Crystal Structure and Photoluminescence of a New Cadmium Complex with 6,7-Dicyanodipyridoquinoxalin

The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reaction gives rise to a coordination polymer [CdCl2(DICNQ)]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1: a = 6.756(1), b = 35.371(6), c = 7.027(1) , V = 1679.1(5) 3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm3, μ = 1.630 mm-1, F(000) = 904, S = 1.005 and T = 293(2) K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I > 2σ(I), and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states (DOS) calculations.     

N，N′-二甲基-N，N′-二辛基-3-氧戊二酰胺从盐酸介质中萃取三价镧系金属的研究

以煤油/辛醇(7:3,V/V)为稀释剂,研究N,N′-二甲基-N,N′-二辛基-3-氧戊二酰胺(DMDODGA)从盐酸介质中萃取三价镧系金属的性能及反应机理;考察了水相盐酸浓度、萃取剂浓度及温度对其萃取性能的影响。结果表明分配比在所研究酸度范围内随盐酸浓度的增加先增大后减小;随萃取剂浓度的增加而增大;萃合物的组成为MCl3.2DMDODGA(M=Sm,Gd,Dy)或MCl3.DMDODGA(M=Er,Lu)。萃取过程为放热反应,升高温度不利于萃取。同时计算出了萃取反应的平衡常数及热力学函数。萃合物的红外光谱表明羰基氧、醚氧均与镧系离子配位。     

杂硼原子簇XB6+ (X=C,Si, Ge,Sn, Pb)的稳定性和芳香性

利用从头算MP2方法和密度泛函理论B3LYP和B3PW91方法, 研究了杂硼原子簇XB₆⁺ (X=C, Si, Ge, Sn, Pb)的结构、稳定性及化学键合情况. 对C, Si, Ge, B使用6-311+G(d)基组, 对Sn和Pb使用LANL2DZ赝势基组. 研究结果表明, 具有C_s对称性的假平面XB₆⁺ (X=C, Si, Ge, Sn, Pb)结构是势能面上的全域极小点, 其稳定性要高于C_6v对称性的锥形结构和C₂对称性的假锥形结构. 在B3LYP水平上, 对这些异构体的势能面的极小点进行了自然键轨道(NBO)的分析; 对最稳定构型的最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差、分子轨道(MO)和核独立化学位移(NICS)进行了计算和讨论. 分析了杂原子和硼原子间、相邻硼原子间的键合情况, 讨论了最稳定构型的芳香性质.     

离子色谱法测定化肥中六种阴离子

提出了离子色谱法同时测定化肥中6种无机阴离子的方法。化肥试样经水超声浸取,采用C18固相萃取柱和Ba固相萃取柱净化,萃取液中氟离子、氯离子、亚硝酸根、溴离子、碘离子、硫氰酸根以IonPac AS18(250 mm×4 mm)为分析柱、IonPac AG18(50 mm×4 mm)为保护柱,氢氧化钾溶液梯度洗脱分离并用电导检测器同时测定了6种阴离子的含量。6种阴离子的检出限(3S/N)在0.001 2~0.013 5 mg.L-1之间。方法的加标回收率在78.9%~103.0%之间,相对标准偏差(n=6)在0.61%~6.5%之间。     

Three Zinc(Ⅱ) Complexes Based on 2-Carboxylic Acid-4-nitropyridine-1-oxide: Synthesis,Crystal Structure,and Fluorescence Properties

Three new metal-organic complexes, namely [Zn(POA)2(H2O)2](1), [Zn(POA)2(H2O)2]·2H2O(2) and [Zn(POA)2]n(3), have been synthesized by organic ligand 2-carboxylic acid-4-nitropyridine-1-oxide(POA) and zinc(Ⅱ) ions. The structures of complexes 1~3 are characterized by single-crystal X-ray analysis, XRD powder diffraction analysis, infrared spectroscopy and thermal stability analysis method. Complex 1 belongs to monoclinic system, space group C2/c with a = 22.8215(15), b = 7.5613(16), c = 10.048(3) ?, β = 109.47°, V = 1634.7(6) ?~3, Z = 4, F(000) = 944, Dc = 1.900 g/cm^3, C(12)H(10)N4O(12)Zn, Mr = 467.61 and μ = 1.584 mm^-1. The whole molecule presents "V" shape. Complex 2 is a centrosymmetric structure in triclinic system with space group P1: a = 7.4728(5), b = 7.6825(6), c = 8.5184(6) ?, α = 65.975(2), β = 79.87(2), γ = 89.855(2)°, V = 4384.1(5) ?~3, Z = 1, F(000) = 256, Dc = 1.908 g/cm^3, C(12)H(14)N4O(14)Zn, Mr = 503.64 and μ = 1.492 mm^-1. Complex 3 is a one-dimensional chain structure belonging to monoclinic system and space group P21/c with a = 4.9456(6), b = 12.5322(14), c = 11.2514(13) ?, β = 97.313(11)°, V = 6916.8(14) ?~3, Z = 2, F(000) = 432, Dc = 2.072 g/cm^3, C(12)H6N4O(10)Zn, Mr = 431.58, and μ = 1.852 mm^-1. In three complexes, six oxygen atoms from the surrounding coordination atoms form a ZnO6 distorted octahedral coordination geometry around the zinc ions. Meanwhile, fluorescent properties of the three complexes were investigated at room temperature. The fluorescence spectroscopic analysis demonstrated that the ligand POA shows red-shift after coordinating with the zinc(Ⅱ) ions.     

