Towards carbohydrate derivatives of the ReI(CO)3 fragment

With the [Re(CO)(3)Br(3)](2-) ion as a precursor for the Re(I)(CO)(3) fragment, the diols (1R,2R)-cyclohexane-1,2-diol [(1R,2R)-Chxd], anhydroerythritol (AnEryt), and (1S,2S)-cyclopentane-1,2-diol [(1S,2S)-Cptd] form dinuclear monoanions in the salts (NBu(4))[(Re(2)(CO)(6){mu-(1R,2R)-ChxdH(-1)}(3)] (1), [K([18]crown-6)][Re(2)(CO)(6)(mu-OMe)(2)(mu-AnErytH(-1))] (2) and (NBu(4))[Re(2)(CO)(6){mu-(1S,2S)-CptdH(-1)}(3)] (3). The monoanionic diolato ligands in these triply bridged dirhenates(I) are monodentate. Bridging triolato ligation in the trirhenates(I) is supported by the anions of glycerol (Glyc) and methyl beta-D-ribopyranoside (Me-beta-D-Ribp), the latter binding in its (1)C(4) conformation, in (DBUH)(2)[Re(3)(CO)(9)(mu(3)-O)(mu(3)-GlycH(-3))]0.5 MeCN (4 a), (NEt(4))[Re(3)(CO)(9)(mu(3)-OMe)(mu(3)-GlycH(-3))] (4 b) and (DBUH)[Re(3)(CO)(9)(mu(3)-OMe)(mu(3)-(1)C(4)-Me-beta-D-Ribp2,3,4H(-3))] (5). The chiral sugar alcohols L-threitol (L-Thre) and D-arabitol (D-Arab) act as tetra- and pentadentate ligands, respectively, in (NEt(4))[Re(2)(CO)(6)(L-ThreH(-3))]MeCN (6) and (NEt(4))(2)(DBUH)(2)[Re(6)(CO)(18)(D-ArabH(-5))(2)] (7). Complexes 6 and 7 are free of supporting oxo or methoxo ligands and use solely the O-atom pattern of the polyol for the connection of the Re(I)(CO)(3) moieties.     

Labeling the planar face of crystalline cellulose using quantum dots directed by type-I carbohydrate-binding modules

We report a new method for the direct labeling and visualization of crystalline cellulose using quantum dots (QDs) directed by carbohydrate-binding modules (CBMs). Two type-I (surface binding) CBMs belonging to families 2 and 3a were cloned and expressed with dual histidine tags at the N- and C-termini. Semiconductor (CdSe)ZnS QDs were used to label these CBMs following their binding to Valonia cellulose crystals. Using this approach, we demonstrated that QDs are linearly arrayed on cellulose, which implies that these CBMs specifically bind to a planar face of cellulose. Direct imaging has further shown that different sizes (colors) of QDs can be used to label CBMs bound to cellulose. Furthermore, the binding density of QDs arrayed on cellulose was modified predictably by selecting from various combinations of CBMs and QDs of known dimensions. This approach should be useful for labeling and imaging cellulose-containing materials precisely at the molecular scale, thereby supporting studies of the molecular mechanisms of lignocellulose conversion for biofuels production.     

聚合物流动诱导结晶研究进展

在外力作用下,半结晶聚合物的结晶形态、结晶动力学等与静态条件下相比,均发生了较大的变化,并继而影响到成型制品的性能.自上世纪六十年代人们从溶液中发现外力诱导结晶现象以来,相继开展了大量相关的理论和实验研究,提出了一些模型,随着测试手段的改进,流动诱导结晶研究取得了较大的进展,但仍存在许多争议.本文回顾了围绕聚合物流动诱导结晶所开展的工作,重点综述了流动诱导结晶形态变化、分子量及其分布、剪切速率、温度等因素对聚合物结晶动力学的影响,并指出了今后的研究方向.     

飞秒激光作用下的硅表面微结构及发光特性

 采用近红外飞秒激光辐照浸泡在硫酸溶液中的N型单晶硅片,激光波长800 nm,脉宽200 fs,重频1 kHz,平均功率为100 mW,而硫酸溶液的质量分数分别选择为0.1%和1%。辐照后硅表面呈直径为5~8 mm,高度15 mm的柱型结构。分析其荧光特性,并通过比较硅材料表面微结构与激光光源、扫描参数、硅片背景环境的关系,确定最佳辐照条件为激光扫描速度750 mm/s,扫描间距5 mm/s。最终在厚度0.5 mm、直径26 mm的硅片上获得10 mm×10 mm的方形扫描区域,荧光光谱显示激光扫描后的区域在700 nm附近有很强的荧光发射。分析结果表明飞秒激光扫描改变了样品的表面微结构尺寸,增大了吸收面积,扩展了荧光激发波长,有效提高了样品的吸收效率和荧光发光相对强度(超过扫描前发光相对强度的2倍),荧光发射谱的变化是由量子限制效应和表面态模型共同作用的结果。     

Triplet Generation Through Singlet Fission in Metal-Organic Framework: An Alternative Route to Inefficient Singlet-Triplet Intersystem Crossing

High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet-triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy-coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin-orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution-stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super-exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (k_ISC) but form triplets in MOF in contrast to the frameworks that are built from linkers with sizable k_ISC but . This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.     

Reply to the Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

White et al., in a recent Correspondence, provided additional structural data to illustrate that CPOS-6 undergoes a single-crystal-to-single-crystal transformation during water adsorption/desorption. This finding gave a better understanding of the relevant experimental phenomena from the perspective of structural transformation and is a good complement to our previous results. However, we wish to emphasize that our research focuses on the kinetic behavior of water during ultrafast adsorption/desorption in nano-confined channels. Herein, we further interpret the rapid transport of water molecules in the nano-confined channels from the perspective of superfluidity.     

Controllable One-Step Assembly of Uniform Liquid Crystalline Block Copolymer Cylindrical Micelles by a Tailored Nucleation-Growth Process and Their Application as Tougheners

The fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one-step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation-growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length-dependent toughening effect.