聚砜中激基缔合物的形成及紫外光辐照的影响

详细研究了芳环在主链上不含脂肪族柔性链的高分子聚砜在二氯甲烷中的荧光光谱。由荧光谱的浓度依赖关系可知聚砜在二氯甲烷中能形成分子间的激基缔台物;由极稀的聚砜的二氯甲烷溶液(5.21×10~(-7)M)的荧光谱看出没有任何种类的激基缔合物产生,但经紫外光照射会形成分子内的激基缔合物。由激基缔合物的荧光强度随温度的变化关系可得出活化能和键能分别为2.55和2.18 kcal/mol。     

聚电解质诱导的硫代黄素 T 激基缔合物及其对温度的荧光比率传感

研究了在水溶液中阴离子聚电解质聚苯乙烯磺酸钠(PSS)对阳离子型染料硫代黄素T(ThT)荧光光谱的影响,并考察了PSS存在下,ThT在水溶液中所形成激基缔合物的影响因素。实验证明,通过静电吸引作用,PSS可以增加ThT的局部浓度,从而显著地促进ThT激基缔合物的形成;ThT单体及其激基缔合物荧光强度(IM及IE)随温度的变化发生有规律的变化,ln(IE/IM)与1/T有较好的线性关系,据此可建立一种新型的对温度敏感的可裸眼识别的荧光比率传感,该传感可有效地消除激发光强度的不稳定性和光强漂移等环境因素的影响,提高了识别的准确度。     

新型酞菁的光致发光性质研究

研究了2,3-四-(2-异丙基一5-甲基苯氧基)氢酞菁在10,77,177和300 K下石英衬底上的浇铸膜和单晶硅衬底上真空镀膜(约200 nm厚)在300 K下光致发光光谱.氢酞菁的浇铸膜光致发光光谱在上述温度下均出现荧光发射和磷光发射峰,在177和300 K下出现了1 673 nm激基缔合物峰.该峰的出现与分子抗聚集能力的强弱有关,在300 K激基缔合物峰比在177 K下的峰强,从氢酞菁分子结构特点讨论了形成激基缔合物的原因.随着温度的升高,可以观察到荧光发射峰渐渐减弱而激基缔合物峰变强.由于浇铸膜和真空镀膜的酞菁分子聚集态不同导致了斯托克司位移的差异,真空镀膜的发光峰峰值在1 140 nm左右,与酞菁浇铸膜的峰值差别较大.浇铸膜的发光峰的半高宽为300 nm,而真空镀膜发光峰的半高宽为100 nm左右.     

螺芴氧杂蒽LB膜的制备及光谱特性研究

为了研究聚芴材料DSFX-SFX分子在气液两相表面的行为,分子处于溶液、LB膜及粉末状态的光学特性,以及分子有序排列对其发光特性的影响,制备了聚芴材料DSFX-SFX的X型LB膜,研究了π-A等温曲线,测量了其紫外-可见吸收谱和稳态荧光光谱。结果表明,分子以face-on形式平躺在亚相表面,单分子面积为4.78 nm2。在氯仿溶液中吸收峰位在354 nm,归属于分子中三聚氧杂蒽部分与芴环间π-π*电子跃迁;荧光发射峰位在396,419,445 nm(肩峰),归属于发色团三聚氧杂蒽,是芴环与氧杂蒽环之间的电荷转移。在LB膜中,吸收谱和荧光光谱与其溶液光谱相比,整体红移6 nm。结果表明:在LB膜中,两个分子形成激基缔合物,与单分子状态相比,激基缔合物的HOMO升高而LUMO降低。与粉末状态相比,该材料在LB膜中有很强的荧光发射,表明该材料形成有序排列超薄膜有利于荧光发射。     

芘与1,4—二氰基苯形成的三分子激基复合物

本文用稳态和瞬态荧光光谱技术研究了芘与１，４－二氰基苯体系形成三分子激基复合物的条件。测定了该体系中激基缔合物，激基复合物，三分子激基复合物的稳态荧光光谱及荧光强度随时间变化的行为和特性，测定了芘在苯溶液中的荧光衰减寿命，讨论了三分子激基复合物形成的光物理机理。     

