含萘酰亚胺荧光聚合物的合成及对Pd2+识别研究

以4-溴-1,8-萘二甲酸酐为原料,经亚胺化、酯化等反应,设计合成了一种新的乙烯基荧光功能单体N-甲基丙烯酰氧乙基-4-溴-1,8-萘酰亚胺(NPMA),并用此单体与N-异丙基丙烯酰胺(NIPAAm)通过自由基聚合制备了荧光共聚物PⅠ、PⅡ和PⅢ.采用1H NMR(核磁共振氢谱)、UV-vis(紫外-可见)光谱和荧光光谱对共聚物的结构及性能进行了表征,结果表明聚合物对金属pd2+具有高灵敏度的选择性识别作用.     

苝酰亚胺衍生物的合成及其荧光性能研究

以3,4∶9,10-苝四羧酸二酐为原料,合成了N,N′-二(1-戊基己基)-1,7-二对叔丁基苯氧基-3,4∶9,10-苝四羧酸二酰亚胺,使用1 H-NMR、MS、紫外-可见吸收光谱、荧光光谱对所合成的化合物进行了表征,并研究了其对常见有机小分子的荧光传感性能,发现对苯胺具有较好的选择性。     

共轭性芳杂环聚甲亚胺的合成及性能研究

以乙二醛分别与2,6-二氨基吡啶、2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑、2,5-二(4'-氨基苯基)-1,3,4-噁二唑、N-乙基-3,6-二氨咔唑缩聚合成了4种新型的共轭性芳杂环聚甲亚胺.采用Uv-vis、IR和1HNMR方法对聚合物的结构进行了表征,并对其热稳定性、导电性及荧光性能进行了研究.结果表明,该类共轭性芳杂环聚甲亚胺具有良好的热稳定性,其热降解温度均在370℃以上.共轭性芳杂环聚甲亚胺具有很好的荧光性,掺杂后荧光性明显增强,电导率从10-10～10-12S/cm增加到10-5～10-6S/cm,达到了半导体水平.     

共缩聚聚酰胺酸与聚酰亚胺的微波辐射合成及荧光性能

研究了4,4′-二氨基二苯砜(DDS)、4,4′-二氨基二苯醚(ODA)与均苯四酸二酐(PMDA)的微波辐射溶液聚合反应,将所得的聚酰胺酸进行固相微波辐射亚胺化,并与热聚合进行比较,用红外及核磁共振的测试方法对聚合物的结构进行了表征。结果表明,微波辐射能提高缩聚物的特性粘数和转化率。固相微波辐射使聚酰胺酸的亚胺化时间缩短,亚胺化度增大。合成的聚酰胺酸和聚酰亚胺都具有较强的荧光性能。     

溶胶—凝胶法制备基于荧光猝灭原理的光纤氧传感器在线监测水中溶解氧

利用氧分子对金属钌化合物的荧光具有猝灭作用的特性,构造出基于荧光猝灭原理的光纤氧传感器。就用于水中溶解氧在线监测的光纤光谱仪的搭建、传感器探头的设制及传感膜的制作过程进行探索,并对传感器的响应性能进行考察。结果表明以联吡啶钌等作为荧光指示剂以溶胶-凝胶法制备的传感膜对溶解氧的响应具有良好的可逆性,稳定性,较快的响应时间和较长的使用寿命。与标准法相对照,用本仪器系统测定了不同盐度的人工海水中的溶解氧浓度,两种方法在不同浓度水平下的溶解氧测定值均无显著性差异。本法的日内和日间RSD在1.7％～5.0％之间。     

三苯胺-PAMAM树枝分子的单／双光子荧光增强

合成了新的发光分子-4-N,N-二苯基氛基苯甲酸琉角酸亚胺(简称TBA-SCM ),利用其琉拍跳亚胺基与PAMAM所含的氛基之间高度反应活性,将三苯胺甲统基组装键合在树枝分子PAMAM (0～3G)表面,构筑新的树枝分子TBA-PAMAM.研究表明,在稀溶液(10-6)下未观测到TBA-PAMAM的荧光增强现象;当浓度...     

