Using a Novel and Easy-to-Use Sandwich Structure Device to Evaluate the Cooling Properties of Cool Materials

A number of cool materials have been designed and used in hot weather to minimize the heat coming from sunlight. Traditionally, solar reflectance and infrared emittance were measured to characterize the cooling properties of cool materials. However, these methods could represent the cooling property only indirectly. In this work, a sandwich structure device that can straightforwardly measure the cooling properties of cool materials was designed. Two cool materials, including high-density polyethylene (HDPE) and polyvinyl chloride (PVC), were selected to verify the device. For the purpose of comparison, UV-vis-NIR spectral characterization was also used to evaluate the cooling properties of the selected materials. The results, especially for the HDPE/Green 260 composite sample, which presents much lower solar reflectance but better cooling property, indicated that the cooling properties cannot be entirely represented by only the reflectance or transmittance, and the sandwich structure device was able to make up for this deficiency.     

One-pot Synthesis,Crystal Structures and Antimicrobial Activities of Two New 1,4-Disubstituted 1,2,3-Triazole-4-Carboxylates

Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a(C10H9N5O4) crystallizes in the triclinic system, space group P1 with a = 5.0894(9), b = 8.9834(13), c = 13.089(2) ?, α= 83.041(7), β= 80.256(7), γ=87.296(8)°, V = 585.24(16)?3, Z = 2, Mr = 263.22, crystal size(mm) = 0.37 × 0.20 ×0.18,(I 2σ(I)) = 8557, 2493, 1229, Rint = 0.057. Compound 1b(C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a = 6.8854(5), b = 21.783(2), c = 9.3986(8) ?,β = 93.239(4)°, V = 1407.4(2)?3, Z = 4, Mr = 291.27, crystal size(mm) = 0.38 × 0.22 × 0.20,(I 2σ(I)) = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.     

Beyond microstructures: Using the Kerr Effect to characterize the macrostructures of synthetic polymers

The macrostructures of synthetic polymers are essentially the complete molecular chain architectures, including the types and amounts of constituent short‐range microstructures, such as the regio‐ and stereosequences of the inserted monomers, the amounts and sequences of monomers found in co‐, ter‐, and tetra‐polymers, branching, inadvertent, and otherwise, etc. Currently, the best method for characterizing polymer microstructures uses high field, high resolution ¹³C‐nuclear magnetic resonance (NMR) spectroscopy observed in solution. However, even ¹³C‐NMR is incapable of determining the locations or positions of resident polymer microstructures, which are required to elucidate their complete macrostructures. The sequences of amino acid residues in proteins, or their primary structures, cannot be characterized by NMR or other short‐range spectroscopic methods, but only by decoding the DNA used in their syntheses or, if available, X‐ray analysis of their single crystals. Similarly, there are currently no experimental means to determine the sequences or locations of constituent microstructures along the chains of synthetic macromolecules. Thus, we are presently unable to determine their macrostructures. As protein tertiary and quaternary structures and their resulting ultimate functions are determined by their primary sequence of amino acids, so too are the behaviors and properties of synthetic polymers critically dependent on their macrostructures. We seek to raise the consciousness of both synthetic and physical polymer scientists and engineers to the importance of characterizing polymer macrostructures when attempting to develop structure–property relations. To help achieve this task, we suggest using the electrical birefringence or Kerr effects observed in their dilute solutions. The molar Kerr constants of polymer solutes contributing to the birefringence of their solutions, under the application of a strong electric field, are highly sensitive to both the types and locations of their constituent microstructures. As a consequence, we may begin to characterize the macrostructures of synthetic polymers by means of the Kerr effect. To simplify implementation of the Kerr effect to characterize polymer macrostructures, we suggest that NMR first be used to determine the types and amounts of constituent microstructures present. Subsequent comparison of observed Kerr effects with those predicted for different microstructural locations along the polymer chains can then be used to identify the most likely macrostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 155–166     

Cocrystals of the antibiotic trimethoprim with glutarimide and 3,3‐dimethylglutarimide held together by three hydrogen bonds

The antibiotic trimethoprim [5‐(3,4,5‐trimethoxybenzyl)pyrimidine‐2,4‐diamine] was cocrystallized with glutarimide (piperidine‐2,6‐dione) and its 3,3‐dimethyl derivative (4,4‐dimethylpiperidine‐2,6‐dione). The cocrystals, viz. trimethoprim–glutarimide (1/1), C₁₄H₁₈N₄O₃·C₅H₇NO₂, (I), and trimethoprim–3,3‐dimethylglutarimide (1/1), C₁₄H₁₈N₄O₃·C₇H₁₁NO₂, (II), are held together by three neighbouring hydrogen bonds (one central N—H...N and two N—H...O) between the pyrimidine ring of trimethoprim and the imide group of glutarimide, with an ADA/DAD pattern (A = acceptor and D = donor). These heterodimers resemble two known cocrystals of trimethoprim with barbituric acid and its 5,5‐diethyl derivative. Trimethoprim shows a conformation in which the planes of the pyrimidine and benzene rings are approximately perpendicular to one another. In its glutarimide coformer, five of the six ring atoms lie in a common plane; the C atom opposite the N atom deviates by about 0.6 Å. The crystal packing of each of the two cocrystals is characterized by an extended network of hydrogen bonds and contains centrosymmetrically related trimethoprim homodimers formed by a pair of N—H...N hydrogen bonds. This structural motif occurs in five of the nine published crystal structures in which neutral trimethoprim is present.     

