聚邻甲基丙烯酰胺基苯甲酸/纳米ZnO复合物的制备及其荧光性能研究

利用原子转移自由基聚合(ATRP)法对合成的新单体邻甲基丙烯酰胺基苯甲酸(o-MAABA)进行聚合,通过核磁验证得到符合预先设计的、结构明确的聚合物,聚合物分子量为7900;将纳米ZnO引入到该聚合物P(o-MAABA)中,得到聚合物/纳米ZnO粒子复合物.用红外光谱和差热分析方法对聚合物和复合物进行了表征,并采用透射电镜(TEM)观察了复合物粒子的形貌.红外光谱表明纳米ZnO确实被引入到聚合物链中,并且与聚合物中的某些官能团发生了一定的相互作用;差热分析表明P(o-MAABA)/纳米ZnO复合物的热稳定性较原来聚合物P(o-MAABA)有所提高;TEM观察表明复合物粒子基本为球状,表面较为光滑.P(o-MAABA)/纳米ZnO复合物表现出特殊的荧光性能,与聚合物相比荧光光谱发生红移,并且复合物溶解性较好,能成膜,可望在发光材料方面得到应用.     

CdS/ZnO纳米复合结构制备及荧光特性研究

为增强CdS纳米粒子的荧光强度,以及稳定性,研究了Cd,S不同质量比,有无稳定剂等条件下CdS纳米粒子的制备及荧光特性。在碱性条件下,利用水热法合成了CdS/ZnO的纳米复合结构,并对所有样品进行了XRD、荧光光谱和SEM表征。测试结果表明所制备的CdS纳米粒子和CdS/ZnO的纳米复合结构粒子成分单一且纯净;ZnO复合在CdS表面;在紫外光(328.5 nm)激发下,CdS/ZnO纳米复合结构的发射峰位于463 nm处,峰形窄而对称,CdS/ZnO纳米复合结构的荧光强度比CdS纳米粒子的荧光强度有显著增强,且CdS和ZnO物质量之比为1∶1条件下,荧光强度最高,其荧光效率比单一CdS纳米粒子高出11%。通过第一性原理计算结果表明,CdS能带结构中,Cd-4d,S-3p和Cd-5s能带分别由5条、3条和1条能级构成,对比不同轨道的分态密度强度,看出CdS的导带边主要由Cd-5s轨道贡献,而价带边主要由S-3p轨道贡献,能量在-7 eV附近的电子态主要由Cd-4d轨道贡献。而ZnO上价带主要由O-2p电子构成,靠近费米能级的价带区域则主要由Zn-3d电子贡献,在导带部分,主要来源于Zn-4s和O-2p电子。由于在两种材料的复合结构中Zn-3d电子的能级和S-3p电子的能级接近,存在着二型带阶结构使能带变窄,容易形成跃迁,减小电子-空穴的复合,从而促进复合结构荧光效率的提高。     

Study on the Interaction Mechanism of Lysozyme and Bromophenol Blue by Fluorescence Spectroscopy

The interaction of lysozyme with bromophenol blue (BPB) in acetate buffer (pH 6.0) was studied by fluorescence quenching method for the first time. It was found that BPB could conspicuously quench the fluorescence of lysozyme by the static quenching process, possibly due to the binding on the active site near Trp62. The binding parameters including the binding constant and the number of binding site were calculated. The thermodynamic parameters ΔH°, ΔS° and ΔG° at different temperatures were obtained. The formation of lysozyme–BPB complex depended on the cooperation of the hydrophobic and electrostatic forces. And the binding average distance between lysozyme and BPB was determined. The effect of common metal ions on the binding constant of lysozyme–BPB was also examined.     

Study of Interaction of Silver Nanoparticles with Bovine Serum Albumin Using Fluorescence Spectroscopy

The interaction between silver nanoparticles (SNPs) and Bovine Serum Albumin (BSA) was investigated at physiological pH in an aqueous solution using fluorescence spectroscopy. The analysis of fluorescence spectrum and fluorescence intensity indicates that SNPs have a strong ability to quench the intrinsic fluorescence of BSA by both static and dynamic quenching mechanisms. Resonance light scattering (RLS) spectra indicated the formation of a complex between BSA and SNP. The number of binding sites ‘n’ and binding constants ‘K’ were determined at different temperatures based on fluorescence quenching. The thermodynamic parameters namely ∆H^°, ∆G^°, ∆S^° were calculated at different temperatures and the results indicate that hydrophobic forces are predominant in the SNP-BSA complex. Negative ∆G^° values imply that the binding process is spontaneous. Synchronous fluorescence spectra showed a blue shift which is indicative of increasing hydrophobicity.     