乙醇-水团簇分子形成激基缔合物及荧光发射机理研究

紫外光照射具有特殊结构的长链式乙醇-水团簇分子时,处于激发态和基态的分子形成了分子间激基缔合物,并发射荧光.根据实验结果分析和能量转移理论可知,激发态单分子和激基缔合物间形成了电子迁移洛合物并发生了能量转移.根据Mulliken理论对电子迁移洛合物进行量子力学处理,得出了团簇分子在基态和激发态能量E^b_N和E^b_E以及由于电子迁移而引起的静电相互作用能E^s;根 关键词： 荧光光谱 激基缔合物 电子迁移 乙醇-水团簇     

有机混合薄膜中的F(o)rster能量转移

通过掺杂不同的染料有机电致发光器件可以得到不同颜色的光发射。掺杂小分子有机材料?p酸四甲酯perylene-3,4,9,10-tetracarboxylicacid(TMEP)到蓝色发光聚合物poly(N-vinyl-carbazole)聚乙烯基咔唑(PVK),得到了很好的绿光发射。TEMP掺杂质量分数为0.01时,295. 5nm激发波长的荧光光谱可以明显观察到在420 nm处PVK和530 nm处TEMP的发射峰值;当TMEP掺杂质量分数达到0.05～0.10之间,器件的电致发光光谱和荧光光谱发射峰几乎完全被TEMP的绿光所占据。光谱的转移归因于从聚合物PVK到小分子有机材料TMEP的Forster能量转移。荧光光谱中随着TMEP掺杂浓度的的增大发射峰值有明显的红移,这种现象被归因于在TMEP高浓度掺杂情况下激基缔合物的形成。激基缔合物的形成从TMEP在薄膜状态下与溶液状态下的荧光光谱的比较中得到证实。     

有机混合薄膜中的Frster能量转移

通过掺杂不同的染料有机电致发光器件可以得到不同颜色的光发射。掺杂小分子有机材料苝酸四甲酯perylene- 3,4,9,10 -tetracarboxylicacid(TMEP)到蓝色发光聚合物poly(N -vinyl carbazole)聚乙烯基咔唑(PVK),得到了很好的绿光发射。TEMP掺杂质量分数为0.01时,295. 5nm激发波长的荧光光谱可以明显观察到在420 nm处PVK和530 nm处TEMP的发射峰值;当TMEP掺杂质量分数达到0.050.10之间,器件的电致发光光谱和荧光光谱发射峰几乎完全被TEMP的绿光所占据。光谱的转移归因于从聚合物PVK到小分子有机材料TMEP的F -rster能量转移。荧光光谱中随着TMEP掺杂浓度的的增大发射峰值有明显的红移,这种现象被归因于在TMEP高浓度掺杂情况下激基缔合物的形成。激基缔合物的形成从TMEP在薄膜状态下与溶液状态下的荧光光谱的比较中得到证实。     

聚β-乙烯基萘与1,4-二氰基苯形成的三分子激基复合物

本文旨在研究聚β-乙烯基萘链内激发态缔合物与基态受体分子1,4-二氰基苯相互作用后,形成三分子激基复合物的机理,用稳态和时间分辨荧光光谱技术证明了分子间的三分子激基复合物形成机理:测定了分子内激基缔合物的形成速度; 三分子激基复合物的形成速度常数,详细讨论了由激发态激基缔合物形成分子间三分子激基复合物的处理模型。     

