Fast and solvent-free microwave-assisted synthesis of thermoresponsive oligo(glycidyl ether)s

Low-molecular weight linear poly(glycidyl ether)s are typically synthesized via the “classical,” oxy-anionic ring-opening polymerization (ROP) of glycidyl ether monomers at elevated temperatures. To reduce reaction times, a fast process was developed to synthesize oligo(glycidyl ether)s (OGEs) in bulk at a gram-scale utilizing microwave heating. Well-defined thermoresponsive copolymers comprising glycidyl methyl ether and ethyl glycidyl ether with molecular weights of up to 3 kDa were synthesized via microwave-assisted ROP with reaction times of approximately 10 min. The fast reaction kinetics were attributed to the rapid and uniform heating and high temperatures reached during the reaction. Consequently, no significant microwave-specific acceleration of the oxy-anionic ROP was observed. The temperature-triggered phase transition of the OGEs in aqueous solution revealed cloud point temperatures that are highly dependent on the OGE molecular weight, concentration, and comonomer composition, which extends previously reported data. Furthermore, oligo(glycidyl ether) acrylates (OGEAs) with reactive, functional end groups were directly accessible via in situ quenching of the anionic, microwave-assisted ROP with acrylic acid chloride. The obtained thermoresponsive OGEA macromonomers represent a promising material for the functionalization of surfaces via radical grafting methods to obtain functional, thermoresponsive coatings with potential application in cell culture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2496–2504     

Existence and multiplicity results for periodic solutions of nonlinear difference equations

We use Brouwer degree to prove existence and multiplicity results for the periodic solutions of some nonlinear second-order and first-order difference equations. We obtain, in particular upper and lower solutions theorems, Ambrosetti–Prodi type results and sharp existence conditions for nonlinearities which are bounded from below or above.     

Re-entrant Photoinduced Morphological Transformation and Temperature-Dependent Kinetic Products of a Rectangular Amphiphilic Diarylethene Assembly

An amphiphilic rectangular-shaped photochromic diarylethene bearing two hydrophobic alkyl chains and two hydrophilic tri(ethylene glycol) chains was synthesized, and its photoinduced morphological transformation in water was investigated. Two unexpected phenomena were revealed in the course of the experiments: a re-entrant photoinduced macroscopic morphological transformation and temperature-dependent kinetic products of supramolecular assembly. When the pure closed-ring isomer was dispersed in water, a re-entrant photoinduced morphological transformation, that is, a photoinduced transition from the hydrated phase to the dehydrated phase and then back to the hydrated phase, was observed by optical microscopy upon irradiation with green light at 20 °C; this was interpreted by the V-shaped phase diagram of the LCST transition. The aqueous assembly of the pure closed-ring isomer was controlled by changing the temperature; specifically, rapid cooling to 15 and 5 °C gave J and H aggregates, respectively, as the kinetic products. The thermodynamic product at both temperatures was a mixture of mostly H aggregate with a small amount of J aggregate. This behavior was rationalized by the temperature-dependent potential energy surface of the supramolecular assembly.     

Broadband spin‐controlled focusing via logarithmic‐spiral nanoslits of varying width

This work presents analytical, numerical and experimental demonstrations of light diffracted through a logarithmic spiral (LS) nanoslit, which forms a type of switchable and focus‐tunable structure. Owing to a strong dependence on the incident photon spin, the proposed LS‐nanoslit converges incoming light of opposite handedness (to that of the LS‐nanoslit) into a confined subwavelength spot, while it shapes light with similar chirality into a donut‐like intensity profile. Benefitting from the varying width of the LS‐nanoslit, different incident wavelengths interfere constructively at different positions, i.e., the focal length shifts from 7.5 μm (at λ = 632.8 nm) to 10 μm (at λ = 488 nm), which opens up new opportunities for tuning and spatially separating broadband light at the micrometer scale.

     

Observation of Unusual Molecular Diffusion Behaviour below the Lower Critical Solution Temperature of Water/2‐Butoxyethanol Mixtures by using Fluorescence Correlation Spectroscopy

The effect of solute affinity on solute diffusion in binary liquids well below the lower critical solution temperature (LCST) was studied by using fluorescence correlation spectroscopy. We measured the hydrodynamic radii of a hydrophobic and an amphiphilic fluorescent dye under systematic variation of the relative molar fractions of water/2‐butoxyethanol and, for comparison, of water/methanol mixtures, which do not show phase separation. We found that the apparent hydrodynamic radius of the hydrophobic dye almost doubled in water/2‐butoxyethanol, whereas it remained largely unchanged for the amphiphilic dye and in water/methanol mixtures. Our results indicate that the translational diffusion of solutes is influenced by transient local solution structures, even at temperatures well below the LCST. We conclude that, even far below LCST, different solutes can experience different environments in binary liquid mixtures depending on both the solute and solvent properties, all of which impact their reactivity.     

高温环境中光触发开关的设计

 针对在高温环境中测试仪器的供电方式问题,利用光敏二极管响应时间短并对光灵敏的优点,将其作为供电电源的开关,吸收高温辐射源发出的红外光信号,通过光电转换,使电源导通,达到开关的效果。文中阐述了这种光控的供电方式的理论依据和实现方式,排除了日光等因素的干扰,并对该方法进行了验证。通过试验证明,该方法操作简单,实用性强,很适用于一些不适合人为操作的场合。     

多目标最优化恰当有效解的稳定性

主要研究当两种类型的参数扰动时,多目标最优化问题中恰当有效解的稳定性.在点集映射的连续性意义下,分析讨论这种稳定性问题并分别给出引起扰动的两参数u,v所对应的点集映射Q1(u)和Q2(v),同时严格证明了在两个闭凸锥U,V上Q1(u)和Q2(v)的连续性定理.最后,通过附注对其进行补充和改进.     

时滞脉冲微分方程三点边值问题解的存在性和唯一性

研究一类时滞与脉冲共存的微分方程三点边值问题,利用上下解与单调迭代方法获得了边值问题解的存在性定理和唯一性定理,给出求解该类问题解析近似解的迭代方法,得出了新的结论.     

Lebesgue积分几何意义的推广

证明了非负有界函数的Lebesgue上积分等于函数下方图形的Lebesgue外测度,其Lebesgue下积分等于函数下方图形的Lebesgue内测度,从而将积分的几何意义从可测情形推广到一般情形.     

D-完全一致混合超图不可着色的一个充要条件

混合超图的上,下色数与C-超边和D-超边数有着必然联系.一般地,增加C边会使下色数x(H)增加,增加D-超边会使上色数(x)(H)减小.本论文对D-完全一致混合超图进行研究,利用组合数学中分划思想及方法得到的D-完全一致混合超图不可着色的一个充要条件,对D-完全一致混合超图能否着色找到了可行的依据,进一步揭示C-超边数...