荧光光谱法研究亚甲基蓝与蛋白质的结合反应

应用荧光光谱法研究了水溶液中亚甲基蓝与牛血清白蛋白分子间的结合反应 ,讨论了亚甲基蓝对蛋白质内源荧光的猝灭机理 ,测定了结合常数 (KA=3 44× 10 5L·mol-1)和结合位点数 (n =1 0 3)。依据F rster非辐射能量转移 ,理论确定了授体 受体间的结合距离 (r=1 6 7nm)和能量转移效率 ,并用同步荧光技术考察了亚甲基蓝对牛血清白蛋白构象的影响     

L-半胱氨酸修饰的金纳米粒子与牛血清白蛋白相互作用的荧光光谱研究

采用荧光猝灭光谱和同步荧光光谱研究了L-半胱氨酸修饰的金纳米粒子(Cys-GNPs)与牛血清白蛋白(BSA)间的相互作用。根据荧光猝灭相关方程计算了Cys-GNPs与BSA相互作用的结合常数和结合位点数,探讨了其荧光猝灭机制为静态猝灭,并且根据热力学参数确定了二者间的作用力类型,推断出Cys-GNPs和BSA间主要靠疏水作用力结合。同步荧光光谱表明,二者的相互作用没有导致牛血清白蛋白的构象及色氨酸残基的微环境发生明显变化。     

Study of Interaction Between Tryptophan,Tyrosine, and Phenylalanine Separately with Silver Nanoparticles by Fluorescence Quenching Method

Using the spectroscopic method, the individual interaction of the three biochemically important amino acids, which are constituents of protein, namely, tryptophan, tyrosine, and phenylalanine with biologically synthesized silver nanoparticles has been investigated. The obtained UV-Vis spectra show the formation of ground-state complexes between tryptophan, tyrosine, and phenylalanine with silver nanoparticles. Silver nanoparticles possess the ability to quench the intrinsic fluorescence of the aforesaid amino acids by a dynamic quenching process. The binding constant, number of binding sites, and corresponding thermodynamic parameters (ΔH, ΔS, and ΔG) based on the interaction system were calculated for 293, 303, and 313 K. In the case of tryptophan and phenylalanine, with increase in temperature, the binding constant K was found to decrease; conversely, it was found to increase with increase in temperature in the case of tyrosine. The thermodynamic results revealed that the binding process was spontaneous; hydrogen bonding and van der Waals interaction were the predominant forces responsible for the complex stabilization in the case of tryptophan and phenylalanine, respectively, whereas in the case of tyrosine, hydrophobic interaction was the sole force conferring stability. Moreover, the Förster non-radiation energy transfer theory has been applied to calculate the average binding distance among the above amino acids and silver nanoparticles. The results show a binding distance of <7 nm, which ensures that energy transfer does occur between the said amino acids and silver nanoparticles.     

ZnO粉末的直流电致发光特性研究

用溶胶凝胶法制备了几种ZnO粉末, 测量了它们的直流电致发光. 在样品中观察到了较强的绿带（556 nm）发射; 对十二胺处理的样品, 绿带发光强度最高可提高8倍, 十八胺处理的样品, 绿带发光强度最高可提高12倍. 在同电压下, 十八胺处理的ZnO的发光强度也较十二胺处理的ZnO的发光强度大1.5～2倍; 并在十二胺处理的样品中, 还观察到了强度较小的蓝光谱带（406 nm）. 在一定电压范围内, ZnO电致发光强度随直流电压增强而线性增强. 所得ZnO样品在2V/μm场强下起亮, 在测量的近1 h内, 发光强度稳定, 重复性好. 分析认为：406 nm处的蓝光谱带是由于VZn空位在禁带中（距离价带0.3 eV）形成缺陷能级, 从导带到价带跃迁的结果, 而556 nm处的绿色发射带是由ZnO中氧空位所导致.     

Fluorescence Interaction and Determination of Sulfathiazole with Trypsin

The mechanism of interaction of trypsin with the sulfathiazole was studied through using fluorescence quenching and UV-visible absorption spectra at pH 7.4. The Stern-Volmer quenching constants, binding constants, number of binding sites and the corresponding thermodynamic parameters ΔH^o, ΔS^o and ΔG^o were calculated at different temperatures. The effect of common metal ions on the constants was also discussed. The results suggest that sulfathiazole can interact strongly trypsin and that there is the formation of trypsin-sulfathiazole complex and the interaction can be explained on the basis of hydrogen bonds and van der Waals forces. The binding distance (r) between the donor (trypsin) and acceptor (sulfathiazole) was 3.52 nm based on the Förster’s non-radiative energy transfer theory. The detection and quantification limits of sulfathiazole were calculated as 2.52 and 8.40 μM in the presence of trypsin, respectively. The relative standard deviation (RSD) was 4.086 % for determinations (n?=?7) of a sulfathiazole solution with the concentration of 7.54 μM.     

