cell culture. The underlying mechanisms are not resolved. Through the use of chemical shift perturbation (CSP) NMR experiments, we identified a low-affinity bile acid binding site of a human GII.4 NoV strain. Long-timescale MD simulations reveal the formation of a ligand-accessible binding pocket of flexible shape, allowing the formation of stable viral coat protein–bile acid complexes in agreement with experimental CSP data. CSP NMR experiments also show that this mode of bile acid binding has a minor influence on the binding of histo-blood group antigens and vice versa. STD NMR experiments probing the binding of bile acids to virus-like particles of seven different strains suggest that low-affinity bile acid binding is a common feature of human NoV and should therefore be important for understanding the role of bile acids as cofactors in NoV infection.     

Ionic liquid-based deep eutectic solvents as novel solvent-cum-catalyst media for thermal dehydrogenation of chemical hydrides

The current work explores the usage of novel synthesized Deep Eutectic Solvent (DES) as a catalyst cum solvent media for the thermal dehydrogenation of chemical hydrides, namely Ammonia Borane (AB) and Ethylene diamine bisborane (EDAB). In the first instance, the quantum chemistry based COSMO-SAC (COnductor like Screening MOdel Segment Activity Coefficient) model was used for the selection of the pertinent solvent. 1-Butyl-3-methylimidazolium methanesulfonate: Imidazole ([BMIM][MeSO₃]:[Im]) turned out to be an ideal eutectic mixture with the highest predicted solubility with amine boranes. The DES was synthesized by combining the Hydrogen Bond Acceptor (HBA), namely 1-Butyl-3-methylimidazolium methanesulfonate and Imidazole as Hydrogen Bond Donor (HBD) at a molar ratio of 1:2 and T = 70 °C. The formation of DES was confirmed by recording the NMR spectra. Further, the thermal dehydrogenation study was performed at a vacuum of 4 × 10^?2 mbar (gauge pressure) of AB/DES and EDAB/DES systems at 105 °C, where a hydrogen equivalent of 1.40 and 2.55 was produced, respectively. The residual samples were further analyzed through ¹H NMR analysis for the reaction mechanism and to confirm the role of Ionic Liquid-based DES as catalyst cum solvent media.     

Magnetic Resonance Signal Amplification by Reversible Exchange of Selective PyFALGEA Oligopeptide Ligands Towards Epidermal Growth Factor Receptors

The biorelevant PyFALGEA oligopeptide ligand, which is selective towards the epidermal growth factor receptor (EGFR), has been successfully employed as a substrate in magnetic resonance signal amplification by reversible exchange (SABRE) experiments. It is demonstrated that PyFALGEA and the iridium catalyst IMes form a PyFALGEA:IMes molecular complex. The interaction between PyFALGEA:IMes and H₂ results in a ternary SABRE complex. Selective 1D EXSY experiments reveal that this complex is labile, which is an essential condition for successful hyperpolarization by SABRE. Polarization transfer from parahydrogen to PyFALGEA is observed leading to significant enhancement of the ¹H NMR signals of PyFALGEA. Different iridium catalysts and peptides are inspected to discuss the influence of their molecular structures on the efficiency of hyperpolarization. It is observed that PyFALGEA oligopeptide hyperpolarization is more efficient when an iridium catalyst with a sterically less demanding NHC ligand system such as IMesBn is employed. Experiments with shorter analogues of PyFALGEA, that is, PyLGEA and PyEA, show that the bulky phenylalanine from the PyFALGEA oligopeptide causes steric hindrance in the SABRE complex, which hampers hyperpolarization with IMes. Finally, a single-scan ¹H NMR SABRE experiment of PyFALGEA with IMesBn revealed a unique pattern of NMR lines in the hydride region, which can be treated as a fingerprint of this important oligopeptide.     

