自动酸碱滴定仪的研制

介绍了一种用测色法来判断滴定终点的全自动酸碱滴定仪。该仪器采用蠕动泵驱动滴定剂,用光电开关检测滴定剂滴数,根据滴数计算所用滴定剂的体积。测量的全过程由微型计算机控制,自动完成滴定过程,实现对微量离子浓度的测量。具体给出了酸碱滴定原理、总体结构及硬件配置。在该滴定装置中,没有与滴定剂溶液接触的活塞,同一滴定装置就可用于酸、碱滴定,简化了滴定装置。     

双亲金属卟啉在SDS胶束中的光谱性质及动力学研究

5,10,15-3(4-羟基酚基)-20-(4-十六烷氧基酚基)卟啉锌(P1Zn)增溶于SDS胶束中,用敏感于微环境变化的紫外-可见光谱,研究了P1Zn在pH正向滴定和逆向滴定过程中Sorer带和Q带的变化与体相pH值的依赖关系。随着pH值由中性变化到强酸性,P1Zn中的锌原子被氢原子取代生成P1,而pH值由强酸性变化到中性,P1中的氢原子并未被锌原子取代生成P1Zn。在中性条件下P1与Zn(Ⅱ)的动力学表明,在pH值变化过程中,其增溶位置可能发生了变化,初步分析了双亲卟啉的结构对于增溶位置的影响。     

溶液的酸碱性对番茄红素荧光光谱的影响

用970CRT荧光分光光度计分别采集了不同pH值下番茄红素-丙酮溶液的荧光光谱,并测量了这些溶液的荧光强度随时间的变化情况。通过对数据的分析得出:与没有经过酸碱滴定的番茄红素-丙酮溶液相比,酸性条件下,荧光强度相对较小,而在碱性条件下,其荧光强度相对较大;pH=1时,番茄红素-丙酮溶液的荧光峰位发生了红移,而pH=11和pH=13时,其荧光峰位又有不同程度的蓝移;在强酸和强碱环境中番茄红素不稳定,其荧光峰强度下降较快,这是因为在强酸环境下重原子效应的影响,和强碱环境下番茄红素参加了阴离子聚合反应;番茄红素在有机溶剂和弱碱环境下比较稳定,其荧光强度下降较慢。     

中红外反射光谱结合偏最小二乘法快速定量分析葡萄酒

利用傅里叶变换中红外光谱(FTIR)和衰减全反射(ATR)技术,结合偏最小二乘算法,建立了一种同时快速测定葡萄酒中总酚含量、滴定酸度、pH值和酒精度的方法。通过光谱预处理方法、异常值诊断和建模参数的优化,提高了模型的预测精度,各指标预测值与实测值相关性良好,总酚含量、滴定酸度、pH值和酒精度模型的相关系数(r2)依次为0.9356,0.9649,0.9935,0.9837;交互验证均方根误差(RMSECV)依次为:0.445,0.378,0.087,0.507。t检验结果表明模型预测结果与标准方法测定结果之间无显著性差异(显著性大于0.05)。     

小分子荧光探针的光谱

运用紫外-可见光谱、荧光光谱法研究了以二烯酮为荧光团的1,5-双(4-羟基)-1,4-戊二烯-3-酮探针的光学性质.一系列pH滴定实验表明探针的紫外吸收和荧光光谱随溶液的pH值的改变而变化.同时,探针紫外吸收光谱发生明显的红移,荧光光谱强度也随之变化,在碱性条件下,相对荧光强度浮动较大.解离常数pK<,α>为9.25,...     

3-氨基苯硼酸-苯胺共聚物薄膜对pH的光学响应

在硫酸介质中,以氧化铟锡(ITO)透明导电玻璃为基质材料,应用循环伏安法制备3-氨基苯硼酸-苯胺共聚物薄膜.用紫外可见光谱方法测定了共聚物薄膜在不同pH下的特征吸收光谱,结果表明,在pH 2-12范围内共聚物薄膜对pH的变化表现了极高的光学敏感性,当pH从2增加到12时,其λmsa从773nm(pH=2)变化到614nm(pH=12);由相应的滴定曲线计算共聚物薄膜的表观pKa为6.21薄膜对pH响应速度快,光谱变化在20s内基本完成;共聚物薄膜对pH响应的重现性较好,重复使用在最大吸收773nm处吸光度的变化为1.0%,在614nm处吸光度的变化为0.7%.     