咪唑基改性的水溶性PDI荧光材料的合成和表征及对Cu2+离子的荧光检测

以3,4,9,10-苝四甲酸二酐为原料合成了水溶性荧光材料-N,N'-二(1-氨丙基-3-丙基咪唑盐)-3,4,9,10-苝四羧酸二酰亚胺(PDI),引入的咪唑基团使PDI不仅溶于DMSO、DMF等有机溶剂,可溶于EtOH/H2O、Acetone/H2O、THF/H2O等的混合溶液,不仅提高了PDI在有机相和有机相/水相的溶解性,同时扩展了PDI的适用范围.对比不同的混合溶剂发现,PDI在EtOH/H2O中的荧光较强,UV-Vis最大吸收波长和荧光最大发射波长分别为526nm和540nm.进而在EtOH/H2O溶剂中,比较了PDI对各种离子的荧光识别作用,其中PDI作为Cu2+的荧光探针时,受干扰小,选择性较高.TG结果表明,PDI拥有高的热稳定性,温度达353℃时质量损失仅为5％.     

水性聚氨酯-分散荧光黄高分子荧光染料的合成与荧光特性

用聚氧化丙烯二醇、2,4-甲苯二异氰酸酯、二羟甲基丙酸、三乙胺和分散荧光黄(DFY)合成了一种新型的水性聚氨酯-分散荧光黄(PU-DFY)高分子荧光染料.红外和紫外-可见吸收光谱显示,DFY已被化学键入聚氨酯链中.荧光光谱表明,PU-DFY和DFY都可在507nm处发出较强荧光,且很低浓度PU-DFY发出的荧光都较高浓度DFY的强.研究还发现,加入二苯胺猝灭剂的PU-DFY,荧光强度随温度的升高而增强,与一般荧光物质荧光强度的温度特性相反.     

含苝单元聚合物的合成及光学性能

利用酐为原料合成出N,N′-二(间羟基苯基)二酰亚胺,再通过与TDI(2,4-甲苯二异氰酸酯)的共聚合成了具有酰亚胺单元的P-π共轭聚合物,利用IR、UV-Vis、元素分析和热重分析对其结构进行了表征。并利用四波混频方法测定了该聚合物的三阶非线性,其响应系数达1.39×10-13esu,响应时间为132.59fs。另外,测得其溶液具有较高的荧光发射强度。     

[1,3,4]-噁二唑衍生物的固相合成及其线性、非线性光谱性质

用固相法合成了2个噁二唑衍生物类有机化合物:5-(4-叔丁基苯基)-[1,3,4]噁二唑-2-苯乙烯基-4-苯基-二苯胺 (化合物1)与9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑 (化合物2),并测定了它们的吸收光谱、单光子荧光光谱和双光子荧光光谱.化合物1和2在二氯甲烷溶液中单光子荧光发射峰分别位于519和476nm.在锁模Nd∶YAG激光器800nm激光照射下,化合物1和2发射出很强的双光子上转换荧光,其最大波长分别在520和485nm.     

Oxygen sensors based on luminescence quenching of metal complexes: osmium complexes suitable for laser diode excitation

Oxygen quenching of a series of Os(II) complexes with α-diimine ligands has been studied in a predominantly poly(dimethylsiloxane) (PDMS) polymer and in Gp-163 (an acrylate modified PDMS). Unlike previous Ru(II) complexes used as oxygen sensors, the Os complexes can be excited by readily available, high-intensity, low-cost, red diode lasers at 635, 650, and 670 nm. Variations in the polymer properties have been made in order to delineate the structural features important for satisfactory use of supports for oxygen sensors. A key factor is matching the hydrophobicity of the sensor and support for optimal compatibility and minimizing the size of low oxygen diffusion domains.     

Photostability of luminescent ruthenium(II) complexes in polymers and in solution

The effects of oxygen on the photochemical properties of ruthenium(II) complexes in solution and in polymers are reported. In solution, the complex is actually protected from decomposition by the presence of oxygen as a result of deactivation of the complex by oxygen quenching before it can undergo ligand loss by monomolecular dissociation; however, in polymers, the presence of oxygen increases photochemical decomposition. Singlet molecular oxygen, a product of the oxygen quenching process, may attack the ground state complex or triplet oxygen may directly attack the excited state of the complex. Both mechanisms may be involved in the photodestruction of the complex. The role of oxygen in the photodecomposition was examined by monitoring the photochemical decomposition of various complexes of different singlet oxygen reactivity, as well as absorption and mass spectroscopy studies. It is suggested that in polymers, unlike in solutions, the newly formed reactive singlet oxygen is not able to diffuse away from the complex. The singlet oxygen, trapped in close proximity to the metal complex, has an enhanced opportunity to attack it. This cage effect is supported by studies using tris(1,10-phenanthroline)ruthenium(II) in poly(ethylene glycol) of increasing molecular weight to create an increasingly constraining cage around the complex. Increased poly(ethylene glycol) molecular weight leads to increased oxygen attack of the complex, supporting the cage effect.     