碳酸盐岩岩溶储层多井评价方法及地质应用

多井评价是建立在单井精细解释对比分析基础上的预测储层及含油气性平面分布规律的技术方法,而常规测井资料无法区分碳酸盐岩岩溶储层,因而利用多井评价结果确定岩溶发育程度在平面上的分布规律就显得十分重要。为此,在岩心标定成像测井的基础上,对四川盆地高石梯—磨溪地区15口井的成像测井岩溶发育特征进行分析,建立了中二叠统茅口组岩溶发育各分带的标准成像图版,利用交会图及直方图分析各分带的常规测井响应特征,在此基础上形成了电成像测井刻度常规测井识别岩溶发育带的新方法。研究结果表明:①高石梯—磨溪地区茅口组岩溶带自上而下可划分为风化壳残积带、垂直渗流岩溶带、水平潜流岩溶带以及受岩溶作用较弱的基岩;②风化壳残积带在成像测井图像显示为"暗—亮—暗"条带状模式,垂直渗流岩溶带为垂直线状与暗色斑状组合模式,水平潜流岩溶带为水平线状—层状与斑状组合模式,基岩整体显示为亮色块状模式偶见线状或斑状特征;③有效储层主要发育在垂直渗流带和水平潜流带的顶部;④该区茅口组岩溶发育主要受裂缝发育控制,而裂缝发育又与断层关系密切。结论认为,该新方法对碳酸盐岩岩溶储层的多井评价具有普遍适用性,为四川盆地中二叠统风险探井的部署提供了技术支撑。     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Random poly(ε‐caprolactone‐L‐alanine) by direct melt copolymerization

A series of random polyesteramides (PEAs) with a range of molar composition from 90/10 to 50/50 were synthesized by direct melt polycondensation of ε‐caprolactone and l ‐alanine. Their structure was fully characterized by Fourier transform IR and NMR spectroscopy. The resulting copolymers are completely amorphous with the exception of PEA‐90/10 which possesses a semicrystalline structure. These PEAs present increasing glass transition temperatures at increasing l ‐alanine contents and exhibit fairly good thermal stability with 10% mass loss temperatures reaching 315 °C. © 2020 Society of Industrial Chemistry     

Proton-Detected Solid-State NMR of the Cell-Free Synthesized α-Helical Transmembrane Protein NS4B from Hepatitis C Virus

Proton-detected 100 kHz magic-angle-spinning (MAS) solid-state NMR is an emerging analysis method for proteins with only hundreds of microgram quantities, and thus allows structural investigation of eukaryotic membrane proteins. This is the case for the cell-free synthesized hepatitis C virus (HCV) nonstructural membrane protein 4B (NS4B). We demonstrate NS4B sample optimization using fast reconstitution schemes that enable lipid-environment screening directly by NMR. 2D spectra and relaxation properties guide the choice of the best sample preparation to record 2D ¹H-detected ¹H,¹⁵N and 3D ¹H,¹³C,¹⁵N correlation experiments with linewidths and sensitivity suitable to initiate sequential assignments. Amino-acid-selectively labeled NS4B can be readily obtained using cell-free synthesis, opening the door to combinatorial labeling approaches which should enable structural studies.     

测井资料在优选压裂层位中的应用

压裂是低孔、低渗油层改造的主要增产措施。根据常规测井资料、岩石物理实验分析数据及试油成果。研究储层四性关系，确定区块的低孔、低渗储层评价标准。进一步对油层进行分类，有针对性地为油层压裂提供施工层位和准确的储层参数。通过商543区块实例，阐述了选择压裂层位的方法。     

泥页岩井壁稳定研究及在临盘地区的应用

从岩石力学和物理化学两个主要因素简要分析了井壁失稳的机理，指出泥页岩井壁失稳是由力学与化学两方面因素共同作用的结果。钻井液与泥页岩存在化学势差，并改变了井壁附近的孔隙压力，降低岩石强度。借助于井壁处有效应力的变化,将泥页岩与钻井液相互作用时页岩水化所产生的力学效应与纯力学效应结合起来，计算出任意井斜方位井眼围岩应力状态，利用测井资料求出有关岩石力学参数和Mohr Couloumb准则，计算得出防塌的临界钻井液密度。