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.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

The single-polarization filter composed of gold-coated photonic crystal fiber

A single-polarization filter comprising a gold-coated photonic crystal fiber based on surface plasmon resonance is designed and investigated. The pattern matching and coupled polarization characteristics analyzed by the full-vector finite element method (FEM) and losses at 1,540 nm are achieved to 1,016.01739 dB/cm (x-pol core mode) and 33.81917 dB/cm (y-pol core mode). The crosstalk (CT) value of the 1,540 nm band is ?853.12653 dB for fiber length $L=1,000\mathrm{\mu }\text{m}$ and the bandwidth is 850 nm. The working wavelength of the filter ranges from 1,280 nm to 1,540 nm by varying the diameter of outer air holes ($d_1$), the diameter of inner air holes ($d_4$), the metal film thickness (t), as well as the liquid refractive index (n).     

Synthesis and characterization of indium and thallium immobilized on isonicotinamide‐functionalized mesoporous MCM‐41: Two novel and highly active heterogeneous catalysts for selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides

Two highly ordered isonicotinamide (INA)‐functionalized mesoporous MCM‐41 materials supporting indium and thallium (MCM‐41‐INA‐In and MCM‐41‐INA‐Tl) have been developed using a covalent grafting method. A surface functionalization method has been applied to prepare Cl‐modified mesoporous MCM‐41 material. Condensation of this Cl‐functionalized MCM‐41 with INA leads to the formation of MCM‐41‐INA. The reaction of MCM‐41‐INA with In(NO₃)₃ or Tl(NO₃)₃ leads to the formation of MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts. The resulting materials were characterized using various techniques. These MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts show excellent catalytic performance in the selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides. Finally, it is found that the anchored indium and thallium do not leach out from the surface of the mesoporous catalysts during reaction and the catalysts can be reused for seven repeat reaction runs without considerable loss of catalytic performance.     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Path integral quantization corresponding to the deformed Heisenberg algebra

In this paper, the deformation of the Heisenberg algebra, consistent with both the generalized uncertainty principle and doubly special relativity, has been analyzed. It has been observed that, though this algebra can give rise to fractional derivative terms in the corresponding quantum mechanical Hamiltonian, a formal meaning can be given to them by using the theory of harmonic extensions of function. Depending on this argument, the expression of the propagator of the path integral corresponding to the deformed Heisenberg algebra, has been obtained. In particular, the consistent expression of the one dimensional free particle propagator has been evaluated explicitly. With this propagator in hand, it has been shown that, even in free particle case, normal generalized uncertainty principle and doubly special relativity show very much different result.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

高雷诺数下非混相Rayleigh-Taylor不稳定性的格子Boltzmann方法模拟

本文采用相场格子Boltzmann方法研究了竖直微通道内中等Atwoods数流体的单模Rayleigh-Taylor不稳定性问题,系统分析了雷诺数对相界面动力学行为以及扰动在各发展阶段演化规律的影响.数值结果表明高雷诺数条件下,不稳定性界面扰动的增长经历了四个不同的发展阶段,包括线性增长阶段、饱和速度阶段、重加速阶段及混沌混合阶段.在线性增长阶段,我们计算获得的气泡与尖钉振幅符合线性稳定性理论,并且线性增长率随着雷诺数的增加而增大.在第二个阶段,我们观察到气泡与尖钉将以恒定的速度增长,获得的尖钉饱和速度略高于Goncharov经典势能模型的解析解[Phys.Rev.Lett.200288134502],这归因于系统中产生了多个尺度的旋涡,而涡之间的相互作用促进了尖钉的增长.随着横向速度和纵向速度的差异扩大,气泡和尖钉界面演化诱导产生的Kelvin–Helmholtz不稳定性逐渐增强,从而流体混合区域出现许多不同层次的涡结构,加速了气泡与尖钉振幅的演化速度,并在演化后期阶段,导致界面发生多层次卷起、剧烈变形、混沌破裂等行为,最终形成了非常复杂的拓扑结构.此外,我们还统计了演化后期气泡与尖钉的无量纲加速度,发现气泡和尖钉的振幅在后期呈现二次增长规律,其增长率系数分别为0.045与0.233.而在低雷诺条件下,重流体在不稳定性后期以尖钉的形式向下运动而轻流体以气泡的形式向上升起.在整个演化过程中,界面变得足够光滑,气泡与尖钉在后期的演化速度接近于常数,未观察到后期的重加速与混沌混合阶段.     

Positive ground state solutions for Schrödinger–Poisson system with critical nonlocal term in ℝ3

This paper is dedicated to studying the following Schrödinger–Poisson system $$\left\{\begin{array}{ll}-\mathrm{\Delta }u+V(x)u-K(x)\varphi |u{|}^{3}u=a(x)f(u),& x\in {ℝ}^3,\\ -\mathrm{\Delta }\varphi =K(x)|u{|}^5,& x\in {ℝ}^3.\end{array}\right.$$ Under some different assumptions on functions V(x), K(x), a(x) and f(u), by using the variational approach, we establish the existence of positive ground state solutions.