一种锌配合物用于炭疽生物标志物的检测

采用溶剂热合成方法,合成了一种新型金属配位聚合物{[Zn₂(L)(H₂O)(DMA)]·DMA·2.3H₂O}_n (1),其中L^4-为完全脱去质子的N,N''-二(4-羧基苄基)-5-氨基间苯二甲酸,DMA为N,N-二甲基乙酰胺。单晶X射线衍射结果显示,该配合物属于三斜晶系,空间群为P$overline{1}$,a=0.989 6(5) nm,b=1.370 5(5) nm,c=1.382 1(5) nm,α=80.067(5)°,β=76.729(5)°,γ=76.611(5)°,结构是由二维金属有机层通过π…π相互作用而扩展成的三维超分子骨架。红外光谱验证了锌离子与L^4-配体成功配位。粉末X射线衍射(PXRD)实验证实了配合物1具有较高的纯度。热重分析结果显示配合物1在室温至416.9 ℃区间内具有较好的热稳定性。在273 nm的激发光下,配合物1在437 nm处有较强的荧光发射,可以在30 s内快速检测乙醇溶液中的炭疽生物标志物——吡啶-2,6-二甲酸,具有选择性高、抗干扰能力强、检测限低(约为15 μmol·L^-1)等特点。结合PXRD图和紫外可见吸收光谱揭示了其检测机理为晶体骨架坍塌而诱导的荧光猝灭。     

The Conformation of Sterically Congested Seven-Membered Rings Containing Tetracoordinate Germanium(IV): A First X-Ray Crystallographic Structure Determination

The X-ray crystallographic analysis of 6,6-dimethyl-2,4,8,10-tetra-tert-octyl-dibenzo[d,f][1,3,2]dioxagermepin, 1 is reported. In the solid-state conformation of 1, the dihedral angle about the C─C sp²-sp ² σ bond connecting the two aryl rings is 50.1°. The observed C₂ symmetry in the solid-state conformation of 1 is consistent with the previously suggested solution conformation.     

Wavespeed analysis: Approximating Arrhenius kinetics with step-function kinetics

The accuracy of using step-function approximations to the Arrhenius exponential in computing the wavespeed in combustion wave propagation is investigated. Gaseous and gasless combustion, and first- and second-order reactions are included in the study. The theoretical analysis is based on Melnikov theory from dynamical systems. The error is shown to be small in most instances. The analytical results are supported with numerical simulations.     

Responsive core–shell microgels: Synthesis,characterization, and possible applications

Core–shell microgels are of increasing interest as smart carriers of catalysts, as sensors, or as building blocks for colloidal superstructures. In the context of colloidal assemblies, photonic applications are probably the most promising ones. This progress report presents and discusses the most recent results in this area focusing on the last 2–3 years, and also gives some background information. In addition, potential perspectives of this area will be outlined. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1073–1083     

Twin liquid crystals and segmented thermotropic polyesters containing azobenzene—effect of spacer length on LC properties

We report systematic studies on a homologous series of twin liquid crystalline (LC) molecules based on phenyl and naphthyl azobenzene ( PnP and NpnNp ) as well as segmented copolyesters based on them. The twin series had the structure azobenzene–oligooxyethylene–azobenzene, where the ethyleneoxy length was varied from 2 to 6 units. The LC properties of the twin series depended on the chemical structure of the azochromophore and also the length of the central oligooxyethylene segment. The PnP series exhibited smectic LC properties for n > three oligooxyethylene units. Conversely, NpnNp series exhibited spherulitic phases only for the shortest member – Np2Np . One non‐LC short spacer twin ( P2P ) and one LC long spacer twin ( P6P ) were incorporated as part of a main chain polyester composed of fully aliphatic segments of sebacate and di or tetraethylene glycol (DEG/TEG) units by melt polycondensation. Non‐LC P2P formed LC polymers even at low (5 mol %) incorporation in DEG‐based copolymers, whereas the LC‐ P6P could do so only at 30 mol % incorporation. The LC properties of the twin molecules as well as copolymers were studied using differential scanning calorimetry, polarized light microscopy (PLM) along with variable temperature wide angle X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A new stable porous Pr-organic framework constructed by multi-iodine-substituted aromatic polycarboxylates: Synthesis,characterization, and selective adsorption of dyes

abstract

Poly[tris(dimethylformamide)(μ3-2,4,6-triiodol-1,3,5-benzene tricarboxylic acid)-praseodymium (III)] {Pr(TIBTC)(DMF)₃}_n (1) (H₃TIBTC = 2,4,6-triiodo-1,3,5-benzene tricarboxylic acid) was synthesized by the reaction of Pr(NO₃)₃·6H₂O and H₃TIBTC at 85°C in a pyrex vial. 1 was characterized by elemental analysis, IR, UV–vis, TGA, PXRD, and atomic force microscopy analytical means. Each of the central Pr ions and the three carboxyl groups from the same ligand constitute a SBU, which is then joined by a carboxyl group to form a building block. In order to further explore the functional properties of 1, we used this compound for adsorption experiments. It is found that 1 can effectively adsorb anionic dyes in aqueous solutions. In particular, there is a good adsorption efficiency for coomassie brilliant blue R-250. Therefore, 1 shows good prospects for selective adsorption of anionic dyes from wastewater solution.     

Model liquid crystalline dimers in a slit pore: Monte Carlo simulation study

ABSTRACT

In this work, we present results from (isobaric–isothermal) Monte Carlo Simulation studies of liquid crystalline dimer systems confined in a slit pore. Liquid crystalline dimer systems of various spacer numbers have been considered. Surface-induced conformational and alignment properties of these systems at different pressures under homeotropic anchoring condition have been investigated. We have used easily manageable coarse grained force fields to model both monomer–monomer and monomer–substrate interaction potentials. According to the simulated result, the anchoring of dimers to the surface and orientation of mesogenic units with respect to the surface normal seem to depend on the spacer number for messogen attractive confinement. Dimers with lower spacer number are able be adsorbed to the surface and most of their mesogens are oriented along the surface normal even at lower pressure. Those with larger spacer number are distributed throughout the volume at lower pressure. In the case of mesogen repulsive confinement, most of the dimers are adsorbed to the surface and most mesogens are randomly oriented at low pressure. As the pressure gets higher, the adsorption and orientability increase depending on the type of confinement and spacer number. As a result, clear submolecular partitioning and smectic A like structure have been identified.     

Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn₁₆(picHA)₁₆ series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)₃](C₃H₅N₂)₃ ⋅ 3H₂O series (Ln=Ce–Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.     

Control the self-assembly of fluorenone-based polycatenars by tuning chain length

Using Suzuki coupling reactions as key steps, a series of fluorenone-based polycatenars, consisting of a central 2,7-diphenyl-9-fluorenone core connected with the 3,4,5-trialkoxybenzoate unit via –COO- linkage at each side have been synthesized. Upon elongation of the terminal alkyl chain, these compounds self-assembled into mesophase sequence of Col_hex/p6mm - Cub_I/$\mathit{Pm}\overline{3}n$ in solid states as well as organogels with interesting morphologies varied from 3D helical fibers to spherical structures in solvents.     

Emergent biaxiality in nematic microflows illuminated by a laser beam

Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions.