4－［2－（9，10－二氰基蒽）乙烯基］－N，N－二甲基苯胺的三荧光发射

４－［２－（９，１０－二氰基蒽）乙烯基］－Ｎ，Ｎ－二甲基苯胺的三荧光发射王华，陈景荣，张宝文，曹怡（中国科学院感光化学研究所光化学开放实验室，北京１００１０１）关键词分子内电荷转移，荧光发射从分子水平进行电子转移，电荷分离的研究是十分重要的，它不仅是...     

苝酰胺单酐和非对称取代苝四羧酰二亚胺的合成

３ ，４ ：９ ，１０ － 苝四羧－ ３ ，４ － 酸酐－ ９ － 羧酸－ １０ － 羧酸钾与一系列脂肪胺水溶液反应制备Ｎ－ 取代的苝四羧单酰胺单酐，苝酰胺单酐通过纯化与芳香胺缩合得到非对称取代的苝四羧酸二亚酰胺。     

Bei酰胺单酐和非对称取代Bei四羧酰二亚胺的合成

３，４：９，１０－Ｂｅｉ四羧－３，４－酸酐－９－羧酸－１０－羧酸钾与一系列脂肪胺水溶液反应制备Ｎ－取代的Ｂｅｉ四羧单酰胺单酐，Ｂｅｉ酰胺单酐通过纯化与芳香胺缩合得到非对称取代的Ｂｅｉ四羧酸二亚酰胺。     

2，5，7，9－四氮杂双环〔4，3，0〕壬－8－酮盐酸盐的亚硝化研究

研究了２，５，７，９－四氮杂双环［４，３，０］壬－８－酮盐酸盐亚硝化合成２，５－二亚硝基－２，５，７，９－四氮杂双环［４，３，０］壬－８－酮的反应。     

2，9，16，23－四－［4－二甲氨基苯氧基］锌酞菁的合成和分子内光致电荷转移反应的研究

２，９，１６，２３－四－［４－二甲氨基苯氧基］锌酞菁的合成和分子内光致电荷转移反应的研究沈淑引，刘恺，周庆复，许慧君（中国科学院感光化学研究所，北京１００１０１）关键词酞菁，电荷转移，荧光量子产率光敏电荷转移是近年来十分活跃的研究领域，人们设计了各种...     

新取代苯基荧光酮试剂的合成及其性质的研究Ⅰ．新型取代苯基荧光酮的合成、提纯、鉴定及离解的研究

合成了３，５－二溴－４－氨基苯基荧光酮、４－偶氮变色酸苯基荧光酮、３，５－二溴－４－氨基变色酸苯基荧光酮、４偶氮肿Ⅰ苯基荧光酮、３，５－二溴－４－偶氮胂Ⅰ苯基荧光酮、４－偶氮间苯二酚苯基荧光酮、３，５－二溴－４－偶氮间并苯二酚苯基荧光酮和３，５－二溴－４－二甲氨基过溴化物苯基荧光酮等８种新有机试剂。对其进行了提纯和结构鉴定，并对试剂离解状态及离解常数进行了研究和测定。     

具有相反电荷取代基的卟啉和酞菁异聚体荧光光谱的研究

用荧光谱的方法研究了由水溶性的中位－四－［对－（Ｎ，Ｎ，Ｎ－三甲基苯基）铵基］卟啉的磺化物和２，６，９，１５－四（４＇－磺酸基）镓酞菁形成的超分子体系，在水溶液中阴离子酞菁与阳离子卟啉能形成杂聚集体。荧光光谱滴定的结果表明：聚集体为杂二聚体，形成平衡常数为１．１７×１０＾８Ｌ／ｍｏｌ。说明了卟啉－酞菁杂二聚体是非常稳定的，没有观察到聚集体的荧光发射。     

时间分辨荧光免疫分析螯合剂BCPDA的合成

合成了新型时间分辨荧光免疫分析螯合剂－４，７－二氯磺基苯－１，１０－菲咯啉－２，９－二羧酸（ＢＣＰＤＡ）。产物的结构经红外光谱，核磁共振谱，元素分析确证。     

新取代苯基荧光酮试剂的合成及其性质的研究Ⅰ.：新型取代苯基…

合成了３，５－二溴－４－基苯基荧光酮、４－偶氮变色酸苯基荧光酮、３，５－二溴－４－氨基变色酸苯基荧光酮、４－偶氮胂Ⅰ苯基荧光酮、３，５－二溴－４－偶氮胂Ｉ苯基荧光酮、４－偶氮间苯二酚苯基荧光酮、３，５－二溴－４－偶氮间并苯二酚苯基荧光酮和３，５－二溴－４－二甲氨基过溴化物苯基荧光酮等８种新有机试剂。对其进行了提纯和结构鉴定，并对试剂离解状态及解常数进行了研究和测定。     

