13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?

Metal–organic frameworks (MOFs) are a class of important porous materials with many current and potential applications. Their applications almost always involve the interaction between host framework and guest species. Therefore, understanding of host–guest interaction in MOF systems is fundamentally important. Solid-state NMR spectroscopy is an excellent technique for investigating host–guest interaction as it provides information complementary to that obtained from X-ray diffraction. In this work, using MOF α-Mg₃(HCOO)₆ as an example, we demonstrated that ¹³C chemical shift tensor of organic linker can be utilized to probe the host–guest interaction in MOFs. Obtaining ¹³C chemical shift tensor components (δ₁₁, δ₂₂, and δ₃₃, where δ₁₁ ≥ δ₂₂ ≥ δ₃₃) in this MOF is particularly challenging as there are six coordinatively equivalent but crystallographically non-equivalent carbons in the unit cell with very similar local coordination environment. Two-dimensional magic-angle-turning experiments were employed to measure the ¹³C chemical shift tensors of each individual crystallographically non-equivalent carbon in three microporous α-Mg₃(HCOO)₆ samples with different guest species. The results indicate that the δ₂₂ component (with its direction approximately being co-planar with the formate anion and perpendicular to the C−H bond) is more sensitive to the adsorbate molecules inside the MOF channel due to the weak C−H···O hydrogen bonding or the ring current effect of benzene. The ¹³C isotropic chemical shift, on the other hand, seems much less sensitive to the subtle changes in the local environment around formate linker induced by adsorption. The approach described in this study may be used in future studies on host–guest interaction within MOFs.     

The 1H and 13C NMR chemical shifts of Strychnos alkaloids revisited at the DFT level

The density functional theory calculation of ¹H and ¹³C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated ¹H and ¹³C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases.     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Computational and dynamic NMR investigation of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane

The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by ¹H- and ¹³C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C₂ symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a C_s transition state with a calculated relative free energy of 11.0 kcal mol⁻¹. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol⁻¹ at 298 K.     

Calculating nuclear magnetic resonance chemical shifts in solvated systems

The nuclear magnetic resonance (NMR) chemical shift is extremely sensitive to molecular geometry, hydrogen bonding, solvent, temperature, pH, and concentration. Calculated magnetic shielding constants, converted to chemical shifts, can be valuable aids in NMR peak assignment and can also give detailed information about molecular geometry and intermolecular effects. Calculating chemical shifts in solution is complicated by the need to include solvent effects and conformational averaging. Here, we review the current state of NMR chemical shift calculations in solution, beginning with an introduction to the theory of calculating magnetic shielding in general, then covering methods for inclusion of solvent effects and conformational averaging, and finally discussing examples of applications using calculated chemical shifts to gain detailed structural information.     

间二甲苯分子在不同外电场下结构和解离特性研究

间二甲苯是挥发性有机物(VOCs, Volatile Organic Compounds)的关键活性成分,研究其在外电场下的性质十分重要.采用密度泛函理论(DFT),在B3LYP/6-311G++基组水平上对间二甲苯分子进行优化,从分子结构研究了不同外电场(-0.025 a.u.～0.025 a.u.)作用下,间二甲苯分子的总能量,键长,电偶极矩,前线轨道,红外光谱和解离势能面.计算结果表明,沿两甲基中C原子连线方向的电场(-0.025 a.u.～0.025 a.u.)增加时,分子总能量和能隙先增大后减小,电偶极矩先减小后增加.通过计算发现外电场对间二甲苯分子不同键长和不同振动模式的红外光谱的影响均有所不同.间二甲苯分子的解离特性表现为:沿两甲基中C原子连线方向施加强度超过0.047 a. u.的电场时,位于电场增加方向的甲基与苯环之间起连接作用的C-C键断裂.以上计算结果可为利用电场降解间二甲苯提供重要理论参考.     

Dynamics of scalar fields in an expanding/contracting cosmos at finite temperature

This study extends the investigation of quantum dissipative effects of a cosmological scalar field by taking into account cosmic expansion and contraction.Cheung,Drewes,Kang,and Kim calculated the effective action and quantum dissipative effects of a cosmological scalar field in a recent work,where analytical expressions for the effective potential and damping coefficient were presented using a simple scalar model with quartic interactions,and the work was conducted using Minkowski-space propagators in loop diagrams.In this work,we incorporate the Hubble expansion and contraction of the cosmic background and focus on the thermal dynamics of a scalar field in a regime where the effective potential changes slowly.Given that the Hubble parameter,H,attains a small but non-zero value,we carry out calculations to the first order in H.If we set H=0,all results match those in flat spacetime.Interestingly,we must integrate over the resonances,which in turn leads to an amplification of the effects of a non-zero H.This is an intriguing phenomenon,which cannot be uncovered in flat spacetime.The implications on particle creations in the early universe will be studied in a forthcoming study.     

压气机悬臂静叶流场非定常数值模拟

以现代高压压气机一排悬臂静叶与一排转叶组成的典型级为研究对象,采用非定常数值模拟方法,分析了非定常与定常数值模拟计算得出的级特性线以及峰值效率点气动参数在展向分布的差异,并对悬臂静叶内部流场结构进行了详细分析,结果表明:当悬臂静叶的轮毂设计间隙为2.5%叶高时,非定常计算的综合喘振裕度比定常大5.85%;在峰值效率点工况下,悬臂静叶总压损失和转子效率的非定常影响范围在10%以内,转叶进口相对气流角沿展向分布的影响在0.5°以内。悬臂静叶根部10%叶高以下区域出现了明显的泄漏流动,3.4%叶高压力系数变化最大,轮毂泄漏流起始于20%弦长附近,发展到70%弦长位置时泄漏损失最大,随后逐渐减弱.     

Complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities

We theoretically study complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities. We investigate quantum dynamics of micro-micro and micro-macro entanglement in the micro-macro system. It is found that strong micro-macro entanglement between Rydberg impurities and the BEC can be generated by the use of initial micro-micro entanglement between two Rydberg impurities, which acts as the seed entanglement to create micro-macro entanglement. We demonstrate a curious complementarity relation between micro-micro and micro-macro entanglement, and find that the complementarity property can be sustained to some extent even though in the presence of the BEC decoherence.     

Analysis,design and simulation of MIM plasmonic filters with different geometries for technical parameters improvement

In this paper, four optical filter topologies based on metal–insulator–metal waveguides are proposed and the designed structures are investigated numerically using finite-difference timedomain method. Triangular-shaped adjunctions have been added to the filter structures to improve their transmission spectrum. These improved structures consist of air as the insulator and silver as the metal. The relative permittivity of metal has been described via the Drude,Drude–Lorentz, and Palik models. The first filter's transmission spectrum shows an acceptable transmittance. In the second optimized filter, the transmission spectrum has been improved. The transmittance spectrum can be tuned through adjusting the edge of the triangle in these four optimized filters. As a result, the bandwidths of resonance spectra can be adjusted. The theory of such tapered structures will be investigated by the tapered transmission line and will be solved with the transfer matrix method. This method shows a better performance and higher transmission efficiency in comparison with the basic structures. On the other hand, the final filter has been chosen as the best one because of its hexagonal resonator. The main reason for having a better result is due to a longer interaction length in comparison with the circular resonator. This in turn creates much better energy coupling and results in higher transmission.