Anharmonic vibrational spectroscopy and investigation of intramolecular mode couplings in adenine

Vibrational frequencies for the nucleobase adenine are calculated by the vibrational self-consistent field (VSCF) and correlation corrected vibrational self-consistent field (CC-VSCF) methods using Hartree-Fock (HF), density functional theory (DFT) and second order Møller-Plesset (MP2) theories. A large number of potential energy surface (PES) points were computed in the anharmonic calculations corresponding to each method. The quartic force field (QFF) approximation was used to generate the full grid of points for the VSCF solver. We have implemented our new procedure for computing the mode-mode coupling integrals in the 2-mode coupling representations of the quartic force field (2MR-QFF) for prediction of coupling magnitudes. Calculations were performed using the 6-31G(d,p) basis set. Comparison of the calculated ab initio anharmonic spectra with Ar matrix experimental data of adenine reported in the literature reveals that, the CC-VSCF (DFT) wavenumbers show the best agreement. The experimental geometric parameters of adenine are compared with the theoretically optimized molecular structural parameters. These are found to be in good agreement. Vibrational assignments are based on the calculated potential energy distribution (PED) values.     

The dimensionality of chromatographic separations

The box-counting or capacity dimension algorithm, known from the fractal mathematics literature, is used to measure the dimensionality D of chromatographic separation techniques for any number of dimensions. It is shown that D has limit properties that match Giddings' sample dimensionality s. D values are shown to be sensitive to the uniformity of peak spacing. A number of examples are given where D is calculated for various limits in one- and two-dimensional separations and for heart-cutting separations. The use of D as a quantitative measure of multidimensional orthogonality is suggested as D, due to the scale-free nature, is not dependent on the effective separation area. The connection to statistical peak overlap theory is discussed.     

H+CH3D→H2+CH2D反应的十维量子动力学研究

本文采用最近发展的十维含时波包方法研究了H+CH₃D→H₂+CH₂D反应的模式选择性,计算了反应物CH₃D在基态、CH₃对称和不对称伸缩振动激发态、CD伸缩振动激发态以及CH₃弯曲模式的基频和倍频激发态等6个初始状态下的反应几率. 计算结果表明,在碰撞能0.0∽1.0 eV区间内,激发CH₃的任意一种伸缩振动模都能增强反应活性,而CD伸缩振动激发对反应的促进作用不明显. CH₃弯曲振动模的基频激发对促进反应活性几乎没有影响,由于CH₃对称伸缩振动模的基频与CH₃弯曲振动模倍频之间的费米共振作用,CH₃弯曲振动模的倍频激发显著增强了反应活性.     

光纤端面衍射场光束参数及其测量

基于非傍轴标量光束的传播理论和横截面上光强的精确描述,分析了光纤端面衍射场光束特征参数的解析表达式,并与傍轴近似条件下的结论进行了比较.证明了傍轴近似对于弱导光纤的合理性,但是随着光纤相对折射率差Δ增大,傍轴近似由于忽略了衍射角度,远场发散角角半径和M2因子比考虑衍射角度时偏小.最后提出了一种可行的实验测量光束参数的方法,这种方法没有忽略衍射角度影响,从理论上说,比傍轴近似更为客观可靠.     

利用辐射场诊断模式成分的病态特性

 根据辐射场测量并确定已知尺寸和工作频率的波导内可能存在的模式(即模式诊断)是一个电磁逆问题。针对该逆问题,利用电磁分析软件计算过模圆波导馈电圆锥喇叭天线的远区辐射场,通过比较多种模式以不同比例组合馈电产生的总辐射场之间的差异,研究模式诊断逆问题的病态程度。结果表明该逆问题病态严重,模式成分比例变化很大,但某些位置上辐射场变化较小甚至没有区别,即辐射场对各模式比例变化不敏感。如果在这些位置上测量则很难判断出各模式的成分,只有通过增加信息量才能缓解病态的严重程度,得到较准确的结果。通过分析,给出了对各模式组合比例变化敏感的测量位置。     

Axion detection with negatively coupled cavity arrays

Using eigenmode analysis and full 3D FEM modelling, we demonstrate that a closed cavity built of an array of elementary harmonic oscillators with negative mutual couplings exhibits a dispersion curve with lower order modes corresponding to higher frequencies. Such cavity arrays may help to achieve large mode volumes for boosting sensitivity of the axion searches, where the mode volume for the composed array scales proportional to the number of elements, but the frequency remains constant. The negatively coupled cavity array is demonstrated with magnetically coupling coils, where the sign of next-neighbour coupling (controlled with their chirality) sets the dispersion curve properties of the resonator array medium. Furthermore, we show that similar effects can be achieved using only positively coupled cavities of different frequencies assembled in periodic cells. This principle is demonstrated for the multi-post re-entrant system, which can be realised with an array of straight metallic rods organised in chiral structures.     

单轴各向异性异向介质平板波导中的导模特性

 推导了介电常数张量和磁导率张量中各分量带有不同符号的单轴各向异性异向介质平板波导的导行条件。根据分量符号的正负组合,分情况讨论了导行TE波的偶模特性,画出了平板波导中为实横波数时的布里渊图。结果表明,在特定条件下此平板波导中有无穷多导模,这与传统介质波导及各向同性异向介质平板中只有有限数量模式存在有很大不同。此外,还发现当分量参数满足一定条件时,出现了多个虚横波数的传输模式解,并且该模式存在高频截止。     

Targeted Synthesis of Anthranilic Diamides Insecticides Containing Trifluoroethoxyl Phenylpyrazole

Aseries of novel anthranilic diamides analogues(9a-9t) containing trifluoroethoxyl pyrazole moiety was designed and synthesized and their insecticidal bioactivities against Mythimna separata(Walker, M. separata) and Plutellaxylostella (P. xylostella) were evaluated. The structures of the title compounds were confirmed by ¹H NMR, ¹³C NMR and HRMS. Preliminary insecticidal activities showed that some of the title compounds possessed good to excellent bioactivities towards M. separata and P. xylostella. Compounds 9c and 9t exhibited 100% mortality rate against M. separate at 0.2 mg/L. For the P. xylostella, the synthesized compounds(9c-9e, 9i and 9o) showed 70%, 80%, 75%, 65% and 60% insecticidal activities at 1×10^-6 mg/L, respectively, higher than that of chlorantraniliprole(0). Based on excellent insecticidal activities, the mode of the action was tested by the calcium-imaging technique, the results of which demonstrated that the novel compounds shared the same target with chlorantraniliprole. The binding pose of the most active compound 9t in RyRs of P. xylostella was predicted by molecular docking, which showed that compound 9t interacted with the residues Glu140(A) and His147(A) via hydrogen bond.     

Deciphering the Biological Activities of Antifungal Agents with Chemical Probes

The growing number of fungal infections caused by pathogens resistant to one or more classes of antifungal drugs emphasizes the threat that these microorganisms pose to animal and human health and global food security. Open questions remain regarding the mechanisms of action of the limited repertoire of antifungal agents, making it challenging to rationally develop more efficacious therapeutics. In recent years, the use of chemical biology approaches has resolved some of these questions and has provided new promising concepts to guide the design of antifungal agents. By focusing on examples from studies carried out in recent years, this minireview describes the key roles that probes based on antifungal agents and their derivatives have played in uncovering details about their activities, in detecting resistance, and in characterizing the interactions between these agents and their targets.