3，4，5－三甲氧基苯甲醛合成工艺改进

羟基苯甲醛在氧化剂存在下溴化生成３，５－二溴－４－羟基苯甲醛，后者用氯化亚铜作催化剂，在ＤＭＦ溶剂中与甲醇钠反应，生成丁香醛。丁香醛在ｐＨ９～１０之间用硫酸二甲酯甲基化得到医药中间体３，４，５－三甲氧基苯甲醛。对各步反应工艺条件进行了探讨。整个工艺路线简便，总收率达７０％。     

Fluorescent thermostable crosslinked poly(dodecylmethacrylate) composites based on porous polyethylene and CdSe/ZnS quantum dots

Hybrid fluorescent polymer–inorganic nanoparticle composites have a broad set of valuable properties that allow them to be considered promising materials for photonics and photovoltaics. The design and methods of preparation of these composites are among the most critical topics of modern materials science. In this work, we have developed an approach to the preparation of composite polymer films with bright fluorescence and high thermostability. These composite films are based on a porous polyethylene (PE) matrix, the pores of which are filled by crosslinked poly(dodecylmethacrylate) and CdSe/ZnS core/shell quantum dots (QDs). The composites obtained are transparent in the visible spectral region and are able to withstand heating to high temperature and a considerable mechanical stress without loss of this property. These QD–PE composite films contain QDs in a high concentration and display very bright fluorescence, while they retain the mechanical properties of the initial porous PE film. Thus, the developed approach makes it possible to obtain composite materials combining the advantageous properties of PE and QDs without appreciable loss of individual component characteristics. A novel approach to the preparation of fluorescence composite polymer films, which have transparency, dimensional thermostability and resistance to mechanical stress, has been developed. © 2018 Society of Chemical Industry     

Preparation of photoluminescence films containing rare earth complexes by UV photograft polymerization

To avoid the fluorescence quenching resulting from the uneven dispersion of fluorescent rare earth complexes in photoluminescence films, which were prepared by blending until recently, photoluminescence films were prepared in which the chemical bond combination occurs between the fluorescent rare earth complexes and the macromolecular material. Acrylic acid (AA) was grafted onto polyethylene (PE) film through liquid‐phase UV photograft polymerization. Then the grafted films (PAA‐g‐PE) were reacted with a solution of Eu³⁺ and thenoyltrifluoroacetone (TTA) in alcohol–water and with a solution of Tb³⁺ and acetylacetone (AcAc) in chloroform–water, respectively. Thus, red (Eu³⁺–TTA–PAA‐g‐PE) and green (Tb³⁺–ACAC–PAA‐g‐PE) photoluminescence films were obtained. The fluorescence and infrared spectra of the photoluminescence films were recorded. Compared with their corresponding solid fluorescent complexes, both the excitation and emission wavelengths of the photoluminescence films prepared in this way had been changed remarkably, indicating that the fluorescent rare earth complexes had been chemically bonded onto the PE film. Moreover, the effects of the conditions (including pH value, reaction time, and temperature) of the reaction of the grafted film with the solution containing Eu³⁺ and TTA on the fluorescence intensity of the red photoluminescence film were investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 662–667, 2003     

调光保温聚乙烯农膜的光色效应研究

研制了含荧光色素、有机颜料、矿物填料的聚乙烯农膜,进行了两年的农田应用和光色效应研究,结果表明：与使用普通聚乙烯农膜相比,可提高棚内红光或蓝光强度,增加棚内温度,促进作物光合作用,提高作物的产量和品质。     

Preparation of silicone containing 2,2,6,6-tetramethyl-4-piperidinol-based N-chloramine for antibacterial polyethylene via interpenetration in supercritical carbon dioxide

Functionalization of polyethylene (PE) with powerful biocides through a friendly and efficient procedure is necessary to obtain extended applications. A novel CO₂-philic 2,2,6,6-tetramethyl-4-piperidinol (TMP)-based N-chloramine silicone was synthesized via Pt-catalyzed silane alcoholysis between the Si H of poly(methylhydrosiloxane) and O H of TMP and followed by chlorination of amine N H originating from TMP to N Cl. The TMP-based N-chloramine silicone was interpenetrated into PE using supercritical carbon dioxide (scCO₂) as working solvent. It was shown that the thickness of the TMP-based N-chloramine silicone layer on PE can be easily controlled by the interpenetration pressure, reaching a maximum value of 70 nm at 28 mp. The synthetic procedures and the interpenetration results were characterized by Fourier transform infrared, scanning electron microscopy, and X-ray photoelectron spectroscopy. In contrast with pristine PE that did not show biocidal ability, the TMP-based N-chloramine silicone modified PE imparted powerful antibacterial abilities, exerting total kills of both Staphylococcus aureus and Escherichia coli of ~10⁷ cfu mL⁻¹ in 30 min. The biocidal functionality was durable toward washings, storage, and ultraviolet exposure and the recoverability of lost chlorines was good. The interpenetration in scCO₂ tactic provides an environmentally friendly and universal approach to functionalize inert substrates due to no needs of harmful solvent and chemical linkages with biocides. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47614.     

