芳醚树枝形聚合物的合成及分子内光敏异构化反应研究

利用收敛法合成了一代到四代外围带有二苯酮、核心带有降冰片二烯的芳醚树枝形聚合物, 初步研究了这些化合物的分子内光敏异构化反应. 以波长大于350 nm的光选择激发外围的二苯酮官能团引起核心处降冰片二烯基团异构化为四环烷, 随着代数的增长, 光敏异构化反应的速率逐渐加快.     

Polyaromatic amines. Part 3: Synthesis of poly(diarylamino)styrenes and related compounds

The title compounds were synthesised and characterised as part of a study into new aromatic amines for charge transporting materials. Compounds 12-16, 20-24 and 27-34 are alkene linked triarylamines, compounds 35-36 are hydrazone derivatives and compounds 38-41 are pyrrole substituted triarylamines. Each compound was characterised by cyclic voltammetry.     

THE EFEFCT OF MAGNETIC FIELD ON POLYMERIZATION OF STYRENE IN THE PRESENCE OF POLYVINYL NAPHTHALENE AND POLYVINYL BENZOPHENONE

In the process of bulk photopolymerization of styrene initiated by AIBN decomposition polyvinyl benzophenone (PVB) can supply an effective cage for triplet-triplet energy transfer between PVB macromolecules and small molecules of AIBN to influence the molecular weight of polystyrene in weak magnetic field (less than 0.035T), that was different from the case of polyvinyl naphthalene (PVN) which supplied cages for this system only in the stronger magnetic field (more than 0.2 T) studies. It was found that in the same conditions, PVN could exert more tremendous influences on the bulk photopolymerizatiou system of styrene than PVB because in the stronger magnetic field the triplet PVN had much longer life time than PVB.     

Wavelength effect on the photoinduced reaction of polymethylmethacrylate

Polymethylmethacrylate (PMMA) containing benzophenone (BP) was photo-irradiated with monochromatic radiation of wavelength 260–360 nm using the Okazaki Large Spec-trograph (OLS). On irradiation of PMMA films containing BP in air, the sensitized main-chain scission and photocrosslinking of PMMA took place simultaneously. These reactions are dependent on irradiation wavelength. The threshold wavelength for both reactions is found to be ca. 380 nm. The number of main-chain scission and amount of gel increased with the increase of BP concentration in PMMA. Photosensitized main-chain scission favors the irradiation of radiation at ca. 280 nm and photocrosslinking takes place efficiently with the exposure of 340 nm radiation. A possible mechanism for photosensitized reaction is proposed. © 1995 John Wiley & Sons, Inc.     

Polymerizable benzophenone derivatives for labeling vinyl acetate‐butylacrylate latex particles

We describe the synthesis and characterization of three new polymerizable benzophenone derivatives [2‐acryloxy‐5‐methyl benzophenone ( 8 ), 4′‐dimethylamino‐2‐acryloxy‐5‐methyl benzophenone ( 9 ), and 4′‐dimethylamino‐2‐(β‐acryloxyethyl)oxy‐5‐methyl benzophenone ( 10 )]. We show that these monomers can successfully be incorporated into vinyl acetate (VAc) copolymer latex particles. These particles were prepared by semicontinuous emulsion polymerization and mini‐emulsion polymerization of VAc with butylacrylate (BA) for VAc/BA = 4/1 by weight. The two monomers 9 and 10 bearing the 4′‐dimethylamino group satisfy the important spectroscopic criteria required of a dye to serve as an acceptor chromophore for nonradiative energy transfer from phenanthrene (Phe) as the donor. Their UV absorption spectra suggest significant overlap with the emission spectrum of Phe, which can be incorporated into P(VAc‐co‐BA) latex through copolymerization with 9‐acryloxymethyl Phe ( 2 ). In addition, these chromophores provide a window in their absorption spectra for excitation of the Phe chromophore at 300 nm. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3001–3011, 2002     

