硫醇衍生化的纳米金与癌胚抗原相互作用的光学分析

纳米金已在在药物靶向传输体系、疾病检测、分子识别、生物标签等领域有着广泛的应用,但是,由于纳米金的表面效应,大量的表面原子具有巨大剩余成键能力,使得纳米金粒子较容易团聚、沉聚,影响了其稳定性。为了实现对肿瘤靶标之一-癌胚抗原的痕量检测,需要制备出对癌胚抗原检测具有良好的增色效应与荧光增敏效应的纳米材料。该工作采用纳米金的硫醇衍生法制备了一种新型的硫醇衍生化的纳米金材料,并对此新型硫醇衍生化的纳米金材料的特性用透射电子显微镜,紫外-可见吸收光谱,荧光发射光谱和红外光谱等方法进行了研究。紫外-可见吸收光谱,荧光发射光谱的实验结果表明,在新的配体乙二硫醇存在下,有更多的电子从配体的轨道跃迁到与中心离子相关的轨道上,导致荧光增强。这种新型硫醇衍生化的纳米金与癌胚抗原作用时表现出增色效应与荧光增敏效应,而纳米金与癌胚抗原作用时看不到这种增色效应与荧光增敏效应。红外方法的研究结果表明,这种材料的蛋白增色机理为当硫醇衍生化纳米金与癌胚抗原蛋白作用时,体系中蛋白的—OH表现出更多的面外弯曲振动,有利于电子从硫醇衍生化纳米金配合物向蛋白转移而导致其增色和荧光增敏效应。因而这种新的硫醇衍生化纳米金材料比纳米金将具有更好的生物检测应用价值。     

发光标记物——异硫氰酸曙红荧光的介质效应

详细研究了介质(pH、有机溶剂、表面活性剂) 对异硫氰酸曙红(Eosin-NCS)荧光的影响。结果表明,体系的pH和极性是影响Eosin-NCS荧光的两个主要因素。Eosin5-NCS在弱酸性介质中的荧光强度明显高于在弱碱性介质中的荧光强度,但荧光强度随溶液pH的变化较敏感,需要小心控制。表面活性剂与Eosin5-NCS的作用表现出明显的电性选择性, CTMAB对Eosin-NCS荧光的影响存在着单分子猝灭和胶束增敏作用两个过程; 当有CTMAB胶束存在时,Eosin-NCS在弱碱性介质中荧光强度可达到甚至超过其在弱酸性介质中的荧光强度。在高含量有机溶剂存在时,Eosin5-NCS荧光亦可显著增强,应充分利用这些特性。     

罗丹明B同步荧光猝灭法测微量磷的条件研究

本文研究了罗庆明Ｂ－磷钼杂多酸离子缔合物体系的荧光特性及测定方法，对实验条件进行了优化选择，并引入非离子表面活性剂ＯＰ对体系增敏，增稳。本法用于黑色食品中磷的测定，结果满意。     

三聚氰胺及其胺化衍生物的荧光特性

研究了三聚氰胺(MA)及其胺化衍生物在不同浓度酸碱溶液中的荧光性能,探索了MA及其衍生物与金属离子作用前后三维荧光光谱的变化规律。结果显示:酸性溶液中MA的荧光强度高于胺化衍生物,而碱性溶液中MA的荧光强度低于胺化衍生物;随着盐酸浓度加大,其荧光峰向长波方向移动,且荧光强度逐渐减小;随着氢氧化钠浓度增加,MA荧光强度逐渐减小,胺化衍生物在氢氧化钠浓度为0.001mol/L时荧光强度最小,浓度为0.01mol/L时达到最大。加入Ni~(2+)、Co~(2+)、Mn~(2+)、Ca~(2+)等金属离子后,MA及其胺化衍生物无响应;但加入Cu~(2+)和Pb~(2+)后,其荧光强度随着金属离子浓度的增大而减弱直至不再变化。并通过摩尔比法求得MA及其衍生物与Cu~(2+)和Pb~(2+)的结合比。     