Synthesis and properties of some fluorescent 1,8‐naphthalimide derivatives and their copolymers with methyl methacrylate

Six new fluorescent derivatives of 1,8‐naphthalimide were synthesized. Three were dyes, and three were fluorescent whitening agents (FWAs) containing a tetramethylpiperidine (TMP) stabilizer fragment. The FWAs were obtained under phase‐transfer catalysis conditions. Five of the compounds were copolymerized with methyl methacrylate, so copolymers with an intense color and/or fluorescence stable against solvents were obtained. The chemical bonding of the synthesized monomers in the polymers was confirmed spectrophotometrically. The participation of the monomer compounds did not significantly affect the process of copolymerization or the molecular masses of the obtained copolymers. The quantity of chemically bonded naphthalimide monomer in the copolymers was determined to be over 60%. The spectral properties of the compounds and their photostability in solution and in the copolymers were studied. The influence of the compounds on the photostability of the copolymers was determined. The compounds, especially those containing a stabilizer (TMP) fragment in their molecules, showed a positive stabilizing effect on the photodegradation of poly(methyl methacrylate). Polyamide fabrics with 2‐allyl‐6‐hydrazino‐benzo[de]isoquinoline‐1,3‐dione, 2‐allyl‐6‐(2‐amino‐ethylamino)‐benzo[de]isoquinoline‐1,3‐dione, and 2‐chloro‐N′‐(2‐methyl)‐1,3‐dioxo‐2,3‐dihydro‐1H‐benzo[de] isoquinoline‐6‐yl) acetohydrazide were dyed, and materials with an intense yellow color and fluorescence were obtained. Cotton fabrics were whitened with 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐methoxy‐benzo[de]isoquinoline‐1,3‐dione, 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐allyloxybenzo[de]isoquinoline‐1, 3‐dione, and 2‐[2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐1,3‐dioxo‐2,3‐dihidro‐1H benzo [de]isoquinoline‐6‐oxy]ethyl‐2‐methacrylate, and materials with bright whiteness and intense bluish fluorescence were obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

脂肪族聚碳酸酯型多异氰酸酯固化剂合成及其涂膜性能研究

采用脂肪族聚碳酸酯二元醇(APC)和三羟甲基丙烷(TMP)组成的混合多元醇与甲苯二异氰酸酯(TDI)反应,合成了可水分散的多异氰酸酯固化剂(WDLCP),并与硅改性的水性丙烯酸树脂(WSA)配制成水性聚氨酯-硅改性水性丙烯酸酯(PUA)水性清漆。考察了混合多元醇中n OH(TMP)∶nOH(APC)对WDLCP在WSA中的分散性能及成膜性能的影响,并与采用聚醚多元醇(PE2000)合成的多异氰酸酯固化剂(WDP)成膜后性能进行对比。结果表明,WDLCP与WSA具有良好的相容性,当n OH(TMP)∶nOH(APC)=0.5∶0.5时,PUA的成膜性较好,相较于WDP,WDLCP合成的涂料的涂膜性能大幅提升。     

Eu3+掺杂TiO2荧光探针的制备及对氯氰菊酯的检测应用

以钛酸四丁酯为前体,采用液相法制备了水溶态纳米Eu3+掺杂TiO2荧光探针,并对其发光性质进行了研究。通过紫外吸收和荧光光谱研究了它和氯氰菊酯之间的相互作用,结果发现,氯氰菊酯对Eu3+掺杂TiO2的荧光具有猝灭作用,根据Stern-Volmer猝灭方程,计算出其猝灭常数为1.017×1011 L/(mol.s),并讨论了猝灭机理。依据氯氰菊酯浓度和Eu3+掺杂TiO2的荧光强度成正比,建立了一种快速检测农药的新方法。其检测范围为2.5×10-10～2.5×10-7mol/L,检出限为2.5×10-11mol/L,回收率在89.25%～93.55%之间。     

Influence of branching on the properties of poly(ethylene terephthalate) fibers

A series of branched poly(ethylene terephthalate) samples was prepared by employing 0.07–0.42 mol % trimethylolpropane (TMP) for melt polycondensation. These polymers were characterized with respect to molar mass, intrinsic viscosity, and melt viscosity. Spinning into fibers took place at spinning speeds ranging from 2500 to 4500 m/min. The molecular orientation of the fibers as measured by birefringence and polarized fluorescence decreases with growing amounts of TMP, as does crystallinity. Thus with slightly branched polymers, higher spinning speeds than with a linear polymer can be used to achieve a certain property profile. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 728–734, 1999     

两种不同光谱类型的R-藻红蛋白的荧光性质研究

红藻中的R-藻红蛋白(R-PE)依照其吸收光谱可分为两种不同的光谱类型,即“双峰型”和“三峰型”.本文通过对不同pH条件下的R-PE的荧光光谱及荧光寿命的研究,发现“三峰型”R-PE的pH稳定范围较“双峰型”R-PE大.在R-PE浓度对荧光光谱的影响实验中,随着蛋白浓度的增加,荧光峰位置逐渐红移。荧光寿命逐渐增大,荧光强度先行增加而后减弱.用碘离子对其荧光进行猝灭,随着碘离子浓度的增大,荧光强度逐渐降低,荧光寿命逐渐缩短,并服从Stem-Volmer规则.