Navier-Stokes方程五模类Lorenz方程组的动力学行为及数值仿真

本文对平面正方形区域上不可压缩的Navier-Stokes方程,进行傅立叶展开后,截断得到五模类Lorenz方程组.给出了该方程组定常解及其稳定性的讨论,证明了该方程组吸引子的存在性,并对其全局稳定性进行了分析和讨论,数值模拟了雷诺数在一定范围内变化时,类Lorenz方程组的动力学行为.     

A transition metal-free approach to a regioselective total synthesis of the natural product derivative 6-methylellipticine,a potent anticancer agent

A transition metal-free and regioselective total synthesis of 6-methylellipticine, a potent anticancer agent, was developed. This synthetic approach mainly involved two key reactions: a direct amination of multi-functional phenol via an alkylation-Smiles rearrangement protocol, and an intramolecular C–H bond arylation reaction promoted by potassium tert-butoxide. These reactions resulted in the formation of two key intermediates, diarylamine and carbazole derivative, under transition metal-free conditions. The last cyclization afforded the target product 6-methylellipticine.     

Computational studies on N-phenyl pyrrole derivatives as MmpL3 inhibitors in Mycobacterium tuberculosis

The fight against tuberculosis (TB) is a time immemorial one and the emergence of new drug resistant strains of Mycobacterium tuberculosis keeps throwing new challenges to the scientific community immersed in finding mechanisms to control this dreaded disease. Computer aided drug designing (CADD) is one of the several approaches that can assist in identifying the potent actives against Mycobacterium. In this work, a series of 109 known Mycobacterial membrane proteins large 3 (MmpL3) inhibitors were pooled and atom based 3D QSAR analysis was performed to understand the structural features essential for inhibitory activity against the MmpL3, known to be a key player in transporting substances critical for cell wall integrity of Mycobacterium. The data set employed was randomly split into training set and test set molecules. The training set of 74 molecules was used to derive CoMFA and CoMSIA models that were statistically reliable (CoMFA: q²_loo = 0.53; r²_ncv = 0.93 and CoMSIA: q²_loo = 0.60; r²_ncv = 0.93). The derived models also exhibited good external predictive ability (CoMFA: r²_pred = 0.78 and CoMSIA: r²_pred = 0.79). The results are quite encouraging and information derived from these analyses was applied to design new molecules. The designed molecule showed appreciable predicted activity values and reasonably good ADMET profile. The strategy used in designing new molecules can be pursued in the hunt for new chemical entities targeting MmpL3, expanding the existing arsenal against TB.     

Modeling double-helix carbon chains inside single-walled carbon nanotubes: Stable structures and XRD analysis

Atomic models are applied to investigate quasi-one-dimensional composites. The study presents the theoretical prediction of stable double-helix carbon chains growing inside single-walled carbon nanotubes as a function of tube radius. Meanwhile, our analysis shows that metastable structures may co-existence with the stable one, for small tubes. The classical molecular dynamics simulation shows that the regular and distorted double-helix C-chains are obtained with the tube's diameter smaller and larger than 13.32 Å, respectively. The temperature plays a minor role in the stable carbon chain structure unit it increases to 2500 K. The geometry optimization and the electronic structural analysis of the obtained optimal structure by the DFT calculation further justify our classical force field analysis. The electronic structure of SWCNTs can be significantly modified by the inserted carbon chain. The orbital hybridization between the host-guest molecules plays a key role in stabilizing the encapsulated double-helix carbon chain. Finally, X-ray powder diffraction (XRD) patterns of stable helical structures inside armchair tubes are presented for guidance of future experimental analyses.     

基于氨基苯甲酰肼衍生物的铬离子荧光探针的合成及性能研究

以对氨基苯甲酸为母体通过系列化学衍生引入丹磺酰胺荧光基团及2-羟基-1-萘醛配位基团构筑了新型、简单的铬离子荧光探针L(1-(二甲基氨基)-5-(4-((2-羟基-1-萘亚甲基)甲酰肼基)苯基)萘磺酰胺)。运用核磁、质谱、元素分析和红外等手段表征了其结构,并通过荧光光谱法研究了探针分子L对Cr3+的识别作用。结果表明,当激发波长为350 nm时,单纯的探针分子L在473 nm(2-羟基-1-萘醛)和514 nm(丹磺酰胺)处显示连体双峰;当向探针分子L中加入Cr3+后,2-羟基-1-萘醛作为受体与Cr3+结合,丹磺酰胺发射峰红移至540 nm,并且强度增强5倍,量子产率Φ=0.28。探针分子L的背景荧光对Cr3+的识别无任何影响,识别过程推测是由CHEF效应和PET(光诱导电子转移)共同引起的。当加入其他金属离子(Na+,K+,Li+,Ca2+,Zn2+,Mn2+,Co2+,Cu2+,Cd2+,Hg2+,Pb2+,Ag+)时,在540 nm处荧光强度未增强,表明L对Cr3+具有高度专一的选择性。通过电喷雾质谱和Job’s plot 曲线确定L和Cr3+为1∶1的配位模式,探针L对Cr3+的最低检测限可达到4.0×10-6 mol·L-1。     

