Several Original Applications of Water-soluble Phthalocyanines as Optical Probes in Analytical Sciences

酞菁化合物大多性质稳定、易于合成、结构可修饰性强，可引入各类活性基团从而获得具有各种功能的衍生物。尤为难得的是，中心配位原子为反磁性的金属酞菁化合物大多具有荧光量子产率高、荧光发射在红色区域且可进行长波激发（因而可有效避开背景荧光和散射光的干扰）等优良荧光特性。本学位论文围绕金属酞菁作为光学分子探针在分析科学的应用而展开，共六章。 第一章首先对酞菁的结构、基本性质与应用作了简要介绍。重点阐述酞菁在分析科学领域的应用，包括酞菁在催化动力学分析中的应用、酞菁作为光学探针的应用以及酞菁作为光学成像探针的应用等。 第二章建立了铋离子的高特异性、高灵敏的定量分析新方法，并对反应机理进行了探讨。在酸性...Phthalocyanine compounds are stable compounds with facile way of synthesis. The parent structure of phthalocyanines can be modified by introducing active groups to obtain a variety of functional derivatives. Intrestingly, when antimagnetic metal ions coordinated with phthalocyanien, the resulting metal phthalocyanines compounds turn to be fluorescent with high quantum yield. Fluorescent phthaloc...学位：医学硕士院系专业：医学院_药理学学号：2452013115355

Application of Cationic Aluminum Phthalocyanine,a Red-Emitting Fluorescent Probe,for Sensitive Quantitative Analysis of RNA at Nanogram Level

荷正电的四取代三甲基碘化铵铝酞菁(Tetra(trimethylammionio)aluminum phthalocyanine,TTMAAlPc)是新近出现的、很有应用潜力的新型红区荧光化合物。研究表明,弱碱性条件,RNA对TTMAAlPc的荧光具有高效猝灭作用,且猝灭程度与RNA含量呈线性正相关。据此发现建立了可测定纳克级RNA的高灵敏定量分析新方法,并对原理进行了讨论。考察了pH、缓冲体系、反应时间、温度、TTMAAlPc浓度的影响,确定了最佳反应条件(pH 8.0的广泛缓冲液、反应5 min、室温、浓度为2×10-6 mol·L-1的TTMAAlPc)。在最佳条件下,方法的线性回归方程为y=-15.0+0.51x,相关系数r=0.998 6,线性范围7.71~1 705.57ng·mL-1,检测限为1.55ng·mL-1。本法灵敏度高、线性范围宽、对RNA测定常见干扰物质包括阴、阳离子、表面活性剂和维生素等的抗干扰能力强,且操作简便。该法应用于实际样品RNA含量的测定,取得了满意的结果。还以参比法首次测定了不同pH下TTMAAlPc的荧光量子产率,结果显示TTMAAlPc具有较高的荧光量子产率,且对大范围的酸度稳定,表明TTMAAlPc是极具应用潜力的新型红色荧光探针,值得深入研究,开拓其应用。Tetrasubstituted trimethyl ammonium iodide aluminum phthalocyanine(TTMAAlPc),apositively charged phthalocyanine compound,is an emerging and potentially useful red-emitting fluorescence probe.The study showed that the fluorescence of TTMAAlPc could be quenched by RNA with high efficiency in weak alkaline media,and the degree of quenching has a linear relationship with RNA in a wide concentration range.The mechanism of quenching behavior of RNA on TTMAAlPc was discussed.It was attributed by the static interaction between RNA and TTMAAlPc,and the assembly of TTMAAlPc induced by RNA.Based on this new discovery,a novel method for quantitative determination of RNA at nanogram level has been established.The factors,including the pH of medium,buffer system,reaction time,reaction temperature,the usage of TTMAAlPc as well as the interferences,which affected the determination,were investigated and discussed.Under optimum conditions,the linear range of the calibration curve was 7.71~1 705.57ng·mL-1.The detection limit for RNA was 1.55ng·mL-1.This method has been applied to the analysis of practical samples with satisfied results.The constructed method is of high sensitivity and has a wide linear range,it also showed strong ability in the tolerance of foreign substances from anions,cations,surfactants and vitamins,all of which are common interferences encountered in the determination of RNA.Besides,it is the first report that the fluorescence quantum yield of TTMAAlPc has been measured at different pH by reference method in this work.The achieved data indicated that the fluorescence quantum yield of TTMAAlPc is larger than 20% and it keeps constant in a wide range of acidity,implying that TTMAAlPc is a high-quality red-emitting fluorescence probe,it has great potential for practical applications,thus is worthy of further study.This work expands the application of phthalocyanine compound in analytical sciences.国家自然科学基金重大研究计划项目(90206016);; 福建省科技重点项目(2012Y0081);; 省属公益类科研院所基本科研专项(2014R1102,2015R1101031-2);; 厦门市科技计划项目(3502Z20143015)资