微乳液进样火焰原子吸收光度法测定食品中的微量锰

研究了多种表面活性剂及微乳液对火焰原子吸收光谱法测定锰的增敏作用，并选择增敏作用最强的微乳液作为锰测定的增敏试剂，拟定了测定锰的新方法。     

过渡金属元素氢化物发生-原子荧光增敏效应研究

基于反应介质酸度对Zn,Cd,Cu和Ni的氢化物发生影响的考察,揭示了氢转移过渡中间态[H+BH-₄]*分解反应氢化物生成机理。分别考察了Co2+离子、Ni2+离子、邻菲咯啉、羟基喹啉对Zn,Cd,Cu和Ni氢化物发生原子荧光信号的影响,探讨了其增敏机理。由于Co和Ni的挥发性物种分解抑制了Cd和Zn氢化物在传输过程中的分解损失,明显提高了Cd和Zn氢化物的传输效率。邻菲咯啉与Co2+离子或8-羟基喹啉与Co2+离子对Zn和Cd信号均具有协同增敏效应,8-羟基喹啉和邻菲咯啉对Zn和Cd信号则没有协同增敏效应。考察了阳离子、阴离子和非离子表面活性剂对氢化物发生的促进作用。结果证实阳离子和非离子表面活性剂均对分析物信号有明显的增敏效果,其原因在于表面活性剂的存在引起溶液的表面张力显著的降低。以石墨炉原子吸收法进一步考察了分析物从表面活性剂吸收液中逸出特性,提出了表面活性剂在氢化物发生和传输过程中的增敏机理。     

表面活性剂对镍、铅增敏效应的研究

本文研究了在火焰原子吸收光谱分析法中,ＴＰＢ,ＣＰ,ＴＰＣ等１０种表面活性剂对金属元素Ｎｉ,Ｐｂ的增敏效应,通过测定加入ＳＤＳ,ＣＴＡＢ、乳化剂－ＯＰ后溶液的表面张力,探讨了表面活性剂对测定金属元素的增敏机理。     

稀土元素荧光增强效应的研究：RE对Eu—苯甲酰三氟丙酮—溴…

本文详细研究了稀土元素Ｌａ＾３＋，Ｇｄ＾３＋，Ｔｂ＾３＋，ＬＵ＾３＋，Ｙ＾３＋及Ｓｃ＾３＋对铕－苯甲酰三氟丙酮－阳离子表面活性剂体系的荧光增经效应。     

香豆素—1的荧光介质效应

详细研究了香豆素－１在环己烷－醇、１，４－二氧六环－水二元溶剂及环糊精，表面活性剂溶液体系中的荧光光谱。通过溶剂－溶质分子间氢键作用及对其非荧光性的ＴＩＣＴ态形成的影响。讨论了这种荧光探针的荧光光谱对环境极性非常敏感的原因，测定了它与环糊精的包结常数和与表面活性剂胶束的结合常数。     

香豆素-3-甲酰氯修饰聚酰胺-胺大分子的荧光性能研究

用香豆素-3-甲酰氯对聚酰胺-胺树状大分子末端修饰合成了树状大分子PAMAM-CMAC,经FTIR,1H-NMR分析确证了其结构。荧光分析表明,PAMAM-CMAC树状大分子具有强的荧光发光,荧光强度比聚酰胺-胺树状大分子荧光强度增加很多。其荧光强度受pH值、溶液浓度和溶剂等各种因素的影响,在酸性条件下,荧光强度受溶液pH影响较大;但在强碱性介质中,氢键被完全破坏,荧光强度明显减弱。pH在7.00～10.00之间时,荧光发光比较稳定。溶液浓度对荧光强度也有影响,浓度太大或太小,荧光强度都相应减小,而且浓度大的溶液比浓度小的溶液荧光猝灭的快。这与理论相一致。同时,随着溶剂极性的增加,荧光发射向长波方向移动。     

有机溶剂中C_(60)荧光的研究

本文研究了C6 0 溶于有机溶剂时 ,荧光能级的变化和荧光强度的大幅度增强。通过拉曼光谱结果显示 ,发现C6 0 分子与溶剂分子之间没有发生显著的化学反应。     

Influence of deformations of a polymer matrix on the characteristics of dual fluorescence of 3-hydroxyflavone