Thermoluminescent and dosimetric properties of X ray phosphors

Rare earth doped oxide, phosphate, etc. are radioluminescent phosphors that have a broad application in X ray imaging, in luminescent screens, image transformers and in fluorescent lamp manufacturing. Some of them have interesting thermoluminescence features as well, which makes the phosphors applicable also in dosimetry. Two of these materials are Sr3(PO4)2 and BaFCl activated with europium. The general radioluminescence (RL) and thermoluminescence (TL) characteristics of these materials was investigated earlier and the preliminary results have already been published elsewhere. The aim of the present work is to investigate the interesting properties of these phosphors mainly from a dosimetric point of view (sensitivity, dose dependence, etc.).     

Sol-gel synthesized Sr4Al14O25:Eu2+/Dy3+ blue–green phosphorous as oxygen sensing materials

In this study, we utilized newly synthesized Sr₄Al₁₄O₂₅:Eu²⁺/Dy³⁺ blue–green phosphors along with silver nanoparticles (AgNPs) for fabrication of oxygen sensitive materials. To the best of our knowledge oxygen sensing mechanism of the offered design is totally different from the previously published works. One-component silicone: poly (1-trimethylsilyl-1-propyne), two component phenyl bearing silicone, plasticized polymethylmethacrylate, and ethylcellulose (EC) were tested as matrix materials. Electrospun fibers, porous and smooth thin films were produced by electrospinning or knife coating technique. Oxygen induced luminescence of the phosphors at 544 nm was followed as the analytical signal. Utilization of silver nanoparticles in silicone along with phosphors resulted with a 7.14 fold enhancement in the signal intensity and significant spectral response towards oxygen competing with the signals of the oxygen sensors utilizing metalloporphyrins or ruthenium complexes. We observed high sensitivity and stability, increased surface area and an enhancement in all sensor dynamics. Linearity of the calibration plots was superior for the pO₂ range of 0.0–20.0% with respect to the previously reported ones. When stored at the ambient air of the laboratory there was no significant drift in signal intensity after 12 months. Our sensitivity and stability tests are still in progress.     

Remote fluorescence imaging of dynamic concentration profiles with micrometer resolution using a coherent optical fiber bundle

Dynamic concentration profiles within the diffusion layer of an electrode were imaged in situ using fluorescence detection through a multichannel imaging fiber. In this work, a coherent optical fiber bundle is positioned orthogonal to the surface of an electrode and is used to report spatial and temporal micrometric changes in the fluorescence intensity of an initial fluorescent species. The fluorescence signal is directly related to the local concentration of a redox fluorescent reagent, which is electrochemically modulated by the electrode. Fluorescence images are collected through the optical fiber bundle during the oxidation of tris(2,2'-bipyridine)ruthenium(II) to ruthenium(III) at a diffusion-limited rate and allow the concentration profiles of Ru(II) reagent to be monitored in situ as a function of time. Tris(2,2'-bipyridine)ruthenium(II) is excited at 485 nm and emits fluorescence at 605 nm, whereas the Ru(III) oxidation state is not fluorescent. Our experiments emphasize the influence of two parameters on the micrometer spatial resolution: the numerical aperture of optical fibers within the bundle and the Ru(II) bulk concentration. The extent of the volume probed by each individual fiber of the bundle is discussed qualitatively in terms of a primary inner-filter effect and refractive index gradient. Experimentally measured fluorescence intensity profiles were found to be in very good agreement with concentration profiles predicted upon considering planar diffusion and thus validate the concept of this new application of imaging fibers. The originality of this remote approach is to provide a global view of the entire diffusion layer at a given time through one single image and to allow the time expansion of the diffusion layer to be followed quantitatively in real time.     