DPPH自由基清除活性的光度微量滴定模型及应用

传统的DPPH自由基清除活性评价方法以半数清除浓度EC₅₀为评价指标,但EC₅₀随DPPH初始加入量增加而增加,随分析体积增加而减小,因此,不同条件EC₅₀值不具有可比性。提出以DPPH与抗氧化剂相互反应的化学计量数比(R)作为评价DPPH清除活性的指标,该指标只与DPPH与抗氧化剂相互反应的化学计量关系有关,与DPPH初始加入量和分析体积等因素无关,解决了EC₅₀可比性差的问题。提出了测定化学计量数比(R)的光度微量滴定法,建立了利用滴定过程吸光度差(ΔA)与抗氧化剂加入量之间的滴定方程计算R值、以R计算EC₅₀的光度微量滴定模型,并利用芦丁对模型进行验证。结果：芦丁与DPPH反应R值在1.817～1.846之间,当DPPH加入量为1.12×10-7,2.24×10-7,4.48×10-7和6.72×10-7 mol时,分别计算得EC₅₀值分别为1.196×10-3,2.392×10-3,4.819×10-3和7.292×10-3 mg·mL-1。在此基础上,基于文献报道的芦丁清除DPPH条件,利用得到的芦丁R值计算出相应EC₅₀,结果与文献报道EC₅₀值相当。方法可比性好,样品消耗量明显降低,简单、成本低,结果可靠,为自由基清除活性评价提出了一种新的思路。     

海水低频声吸收与pH值的关系

本文用共振器法测量了天然海水低频声吸收与pH值的关系。测量频率为2.91、6.82和10.76kHz;pH值范围为6.48—8.51;温度为12.6℃。测量结果与不同的声吸收公式计算值进行了比较。本文实验的主要目的之一是通过将pH值减小到足够小的数值来检验海水中MgSO_4吸收的贡献。实验结果表明:为了能用一个统一的公式较准确地预估低频和高频的海水声吸收,此公式看来应该既包括MgCO_3吸收项,又包括MgHCO_3~ 吸收项。     

铬离子与酪氨酸作用的光谱研究

在pH 5.6的0.1mol/LN-2-羟乙基哌嗪-N1-2-乙磺酸(Hepes)及室温条件下,用荧光光度计进行了Cr3+对酪氨酸(Tyr)的滴定.结果表明Cr(Ⅲ)与Tyr形成1∶1的配合物.再用不同比例的[EDTA]/[Cr3+]系列溶液分别滴定Tyr,由EDTA与Tyr的竞争结合,间接求得Cr(Ⅲ)与Tyr的结合...     

自由配体分布系数对数图与光度法测定的最低pH值

从弱酸自由配体分布系数负对数与pH值的关系推导出光度法测定时溶液最小pH值的简便计算公式,并给出了计算光度法测定时适宜酸度范围的方法。     

Adsorption and thermodynamic studies of Cu(II) and Zn(II) on organofunctionalized-kaolinite

Kaolinite-bearing clay samples from Perus, São Paulo state, Brazil, were used for chemical modification process with dimethyl sulfoxide and organofunctionalized with the silyating agent (RO)₃Si(CH₂)₃NH(CH₂)₂NH₂ in the present study. The resulting material and natural kaolinite were subjected adsorpion process with Cu(II) and Zn(II) from aqueous solution at pH 6.0 and controlated temperature of 298 K. The Langmuir adsorption isotherm model has been applied to fit the experimental data. The results showed that the chemical modification process increases the basal spacing of the natural kaolinite from 0.711 to 0.955 nm. The energetic effects caused by Cu(II) and Zn(II) interactions were determined through calorimetric titration at the solid–liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.     

Studies on ground and excited state prototropic equilibria of 2-fluorenaldehyde 2-pyridylhydrazone

The ground and excited state pK values of 2-fluorenaldehyde 2-pyridylhydrazone obtained from variations in fluorescence intensity with pH are reported. The two acid-base equilibria are separately treated by instrumental and chemical means. Absorption and fluorescence spectral shifts are employed to show that solute-solvent interactions through hydrogen-bonding are responsible for the disagreement between the excited state pK values obtained from Förster cycle calculations and from fluorimetric titration measurements.     

