Toward direct determination of conformations of protein building units from multidimensional NMR experiments. V. NMR chemical shielding analysis of N-formyl-serinamide,a model for polar side-chain containing peptides

Knowledge of chemical shift-structure relationships could greatly facilitate the NMR chemical shift assignment and structure refinement processes that occur during peptide/protein structure determination via NMR spectroscopy. To determine whether such correlations exist for polar side chain containing amino acid residues the serine dipeptide model, For-L-Ser-NH(2), was studied. Using the GIAO-RHF/6-31+G(d) and GIAO-RHF/TZ2P levels of theory the NMR chemical shifts of all hydrogen ((1)H(N), (1)H(alpha), (1)H(beta1), (1)H(beta2)), carbon ((13)C(alpha), (13)C(beta), (13)C') and nitrogen ((15)N) atoms have been computed for all 44 stable conformers of For-L-Ser-NH(2). An attempt was made to establish correlation between chemical shift of each nucleus and the major conformational variables (omega(0), phi, psi, omega(1), chi,(1) and chi(2)). At both levels of theory a linear correlation can be observed between (1)H(alpha)/phi, (13)C(alpha)/phi, and (13)C(alpha)/psi. These results indicate that the backbone and side-chain structures of For-L-Ser-NH(2) have a strong influence on its chemical shifts.     

[IrBr6]2-的反对称极化率与圆偏振激光诱导的ESR谱频移

在理论上研究了顺磁性粒子体系的圆偏振激光诱导的ＥＳＲ谱频移效应。给出磁场中分子反对称极化率的公式，并以［ＩｒＢｒ６］＾２－离子为例讨论了吸收带半高宽的影响。计算了［ＩｒＢｒ６］＾２－的ＥＳＲ谱在圆偏振激光作用下的频移。结果发现：在光学共振区附近，ＥＳＲ频移可达１ＭＨｚ的量级，与钠原子体系结果类似。     

Chemical mass shifts in resonance ejection experiments in the quadrupole ion trap

Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions.     

Evaluation of the reactivity of new activated difluoroaromatic compounds

To evaluate the reactivity of new difluroroaromatic compounds in nucleophilic substitution, the positive charges on carbon atoms of C−F bonds were calculated using the quantum-chemical semiempirical PM3 method. A correlation between the charges calculated and the chemical shifts in the¹⁹F NMR spectra was established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 623–625, April, 1998.     

杨氏双缝干涉实验的光谱变化

从理论和实验上研究了当部分相干光照射在双缝上时,杨氏双缝干涉实验干涉场中的光谱变化.指出干涉场中的归一化光谱在某些空间点处出现了蓝移,在另外一些空间点处出现了红移,而在这些空间点的中间,光谱分裂为等值的两条,出现了光谱开关现象.发现当观察点从轴上向轴外移动的过程中,在很多空间观察点处都出现了光谱开关现象.此外,研究结果还表明光谱相干度将对光谱的移动和光谱开关现象产生重要的影响.     

多信道接入微谐振环波长选择开关特性

对一种新型结构微谐振环波长选择开关的特性进行了研究.分析了器件的工作状态和相应的开关操作,利用新型光强传递函数公式,对器件不同工作状态的光谱响应和不同开关操作的开关响应进行了数值模拟,讨论了耦合系数和损耗对光谱响应和开关响应的影响.结果表明,该器件可以实现三个信道同时接入、两个信道同时接入、单信道接入以及无信道接入等四种方式的信号波长选择性接入.多信道接入方式的开态串扰性能变差,关态的串扰性能不受影响.实现器件上述接入方式之间转换的开关操作可以分成三类,开关操作达到最佳关态串扰时的小微环折射率变化值都在6.0×10－3左右,而实现完全开关时的小微环折射率变化值小于8.0×10－4,表明易于通过热-光效应实现开关操作,并且温度调制的控制容差较大.损耗对器件开关特性的影响结果表明可根据损耗的实际数值,优化信道关闭时的微环折射率取值.     

New Chemotypes for the Inhibition of (p)ppGpp Synthesis in the Quest for New Antimicrobial Compounds

Antimicrobial resistance (AMR) poses a serious threat to our society from both the medical and economic point of view, while the antibiotic discovery pipeline has been dwindling over the last decades. Targeting non-essential bacterial pathways, such as those leading to antibiotic persistence, a bacterial bet-hedging strategy, will lead to new molecular entities displaying low selective pressure, thereby reducing the insurgence of AMR. Here, we describe a way to target (p)ppGpp (guanosine tetra- or penta-phosphate) signaling, a non-essential pathway involved in the formation of persisters, with a structure-based approach. A superfamily of enzymes called RSH (RelA/SpoT Homolog) regulates the intracellular levels of this alarmone. We virtually screened several fragment libraries against the (p)ppGpp synthetase domain of our RSH chosen model Rel_Seq, selected three main chemotypes, and measured their interaction with Rel_Seq by thermal shift assay and STD-NMR. Most of the tested fragments are selective for the synthetase domain, allowing us to select the aminobenzoic acid scaffold as a hit for lead development.     

氨对硅基铁纳米薄膜高温重凝核的影响

采用弧过滤离子沉积系统（arc filtered deposition,AFD）在纯硅表面制备铁纳米薄膜。研究了750℃下铁纳米薄膜在氢气氛围以及氨气氛围中重凝核的规律。研究表明,在氢气氛围中,铁纳米薄膜重凝核以后形成的铁纳米颗粒随薄膜的厚度增加以及保温时间的延长而增大;但在氨气氛围中,铁纳米薄膜重凝核后形成的纳米颗粒的尺寸随保温时间的变化更为复杂：在氨气作用的初始阶段,铁颗粒的尺寸随氨气作用时间的延长而逐渐变大,但一段时间以后,铁颗粒的尺寸又随氨气作用时间的延长而变小,直到铁颗粒平均直径达到一个最小值（大约在氨气介入后的12min）,随后铁颗粒的尺寸又逐渐变大,并最终达到一稳定值。     

类氢氖在高温高密度等离子体中的光谱漂移

 采用离子球模型,通过自洽求解Poisson方程和Dirac方程,得到氖的类氢离子低能级组态的能级能量随等离子体电子温度和电子密度的变化关系,进一步研究了等离子体电子温度和电子密度对光谱漂移的影响。结果表明：光谱漂移随着等离子体电子密度的增大而增大,随着电子温度的升高而减小;谱线精细结构分裂随着电子密度的增大而减小,随着电子温度的升高而增大。等离子体对束缚电子的屏蔽是决定光谱漂移的主要原因。这些变化规律不仅对等离子体光谱模拟结果产生影响,而且使实验上观测光谱的相对或绝对漂移成为可能,从而为高密度等离子体诊断的新方法提供了理论依据。     

4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯的合成及其NMR研究

以对硝基甲苯、3, 4-二甲氧基苯甲醛为起始原料,经过缩合,还原,重氮化水解,亲核取代反应,最终合成了新的化合物4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯,用¹H 和¹³C NMR及多种二维核磁共振谱确定了该化合物的结构,完成了¹H 和¹³C NMR的归属,给出了分子中各氢,碳原子的准确化学位移.