四磺基铝酞菁与爱尔新蓝的缔合作用在核酸定量中的应用

阴离子荧光染料四磺基铝酞菁与阳离子荧光染料爱尔新蓝的缔合作用 ,使四磺基铝酞菁发生荧光猝灭 ,而当核酸存在时 ,染料缔合平衡受到影响而导致四磺基铝酞菁的荧光恢复。根据这一原理 ,建立了核酸定量测定的新方法。方法具有很高的灵敏度和较好的选择性 ,其线性范围为 0～ 2 0 0 μg/L ;检测限分别为 1.8μg/L(SMDNA)、2 .0 μg/L(CTDNA)、5 .4μg/L(酵母RNA)。将方法用于实际样品金黄色葡萄球菌中DNA含量的测定 ,获得满意结果     

四氨基铝酞菁作为过氧化物酶模拟酶新型红区荧光底物的研究

本文按照文献[1]合成了一种优良的红区荧光探针－四氨基铝酞菁（TAAIPc,在强酸性介质中,它的最大激发与最大发射波长分别在610nm和678nm处）,并将它作为过氧化物酶模拟酶的红区荧光底物用于痕量过氧化氢的测定。由于在长波区具有荧光的天然物质很少,且溶液体系的散射光强度与1／λ^4成正比,因而在长波处进行样品测定时可以很好地避开背景荧光和散射光的干扰,检测限可得到较大的改善。     

新型四羧基铝酞菁-二氧化硅荧光纳米粒子的合成及在酸度测定中的应用

首次制备出红区荧光染料四羧基铝酞菁掺杂的二氧化硅纳米粒子,并对其进行了表征。将环己烷、正己醇和表面活性剂Triton X-100按一定体积比(12.3∶1.04∶1)混合均匀,形成清澈透明的溶液;将适量的四羧基铝酞菁溶解到浓氨水中,加入到上述混合溶液中,形成反向胶束。搅拌10 m in后加入一定量的四乙氧基硅烷,加快搅拌速度,促使四乙氧基硅烷进入反相胶束中的“纳米水池”,在碱性条件下,四乙氧基硅烷水解形成二氧化硅纳米粒子。采用该方法制备的核壳荧光纳米颗粒荧光稳定性强,生物相容性高,抗干扰能力强。将一定量四羧基铝酞菁掺杂的二氧化硅纳米粒子溶于水溶液中,随溶液pH值的增加,荧光强度增强,并在pH 5.02~11.98的范围内,荧光强度与溶液酸度有良好的线性关系。该法已成功地用于自来水和模拟生物体系中pH的测定。预期该技术有望用于细胞内H 的实时监测。     

甲磺基铝酞菁与爱尔新蓝的缔合作用在核酸定量中的应用

阴离子荧光染料四磺基铝酞菁与阳离子荧光染料爱尔新蓝的缔合作用，使四磺基铝酞菁发生荧光猝灭，而当核酸存在时，染料缔合平衡受到影响而导致四磺基铝酞菁的荧光恢复。根据这一原理，建立了核酸定量测定的新方法。方法具有很高的灵敏度和较好的选择性，其线性范围为0-200цg/L；检测限分别为1.8цg/L(SMDNA)、2.0цg/L(CTDNA)、5.4цg/L（酵母RNA）。将方法用于实际样品金黄色葡萄球菌中DNA含量的测定，获得满意结果。     

金属酞菁的合成及其激光解吸质谱研究

通过简便的合成方法,以邻苯二甲酸酐和尿素为起始原料,经过亚胺化、硝化、氨解步骤,经固相熔融法分别合成四硝基酞菁铜和四硝基酞菁镍,最后经还原得四氨基酞菁铜和四氨基酞菁镍.然后分别测定无取代酞菁镍、四氨基酞菁铜和四氨基酞菁镍的激光解析质谱图,理论值与实测值相吻合,并且化合物含量均在96%以上.     

