Phase Separation in Methylsiloxane Sol-Gel Systems in a Small Confined Space

The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels.     

Kinetic model of induced codeposition of Ni-Mo alloys

The kinetic model of induced codeposition of nickel-molybdenum alloys from ammoniun citrate solution was studied on rotating disk electrodes to predict the behavior of the electrode-position. The molybdate (MoO42-) could be firstly electro-chemically reduced to MoO2, and subsequently undergoes a chemical reduction with atomic hydrogen previously adsorbed on the inducing metal nickel to form molybdenum in alloys. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The electrochemical rate constants for discharge of nickel, molybdenum and water could been expressed as k1(E) = 1. 23 × 109 CNi exp( - 0.198FE/RT) mol/(dm2·s), k2(E) =3.28× 10-10 CMoexp( - 0. 208FE/ RT) mol/(dm2·s) and k3(E) = 1.27 × 10-6exp( - 0.062FE/ RT) mol/(dm2 · s), where CNi and CMo are the concentrations of the nickel ion and molybdate, respectively, and E is the applied potential vs. saturated calomel electrode (SCE). The codeposition p     

环氧氯丙烷作重原子微扰剂在环糊精诱导室温磷光法中的应用

本文报道一种新型的重原子微扰剂－环氧氯丙烷（ＥＣＨ）,在此重原子微扰下,建立了β－环糊精诱导室温磷光法（β－ＣＤ－ＲＴＰ）测定痕量溴代萘（ＢｒＮ）的方法,结果令人满意。同时还在该体系中测定了溴代萘的ＤＴＰ寿命、猝灭常数、三元包合物的包接常数。实验结果证明,α－ＢｒＮ／ＥＣＨ／β－ＣＤ三分子包接配合物比β－ＢｒＨ／ＥＣＨ／β－ＣＤ三分子包接络合物包接更加有效,而且稳定性更强。     

治疗骨骼疾病药物阿屈酸的电喷雾质谱研究

阿屈酸的极性很强且热稳定性很差，因此不适合用电子轰击质谱来研究，该文研究了它的正离子和负离子电喷雾质谱的行为，结果表明阿屈酸既可作负离子电喷雾质谱分析，也可作正离子电喷雾质谱分析，且正离子电喷雾质谱分析的灵敏度高于负离子；电喷雾源内碰撞诱导解离分析时正离子和负离子的裂解方式相似，但不完全相同，且正离子有明显的[M Na]^ 峰和[M H]^ 及[M Na]^ 与M的非共价键簇离子峰，这对确定类似未知物的相对分子质量有很大的帮助。     

Influence of Atomistic Protrusion on the Substrate on Molecular Luminescence in Tunnel Junctions

Scanning tunneling microscope (STM) induced luminescence can be used to study various optoelectronic phenomena of single molecules and to understand the fundamental photophysical mechanisms involved. To clearly observe the molecule-specific luminescence, it is important to improve the quantum efficiency of molecules in the metallic nanocavity. In this work, we investigate theoretically the influence of an atomic-scale protrusion on the substrate on the emission properties of a point dipole oriented parallel to the substrate in a silver plasmonic nanocavity by electromagnetic simulations. We find that an atomic-scale protrusion on the substrate can strongly enhance the quantum efficiency of a horizontal dipole emitter, similar to the situation with a protrusion at the tip apex. We also consider a double-protrusion junction geometry in which there is an atomic-scale protrusion on both the tip and the substrate, and find that this geometry does provide significantly enhanced emission compared with the protrusion-free situation, but does not appear to improve the quantum efficiency compared to the mono-protrusion situation either at the tip apex or on the substrate. These results are believed to be instructive for future STM induced electroluminescence and photoluminescence studies on single molecules.     

Computational design of rasagiline derivatives: Searching for enhanced antioxidant capability

A set of new rasagiline derivatives is presented. They were designed to be antioxidant compounds with the potential to be used for treating neurodegenerative disorders. They are expected to be multifunctional molecules that can help reduce oxidative stress, which is thought to contribute to neurodegenerative disorders. The CADMA-Chem computational protocol was used to produce rasagiline derivatives and to evaluate their likeliness as oral drugs and antioxidants. Three of them were identified as the most promising ones. They are proposed to be better free radical scavengers than rasagiline. In addition, they are expected to keep the parent's molecule neuroprotective capability. Hopefully, the results presented here would promote further experimental and theoretical investigations on these compounds.     