有机混合薄膜中的Foerster能量转移

通过掺杂不同的染料有机电致发光器件可以得到不同颜色的光发射。掺杂小分子有机材料苝酸四甲酯perylene-3，4，9，10-tetracarboxvlicacid(TMEP)到蓝色发光聚合物poly(N—vinyl—carbazole)聚乙烯基咔唑(PVK)，得到了很好的绿光发射。TEMP掺杂质量分数为0．01时，295．5nm激发波长的荧光光谱可以明显观察到在420nm处PVK和530nm处TEMP的发射峰值；当TMEP掺杂质量分数达到0．05～0．10之间，器件的电致发光光谱和荧光光谱发射峰几乎完全被TEMP的绿光所占据。光谱的转移归因于从聚合物PVK到小分子有机材料TMEP的Foerster能量转移。荧光光谱中随着TMEP掺杂浓度的的增大发射峰值有明显的红移，这种现象被归因于在TMEP高浓度掺杂情况下激基缔合物的形成。激基缔合物的形成从TMEP在薄膜状态下与溶液状态下的荧光光谱的比较中得到证实。     

Molecular engineered silica surfaces with an assembled anthracene monolayer as a fluorescent sensor for organic copper(II) salts

A novel fluorescence film has been fabricated by covalently coupling anthracene on a glass plate surface via a long flexible “Y” type spacer. Fluorescence measurement demonstrated that the emission of the film is dominated by anthracene monomer emission, and the emission can be selectively quenched by organic copper(II) salts including copper acetate, copper citrate, copper tartrate, etc. Addition of inorganic copper(II) salts like Cu(NO₃)₂, CuSO₄, CuCl₂, etc., however, has little effect upon the emission of the film. This observation was explained by considering the screening effect of the spacer layer, or spacer clusters, or even spacers adopting compact coiled conformation. Different from the reported fluorescence films with similar structures, immobilization of anthracene via a “Y” type spacer on a glass plate surface makes the fluorophore moieties exist in two different states, that is some of them were embedded within the spacer structures, and some of them might stay out of the structures. This hypothesis has been confirmed by model system, solvent effect and quenching mechanism studies. The emission of the film is sensitive to the presence of organic copper(II) salts like copper acetate. The response of the film to copper acetate is fully reversible. Presence of other inorganic salts, including Pb(Ac)₂, Cd(Ac)₂, Zn(Ac)₂, and inorganic copper(II) salts has little effect upon the sensing performance of the film to copper acetate.     

ANALYSIS OF THE FLEXURAL VIBRATION OF A THIN-PLATE BOX USING A COMBINATION OF FINITE ELEMENT ANALYSIS AND ANALYTICAL IMPEDANCES

Many practical built-up thin-plate structures, e.g., a modern car body, are essentially assemblies of numerous thin plates joined at their edges. The plates are so thin that they invariably support the weight of the structure and machinery using their substantial in-plane stiffness. Consequently, vibrational power injected into the structure from sources mounted at these stiff points is controlled by high impedance long-wavelength in-plane waves in the plates. As the long in-plane waves propagate around the structure, they impinge upon the numerous structural joints at which short-wavelength flexural waves are generated in adjoining plates. These flexural waves have much lower impedance than the in-plane waves. Hence, the vibration of thin-plate structures excited at their stiff points develops into a mixture of long in-plane waves and short flexural waves. In a previous paper by the same authors, a numerically efficient finite element analysis which accommodated only the long in-plane waves was used to predict the forced response of a six-sided thin-plate box at the stiff points. This paper takes that finite element analysis and, drawing on theory developed in two additional papers by the same authors, couples analytical impedances to it in order to represent the short flexural waves generated at the structural joints. The parameters needed to define these analytical impedances are identified. The vibration of the impedances are used to calculate estimates of the mean-square flexural vibration of the box sides which compare modestly with laboratory measurements. The method should have merit in predicting the vibration of built-up thin-plate structures in the so-called “mid-frequency” region where the modal density of the long waves is too low to allow confident application of statistical energy analysis, yet the modal density of the short flexural waves is too high to allow efficient finite element analysis.     