Higher triplet excited states of benzophenones and bimolecular triplet energy transfer measured by using nanosecond-picosecond two-color/two-laser flash photolysis

The lifetimes of benzophenone in the higher triplet excited state (BP(T(n))) and several BP derivatives in the T(n) states were measured directly to be tau(T(n))=37+/-7 ps and 20-33 ps, respectively, by using the nanosecond-picosecond (ns-ps) two-color/two-laser flash photolysis method. Based on the direct measurements of tau(T(n)) of BP(T(n)), the triplet energy transfer (TET) from BP(T(n)) to quenchers (Q), such as carbon tetrachloride (CCl4), benzene (Bz), and p-dichlorbenzene (DCB), was investigated. The fast TET from BP(T(n)) to Q can be attributed to the lifetime-dependent quenching process, according to the Ware theoretical model of the bimolecular energy transfer reaction. The contribution of the lifetime-dependent term on k(TET) was 27, 60, and 86% for CCl4, Bz, and DCB as the Q of BP(T(n)), respectively, indicating that the TET from BP(T(n)) to Q is influenced not only by tau(T(n)), but also by the size of Q.     

Synthesis of 4,4′-bis(4-aminophenoxy)benzophenone and polyimides based on this compound

Synthesis of 4,4-bis(4-aminophenoxy)benzophenone was performed starting from chloral. Various polyimides were obtained by reactions of 4,4 -bis(4-aminophenoxy)benzophenone with aromatic tetracarboxylic acid dianhydrides. Some of the polyimides obtained are crystalline compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 673–676, March, 1996.     

Effect of Polymerizable Photoinitiators on the UV‐polymerization behaviors of photosensitive polysiloxane

In this contribution, three polymerizable benzophenone photoinitiators containing maleimide group including 4‐maleimidebenzophenone (MBP), 4‐chlorine‐4′‐maleimide benzophenone (CMBP), and 4‐maleimide‐4′‐[(4‐maleimide)thiophenyl]benzophenone (MMTBP) were designed and synthesized to enhance the polymerization degree of photosensitive polysiloxane containing methacryloxy active groups (MAPSO). The polymerization behaviors of the MAPSO cured by different photoinitiators were investigated using Fourier transform infrared (FTIR). It was noted that the MAPSO initiated by MMTBP showed a high carbon–carbon double bond conversion above 80% because of the existence of thiophenyl group which could generate more radicals from the photolysis reaction at the C? S bond. In addition, the thermal stability of the UV‐cured MAPSO were studied by thermogravimetric analysis (TGA), the result showed that the initial 5% mass loss (T _5%) and residual weight percent at 800 °C in nitrogen of the UV‐cured MAPSO initiated by MMTBP systems was 200 °C and 33.8%. Thus, this work provides a new perspective and efficient strategy to improve the polymerization degree of UV‐curable polysiloxanes with carbon–carbon double bonds. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1696–1705     

Study on the Synthesis and Bioactivity of Novel Mahkoside A Derivatives

Abstract

A series of novel Mahkoside A derivatives was synthesized, and their in vitro cytotoxic activities were evaluated against the human cancer cell line Ec‐9706. A Preliminary structure–activity relationship study showed compounds 7 and 8 have obvious cytotoxic activities (IC₅₀: 30.0 and 12.5 µg · mL^?1, respectively).     

Luminous Butterflies: Efficient Exciton Harvesting by Benzophenone Derivatives for Full‐Color Delayed Fluorescence OLEDs

Butterfly‐shaped luminescent benzophenone derivatives with small energy gaps between their singlet and triplet excited states are used to achieve efficient full‐color delayed fluorescence. Organic light‐emitting diodes (OLEDs) with these benzophenone derivatives doped in the emissive layer can generate electroluminescence ranging from blue to orange–red and white, with maximum external quantum efficiencies of up to 14.3 %. Triplet excitons are efficiently harvested through delayed fluorescence channels.