核壳硅碳复合微球固定相的制备及其在糖类分离中的应用

采用一步法在二氧化硅(SiO₂)表面涂覆酚醛树脂聚合物(PF),并在氮气气氛下碳化,制备了核壳硅碳复合微球(Sil@MC)固定相。实验对Sil@MC固定相进行形貌观察和孔结构分析,表明制备出的Sil@MC固定相具有良好的单分散性,包覆后的Sil@MC材料比表面积为302 m²/g,平均孔径为9.5 nm,孔容为0.63 cm³/g,说明通过共聚反应成功地将碳材料固定在二氧化硅上。将制备的Sil@MC材料作为HPLC固定相,采用匀浆法装柱,以乙腈-水(含0.1%(v/v)甲酸)作为流动相,发现Sil@MC色谱柱在高效液相色谱-质谱中可以实现4种极性糖类化合物(D-(+)-氨基葡萄糖盐酸盐、葡萄糖、D-(+)-海藻糖二水合物和棉子糖)的分离,然而未涂覆酚醛树脂的SiO₂材料未能对这4种极性糖类化合物实现分离。实验进一步对Sil@MC固定相的性能进行了评价,代表性的低聚糖异构体松三糖和棉子糖、耐斯糖和水苏糖及乳寡糖异构体3'-唾液酸乳糖和6'-唾液酸乳糖、乳-N-四糖和乳-N-新四糖在Sil@MC色谱柱中被成功分离,峰形良好,展现了基于酚醛树脂衍生碳的核壳硅碳复合材料在在极性化合物色谱分离方面具有应用潜力。     

微波消解-电感耦合等离子体质谱法同时检测大米中的6种重金属元素

采用微波消解技术,建立了电感耦合等离子体质谱法同时测定大米中Pb,Cd,As,Tl,Cr和V6种重金属元素的方法。完善了样品前处理条件,优化了仪器工作参数,并选取115In,209Bi和45Sc作为内标元素,有效地克服了基体效应和仪器波动的影响。在最优的实验条件下,方法的检出限为0.067~27.5ng/L,测定元素的标准曲线相关系数均大于0.999。方法经国家一级植物标准物质验证,结果与推荐值相符。     

CYP2C9酶与Warfarin结合模型的立体选择性理论研究

对CYP2C9酶与S-Warfarin复合物的晶体结构进行分子对接、分子动力学模拟、通道分析及结合自由能计算,发现原晶体结构中的结合模式为"亚稳态",提出了CYP2C9与S-Warfarin结合的可催化模式;比较了CYP2C9与S-和R-Warfarin结合的异同,确定了在结合过程中起重要作用的锚定氨基酸残基,尤其是位于活性位点区域的苯丙氨酸簇.在结合过程中这些残基通过芳香环的移动对稳定底物的结合模式起到至关重要的作用,阐明了该酶呈现相关底物选择性的原因.对于CYP2C9与底物对接模式及立体选择性的研究有助于在分子层面上理解特异性底物与酶的结合特点,为潜在的药物设计提供了合理可信的理论依据.     

Study of In Situ Formation of Magnesium Hydroxide Whisker via Basic Magnesium Chloride Whisker Regulated by Organic Parcels at Low Temperature

In this work, we demonstrate an in situ phase conversion from basic magnesium chloride（BMC） into magnesium hydroxide whisker by using polar organic solvent at low temperature. The morphology and phase composition of magnesium hydroxide whiskers prepared at different reaction temperature, alkali concentration and organic solvent were analyzed by X-ray diffraction（XRD） and scanning electronic microscope（SEM）. It was found that when one of the organic solvents such as absolute ethyl alcohol, butanol, polyethylene glycol（PEG-400）, acetone, et al. was selected as the template, the precursor BMC can transform into whisker-like magnesium hydroxide through precipitate transformation in low temperature and non-hydrothermal system. It can be reasonably explained that the regulation of Mg^2＋ solubility by those organic solvents and the sustained release of Mg^2＋ dissolution by organic adsorption played a significant role in the formation of magnesium hydroxide whisker via BMC whisker as the precursor.     

Vulcanization kinetics of graphene/styrene butadiene rubber nanocomposites

This paper presents the influence of graphene on the vulcanization kinetics of styrene butadiene rubber （SBR） with dicumyl peroxide. A curemeter and a differential scanning calorimeter were used to investigate the cure kinetics, from which the kinetic parameters and apparent activation energy were obtained. It turns out that with increasing graphene loading, the induction period of the vulcanization process of SBR is remarkably reduced at low graphene loading and then levels off; on the other hand, the optimum cure time shows a monotonous decrease. As a result, the vulcanization rate is suppressed at first and then accelerated, and the corresponding activation energy increases slightly at first and then decreases. Upon adding graphene, the crosslinking density of the nanocomposites increases, because graphene takes part in the vulcanization process.