Immobilization of pyrene via diethylenetriamine on quartz plate surface for recognition of dicarboxylic acids

A novel photo-luminescence film has been prepared by immobilizing pyrene on a quartz plate surface via diethylenetriamine. Imino structure was intentionally introduced into the long flexible spacer due to their hydrogen bond forming abilities with carboxylic acids. It has been found that the film shows combined monomer and excimer emission of pyrene both in wet and dry states. Steady-state and time-resolved fluorescence emission measurements demonstrated that the excimer emission mainly came from direct excitation of ground state dimers, and/or monomers in aggregated state. The structures of the excimers formed during the excitation are mixtures of “standard excimers” and “distorted excimers” of the fluorophore moieties. Fluorescence lifetime measurements showed that the decay of the film is complex, and a four exponential fit is necessary for getting a satisfied result. The photophysical behavior of the present film could be rationalized by employing the model proposed before. Sensing property studies showed that the emission of the film is sensitive to the presence of dicarboxylic acids, including ethanedioic acid, malonic acid, etc. In contrast, presence of monocarboxylic acids, such as formic acid and acetic acid, had little effect upon the fluorescence emission of the film. Compared with the films taking ethylenediamine or 1,3-diaminopropane as their spacer component, introduction of diethylenetriamine into the spacer improved the performance of the film greatly. In addition, the sensing process is reversible, and the film is stable within a number of months provided it is properly preserved. These characteristics showed that the film is worthwhile for further exploration.     

Optical waveguide spectrometer based on thin-film glass plates

Commercially available thin-film glass plates have been successfully used for optical waveguide spectroscopy of chemical and biological films adsorbed upon the plates' surfaces. A 50-mum -thick glass plate was placed in contact with two parallel strips of silicone rubber supported on a slide glass. The plate area between the rubber strips served as the waveguiding region, eliminating the negative effect of the substrate on absorbance sensitivity. We coupled white light into the waveguide by focusing the light from a xenon lamp onto one end of a glass fiber and then inserting the other end into a glycerol drop overlaid upon the plate's surface. With a CCD detector, light at wavelengths as short as 360 nm was found to transmit out of the plate's end face. The propagation loss of the waveguide was measured to be 相似文献   

A Study of Boronic Acid Based Fluorescent Glucose Sensors

Boronic acid based anthracene dyes were designed, synthesized, and immobilized to solid phase, creating a continuous glucose sensor. Glucose sensitivities of dyes can decrease drastically after immobilization, therefore how to immobilize a dye to solid phase without changing the dye property is a key issue in developing the sensor. The glucose sensitivity of the simplest 1st generation sensor, which is based on an immobilized mono-phenylboronate/single-arm type, came short of the sensitivity requirement for practical use, because of the very moderate fluorescence intensity change over the physiological glucose range. However, the 2nd generation, an immobilized bis-phenylboronate/double-arm type sensor, which contained two boronate groups in the dye moiety in expectation of a large intensity change, brought about considerable improvement on its glucose sensitivity. We tried to introduce functional groups onto an anthracene ring in order to improve the dies' fluorescence properties. Acetyl or carboxyl substitution on anthracene contributed to shift the fluorescence wavelength into the more visible range (red-shift) and a divergence of wavelength between an excitation peak and an emission peak. This improvement is advantageous to the design of an optical detection system. Furthermore, single arm immobilization to this carboxyl group, thus linking directly to the fluorophore led to a 3rd generation sensor, an immobilized bis-phenylboronate/single-arm type, that was twice as sensitive as that of the 2nd generation sensor, presumably due to increased mobility of the dye moiety. The results of our study advance closer toward a clinically useful continuous fluorescent glucose sensor.     

Covalent immobilization of glucose oxidase onto Poly(St-GMA-NaSS) monodisperse microspheres via BSA as spacer arm

In this study, the immobilization of glucose oxidase (GOD) onto micron-size monodisperse Poly(Styrene-Glycidyl Methacrylate-Sodium Sulfonate Styrene) microspheres was investigated. In order to improve their surface biocompatibility, bovine serum albumin (BSA) was introduced onto the microspheres’ surface as a new type of spacer arm. Both the immobilization amount and enzymatic activity were determined in different experimental conditions (enzyme concentration, pH, temperature, etc.). It was found that BSA could serve as a good spacer because it increases both the immobilization amount and enzymatic activity of GOD. The tolerance of immobilized GOD against pH, temperatures was examined. Moreover, the kinetic parameters for native and immobilized GOD were obtained and compared.     