Inorganic lanthanide nanophosphors in biotechnology

Recently different types of fluorescent nanoparticles and other nanostructures have been promoted as alternatives for the fluorescent organic dyes that are traditionally used in biotechnology. Quantum dots, dye-doped polymer and silica particles have found many applications in biochemical protocols and are extensively discussed in the literature. Nanostructures based on inorganic phosphors (nanophosphors) are a new emerging class of materials with unique properties that make them very attractive for bio-application. Some results for the successful application of nanophosphors in biochemical applications have been reported. In this review we summarize the types of materials, their properties that are relevant to bio-applications, and the current status of their implementation in biotechnology.     

单基质白光LED荧光粉研究进展

白光LEDs(White Light-Emitting Diodes, WLEDs)作为一种新型的固体照明光源, 相对于已有光源(白炽灯、荧光灯等)具有发光效率高、响应速度快、寿命长等优势, 在照明和显示领域有着广阔的应用前景。目前获取WLEDs最常用的方法是蓝光LED芯片激发YAG : Ce ³⁺黄光荧光粉以及紫外-近紫外芯片激发三基色荧光粉(RGB混合荧光粉), 相比于以上两种方式, 单基质WLEDs荧光粉由于能克服传统RGB荧光粉颜色再吸收及配比调控的问题, 获得较高的流明效率及较高色彩还原性而受到越来越多的关注。目前关于单基质白光荧光的研究已有大量文献报道, 涉及多种材料体系, 按照发光原理的不同, 可以将其地简单分为单离子激发体系、多离子激发体系以及不依赖于稀土离子发光的其他体系等。本文综述了单基质WLEDs荧光粉的研究进展, 指出了其发展中存在的问题, 并对未来发展趋势作了展望。     

Compact fluorescent lamp phosphors in accidental radiation monitoring

The application of lamp phosphors for accidental dosimetry is a new concept. Since the materials used in fluorescent lamps are good photo luminescent materials, if one can either use the inherent defects present in the phosphor or add suitable modifiers to induce thermoluminescence (TL) in these phosphors, then the device (fluorescent lamp) can be used as an accidental dosemeter. In continuation of our search for a suitable phosphor material, which can serve both as an efficient lamp phosphor and as a good radiation monitoring device, detailed examination has been carried out on cerium and terbium-doped lanthanum phosphate material. A (90)Sr beta source with 50 mCi strength (1.85 GBq) was used as the irradiation source for TL studies. The TL response as a function of dose received was examined for all phosphors used and it was observed that the intensity of the TL peak vs. dose received was a linear function in the dose range 0.1-200 Gy in each case. Incidentally LaPO(4): Ce,Tb is a component of the compact fluorescent lamp marketed recently as an energy bright light source. Besides having very good luminescence efficiency, good dosimetric properties of these phosphors render them useful for their use in accidental dosimetry also.     

Early events in the apoptotic cascade initiated in cells treated with medium from the progeny of irradiated cells

Genomic instability and the bystander effect have recently been linked experimentally. It has previously been shown that medium from irradiated cells can induce early events in the apoptotic cascade, such as mobilisation of intracellular calcium, loss of mitochondrial membrane potential and an increase in reactive oxygen species, in unhit cells. The aim of this study was to determine if medium from the progeny of irradiated cells could also initiate apoptosis in unhit cells. Human keratinocytes were irradiated (0.5 and 5 Gy) and medium was harvested up to the 7th passage post-irradiation and transferred to unirradiated keratinocytes. Intracellular calcium levels, mitochondrial membrane potential and the level of reactive oxygen species were all monitored for a period of 24 h following medium transfer. Rapid calcium fluxes (within 30 s), loss of mitochondrial membrane potential and increases in reactive oxygen species (from 6 h after medium transfer) were observed. There was no significant difference between medium generated by cells irradiated at the different doses. The data suggest that initiating events in the apoptotic cascade were induced in unhit cells by a signal produced by irradiated cells and that this signal can still be produced in the progeny of irradiated cells.     

烷基铝在α-二亚胺镍催化体系中的应用

综述了烷基铝对α-二亚胺镍催化体系在聚合反应中所产生的影响。甲基铝氧烷(MAO)以其较高的活化能力广泛运用于α-二亚胺镍等催化体系中。三甲基铝(TMA)、三异丁基铝(TiBA)等无氯烷基铝也都有一定的活化能力,但远不如MAO。二乙基氯化铝(DEAC)、倍半乙基氯化铝(EASC)等含氯烷基铝有较强的活化能力,甚至比MAO的活化作用强得多,其中EASC和α-二亚胺镍配合可以使乙烯的聚合速率高达3966 kg PE/(mol Ni.h)。