3-甲基-4-对甲基苯基-5-(2-吡啶)-1,2,4-三唑桥联的双核铜配合物的磁性理论研究

采用对称性破损态方法结合密度泛函理论,选用反铁磁双核配合物[Cu2(MMBPT)2Cl4(H2O)2.5](MMBPT=3-甲基-4-对甲基苯基-5-(2-吡啶)-1,2,4-三唑)作为研究对象,通过与实验数据相比较,探讨了不同密度泛函方法与基组对计算铜配合物交换耦合常数的准确度.结果表明,4种混合密度泛函DFT(B3LYP,B3P86,B3PW91和PBE0)的计算结果都能和实验所观察到的值-31cm-1符号一致,但只有B3PW91方法得到的结果和实验结果吻合程度最好,同时采用方法B3PW91方法计算所得的交换耦合常数Jab对基组的依赖性较大.研究表明,2个Cu(Ⅱ)离子之间弱的反铁磁相互作用主要源于单占据分子轨道SOMOs小的能量劈裂.     

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Different ratios of methane/air in the low power arc discharges assisted methane combustion were studied at atmospheric pressure. Plasma emission spectroscopy was recorded by an optical emission spectrometer. The possible physical and chemical reaction process and mechanisms were discussed. With a plasma in the on or off state, the physical appearances of the methane combustion flame were observed and compared, the temperature of the flame in the main combustion zone was investigated. The gas compositions of CH₄, CO and O₂ were analyzed by the gas chromatography and flue gas analyzer. The results showed that when plasma was in the on state, the temperature of flame increased and the combustion efficiency enhanced in stable combustion due to decrease of CH₄, CO and O₂; the combustion enhancement was more obvious at low ratio of methane/air; the rich combustion limits in terms of the ratio of methane/air was extended from 16% to 21%.     

基于B样条的TERS形貌成像背景扣除方法

在针尖增强拉曼光谱(TERS)形貌成像过程中，由于针尖与扫描台无法绝对平行、样品电子密度骤变处针尖快速升降以及扫描控制系统响应时间特性差等综合原因的影响，往往使形貌图中带有倾斜或边界面卷曲的成像背景。成像背景对样品形貌的识别和分析带来十分不利的影响，而背景扣除就是解决该问题的重要手段，也是形貌成像预处理的重要组成部分。背景扣除的原理一般是通过拟合背景的方法来扣除成像中的背景。传统的背景扣除方法是利用多项式拟合的方法对成像进行逐行的基线校正，但是该方法在处理形貌成像时常常会由于过拟合而造成样品形貌的失真，同时容易在图片上留下明显的线条纹理。针对传统方法的缺点，本文提出采用B样条曲面拟合方法，直接对样品形貌图进行曲面背景拟合，发挥B样条低阶光滑的优点，能够有效克服传统方法的缺陷。在实验中，同时利用传统方法和该方法对金单晶和合成金片的形貌图进行背景扣除，实验结果表明，两种方法都能够扣除样品形貌图中的成像背景，但与传统方法相比，所提出的方法不会造成样品形貌的失真，且不会留下线条纹理，获得了更加良好的背景扣除效果，为进一步分析样品形貌特征提供了更准确可靠的信息，是一种更加有效的TERS形貌成像背景扣除算法。     

鲍曼不动杆菌LpxC的同源模建及分子对接

鲍曼不动杆菌已成为最普遍的医院致病菌,且耐药情况严峻.LpxC作为新抗菌药物靶点被大量研究,但鲍曼不动杆菌LpxC晶体尚未解析得到,基于其结构的药物设计等工作无法开展.以铜绿假单胞菌LpxC晶体结构为模板,通过同源模建方法获得鲍曼不动杆菌LpxC结构模型.较好的Ramachandran plot分布和Profile-3D结果验证了模型的合理性.用分子动力学模拟优化鲍曼不动杆菌LpxC模型,修补部分不合理构象.后续分子对接结果显示S构型的苄氧乙酰基羟肟酸类抑制剂比R构型分子能更有效地结合在F191,H237和K238组成的较浅口袋中,这可能是S构型抑制剂活性更高的主要因素,模拟结果与实验数据吻合较好.     