Comparison and application of the experimental methods for multi-layer prediction of acoustical properties of noise control materials in standing wave-duct systems

A comparison among the existing experimental methods used for measuring and predicting acoustical properties, such as absorption ratio and transmission loss, of noise control materials was accomplished in this paper. Four methods for absorption ratio and five methods for transmission loss, which can be generalized as standing wave ratio method, two-cavity method and two-load method, were performed in a special standing wave-duct with two configurations of two- and four-microphone holders and compared with the theoretical expressions in the literature. Conclusions were drawn that the standing wave ratio method with two and four-microphones was more reliable, faster, and easier to use for measuring absorption ratio and transmission loss, respectively. The two-cavity and two- load methods, which may be used to predict acoustical properties of an exceedingly thick sample or a multi-layered treatment consisting of variant materials, have different conditions of using limits. The two-cavity method, especially, can be easily conducted and is suitable for the materials with properties of symmetry and reciprocity. The two-load method, however, is more cumbersome to apply, due to the fact of its complex calibration and measurement procedure. Furthermore, some prediction examples for a set of multi-layered treatments of materials were executed by a newly proposed approach, so-called experimental hybrid multi-layer prediction. In view of applications, the works done in this paper may be directly applied in standing wave-duct systems or other noise control configurations to measure, predict and/or optimize their in situ designs.     

Electrochemical functionalization of multi-walled carbon nanotubes for solvation and purification

The chemical modification of multi-walled carbon nanotubes using electrolysis is described. It is found that the evolution of the halogens chlorine or bromine on an anode made from a foil of carbon nanotubes couples halogen atoms to the nanotube lattice. Furthermore, oxygen bearing functional groups, such as hydroxyl and carboxyl groups, are formed at the same time aiding solvation of the nanotubes in water or alcohol without any surfactant. Impurities and low grade modified nanotubes remain insoluble. The halogenated carbon nanotubes can be converted with sodium amide or triphenylmethyllithium to add the corresponding functional groups.     

关于Hamltion线图的一个结果

设Ｇ是一个简单图，(?)ｅ∈Ｅ（Ｇ），定义ｅ＝ｕｖ在Ｇ中的度ｄ（ｅ）＝ｄ（ｕ）＋ｄ（ｖ），其中ｄ（ｕ）和ｄ（ｖ）分别为ｕ和ｖ的度数。若连通图Ｇ的每个桥都有一个端点度数为１，则称Ｇ是几乎无桥的图。本文的主要结果是：设Ｇ是ｐ≥２阶几乎无桥的简单连通图，且Ｇ≠Ｋ_{１，ｐ－１}若对任何无公共顶点的两边ｅ₀及ｅ₁，ｄ（ｅ₀）＋ｄ（ｅ₁）≥ｐ＋４，则Ｇ有一个Ｄ－闭迹，从而Ｇ的线图Ｌ（Ｇ）是哈密顿的。     

Direct amination of isobutylene over zeolite catalysts with various topologies and acidities

The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore(MRP) to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter(larger than 0.5 nm or with large side pockets/cups in the outside surface) and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%(46.42% of the equilibrium conversion) under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al_2 ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity(isobutylene conversion) had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.     

杂原子介孔Ce-MCM-41分子筛的制备及其吸附脱除甲硫醚性能

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯(TEOS)为硅源,硝酸铈为铈源,采用水热法合成了杂原子介孔分子筛Ce-MCM-41。XRD和FT-IR表征结果表明,当加入的Ce/Si物质的量比小于0.04时合成了规整有序的介孔结构,并将Ce原子引入到MCM-41骨架中。N₂吸附-脱附测试获得MCM-41和Ce-MCM-41(Ce/Si物质的量比为0.04)的平均孔径分别为2.82和2.46 nm,孔容分别为0.762 1和 0.689 4 m³/g,BET比表面积分别为986.42和756.8 m²/g。NH₃-TPD表征结果表明,Ce-MCM-41的酸性要明显强于MCM-41,但两种分子筛的酸性均较弱。利用合成的MCM-41和Ce-MCM-41吸附脱除甲硫醚浓度为58 μg(甲硫醚)/g的甲硫醚/氮气混合气中的甲硫醚。甲硫醚分子尺寸的模拟结果为0.464 8 nm,可以很容易地进入分子筛的介孔孔道中。由于Ce-MCM-41分子筛具有较多的酸量,其硫吸附容量7.52 mg(S)/g明显高于MCM-41的4.57 mg(S)/g。MCM-41和Ce-MCM-41都具有较好的再生性能,再生3次后硫吸附容量仍可恢复到初始容量的80%,分别为3.52和 5.86 mg(S)/g。