Allyl sulfides and α‐substituted acrylates as addition–fragmentation chain transfer agents for methacrylate polymer networks

The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition–fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth)acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well‐performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real‐time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 394–406     

Counterion-Trapped-Molecules: From High Polarity and Enriched IR Spectra to Induced Isomerization

We report extensive computational studies of some novel intermolecular systems and their properties. Recombination of alkali-halide counterions separated by a noncovalently trapped hydrocarbon molecule is prevented by significant potential energy barriers, resulting in unusual metastable insertion complexes. These systems are extremely polar, while the inserted molecule is strongly counter-polarized, leading to significant cooperative nonadditivity effects. The compression and electric field produced by the counterions favours isomerization of the trapped molecule via a significant reduction of the barriers to bond rearrangement, in a field-induced mechanochemical process. The predicted IR intensity spectra clearly reflect (1) formation of the insertion complex, rather than simple attachment of alkali halide, and (2) isomerization of the trapped molecule, thus allowing experimental access to these events.     

工业SO2及碳黑颗粒紫外成像遥感监测技术

为了准确有效监测工业烟囱排放,基于SO2及碳黑颗粒物的光学特性,设计并研制出一套双通道紫外成像遥感监测系统.该成像系统的两个光谱通道的中心波长分别定于310 nm和330 nm,利用两个通道的光学厚度之差反演SO2浓度图像,颗粒物浓度图像由330 nm通道获取,根据浓度图像结合光流法获取烟羽运动速度,进而计算得出SO2和碳黑颗粒物的排放速率.结果表明,该工业烟囱的SO2及碳黑颗粒物排放速率分别为72.48±3.16 kg/h和6.33±1.18 kg/h.实验采用紫外相机同时对工业烟囱排放的SO2及碳黑颗粒物进行监测,实验表明双通道紫外成像遥感监测兼具高时间分辨率与高空间分辨率,测量结果准确直观,在工业废气污染、船舶尾气污染以及火山喷发污染排放遥感监测中具有非常明显的技术优势及巨大的应用前景.     

昆明物理研究所分子束外延碲镉汞薄膜技术进展

碲镉汞(MCT)自从问世以来一直是高端红外(IR)探测器领域的首选材料,分子束外延碲镉汞技术具有低成本异质外延、材料能带精准调控、原位成结等优势,是第三代红外焦平面陈列(FPA)器件研制的重要手段。本文报道了昆明物理研究所分子束外延(MBE)MCT薄膜技术进展,包括材料结构、晶体质量、表面缺陷、材料均匀性、掺杂浓度等参数优化控制的研究结果。异质衬底、碲锌镉衬底上MCT薄膜尺寸分别为4英寸(10.16 cm)及2.5 cm×2.5 cm,材料EPD值分别在1×10⁶ cm^-2附近及(3~30)×10⁴ cm^-2范围,表面宏观缺陷密度分别在30 cm^-2附近及100~300 cm^-2范围,薄膜质量与国内外先进水平相当。采用分子束外延MCT薄膜实现了2 048×2 048中波红外(MWIR)、2 048×2 048短波甚高分辨率红外(SWIR)焦平面、640×512中短双色红外(S-MWIR)、320×256中中双色红外(M-MWIR)FPA探测器的研制和验证。     

Time-resolved photoluminescence study of excited states in nanostructured melanin

Abstract

Time resolved emission spectra (TRES), 3D maps of photoluminescence excitation-emission (PLE maps), 3D maps of TRES, and kinetics of photoluminescence (PL) spectra of natural and synthetic melanin, as well as melanin composites with surfactant, sodium dodecyl benzenesulfonate, have been studied. The kinetics of PL and TRES for the melanin and the composites were investigated at low temperatures that allowed to discuss melanin’s intermolecular complexation, nano-aggregation and formation of charge transfer states. Particularly, the radiation of Frenkel excitons from fragments of different degrees of conjugation that are the parts of molecular nanodisks of melanin is observed. Furthermore, charge transfer excitons (CT-excitons) can be formed and observed at both room and helium temperatures. Some bands in the PL spectra of melanin, depending on temperature, behave like excimer radiation. The studies are aiming to understand the electronic properties of various melanins, particularly natural ones.     

Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines

A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds.     

应变对单层砷烯结构拉曼散射的影响

应用密度泛函理论对应变下的单层砷烯拉曼光谱的变化进行研究.由于材料的结构对称性较低，由外部应力诱发的形变不仅可以造成拉曼模式分裂，还可以引发拉曼模式偏移.计算表明：拉曼峰位的变化与应变正相关，建立了应变与峰位移动间的定量关系，为在实验中识别砷烯结构的应变提供依据.     

Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs₂Cl][Ga₃S₆] ( 1 ), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS₄ tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS₂), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap.