1H NMR探究空间效应对表面活性剂复配体系中协同作用的影响

通过核磁共振氢谱（¹H NMR）实验测量了温度为298.0 K时3种表面活性剂——十六烷基三甲基溴化铵（CTAB）、辛基苯基聚氧乙烯醚（TX-100）和十二烷基硫酸钠（SDS）组成的复配体系CTAB/TX-100、SDS/TX-100和CTAB/TX-100/SDS中各组分的化学位移,得到了各混合体系中CTAB、TX-100和SDS的临界胶束浓度（CMC）.对不同体系中各组分CMC随摩尔分数的变化曲线进行比较,发现了空间效应对表面活性剂复配体系中协同作用的影响在一定的情况下并不逊于静电相互作用：表面活性剂分子的截面积越大,对体系中其他组分的协同作用越强;当组分间存在弱的静电相互作用时,空间效应对协同作用起到更主要的影响.     

吖啶橙-PAR-钒(Ⅴ)能量转移荧光猝灭法的研究及分析应用

在pH 5.5的Na2HPO4-柠檬酸缓冲溶液中,吖啶橙（AO）与PAR-钒（Ⅴ）络合物之间发生有效的能量转移,使吖啶橙526 nm处的荧光猝灭,据此建立了能量转移荧光测定痕量钒的新方法。实验表明,在pH5.5的3.0×10^-5mol.L^-1AO-4.0 mg.L^-1PAR体系中,钒的含量c在0.12-0.5μg.mL^-1范围内与荧光猝灭强度ΔF呈良好线性关系,线性回归方程为ΔF=165.4c＋2.5,方法检出限为0.0045μg.mL^-1,相对标准偏差为0.6%。该荧光猝灭反应15 min内完全,其相对荧光强度在2.5 h内基本保持不变。用该方法测定生物样品中钒的含量,相对误差小于5%,结果满足痕量分析要求。     

β-环糊精包合物的1H NMR研究

用¹H NMR研究外消旋和光学纯的色氨酸(Try) 分子与β-环糊精(β-CD)形成的包埋复合物,通过主-客体分子的化学位移的变化说明这种主-客体包埋系统的手性识别过程.     

PAMAM树状大分子与5-氟尿嘧啶相互作用的NMR研究

本文利用多种核磁共振（NMR）技术研究了聚酰胺-胺树状大分子（PAMAM）与5-氟尿嘧啶（5-FU）在水溶液中的相互作用.¹H NMR化学位移滴定结果表明5-FU分子结合在PAMAM分子表面,¹³C NMR化学位移滴定分析结果表明5-FU分子通过氢键或疏水间相互作用进入到PAMAM的内部疏水空腔.¹H核和¹⁹F核自旋-晶格弛豫时间（T₁）的测定结果也说明了二者之间存在相互作用.NOESY实验进一步验证了5-FU分子进入到PAMAM分子的内部空腔.本研究为研究树状大分子和药物小分子的相互作用提供了系统的NMR分析方法.     

四卤化锡混合物中受扩散控制的卤原子交换动力学研究

以¹¹⁹Sn NMR 方法研究了四氯化锡和四溴化锡混合物（1∶1, 摩尔比）交换体系在不同条件下的动力学性质. 测定了在不同浓度的氘代氯仿溶液中5个交换组份的表观纵向弛豫时间（T¹）及5个组份相互间的交换速率常数（k）,结果表明交换速率常数与表观纵向弛豫速率成正比关系;同时,根据¹¹⁹Sn 1D NMR信号的线宽估测了有效横向弛豫时间（T^*₂）,并由T₁/T^*₂推断在所研究的体系中分子的运动属NMR慢运动极限. 从实验结果可推断在所研究的复杂交换体系中5个组份间的交换与分子自扩散运动有关,即化学交换与交换主体的扩散运动有必然的联系.     

β-环糊精增敏荧光光谱法对柔红霉素的定量测定

采用荧光光谱法对β-环糊精（β-CD）与柔红霉素（DNR）包结物溶液进行表征。研究了β-CD与DNR之间的超分子包结作用机理,讨论了时间、温度和β-CD浓度对包结反应的影响,建立了新的定量检测微量DNR的方法。研究结果表明,DNR本身具有天然荧光,与β-CD形成1：1的超分子包结络合物后,荧光强度增大,β-CD对DNR有较强的荧光增敏作用。在25℃,pH7.0时,包结常数K=1.26×106L/mol。β-CD增敏荧光定量测定DNR的线性回归方程为y=1.78×107x＋312.76,相关系数为r=0.9953,检测下限为3.77×10-6mol/L。     

芳基重氮盐及其冠醚络合物的核磁共振研究

本文报道一系列取代苯基重氮盐及其18-冠-6,二苯并-24-冠-8分子络合物的¹H和¹³C NMR,考察它们在络合前后的化学位移变化,推测这类络合物的结构和络合成键状况。     

三价铕荧光络合物与聚乙烯吡咯烷酮复合物研究

为研究稀土荧光络合物与高分子形成的复合物的结构与发光性能间的关系,利用α-噻吩甲酰三氟丙酮（TTA）和三苯基氧化膦（TPPO）与氯化铕（EuCl₃）分别制备了Eu(TTA)₃·2H₂O和Eu(TTA)₃·(TPPO)₂络合物,及其与聚乙烯吡咯烷酮（PVP）的复合物。采用荧光光谱,红外光谱和透射电镜等方法对复合物进行了表征。荧光光谱测定结果表明Eu(TTA)₃·2H₂O与PVP K30结构单元摩尔比为1∶35的PVP/Eu(TTA)₃·2H₂O复合物的612　nm发射峰的荧光强度较Eu(TTA)₃·2H₂O络合物有显著提高。红外光谱研究表明络合物的Eu3+与PVP分子的羰基之间存在着明显的配位作用,并且存在多种配位方式。透射电镜观察结果表明复合物具有微相分离结构,其中的稀土络合物为无定形结构,这进一步表明PVP与络合物分子间存在相互作用。     

钡-玫红酸络合物荧光光谱法测定钡餐在水中的溶解度

以荧光衍生光谱法研究了氯化钡与玫红酸形成络合物的荧光光谱,建立了钡离子的荧光光谱分析方法,在优化条件下:溶液pH=11.2,反应时间为5min,乙醇与水溶剂的比为15％.在2.5×10-11-5×10-5mol/L范围内,络合物的荧光强度与钡离子浓度存在两段线性关系,检出限为2.5×10-11mol/L.方法用于钡餐在水中溶解度的测定,结果与文献报道值一致.     

基于四甲基联苯胺和吖啶橙间荧光共振能量转移的比率型荧光测定左氧氟沙星

基于3,3’,5,5’(四甲基联苯胺(3,3’,5,5’-tetramethylbenzidine, TMB)和吖啶橙(AO)之间荧光共振能量转移(FRET),建立了一种快速、低背景干扰、高灵敏度测定盐酸左氧氟沙星(LVF)的新型比率型荧光探针。在pH 5.0 NaAc-HCl缓冲溶液中,在310 nm的光激发下,TMB在350～500 nm处的荧光光谱和AO的吸收光谱重叠。以TMB作为能量供体,AO作为能量受体,构建了FRET体系。根据能量转移理论,该体系的荧光共振能量转移效率为62.5%,供体-受体间距离为2.17 nm,进一步说明TMB和AO之间发生了FRET。当在体系中加入LVF后,TMB将荧光能量转移给LVF, LVF又作为供体将能量转移给AO。LVF在TMB和AO之间起到桥梁作用,LVF将吸收的TMB荧光能量转移给AO,使得TMB荧光强度明显降低,AO的荧光强度则显著增加,从而提高了体系的FRET效率。在最优实验条件下,F_{546 nm}与F_{402 nm}之比与LVF浓度(2～80μmol·L^-1)之间存在良好的线...     

荧光光谱滴定法研究葫芦脲[7]对亚甲基蓝的包结作用

采用荧光光谱滴定法研究了不同温度下及醋酸缓冲溶液中,葫芦脲[7](CB7)对亚甲基蓝(MB)的包结作用。在一定的浓度范围内,体系的荧光强度随着CB7浓度的增大而增强,且荧光峰位有一定的蓝移,结果显示二者形成了1∶1的包结配合物,同时计算了它们的包结稳定常数以及相关热力学常数ΔG,Δh和ΔS,热力学常数数值说明反应是焓变驱动的。此外,利用1H NMR谱图,结合葫芦脲[7]以及客体亚甲基蓝的结构特征,对其包结机理及主客体作用模式进行了探讨。     

Synthesis of Novel Fluorescent Cyclohexenone Derivatives and their Partitioning Study in Ionic Micellar Media

An approach is demonstrated toward the synthesis of four novel cyclohexenone derivatives (CDs) via a convenient route of Michael addition of ethyl acetoacetate. The molecular structures of CDs were confirmed by means of FT-IR, ¹H NMR, EIMS, UV and also by X-ray single crystal structure analysis. CDs are strongly fluorescent compounds and their fluorescent spectra exhibits intense violet fluorescence. To model the binding to biological membranes the behavior of CDs in micellar solutions of a cationic surfactant, cetyltrimethylammonium bromide (CTAB) and an anionic surfactant, sodium dodecylsulfate (SDS) has also been examined. The characteristics of partition and binding interactions of CDs with CTAB and SDS were investigated by UV-Visible and fluorescence spectroscopic techniques. Higher values of all mentioned interactions in case of CTAB, compared to SDS, indicate that there are greater interactions between the CDs and CTAB than with SDS.     

Spectrophotometric and spectrofluorimetric investigation of different equilibria of a recently synthesized Schiff base with the aid of chemometric methods

In this study ground and excited states acidic dissociation constants of a recently synthesized Schiff base was obtained in a DMF:water mixture of 30:70 (v/v) using absorption and fluorescent spectra of the Schiff base in different pH values with the aid of chemometric methods. In addition, the fluorescent of the two kinds of tautomers of this Schiff base was investigated and the rate of tautomerization was obtained using rank annihilation factor analysis (RAFA). The effect of different kinds of surfactants such as sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and Triton X-100 on fluorescence spectrum of the Schiff base in a DMF:water mixture of 2:98 (v/v) was investigated. CTAB increased the fluorescence intensity of the Schiff base while SDS and Triton X-100 had no significant effect on it. β-Cyclodextrin increased the fluorescence intensity of the Schiff base. Also the sensing behavior of this Schiff base toward metal ions was studied in DMF and ethanol by fluorescence spectroscopy. The Schiff base showed prominent fluorescent signal in the presence of Zn²⁺, whereas other metal ions failed to induce response and ground-state dissociation constant of the complex was determined by direct fluorimetric titration as a function of Zn²⁺ concentration.     

丝素肽和β-环糊精包合作用及表面活性剂影响

在pH为2和包合时间是60min的最佳条件下,采用光谱法（荧光光谱与紫外-可见光谱）测得β-环糊精（β-CD）与丝素肽构成的包合体系包合比均是2∶1,平均包合常数是3.3×105。两种阴离子表面活性剂十二烷基硫酸钠、十二烷基苯磺酸钠对包合体系有阻抑作用,阳离子表面活性剂十六烷基三甲基溴化铵和非离子表面活性剂＂平平加O＂对包合体系没有影响。     

Significant effect of surfactant micelles on pH dependent fluorescent off-on-off behavior of Salicylaldehyde-2,4-Dinitrophenylhydrazone

The fluorescence response to pH of 2,4 dinitrophenolhydrazone in 1:1 CH₃OH:H₂O and micellar mediums—negatively charged sodium dodecylsulphate (SDS), positively charged cetyltrimethyl ammonium bromide (CTAB) and neutral Triton X-100 (TX-100), is reported. At pH 4.0 the fluorescence of the molecule can be switched “on” by selecting CTAB as the solvent. At pH 6.0 if the medium is TX-100 the fluorescence is “off”, but remains “on” for the other three solvents. At pH 8.0, fluorescence is “on” in the solvents except CTAB. SDS and TX-100 switch the fluorescence “on” at pH 13.0 but for the other two solvents the fluorescence is “off”.     

Design of Two Pyrazole-Based Sensors with Similar Configuration and Different Fluorescent Response to Anions

Two simple fluorescent anion receptors based on 1-phenyl-3-methylpyrozole-5-one-4-one phenylhydrazone (L1) and 1-phenyl-3-methylpyrozole-5-one-4-one p-nitrophenylhydrazone (L2) were designed, synthesized and characterized with ¹H NMR, COSY spectrum, ¹³C NMR, ESI-mass and elemental analyse. Interestingly, two receptors with similar configuration exhibited different anion binding behaviors in DMSO solution. The results of Job plots and ESI-mass spectrum indicate that L1 bind anions such as F⁻, AcO⁻, H₂PO₄⁻ to form 2:1 host-guest complexation, while L2 bind anions to form 1:1 host-guest complexation in the solution.     