尺寸均匀的ZnO纳米颗粒的固相生长及性能

用Zn的酮酸肟化盐及该盐在NaCl和Li2CO3中的分解生长了ZnO纳米颗粒,观察了纳米颗粒的形态和尺寸分布,分析了纳米颗粒的结构和光谱特性,讨论了NaCl和Li2CO3的作用及生长温度对ZnO形态和尺寸的影响。在320℃下,纯的Zn酮酸肟化盐单独分解和在NaCl或NaCl和Li2CO3中分解都形成半径约7nm的球形颗粒,但在NaCl或NaCl和Li2CO3中分解形成的颗粒尺寸比较均匀,并且颗粒具有强的紫外光荧光;生长温度降低到300℃无ZnO形成,温度升高到450℃颗粒聚集长大,进一步升高温度,出现大尺寸的棒状结构,ZnO的尺寸和形态主要依赖于分解温度。     

ZnO纳米颗粒中的表面态发射特性研究

研究了不同粒径ZnO纳米颗粒样品(17～300nm)的时间光谱,通过对各粒径样品时间积分光谱的谱带结构进行高斯拟合解迭,发现光子能量位于ZnO谱带低能侧的高斯拟合成份Xc3的荧光中心波长随粒径的减小而红移,同时发光带的寿命也随之缩短.基于ZnO谱带低能侧的高斯拟合峰发光带强烈依赖于ZnO样品粒径的谱带特性,提出了与ZnO禁带内的表面态能级有关,同时研究表明,表面态在尺寸降到一定程度的纳米体系中起着重要的作用.     

Fluorescence Correlation Spectroscopy of Gold Nanoparticles

Diffusion dynamics of gold nanoparticles (GNPs) was studied by fluorescence correlation spectroscopy (FCS). The fluorescence was studied by exciting the particles by green laser (532 nm), which is far from longitudinal plasmon band of nanorods. Transmission electron microscope (TEM) and UV-Vis-NIR spectrometer were used to characterize the gold nanoparticles. Despite their low quantum yields, GNPs possess the native fluorescence. The excellent antiphotobleaching behavior of gold nanorods leads to prospects of using FCS for its detailed studies. Using FCS, dynamic information can be extracted from the fluorescence fluctuations in the system by autocorrelation function. Maximum entropy method (MEMFCS) was used to identify the number of distinct components present in the system. The particle sizes obtained from FCS were found to be higher (by few orders of magnitude) compared to TEM analysis. This might be due to the possible contributions from cetyltrimethyl ammonium bromide (CTAB) capping in the system.     

蓝光ZnO薄膜的特性研究

采用反应溅射法在n型硅（100）衬底上制备了ZnO薄膜,分别用X射线衍射仪、原子力显微镜和荧光分光光度计对样品的结构、表面形貌和光致发光特性进行了表征。X射线衍射结果表明,实验中制备出了应变小的c轴择优取向的ZnO薄膜;原子力显微镜观察表明,薄膜表面平整,颗粒大小约为50nm,为柱状结构,颗粒垂直于硅衬底表面生长;在室温光致发光（PL）谱中观察到了波长位于434nm处的较窄的强蓝光发射峰,该蓝光峰的半峰全宽约为50meV。对蓝光峰的发光机制进行了讨论,并推断出该蓝光峰来源于电子从Zn填隙缺陷能级向价带顶跃迁。     

Interaction of Alkali Blue 6B with Cetyltrimethylammonium Bromide

The microsurface adsorption–spectral correction (MSASC) technique has been applied to investigate the interaction of alkali blue 6B (AB6B) with cetyltrimethylammonium bromide (CTAB). The aggregation of AB6B on CTAB obeys the Langmuir isothermal adsorption. The aggregate was characterized by MSASC. For the monomer aggregate AB6B₂CTAB formed, its binding constant is calculated to be K = 3.01·10⁵ and its molar absorptivity to be 2.45·10⁶ liters·cm^–1 at = 690 nm. The adsorption has been used to carry out quantitative detection of cationic surfactant in samples.     

血卟啉及金属血卟啉与甲氧卞氨嘧啶相互作用的荧光光谱研究

荧光光谱法研究了甲氧卞氨嘧啶与血卟啉及金属血卟啉的作用情况 ,考察了酸度对甲氧卞氨嘧啶荧光强度的影响。在 p H=11.0的 KH2 PO4- Na2 HPO4缓冲液中 ,甲氧卞氨嘧啶有较强的荧光峰 ,血卟啉及金属血卟啉对甲氧卞氨嘧啶有明显的识别作用 ,结合常数大于 10 5,结合比均为 1∶ 1。金属血卟啉与甲氧卞氨嘧啶的结合常数小于血卟啉与甲氧卞氨嘧啶的结合常数 ,并对识别机理进行了探讨。     

稀磁ZnO纳米颗粒的生长和性能

利用Zn、Fe、Mn、Co的铜铁试剂盐为前驱体,胺为表面包裹剂,在200℃N2保护下生长了2%的过渡金属离子掺杂的ZnO稀磁纳米晶体,研究了纳米晶体的结构、形态、光学和磁学性能。所有ZnO纳米晶体均为近圆形的颗粒,晶体结构为六角纤锌矿结构,无其他氧化物相的析出,但过渡金属离子的掺入使纳米颗粒的尺寸增大。在掺杂纳米颗粒的吸收谱和发射谱中均可以观察到明显的激子吸收和发射峰,所有纳米颗粒在温度高于43K时只有顺磁性。     

发光性质可调的金属-有机骨架材料 的合成及发光性质

以对苯二甲酸(H₂BDC)为配体,以锌为中心离子,采用沉淀法合成了具有一维结构的金属配合物 纳米晶,将化合物分散到不同浓度的8-羟基喹啉(8-Hq)溶液中,得到系列配位聚合物 。分别用FT-IR和XRD对目标产物的结构进行了表征。固态发光性质研究显示: 及其配位聚合物具有强的发光,配位聚合物随着8-Hq量的增加,其发光发射光谱有规律地红移,表明该配位聚合物能够通过改变8-Hq与骨架材料间的量的比实现对材料发光性质的调控。     

荧光光谱法和分子模拟技术研究考马斯亮蓝G-250与牛血清白蛋白的相互作用

采用多种光谱技术结合圆二色谱技术研究了考马斯亮蓝G-250(CBBG-250)相互作用于牛血清白蛋白(BSA),探究了两者之间的作用机理。荧光光谱结果表明BSA与CBBG-250结合形式是静态猝灭,随CBBG-250浓度增加,其形成常数随温度逐渐减小,结合比为1∶1,根据Stern-Volmer曲线计算焓变值(ΔH)和熵变值(ΔS)分别为-4.38kJ·mol~(-1)和-6.16J·mol~(-1)·K~(-1),均小于零,证明该过程是一个自发过程。傅里叶红外光谱测定结果表明CBBG-250的加入引起BSA结构的变化,随着CBBG-250溶液浓度的增加,BSA中色氨酸微环境极性被改变,在1 600~1 700cm~(-1)(酰胺带Ⅰ)和1 600~1 500cm~(-1)(酰胺带Ⅱ)处的特征吸收带蓝移。其中1 650cm~(-1)移动至1 710cm~(-1),1 544cm~(-1)移动到1 573cm~(-1),显示BSAα-螺旋(1 650~1 658cm~(-1))和β-折叠(1 620~1 640cm~(-1),1 675cm~(-1))结构发生变化,且α-螺旋含量比结合前有所降低。圆二色谱分析结果表明,两者间通过氢键和范德华力为主的作用力使得BSA二级结构发生变化,α-螺旋含量由42.15%下降至1.27%,该结果进一步被分子建模对接技术证明。     

温敏性微凝胶颗粒的制备与荧光性质研究

通过沉淀聚合法制备了聚(N-异丙基丙烯酰胺-co-丙烯酸(P(NIPAM-co-AAc)微凝胶颗粒,继而在无水乙醇中使不同浓度的稀土离子Eu(Ⅲ)与P(NIPAM-co-AAc)微凝胶颗粒复配,制得了P(NIPAM-co-AAc)-Eu(Ⅲ)的复配颗粒。分别对P(NIPAM-co-AAc)微凝胶颗粒与P(NIPAM-co-AAc)-Eu(Ⅲ)的复配颗粒进行了扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、荧光光谱(RF)以及紫外光谱(UV)表征,得到了所制微凝胶颗粒的形态、结构、荧光性能和温敏性能方面的相关信息。实验结果表明：聚(N-异丙基丙烯酰胺-co-丙烯酸)微凝胶颗粒平均粒径在365 nm左右,粒径分布均匀、形态较规则;P(NIPAM-co-AAc)-Eu(Ⅲ)的复配颗粒中,P(NIPAM-co-AAc)微凝胶颗粒和Eu(Ⅲ)之间能发生能量传递,可增强Eu离子的特征荧光发射和基体高分子的发射;微凝胶颗粒在复配后粒径变化不大,形态更加规则;具有明显的温敏性。     

新铜试剂的荧光光谱

研究了新铜试剂在水溶液中的荧光光谱和荧光量子产率,发现在强酸性条件下,其最大激发和发射波长分别为332nm和429nm,探讨了荧光产生的机理,以罗丹明6G为参比,测得新铜试剂的荧光量子产率为15.2%.