Sensitive Determination of Chondroitin Sulfate by Fluorescence Recovery of an Anionic Aluminum Phthalocyanine-Cationic Surfactant Ion-Association Complex Used as a Fluorescent Probe Emitting at Red Region

硫酸软骨素的测定在生物医学领域有重要价值,但常规检测法在灵敏度、选择性或简易性方面尚存在不足。本文基于带正电基团的阳离子表面活性剂对具有红区发射特性的强荧光化合物—荷负电的四磺基铝酞菁具有高效荧光猝灭作用,而在生物多糖硫酸软骨素存在下,上述荧光猝灭体系荧光显著恢复的现象,提出酞菁-表面活性剂离子缔合物荧光恢复高灵敏测定硫酸软骨素的新方法,并用于实际样品分析。研究表明,中性介质中,红区荧光探针四磺基铝酞菁(TETrASulfOnATEd AluMInIuM PHTHAlOCyAnInE,AlS4PC)与阳离子表面活性剂十四烷基二甲基苄基氯化铵(TETrAdECyldIMETHylbEnzylAMMOnIuM CHlOrIdE,TdbAC)发生强烈的缔合作用,导致AlS4PC的荧光几乎完全猝灭,从而获得暗背景的荧光体系。在加入带有阴离子基团(磺酸基)的生物多糖硫酸软骨素(CHOndrOITIn SulfATE,CS)后,由于竞争结合作用,AlS4PC被释放而使体系的荧光大幅度恢复,且恢复程度与CS呈线性正相关。优化了反应条件,考察了共存物质的影响,结果表明本法具有较好的选择性。在最佳条件下,线性范围为0.20~10.0μg·Ml-1,检测限为0.070μg·Ml-1,工作曲线方程y=1.04X+2.09,r=0.999 5。该法操作简便,灵敏度、稳定性与准确性好,实际样品的分析结果令人满意。酞菁荧光化合物在分析科学中的应用尚不多见,本文工作进一步开拓了酞菁红区荧光探针的新应用。Determination of chondroitin sulfate in the biomedical field has an important value.The conventional methods for the assay of chondroitin sulfate are still unsatisfactory in sensitivity,selectivity or simplicity.This work aimed at developing a novel method for sensitive and selective determination of chondroitin sulfate by fluorimetry.We found that some kinds of cationic surfactants have the ability to quench the fluorescence of tetrasulfonated aluminum phthalocyanine(AlS4Pc),a strongly fluorescent compound which emits at red region,with high efficiency.But,the fluorescence of the above-mentioned fluorescence quenching system recovered significantly when chondroitin sulfate(CS)exits.Tetradecyl dimethyl benzyl ammonium chloride(TDBAC)which was screened from all of the candidates of cationic surfactants was chosen as the quencher because it shows the most efficient quenching effect.It was found that the fluorescence of AlS4 Pc was extremely quenched by TDBAC because of the formation of association complex between AlS4 Pc and TDBAC.Fluorescence of the association complex recovered dramatically after the addition of chondroitin sulfate(CS)due to the ability of chondroitin sulfate to shift the association equilibrium of the association,leading to the release of AlS4 Pc,thus resulting in an increase in the fluorescence of the reaction system.Based on this phenomenon,a novel method with simplicity,accuracy and sensitivity was developed for quantitative determination of CS.Factors including the reaction time,influencing factors and the effect of coexisting substances were investigated and discussed.Under optimum conditions the linear range of the calibration curve was 0.20~10.0μg·mL-1.The detection limit for CS was 0.070μg·mL-1.The method has been applied to the analysis of practical samples with satisfied results.This work expands the applications of AlS4 Pc in biomedical area.福建省科技重点项目(2012Y0081); 福建省公益类科研院所基本专项项目(2010R1101;2014R1102); 厦门市科技项目(3502Z20143015)资

