D-A type hybrid polymers based on EDOT and various benzodiazoles for electrochromic materials

Two donor units (D)-acceptor units (A) type monomers were synthesized by Stille coupling reaction, and then three D-A type hybrid polymers based on 3,4-ethylenedioxythiophene and various benzodiazoles were synthesized by electrochemical polymerization. Spectroelectrochemical and kinetic studies of these polymers showed that all polymer films exhibited excellent electrochromic behavior, obvious optical contrast, and excellent stability. Among them, the response time of P3 film was the shortest (t_c = 1.6 s, t_b = 2.2 s), the coloring efficiency of P2 film was the highest (CE = 333 cm²·C⁻¹), and the stability of P1 was the best (the ΔT loss of P1 after 1000 s cycles is only 2.3%). Therefore, these data prove that these new polymers have great potential in applications as electrochromic materials.     

Processing Chemical and Photonic Signals by Artificial Multicomponent Molecular Systems

Miniaturization has been an essential ingredient in the outstanding progress of information technology over the past fifty years. The next, perhaps ultimate, limit of miniaturization is that of molecules, which are the smallest entities with definite size, shape, and properties. Molecular-level systems that respond to external stimulation by changing some physical or chemical properties can be viewed as input–output devices and therefore may be useful for transferring, processing, and storing information. Some of these nanoscale devices can, in fact, perform logic operations of remarkable complexity. This research — although far from being transferred into technology — is attracting interest, since the nanometer realm seems to be out of reach for the “top-down” techniques currently available to microelectronics industry. Leaving aside futuristic speculations related to the construction of a chemical computer, molecular logic devices could be interesting for specific applications in areas such as diagnostics, medicine, and materials science, where problems need to be addressed in places — for example, inside a cell — that are out of reach for a silicon-based computer. Here we discuss the idea of processing information with artificial multicomponent molecular systems in solution by illustrating a few recent examples developed in our laboratory.     

Thiol‐ene photofunctionalization of 1,4‐polymyrcene

1,4‐Polymyrcene was synthesized by anionic polymerization of β‐myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3‐mercaptopropionate, butyl 3‐mercaptopropionate, ethyl 2‐mercaptopropionate and 2‐methyl‐2‐propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4‐polymyrcene decreased in the order 1° thiol (ca 95%) > 2° thiol (ca 80%) > 3° thiol (<5%), due to the reversibility of the thiol‐ene reaction. Remarkably, thiol addition to the side‐chain double bonds was 8 ? 10 times (1° thiol) or 24 times (2° thiol) faster than to the main‐chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10‐fold excess of thiol with respect to myrcene units, the thiol‐ene addition was accompanied by chain coupling reactions, which in the extreme case of 3° thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl‐thioglycolate‐functionalized 1,4‐polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. © 2018 Society of Chemical Industry     

Pyrene functionalized side chain alanine and histidine containing copolyacrylates prepared by free radical copolymerization

An optically active copolyacrylate, poly(N‐acryloyl‐L‐alanine‐co‐N‐acryloyl‐L‐histidine), is prepared by classical radical copolymerization of N‐acryloyl‐L‐alanine and N‐acryloyl‐L‐histidine, and further chemically modified with 1‐pyrene‐methanol. The structures of the synthesized compounds are confirmed by spectral analysis (FTIR, ¹H/¹³C‐NMR, UV, fluorescence spectroscopy), thermal methods, and molecular weight measurements. Also, their optical activity is studied using circular dichroism (CD) spectroscopy and optical rotation measurements. The specific rotation values reveal that the direction of rotation of the parent copolymer is dictated by the monomer containing L‐alanine. CD data suggest negative and positive Cotton effects regarding the monomers with amino acids. In the case of the unmodified copolymer it is noted the changes of ellipticity values with increasing pH while the random‐coil conformation is preserved, which makes it suitable as a pH‐responsive system. Photochemical and photophysical investigations reveal that the pyrene‐functionalized chiroptical copolyacrylate can be used as a fluorescent chemosensor for the detection of nitro‐derivatives in organic media. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44457.     

Design and synthesis of caged fluorescent nucleotides and application to live-cell RNA imaging

A binary photocontrolled nucleic acid probe that contains a nucleotide modified with one photolabile nitrobenzyl unit and two hybridization-sensitive thiazole orange units has been designed for area-specific fluorescence imaging of RNA in a cell. The synthesized probe emitted very weak fluorescence regardless of the presence of the complementary RNA, whereas it showed hybridization-sensitive fluorescence emission at 532 nm after photoirradiation at 360 or 405 nm for uncaging. Fluorescence suppression of the caged probe was attributed to a decrease in the duplex-formation ability. Caged fluorescent nucleotides with other emission wavelengths (622 and 724 nm) were also synthesized in this study; they were uncaged by 360 nm irradiation, and emitted fluorescence in the presence of the complementary RNA. Such probes were applied to area-specific RNA imaging in a cell. Only probes in the defined irradiation area were activated by uncaging irradiation, and subnuclear mRNA diffusion in a living cell was monitored.     

含CL-20改性双基推进剂激光点火特性

采用CO2激光点火方法,研究了含六硝基六氮杂异戊兹烷(CL-20)改性双基(CMDB)推进剂在不同功率密度作用下的点火特性,探讨了Al粉含量和燃烧催化剂对该类推进剂激光点火性能的影响。实验结果表明,在激光功率密度25.5~127.0 W/cm2范围内,不含催化剂的CL-20-CMDB推进剂点火延迟时间随功率密度增加而递减,且点火延迟时间变化逐渐减缓,点火均首先在推进剂表面产生;而含有催化剂推进剂试样的点火延迟时间和点火过程则与功率密度密切相关:在高激光功率密度时,含催化剂的推进剂点火没有发生在推进剂表面,而是在试样表面的气相中,且点火延迟时间增加。Al粉含量对其点火延迟的影响在低激光功率密度时较大,随着功率密度增加影响减弱。