二吡啶四硝基酞菁钴的合成及光谱—电化学性质研究

本文报道了以钼酸铵为催化剂,将4—硝基邻苯二甲酸酐、脲和氯化铵混合,于220℃加热合成四硝基酞菁钴,将此配合物溶于吡啶,于115℃加热反应6天合成了二吡啶四硝基酞菁钻配合物。并对二吡啶四硝基酞菁钴的氧化还原半波电势、电解氧化还原产物的电子吸收光谱进行了研究。     

四磺基铝酞菁-阳离子表面活性剂体系应用于白酒中乙醇含量的测定

基于四磺基铝酞菁（AIS4Pc)在阳离子表面活性剂存在下发生诱导缔合而导致体系荧光猝灭,而在乙醇存在下AIS4Ps解聚体而使体系荧光恢复的原理,建立了测定白酒中乙醇含量的新方法。方法的线性区间为0．5％－90％（V／V）乙醇,检测限为0．48％（V／V）。本法已应用于实际酒样中乙醇的直接测定,结果满意。     

分子光谱法研究铝酞菁与牛血红蛋白的相互作用

利用紫外可见吸收光谱和荧光光谱研究了在生理pH条件下铝酞菁与牛血红蛋白(BHb)的相互作用.实验结果表明:铝酞菁分子与BHb发生反应生成基态复合物,导致BHb内源荧光的猝灭,该猝灭属于静态猝灭.测定了不同温度下该反应的表观结合常数、结合位点数及结合热力学参数,热力学参数的变化表明铝酞菁与BHb之间以静电和疏水作用力为主;根据Frster能量转移理论,测得供体与受体间结合距离r和能量转移效率E;并用同步荧光光谱法探讨了铝酞菁对BHb构象的影响.     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

阳离子铝酞菁-黏多糖缔合物荧光探针测定生物样品中的溶菌酶

在弱酸性介质中,具有红区发射特性的强荧光化合物阳离子铝酞菁(TTMAAlPc)在带磺酸基团的低浓度阴离子黏多糖(肝素,HP)的存在下,发生诱导聚集,导致酞菁荧光几乎完全猝灭。此聚集缔合物可作为溶菌酶的荧光底物,在溶菌酶的水解作用下,HP降解为小分子片段,破坏了TTMAAlPc的诱导聚集行为而使其释放,体系荧光显著恢复。据此现象,建立了测定溶菌酶的新方法。结合荧光光谱与荧光各向异性技术对反应机理进行了探讨。确定了最佳反应条件(醋酸缓冲体系,pH4.0、反应温度70$C、反应时间30 min),考察了共存物质的影响。在最佳条件下,方法的线性回归方程为y=#30.12121+214.65772x,r=0.99871,线性范围为0.2~2 mg/L,检出限0.015 mg/L。本研究操作简便且有较好的选择性和灵敏度。本方法用于溶菌酶实际样品的测定,并与常规的比浊法进行了比较,结果符合良好。本研究将阳离子金属酞菁荧光探针用于酶分析,开拓了酞菁荧光探针的应用范围。     

Sensitive fluorimetric method for the determination of aniline by using tetra-substituted amino aluminium phthalocyanine

This is the first report of the determination of aniline with tetra-substituted amino aluminium phthalocyanine (TAAlPc) by a fluorimetric method. In KBr-HCl solution, nitrite ion diazotizes TAAlPc, thus, the fluorescence of TAAlPc is dramatically quenched. However, there is less quenching in the presence of aniline and the recovery in fluorescence intensity is linear with the concentration of aniline. Based on this, a novel method has been developed for the determination of aniline in aqueous solutions. Under the optimal conditions, the calibration graph for aniline is from 5 to 300 ng ml⁻¹ with a 3σ limit of detection of 1.8 ng ml⁻¹. The relative standard deviation for nine replicate measurements of 100 ng ml⁻¹ aniline is 1.7%. The method was applied to the analysis of water samples with satisfactory results.     

Determination of proteins at nanogram levels by a resonance light-scattering technique with tetra-substituted sulphonated aluminum phthalocyanine

This is the first report on the determination of proteins with tetra-substituted sulphonated aluminum phthalocyanine (AlS₄Pc) by resonance light-scattering (RLS). At pH 3.0, the weak RLS of AlS₄Pc can be enhanced by the addition of proteins. Based on this, a novel quantitative method has been developed for the determination of proteins in aqueous solutions. Under optimal conditions, the linear ranges of the calibration curves were 0.050–2.0 μg ml⁻¹ for both human serum albumin (HSA) and human r-IgG. The detection limits were 12.7 ng ml⁻¹ for HSA and 16.1 ng ml⁻¹ for human r-IgG. The method has been applied to the analysis of total protein in human serum samples collected from the hospital and the results were in good agreement with those reported by the hospital, which indicates that the method presented here is not only sensitive, simple, but also reliable and suitable for practical applications.     