红外透过、反射吸收光谱研究手性液晶(M1)LB膜的结构与取向

利用ＦＴＩＲ光谱研究了一种手性液晶化合物（Ｍ１）ＬＢ膜的结构与取向,该化合物可以形成稳定的单层与多层膜。手性分子中,芳香环平面向于垂直基片表面,分子中的烷基链部分则与基底表面法线方向成一定的角度。     

Transient behavior of the strong violet electroluminescence of Ge-implanted SiO2 layers

Si-based light emitters will be a key element of future optoelectronics. One of the most promising approaches is Ge implantation into thin SiO₂ films on crystalline Si. This system exhibits a strong violet electroluminescence with a power efficiency up to 0.5% [18], but the mechanism of electrical excitation is not yet fully understood. In this paper the electrical excitation of the luminescence centers is investigated by means of electrical and electroluminescence transient measurements. It is found that the most probable way to excite luminescence centers is the impact excitation by hot electrons. Whereas the injection is explained by trap-assisted tunneling of electrons from the substrate into the oxide, the electrons will be transported via traps or in the SiO₂ conduction band. Furthermore, the electroluminescence rise and decay time is estimated to be of the order of 100 μs. Received: 26 September 2001 / Published online: 29 November 2001     

Chemolabile cellular microarrays for screening small molecules and peptides

Microarrays that mediate the uptake of small molecules into living cells are described. Tissue culture cells were seeded onto glass substrates functionalized locally with fluorescently labelled test substances. In order to enable a localized transfer of substances after contact of cells with the substrate, substances were immobilized on the surface either by non-covalent interactions or chemolabile linker groups. These chemolabile linker groups were incorporated into covalently immobilized compounds. Different ester linkages were evaluated as chemolabile linker groups. As model compounds, esters of the carboxy group of a cysteine with the hydroxy groups of carboxyfluorescein-labelled serine amide and tyrosine amide residues or the thiol group of another fluorescein-labelled cysteine amide were generated. Covalent immobilization occurred on maleimide-functionalized glass cover slips. The surface functionalization and release kinetics were assessed by confocal laser scanning microscopy. The fastest release was obtained for the phenolic tyrosine ester. Alternatively, fluorescently labelled peptides were immobilized by non-covalent interactions on glass and on a hydrogel matrix. In order to increase the efficiency of cellular uptake, peptides were N-terminally extended with a cell-penetrating peptide. Uptake of these peptides into cells was confined to the functionalized spots, and was specific for peptides extended with the cell-penetrating peptide.     

一种高灵敏压电平面水声换能器

设计并制作了一种高灵敏压电平面水声换能器。该换能器敏感元件是对1-3-2型压电复合材料结构的改进,即在带基底的压电陶瓷小柱阵列间不注入聚合物,并在其上表面直接覆盖金属板,构成“带基底的压电小柱阵列+金属盖板”结构敏感元件(称为“空气填充型”敏感元件)。对“空气填充型”敏感元件的谐振频率进行了理论计算和有限元仿真,与实测结果较吻合。为便于对比性能,同时制作了同尺寸“1-3-2型压电复合材料+金属盖板”结构敏感元件(称为“聚合物填充型”敏感元件)换能器。分别对“空气填充型”和“聚合物填充型”敏感元件换能器的有效机电耦合系数、发送电压响应和接收灵敏度进行有限元仿真和实测,结果均显示,“空气填充型”敏感元件换能器具有较高的接收灵敏度,相较于“聚合物填充型”敏感元件换能器可提高21 dB。该敏感元件换能器能有效提高灵敏度,可为研制高灵敏换能器提供参考。