Biocatalytic process intensification via efficient biocatalyst immobilization,miniaturization, and process integration

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非典型发光化合物的簇聚诱导发光

不含大共轭结构的非典型发光化合物因其理论研究的重要性和潜在应用前景引起研究者的广泛关注。非典型发光化合物的结构通常含有N、O、S、P等杂原子,C≡N、C=O、C=C等不饱和单元,及相应的组合功能团(如羟基、胺基、酯基、酐、酰胺、脲基、肟基、砜基等)。近年来,尽管这一领域正快速发展,其发光机理仍存争议。前期,我们提出了簇聚诱导发光(CTE)机理,即含π电子和/或孤对(n)电子的非典型生色团的簇聚及其带来的空间共轭使体系离域扩展,构象刚硬化;同时,其他分子内/间相互作用也有利于簇生色团的刚硬化,从而易于受激发射。基于CTE机理,本文综述了非典型发光化合物的发光特性,包括浓度增强发光、聚集诱导发光(AIE)、激发波长依赖性及磷光发射。CTE机理可合理解释天然产物、合成化合物、生物分子等不同体系的光物理行为,并可用来指导发现和设计新的非典型发光化合物。本文总结了上述不同体系的发展,并对未来研究进行了展望。     

Photochemical synthesis: Using light to build C–C bonds under mild conditions

A review of recent advancements in metal-free arylations via photogenerated triplet aryl cations and decatungstate anion ([W₁₀O₃₂]⁴⁻) photocatalyzed C–C bond formation is reported herein. These approaches are two examples of the great potentialities of photons as green activants in organic synthesis, allowing the functionalization of different chemical substrates under mild conditions (room temperature, aqueous solvents, absence of aggressive and unstable reactants and of expensive transition metal-based catalysts, and chance to use solar light as the energy source).     

小麦粉衍生中孔氮掺杂颗粒炭负载金催化剂用于乙炔氢氯化反应（英文）

聚氯乙烯是五大工程塑料之一,在国民经济中占有重要的地位.基于中国富煤少油缺气的能源格局,我国主要采用基于煤化工的电石法氯乙烯生产工艺,但该工艺必须采用氯化汞催化剂,受到国际限汞公约的影响,无汞催化剂的开发迫在眉睫.其中炭负载金催化剂在该反应中活性最高,近几年来取得了较大进展,有望实现产业化.氮掺杂的炭材料在诸多反应中展现了较好的性能,其负载金属催化剂可以有效提高金属的分散度及稳定性,成为近几年多相催化领域的一个研究热点.最近我们课题组报道了一种氮掺杂中孔成型的制备方法:以小麦粉为原料,通过直接炭化法制备了氮掺杂中孔成型炭,这种氮掺杂中孔成型炭作为无汞催化剂在乙炔氢氯化反应中显示出了优异的催化性能.小麦粉衍生的氮掺杂中孔成型炭具有成型容易.原料价廉易得、易于放大生产等优点,是优选的工业化催化剂的载体.本文以这种氮掺杂的成型炭为载体制备了负载型金催化剂,研究其催化乙炔氢氯化性能.结果表明,氮的掺杂使得中孔炭负载金(Au/N-MC)催化剂上乙炔氢氯化活性明显提高.在氯化氢/乙炔比例1.1、反应温度180℃、乙炔空速600 h~(-1)的条件下,Au/N-MC上的乙炔转化率为50%,是Au/MC催化剂活性的2倍.通过对催化剂的表征发现,氮的掺杂能有效地锚定Au/N-MC催化剂中活性组分Au~(3+),抑制催化剂制备过程中Au~(3+)还原为Au~0,从而提高催化剂活性和稳定性.小麦粉衍生的氮掺杂中孔炭的原料廉价易得,生产工艺简单,易成型,也容易实现工业化生产,是负载型金属催化剂的优良载体,其负载的无汞催化剂性能优越,有望取代电石法氯乙烯产业的汞催化剂,成为新一代无汞催化剂.