极长与极短的铜铜距离-吡唑环三核亚铜配合物亲铜作用本质及发光调控

本文结合近年来亲金属作用研究领域的进展,针对本课题组在环三核亚铜配合物方面的最新研究成果,讨论了两个铜(I)–铜(I)作用相差悬殊的体系。一是通过构筑具有环三核单元的三棱柱笼状配合物,确认在正堆积模式下即使环三核单元之间亲铜作用极弱依然可以在磷光发射态中产生强亲铜作用,且通过配体的预留配位点与Cu_2I_2簇连结从而得到自校准大范围发光温度计;二是通过与亲铜作用正交的Br―Br卤键,实现环三核亚铜配合物前所未有的极短铜(I)–铜(I)距离,通过各种电子结构分析方法研究其本质。结果表明即使当铜(I)–铜(I)距离很接近铜的范德华半径和时,其本质依然为闭壳层作用,而Br―Br作用总为闭壳层作用,且该体系中最强的Br―Br作用很好地体现出一个Br原子的σ穴和另一个Br原子的负静电势区域的匹配性。     

Free volume,molecular grains,self-organisation,and anisotropic entropy: machining materials

ABSTRACT

In this article, the relationship between molecular architecture and the formation of twist-bend phases is reviewed under the context of shape dependency. We conclude that the twist-bend phase is a universal phenomenon, which occurs in a wide variety of materials, for dimers through to main chain polymers. In the process, the chemical information on molecular design is effectively lost or irrelevant, and molecular topology takes precedence over electrostatic interactions in mesophase formation. As a consequence of this macro-scale material, engineering by shape alone becomes a possibility, potentially more phases may be realised, and entropy is anisotropic.     

GC-MS/MS法对焙烤食品及其塑料包装材料中25种磷酸三酯类与邻苯二甲酸酯类化合物的同时测定

建立了气相色谱-质谱/质谱(GC-MS/MS)测定焙烤食品及其塑料包装材料中25种磷酸三酯类及邻苯二甲酸酯类化合物的高通量检测方法。焙烤食品以乙腈-丙酮(8∶2,体积比)超声提取,采用50 mg C18和50 mg PSA混合填料进行Qu ECh ERS净化;塑料包装材料经二氯甲烷-甲醇超声提取后直接检测。样液经DB-5 ms色谱柱分离,选择反应监测(SRM)模式测定。25种化合物在各自线性范围内的相关系数不小于0.997 5,方法检出限为10~500μg/kg,平均回收率为80.2%~119.6%,相对标准偏差(n=6)为1.5%~9.4%。该方法操作简单,净化效果好,可有效消除基质效应,适用于不同焙烤食品及其塑料包装材料中磷酸三酯类及邻苯二甲酸酯类化合物的同时测定。     

Measurement of dense plasma temperature of the shock-compressed silicon

Measurements of the brightness temperature and compressibility of a dense silicon plasma formed by powerful shock waves (SWs) passing through a single-crystal sample have been carried out. Plane SWs were created using an explosive technique: the traditional plane acceleration of a steel driver plate made it possible to obtain pressures in silicon up to 133 GPa, and the use of “Mach” cumulative generators realized the pressures up to 510 GPa. The shock Hugoniot of silicon was determined by the impedance matching with α-quartz as the reference. The intensity of emitted thermal radiation was measured in the infrared range λ ∼ 1.5 μm, where silicon is optically transparent, and in the visible range of the spectrum. A significant (up to five times) understatement of the measured values of the brightness temperature in comparison with the values calculated by the equation of state was found. Taking into account the reflective properties of the SW in silicon does not lead to an agreement with the experiment. The estimates of relaxation processes behind the shock front suggest the presence of a zone of the establishment of ionization equilibrium with a width of ∼10 μm.     

Co‐ and Counterion Effect on the Micellization Characteristics of Dodecylpyridinium Chloride

Micellization parameters, critical micelle concentration (cmc), degree of counterion dissociation (α), aggregation number (n), critical packing parameter, and hydrophobic core volume of Dodecylpyridinium chloride (DPC) micelles were determined in presence of varying concentrations of sodium chloride (NaCl), sodium acetate (SAc), sodium propionate (SPr), ethylammonium chloride (EACl), diethylammonium chloride (DEACl), tetraethylammonium chloride (TEACl), and propylammonium chloride (PACl) through conductometric investigations at 298.15 K. The resulting data suggests that both counter and coions affect the cmc values‐cmc depressing tendency of the salts varies in order PACl≈NaCl>EACl>DEACl>TEACl>SPr>SAc, while the degree of counterion dissociation is dependent on the nature and concentration range of the added salt. Increasing salt concentration increases the relative hydrophobic volume of the micelles and coion has not much effect on aggregation number.     

Linear and Cyclic Hybrids of Alternating Thiophene–Amino Acid Units: Synthesis and Effects of Chirality on Conformation and Molecular Packing

The dipeptide isostere 5‐aminothiophene carboxylic acid has been combined with L ‐phenylalanine moieties to provide linear and cyclic hybrid oligopeptides. A suitable protecting group strategy and appropriate coupling methods have been developed to guarantee a high degree of enantiopurity of the resulting amides. Cyclic tetraamides have been efficiently obtained by macrocyclization of the linear derivatives. In the case of racemized cyclization precursors, two diastereomeric macrocycles (S,S/R,R and meso) have been isolated. Their crystal structures show clear effects of the stereogenic centers on the ring conformations and molecular packing.     

颗粒有序堆积多孔介质对流换热实验研究

本文采用"瞬态单吹反问题研究方法"对颗粒有序堆积多孔介质内的强制对流换热进行了实验研究。详细研究了颗粒堆积方式变化对多孔介质内对流换热的影响,并对均匀与非均匀颗粒堆积多孔介质内的对流换热特性进行了对比分析。研究表明:通过对颗粒进行合理有序堆积,可以使相应多孔介质内的压降显著降低,其综合换热效率明显提高;通过拟合获得了颗粒有序堆积多孔介质内的宏观流动换热实验关联式,其形式与传统经验公式(Ergun公式和Wakao公式)一致,但部分模型参数值远低于传统经验公式。     

快速床动力学统一模型Ⅱ:上部稀相与下部浓相固含率的预报

在前文建立的分相共存快速床动力学模型的基础上,对分相模型中存在颗粒团聚物时的上升稀相进行了受力分析。以有限直径提升管中颗粒终端速度的修正,导出了上升稀相受力关于等效管径与浓稀相滑移速度的修正表达式。将本模型预报的上部稀相固含率与已有的实验数据经验关联式进行了对比,并根据所得结果初步优化了模型参数(k=8,n=6)。进而,根据所得模型参数计算了下部浓相固含率随曳力函数f(ε)的变化规律;与李佑楚经验关联式相比,同样具有合理的一致性。本文工作进一步验证了快速床动力学统一模型的整体合理性。     

112 Gbit/s信号混传多种速率信号的非线性效应影响

主要研究在波长间隔50GHz的密集波分复用系统中,112Gbit/s偏分复用差分四相移键控信号在不同速率的相邻信道影响下经过长距离传输后的非线性容忍度。实验结果表明,112Gbit/s信号结合43Gbit/s信号或者10Gbit/s信号传输时系统得到较好的非线性容忍度,验证了在严重的非线性效应存在的情况下同步传输系统的可行性。