The possibility of considerably changing the conditions for the proton transfer reaction in 3-hydroxyflavone molecules in polyvinyl alcohol (PVA) polymer matrices by stretching deformations is demonstrated. Samples of this kind are traditionally used to obtain ensembles of fluorophore molecules oriented along a chosen axis and for polarization measurements. The fluorescence spectrum of 3-hydroxyflavone in PVA has two characteristic bands in the violet and green spectral regions, which indicates excited-state proton transfer. Stretching leads to a strong reduction in the violet band, whose contribution in undeformed samples is comparable to the contribution of green fluorescence. Even twofold stretching of PVA films strongly decreases the violet band intensity, which is more pronounced in the case of sixfold stretching. In the latter case, the fluorescence spectrum behavior is very close to the pattern observed in nonpolar and aprotic solvents, in which the violet fluorescence intensity is very low. The data obtained indicate that mechanical stretching allows one to eliminate the main intermolecular factors that slow down the proton transfer between the active groups in PVA.     

Study on the Electrospinnability of Polyvinyl Alcohol Solutions by Using Water/N,N-dimethylacetamide or Water/N,N-dimethylformamide as Solvents

The electrospinning of poly(vinyl alcohol) (PVA) (99% hydrolysis degree) aqueous solution with added organic solvents N, N-dimethylacetamide (DMAc) or N, N-Dimethylformamide (DMF) was investigated. After the addition of the organic solvents to the PVA aqueous solutions, the surface tension and conductivity decreased and the viscosity significantly increased, which caused an improved electrospinnability of the PVA solutions. The micro-structures of the three solutions were investigated by dynamic light scattering (DLS), differential scanning calorimetry (DSC) and dynamic viscoelastic measurements. The DLS data revealed that the swelling of the PVA coils was slightly increased but the overlaps of PVA coils decreased greatly after one of the organic solvents was added to the aqueous solution. The DSC data showed both the water-rich phase and PVA-rich phase were destroyed and the solution became more homogenous after the addition due to the interaction between the organic solvent and water. Viscoelastic data showed there was an obvious difference in the storage modulus behavior between the aqueous solutions and the water/solvents solutions. These changes in the micro-structure and properties were the reason for the improved electrospinnability of the PVA solution. According to scanning electron microscopy (SEM), the average diameter of the electrospun PVA nanofibers was about 308 nm for the DMF/water system, and 255 nm for the DMAC/water system, as compared with uneven diameter nanofibers for the water system.     

A Highly Efficient Turn-On Fluorescent Sensor for Determination of Water in Organic Solvents

2, 3 biphenyl quinoxaline 6-amine is a fluorescent compound in some organic solvents with an excitation wavelength at 435?nm and a fluorescence emission at 518?nm. The fluorescence intensity of 2, 3 biphenyl quinoxaline 6-amine is significantly reduced in the presence of bis-(2, 4, 6-trichlorophenyl) oxalate (TCPO) and Zn(2+) due to the nonfluorescent complex formation. The low stability of the complex in presence of trace amount of water results in decomposing complex, thereby recovering the photoluminescence of 2, 3 biphenyl quinoxaline 6-amine. Based on this fact, a turn-on fluorescence photoluminescence sensor for determination of water content in organic solvents was introduced for the first time.The fluorescence intensity of 2, 3 biphenyl quinoxaline 6-amine as a function of water concentration was used as a simple, sensitive and rapid method for determining trace amount of water in some organic solvents such as ethanol and methanol. The obtained results showed a good linear relationship between fluorescence intensity and the water content with a dynamic range of 0.0094 -1(v/v%), related coefficient of 0.9922 and limit of detection of 0.0026(v/v%). %).     

A study on excited states dipole moments of 9,9′-bianthryl

The influence of an external electric field on the fluorescence intensity of 9,9′-bianthryl in non-polar and medium polar solvents and solvent mixtures is studied experimentally. The results show that the single fluorescence band observed in these solvents is not due to a homogeneous transition between two states.     