光学调节架

 一种光学调节架,包括：一调节架固定架,分别开有螺纹孔、通孔及圆孔；一第一镜片夹持板,概似三角形,位于调节架固定架上部三角形的一侧,在第一镜片夹持板三角形的两斜边之间与调节架固定架的圆孔对应开有两个下沉孔；一第二镜片夹持板,概似三角形,位于第一镜片夹持板的外侧,与第一镜片夹持板用螺丝固定,第一、第二镜片夹持板之间用于夹持镜片；一底座,为倒T形,位于调节架固定架的下部,调节架固定架固定在底座一侧,在底座的顶部开有用于托住镜片的弧形凹槽；两个弹簧用销钉固定于调节架固定架上的圆孔和第一镜片夹持板上相应的两个下沉孔内；三个调节螺钉,螺固于调节架固定架上的螺纹孔内

大洋多金属结核高压低质量分数碱浸过程中sio2溶出行为

为提高综合利用率,对大洋多金属结核碱浸进行预处理研究,考察大洋多金属结核高压低质量分数碱浸过程中Na OH初始质量分数、反应温度、液固比、浸出时间等因素对SiO_2溶出影响,并对高压碱浸脱硅动力学进行研究。研究结果表明:在浸出温度为180℃、质量分数为10%Na OH溶液、液固比为3.0:1.0条件下反应70 min,可制得118.51 g/L的Na2Si O3溶液,其余Na2Si O3以方沸石(Na(Si2Al)O6?H2O)形式析出,SiO_2高压浸出反应的表观活化能为50.08 k J/mol,遵循化学反应控制的收缩核模型。通过高压低质量分数碱浸可选择性浸出其中的SiO_2,并生成有良好..

大洋多金属结核高压低质量分数碱浸过程中SiO_2溶出行为

为提高综合利用率,对大洋多金属结核碱浸进行预处理研究,考察大洋多金属结核高压低质量分数碱浸过程中Na OH初始质量分数、反应温度、液固比、浸出时间等因素对SiO_2溶出影响,并对高压碱浸脱硅动力学进行研究。研究结果表明:在浸出温度为180℃、质量分数为10%Na OH溶液、液固比为3.0:1.0条件下反应70 min,可制得118.51 g/L的Na2Si O3溶液,其余Na2Si O3以方沸石(Na(Si2Al)O6?H2O)形式析出,SiO_2高压浸出反应的表观活化能为50.08 k J/mol,遵循化学反应控制的收缩核模型。通过高压低质量分数碱浸可选择性浸出其中的SiO_2,并生成有良好...</p

大洋多金属结核高压低质量分数碱浸过程中sio2溶出行为

为提高综合利用率,对大洋多金属结核碱浸进行预处理研究,考察大洋多金属结核高压低质量分数碱浸过程中Na OH初始质量分数、反应温度、液固比、浸出时间等因素对SiO_2溶出影响,并对高压碱浸脱硅动力学进行研究。研究结果表明:在浸出温度为180℃、质量分数为10%Na OH溶液、液固比为3.0:1.0条件下反应70 min,可制得118.51 g/L的Na2Si O3溶液,其余Na2Si O3以方沸石(Na(Si2Al)O6?H2O)形式析出,SiO_2高压浸出反应的表观活化能为50.08 k J/mol,遵循化学反应控制的收缩核模型。通过高压低质量分数碱浸可选择性浸出其中的SiO_2,并生成有良好..