Spectrofluorimetric study on the inclusion behavior of p-sulfonated calix arene with cetyltrimethylammonium bromide and analytical application

The characteristics of host-guest complexation between p-sulfonated calix [G. Arena, S. Gentile, F. G. Gulino, D. Sciotto, C. Sgarlata, Tetrahedron Lett. 45 (2004) 7091] arene (SC6A) and cationic surfactant cetyltrimethylammonium bromide (CTAB) were studied by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and the complex constant was also calculated by a deduced equation. It was found the fluorescence of the complex could be remarkably quenched by an appropriate amount of ceftriaxone sodium (CTRX). Based on the results, a novel spectrofluorimetric method for determination of CTRX was developed with a linear range of 9.2×10⁻⁷-8.5×10⁻⁵ mol L⁻¹ and a detection of 3.5×10⁻⁷ mol L⁻¹. The proposed method was used to determine CTRX in their commercial preparations with satisfactory results. Moreover, the probable interaction mechanisms of the systems were also discussed.     

Investigation of the inclusion behavior between p-sulfoniccalix[8]arene and norfloxacin by fluorescence spectroscopy

The host-guest complexation between p-sulfoniccalix[8]arene (SC₈A) and norfloxacin (NFLX) in aqueous solution was investigated by fluorescence spectroscopy. Strong fluorescence intensity of the NFLX aqueous solution alone and obvious fluorescence quenching of NFLX solution in the presence of SC₈A were observed. The fluorescence lifetimes of NFLX and SC₈A-NFLX inclusion complex were determined and the effect of temperature on SC₈A-NFLX inclusion complex was studied. The static quenching of the inclusion was obtained, that is the SC₈A can form a nonfluorescent ground-state inclusion complex with NFLX. As the results show, the combined ratio (n) was 1:1 and association constant K was 1.17×10⁵ L/mol. Based on the experimental results, the mechanism of the inclusion complex was explored. The space matching, electrostatic force and hydrogen bond play important effects in the inclusion process. Subsequently, the addition of bovine serum albumin (BSA) solution led to the recovery of fluorescence intensity. It is indicated that BSA can liberate the NFLX into the solution by destructing the SC₈A-NFLX inclusion complex. Hence SC₈A may be used for controlled-release drug delivery in the pharmaceutical industry.     

光谱法研究CTAB对木瓜酶酶活和构象的影响

采用荧光光谱、圆二色谱(CD)和紫外光谱研究了十六烷基三甲基溴化铵(CTAB)在NaHPO4-NaH2PO4缓冲溶液中对木瓜酶构象变化及其酶活的影响,并探讨了CTAB与木瓜酶的作用机理.荧光光谱表明,在CTAB存在下,木瓜酶的荧光强度增强,荧光峰发生红移,CTAB使木瓜酶分子链趋于伸展,酪氨酸等发色基团更多地暴露在水中.CD谱表明,当CTAB浓度(CCTAB)为0.5 mmol/L时,木瓜酶的a-螺旋构象和β-折叠构象含量比纯木瓜酶(Papain)体系分别增加了1.3％和0.1％,回转构象和无定型构象含量则分别减少了0.3％和1.2％.酶活测定结果表明,CTAB对木瓜酶的酶活有较大影响,当CCTAB由0增加到 1.5mmol/L时,木瓜酶酶活由11.2×105U/g增大到16.3×105U/g,当CCTAB由1.5mmol/L增加到3.5mmol/L时,木瓜酶的酶活又由峰值(16.3×105U/g)降到11.7×105U/g.CTAB使木瓜酶酶活增强与木瓜酶的构象有序度提高有关.     

A turn-on fluorescent anion receptor based on N,N′-di-β-naphthyl-1,10-phenanthroline-2,9-diamide

A simple turn-on fluorescent anion chemosensor with amide moiety as binding sites was designed, synthesized and characterized. Binding ability of the receptor 1 with anions was evaluated through the fluorescence titration in DMSO and the ¹H NMR titration in DMSO-d₆ and coordination of anions to 1 led to a visible enhancement in fluorescence intensity. The fluorescence enhancement could be explained on the basis of two signaling transduction mechanisms: (1) inhibition of a photoinduced electronic transfer (PET) mechanism and (2) anion-induced increase of the rigidity of the host molecules. In addition, the results of ¹H NMR titrations suggested that a host-guest hydrogen-bonding complex with an association constant K_ass=7379 mol⁻¹ L was formed between 1 and F⁻ and the mode of host-guest interactions was provided.