Dual fluorescence of <Emphasis Type="Italic">N</Emphasis>-pyrrolobenzonitrile in extended polyvinyl alcohol films

The possibility of radically changing the conditions for charge transfer (CT) photoreaction in N-pyrrolobenzonitrile molecules in polymer matrices of polyvinyl alcohol (PVA) under their extension has been demonstrated. The fluorescence spectrum of N-pyrrolobenzonitrile in PVA has two characteristic bands in the UV and visible spectral ranges, which are indicative of the CT reaction that occurs in the excited state. Extension significantly reduces the intensity of the UV band, the contribution of which in unstrained samples is comparable with the violet fluorescence intensity. Even a single extension of PVA films significantly reduces the intensity of the UV band, while a sixfold extension dramatically enhances this effect. In the latter case, the fluorescence spectrum contains a strong CT band whose relative intensity exceeds that for highly polar aprotic solvent acetonitrile by a factor of five. The data obtained indicate that, using extension, one can change the main intermolecular factors affecting the CT rate in PVA samples.     

Fluorescence of N,N′-dimethylaminobenzonitrile in polyvinyl alcohol stretched films

We have demonstrated that the conditions of the charge-transfer (CT) reaction in the N,N′-dimethylaminobenzonitrile (DMABN) molecule in polyvinyl alcohol (PVA) polymer matrices can be considerably changed upon their stretching deformation. The fluorescence spectrum of DMABN in PVA has two characteristic bands in the ultraviolet (UV) and visible spectral ranges, which indicates that a CT reaction proceeds in the excited state. Stretching leads to a strong decrease in the intensity of the UV band, the contribution of which in undeformed samples is comparable with the emission in the violet range. Even single stretching PVA films strongly reduces the emission intensity of the UV band, with this effect being dramatically enhanced upon sixfold stretching. In the latter case, The fluorescence spectrum is characterized by a strong CT band, the relative intensity of which is 3.5 times higher than even in a strongly polar aprotic solvent, such as acetonitrile. The obtained data indicate that, as a result of mechanical stretching, it becomes possible to change basic intermolecular factors that affect the CT rate in PVA samples.     

醋酸N-正辛基吡啶离子液体在不同溶剂中的荧光光谱分析

离子液体具有熔点低、可忽略的蒸气压、电化学窗口宽、热稳定性高和良好的导电性等独特性能,引起了化学工业和相关领域的广泛关注。离子液体具有低蒸气压,不会造成空气污染,但这并不意味着它们对环境完全无害。大多数离子液体易溶于水,可能会因为意外泄漏或通过污水进入水生环境。常用离子液体[BMIM][PF₆]和[BMIM][BF₄]的水溶液中,很容易形成氢氟酸,磷酸,具有一定的腐蚀性。将离子液体列为绿色溶剂,也需要提供其关于代谢和降解的毒性、生态毒性研究数据,或者其对环境影响的数据,离子液体在不同溶剂中的检测方法是非常重要的。离子液体的光谱分析法用量较少、方法简单、结果准确。离子液体和许多有机溶剂互溶,可形成均一、稳定的溶液。荧光检测法具有灵敏度高,选择性好,线性范围宽和受外界干扰少等优点。本工作研究了醋酸N-正辛基吡啶（OP-OAc）离子液体在水、乙醇、乙腈、乙酸等4种溶剂中的荧光光谱。研究结果表明,OP-OAc离子液体在不同溶剂中的荧光强度：I_乙酸＞I_乙腈＞I_乙醇＞I_水;最大发射波长的大小顺序：λ_{em, 水}＞λ_{em, 乙醇}＞λ_{em, 乙腈}＞λ_{em, 乙酸};它们的最大发射波长相对于激发波长发生红移;水中OP-OAc的荧光强度与浓度存在较高的相关性;当加入的甲醇、乙醇、乙腈溶剂不断增加时,OP-OAc离子液体的荧光强度增加,溶剂与水的比例为8∶2时,OP-OAc离子液体的荧光强度最强,溶剂的比例超过80%时,荧光强度突然降低;水中OP-OAc离子液体在pH 10时,荧光强度最高,在pH 14时,荧光强度最低。     

4-四氢喹啉酮的合成及发光性能

对喹吖啶酮结构改造合成了新型结构荧光体4-四氢喹啉酮,对其吸收光谱及荧光光谱进行了研究,发现该化合物的吸收峰及荧光发射峰随溶剂极性的增加而不断红移,表明荧光来源于分子内激发态电荷转移发光.该化合物在固态即显示荧光,表明经结构改造后,消除了喹吖啶酮类的固态荧光猝灭效应.4-四氢喹啉酮结构简单,易于合成和结构修饰.这对于寻找新的主体荧光发射材料具有重大意义.