Evaluating a four-directional benzene-centered aliphatic polyamine curing agent for epoxy resins

A four-directional benzene-centered aliphatic polyamine, MXBDP, with high functionality and low volatility, is used to cure epoxy resin (DGEBA). Herein we originally report the isothermal cure kinetics and dynamic mechanical properties of DGEBA/MXBDP. Differential scanning calorimetry confirms that MXDBP is more reactive than commercial linear metaxylenediamine and branched Jeffamine T-403 and the isothermal curing reaction is autocatalytic. The Kamal model is found to be able to well describe the curing rate up to the onset of diffusion control, and the excellent match over the whole conversion range is achieved using the extended Kamal model. Interestingly, the isoconversional kinetic analysis indicates that the effective reaction activation energy (E _α ) changes substantially with conversion, and ultimately decreases to a very small value (<10 kJ mol^?1) because of the diffusion-controlled reaction kinetics. Then, dynamic mechanical analysis reveals that DGEBA/MXBDP exhibits the higher α- and β-relaxation temperatures and the much higher crosslink density than DGEBA/metaxylenediamine. Our experiment results support that MXBDP has the high reactivity and improved thermal resistance in combination with the advantages of the high functionality, low volatility and decreased CO₂ absorption. Therefore, MXBDP may be especially suitable for room temperature-cure epoxy coatings and adhesives.     

1,2-Dihydroparatocarpin A的全合成

以对羟基苯甲醛和2,4-二羟基苯乙酮为起始原料,经C-异戊烯基化、保护酚羟基、羟醛缩合、DDQ环化及对甲基苯磺酸催化环化等反应,首次完成了天然异戊烯基查尔酮衍生物1,2-Dihydroparatocarpin A的全合成,总收率21.8%。化合物的结构经1H NMR,IR和MS确认。     

Raney Ni催化二亚糠基丙酮加氢制取长链烷烃前驱体的特性研究

采用Raney Ni为催化剂,考察了反应温度、压力、时间和溶剂对二亚糠基丙酮加氢制取长链烷烃前驱体催化性能的影响。结果表明,Raney Ni对二亚糠基丙酮具有很好的低温加氢性能,升高反应温度和压力均有利于加氢反应的进行,但过高的温度反而不利于加氢反应。在50℃和2.5 MPa下反应2 h,二亚糠基丙酮转化率达99.5%以上,饱和加氢产物的总选择性达到80.8%。此外,加氢中间产物的变化结果表明,二亚糠基丙酮的双键加氢容易程度为,烯键>呋喃环双键>C=O双键。Raney Ni 在甲醇溶剂中的加氢性能明显高于在四氢呋喃、环己烷或水溶剂中的加氢性能。     

Synthesis, Structure and Properties of a Novel Cobalt(Ⅱ) Bromide Complex Supported by Phosphine Ligands

<正>The C-Br bond of 2-bromothiophene was successfully cleavaged by tetrakis(trimethylphosphine)cobalt(0). Penta-coordinate cobalt(II) bromide complex 1 (α-C_4H_3S)CoBr(PMe_3)_3 as C-Br bond activation product was obtained. The molecular and crystal structures of complex 1 were determined by single-crystal X-ray diffraction. Complex 1 belongs to the orthorhombic crystal system, space group Pnma with a = 20.428(4) , b =11.036(2) , c = 9.201(2), V = 2074.3(7)~3, Z = 4, D_c = 1.442 g/cm~3, μ = 0.401 mm~(-1), F(000) = 924 and T = 273 K. Complex 1 was also characterized by elemental analysis, IR, UV-Vis, photoluminescence (PL) spectroscopy and TGA.     

氢键准则在DMSO水溶液中应用的评价

利用分子动力学模拟方法, 分别采用几何准则和能量准则分析了不同浓度下的二甲基亚砜(DMSO)水溶液的氢键统计和动力学等特性. 结果显示, 两种氢键准则可以很好地反映出溶液的氢键性质随浓度的变化趋势. 通过分析比较发现, 由于几何准则不能有效地排除具有弱对势能的分子对, 因此其统计的氢键数量要大于能量准则的结果.此外, 能量准则对于分子间相对取向的区分存在不足, 进而引起氢键寿命的计算结果偏大.因此,为使氢键分析更加准确, 本文建议使用几何-能量混合型氢键准则.