Three‐dimensional structure of cyclic antibiotic teicoplanin aglycone using NMR distance and dihedral angle restraints in a DMSO solvation model

The three‐dimensional solution conformation of teicoplanin aglycone was determined using NMR spectroscopy. A combination of NOE and dihedral angle restraints in a DMSO solvation model was used to calculate an ensemble of structures having a root mean square deviation of 0.17 Å. The structures were generated using systematic searches of conformational space for optimal satisfaction of distance and dihedral angle restraints. Comparison of the NMR‐derived structure of teicoplanin aglycone with the X‐ray structure of a teicoplanin aglycone analog revealed a common backbone conformation with deviation of two aromatic side chain substituents. Experimentally determined backbone ¹³C chemical shifts showed good agreement with those computed at the density functional level of theory, providing a cross validation of the backbone conformation. The flexible portion of the molecule was consistent with the region that changes conformation to accommodate protein binding. The results showed that a hydrogen‐bonded DMSO molecule in combination with NMR‐derived restraints together enabled calculation of structures that satisfied experimental data. Copyright © 2015 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of the Proposed C79–C104 Fragment of Symbiodinolide

Stereoselective and streamlined synthesis of the proposed C79–C104 fragment 2 of symbiodinolide ( 1 ), a polyol marine natural product with a molecular weight of 2860, was achieved. In the synthetic route, the proposed C79–C104 fragment 2 was synthesized by utilizing a Julia–Kocienski olefination and subsequent Sharpless asymmetric dihydroxylation as key transformations in a convergent manner. Detailed comparison of the ¹³C NMR chemical shifts between the natural product and the synthetic C79–C104 fragment 2 revealed that the stereostructure at the C91–C99 carbon chain moiety of symbiodinolide ( 1 ) should be reinvestigated.     

Preparation of free‐standing silicone particles in aqueous heterogeneous system

To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D₄) as the monomer and dimeric D₄ (bis‐D₄) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D₄ in monomer droplets and upon polycondensation of hydrolyzed D₄, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D₄ in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity.     

Malliavin and Dirichlet structures for independent random variables

On any denumerable product of probability spaces, we construct a Malliavin gradient and then a divergence and a number operator. This yields a Dirichlet structure which can be shown to approach the usual structures for Poisson and Brownian processes. We obtain versions of almost all the classical functional inequalities in discrete settings which show that the Efron–Stein inequality can be interpreted as a Poincaré inequality or that the Hoeffding decomposition of $U$-statistics can be interpreted as an avatar of the Clark representation formula. Thanks to our framework, we obtain a bound for the distance between the distribution of any functional of independent variables and the Gaussian and Gamma distributions.     

基于复杂网络的能源互联网信息物理融合系统跨空间风险传递研究

能源互联网呈现物理信息深度融合的趋势,为电力系统管理研究定义了新的研究框架。作为一个先进的复杂系统,能源互联网信息物理系统(Energy Internet Cyber-Physical System,ECPS)在其发展过程中面临着一些新的挑战,其中一个就是耦合结构下的风险管理。本文结合复杂网络理论和风险传递理论,着重在拓扑层面分析了ECPS跨空间交互机理,并在此基础上定义了交互路径和交互系数;接着建立了ECPS跨空间风险传递模型,量化描述了风险的传递和演化过程,并进行了风险影响评估;最后,通过仿真实验分析了三种不同交互系数节点故障的风险传递过程和不同攻击模式下系统的崩溃过程。对仿真结果的讨论阐述了能源互联网风险跨空间传递的特点,为更深入地研究ECPS的风险管理提供了参考。     

通过宽线固体核磁共振氢谱研究半晶高分子的相结构

宽线固体核磁共振氢谱（¹H NMR）是一种研究半晶高分子相结构的经典方法.本文以半晶聚乙烯的宽线固体¹H NMR谱为例，探讨了通过Gaussian/Sinc、Gaussian和Lorentzian函数组合对宽线固体¹H NMR谱图进行拟合的方案，并根据半晶聚乙烯的相结构成分对拟合得到的各信号成分进行归属.并在此基础上探讨了各个相结构中分子链运动与信号线型的相关性，以及利用宽线固体¹H NMR谱测量半晶高分子结晶度存在的困难.