Fluorescence Titration of Some Purines Determination of Lowest Excited-State Ionization Constants

Abstract

Excited-state ionization equilibria of 6-methyl purine and xanthine were investigated in a wide range of pH.

6-Methyl purine is known to have two ionization equilibria in its ground-state. It was found that it had one more ionization equilibrium in strongly acidic region. In the excited state, four ionization equilibria were observed. The pK? values of three of them were determined by means of fluorescence titration.

In the case of xanthine, there exist three ground-state equilibria. In the excited-state, four equilibria were observed. The pK? values of two of them were determined by means of fluorescence titration.     

含硼盐卤体系中碳酸根和碳酸氢根分析方法改进

利用甘露醇法测定硼、双指示剂法测定总碱度,同时借鉴血清中HCO-₃的检测方法,建立了一种分光光度-滴定分析联用方法,用于准确测定含硼盐卤体系中硼及CO2-₃和HCO-₃的准确含量。以酚红为显色剂,考察了测定波长、显色剂用量、显色反应温度、pH等测试条件的影响,并从浓度与吸光度的线性关系,检出限及加标回收率等方面进行了系统研究,结果表明：在显色剂用量为1 mL,控制pH 8.4,室温下进行显色反应;在波长558 nm处,CO2-₃在0~10 mmol·L-1内吸光度与浓度有良好线性关系,线性相关系数R2=0.999 8,检出限为2.53×10-3 mmol·L-1。样品加标回收率范围在97.75%~101.76%间,相对误差在-1.67%~-1.95%。该方法简便易行,精密度好,准确度高,优化了共存硼体系中CO2-₃和HCO-₃含量的测定方法,为含硼盐卤体系中体系碳酸根和碳酸氢根含量的准确测定提供了一种新的方法,对于盐湖卤水的基础研究和实际应用提供了新的思路和实验方法。     

A functionalized dianthryl tetraaza macrocycle having the recognizing and switching ability

The synthesized macrocycle L is the novel fluorescent receptor having the switching ability by the external stimuli as well as having the recognizing ability of various metal ions. In particular, this macrocycle L shows the possibility of the selectivity of metal ions even in the same charge ions of a different metal, and the values of association constant (M⁻¹) of that for metal ions are consistent with the tendency of increasing charge number of metal ion. In addition, the values of quantum yield (Φ_F) of metal complexes of macrocycle L were ranged from 0.021 to 0.111 enough to recognize the metal ions in macrocycle L. We know from the fluorescent pH titration of macrocycle L by acid/base that the change of fluorescence intersects at about pH=5.     

烟草中CuZnSODⅢ的荧光光谱及pH值和H2O2敏感性

考察了烟草中CuZnSODⅢ在不同pH值和H2O2加入量前后的荧光光谱。用同步荧光技术区分蛋白质分子中酪氨酸和色氨酸残基的荧光,进一步结合荧光猝灭现象和三维荧光特征,探讨发色团微环境及蛋白质分子构象行为,推断得出H2O2对荧光的猝灭属于氧化还原猝灭和双分子碰撞猝灭双重机制,及色氨酸残基对pH值和H2O2更为敏感的结论。     

Considerations for brain pH assessment by 31P NMR

Recently in vivo NMR spectroscopy has been used to measure brain pH non-invasively. Both the inorganic orthophosphate (Pi) chemical shift (delta) and the difference between the chemical shifts of phosphocreatine (PCr) and Pi(delta delta PCr-Pi) have been proposed as indicators of brain pH. However, the precise delta of Pi may be difficult to determine under normoxic conditions as is the delta of PCr under hypoxic/ischemic conditions. Ideally one needs a NMR delta parameter that: (1) linearly changes between pH 6.0-8.0, (2) is either relatively unaffected or predictably affected by cations (e.g., Mg2+) other than H+, and that (3) comes from readily observable 31P NMR resonances whose delta's can be accurately assessed under all physiological conditions. Therefore, we undertook a systematic 31P NMR study of the pH and Mg2+ titration curves for 16 phosphorus-containing metabolites observed in brain by 31P NMR. On the basis of the titration curves, the delta delta's for PCr-Pi, phosphoethanolamine (PE)-Pi, and PCr-PE fulfill criteria (1) and (2), but not criterion (3). However, the delta delta of ATP gamma-alpha fulfills all three criteria and potentially provides information on the intracellular Mg2+ concentration.