四羧基铝酞菁与硫酸庆大霉素相互作用的共振散射光谱及其分析应用

在弱酸性介质中, 四羧基铝酞菁和硫酸庆大霉素本身的共振散射(RLS)均较弱, 但两者相互作用形成离子缔合物时, RLS显著增强, 在350～500 nm之间有一个强散射带, 最大散射峰位于401 nm. 而且散射强度与硫酸庆大霉素的浓度成正比, 可用于硫酸庆大霉素的定量测定, 线性范围为0.025～1.5 μg/mL, 检出限0.018 μg/mL. 方法可用于市售硫酸庆大霉素注射液含量的测定.     

不同代硝基芳基苄醚树枝配体轴向取代硅(Ⅳ)酞菁光物理性质的比较

在二氯硅酞菁轴向位置引入硝基芳基苄醚树枝配体是一种减少酞菁配合物聚集体形成,提高其光动力活性的有效方法。本文采用UV/Vis、稳态和瞬态荧光光谱法比较了1-3代硝基芳基苄醚树枝配体轴向取代硅(Ⅳ)酞菁的光物理性质。研究结果表明,随着轴向树枝配体代数的增加,Q带最大吸收峰强度增大,酞菁核荧光强度增强,荧光量子产率降低,荧光寿命增长。研究结果将为开发轴向取代硅(Ⅳ)酞菁配合物作为新型光敏剂提供重要的理论依据。     

Studies on tetra-amine phthalocyanines

Metal(II) tetranitro phthalocyanines of cobalt, nickel and copper are synthesized in pure state by a novel modified method. The complexes are characterized using elemental, electronic and IR spectral studies. Pure metal(II) tetra-amino phthalocyanines of cobalt, nickel and copper are synthesized by reducing the nitro groups of the above complexes using sodium sulphide. These complexes are also characterized by elemental, electronic, IR spectral and magnetic susceptibility measurements. The nature of the electrical conductivities of the above three metal(II) tetra-amino phthalocyanine derivatives are studied in the temperature range 303-473 K and the data are presented. Among the effect of various substituent groups on the electrical conducting property of phthalocyanine, amine group substituent on the peripheral benzene ring of the phthalocyanine molecule has been found to increase electrical conductivity to a greatest extent. These complexes showed about 10⁵-10⁶ times higher electrical conductivities compared to their parent phthalocyanine compounds.     

Using silica nanoparticles as a catalyst carrier to the highly sensitive determination of thiamine

The preparation and utilization of silica nanoparticles as a carrier of tetra-substituted carboxyl iron phthalocyanine (TCFePc, a novel mimetic peroxidase) is reported in this article. Compared with free TCFePc, the experimental results indicated that the TCFePc entrapped in silica nanoparticles exhibited an improved catalytic activity and good reusability. By using tetra-substituted carboxyl iron phthalocyanine-silica nanoparticles (TCFePc-SiO₂ Nps) to catalyze the oxidation reaction of thiamine by hydrogen peroxide, a new fluorimetric method was developed for the quantitative analysis of thiamine in pharmaceutical tablets. The influences of different conditions, such as the medium acidity, the reaction time and temperature, the concentrations of reagents and foreign substances, were all investigated. Under the optimum conditions, the calibration graph for thiamine was linear over the range of 5.0 × 10^− 9-1.0 × 10^− 6 mol L^− 1, with a detection limit of 2.0 × 10^− 9 mol L^− 1. The proposed method was successfully applied to the direct analysis of thiamine in two kinds of pharmaceutical tablets, and offered the advantages of simple pretreatment, rapid determination, high sensitivity and good reusability. Hence, as a carrier of the mimetic enzyme, the silica nanoparticles are effective for enzymatic reaction processes. This method is supposed to be hopeful for the determination of thiamine in other complex raw materials.     

Heteroaggregation between porphyrin and phthalocyanine bearing oppositely charged substituents

Heteroaggregates composed of cationic porphyrin, meso-tetra(p-trimethylamino)-porphyrin iodide, its zinc complex and anionic phthalocyanine sodium hydroxygallium 4,4',4",4"'-tetrasulfonated phthalocyanine have been investigated by absorption and fluorescence spectroscopy. It has been found that both free base cationic porphyrin and its zinc complex can form very stable heterodimers with anionic phthalocyanine in water, methanol and dhnethylfonnamide. The stability of the aggregate depends on the polarity as well as the ligation ability of the solvent. No evidence of higher aggregates was detected. Besides axial coordination, steric hindrance which influence the relative orientation of the macrocycles are considered.