Effect of Mobile Phase pH* on Chromatographic Behaviour in Chiral Ligand-Exchange Thin-Layer Chromatography (CLETLC) of Amino Acid Enantiomers

The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated. It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7. The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7.     

Equations for calculation of the pH of buffer solutions containing sodium or potassium dihydrogen phosphate, sodium hydrogen phosphate, and sodium chloride at 25°C

Published thermodynamic data measured in aqueous mixtures of sodium or potassium dihydrogen phosphate with hydrogen phosphate and chloride at 25°C were used to test recently developed methods for calculation of the pH of phosphate buffer solutions. Equations for ionic activity coefficients are used in these methods. It is shown that all data used in the tests up to an ionic strength of about 0.5 mol-kg^-1 can be accurately predicted by the two methods recommended. In one of these methods, equations of the Hückel type are used for ionic activity coefficients and in the other equations of the Pitzer type. Several sets of phosphate buffer solutions are recommended,e.g., for calibrations of glass electrode cells. In the recommended sets, the pH of the buffer solutions can be calculated either by the Hückel or Pitzer method, and the pH predictions of these methods agree in most cases within 0.005 at least up to ionic strengths of about 0.2 mol-kg^-1. The pH values of the two primary pH standards endorsed by IUPAC based on aqueous mixtures of KH₂PO₄ and Na₂HPO₄,i.e., pH values of 6.865 and 7.413, can also be accurately predicted by the equations recommended in this study.     

Hydrolysis and polycondensation of ethyl silicates. 2. Hydrolysis and polycondensation of ETS40 (ethyl silicate 40)

The effects of catalysts, pH and reaction conditions on the course of the hydrolysis and condensation of ETS40 (ethyl silicate 40), and on the composition of the reaction products were studied with the aid of gas and gel chromatography, potentiometry and gelation tests. Strong acids (HCl, HClO₄, HNO₃, H₂SO₄, p-toluenesulphonic acid), weak acids (Cl₃, CCOOH, ClCH₂COOH, (COOH)₂, CH₃COOH and HCOOH) and bases (LiOH, NH₄,OH) were used as catalysts.

The hydrolysis rate increased with increasing temperature, catalyst concentration, initial water concentration and initial ethyl silicate concentration, whereas it decreased with increasing number of Si atoms in the ethyl silicate molecules. At pH 0–7 the hydrolysis was acid catalysed, but at pH above 7.0 it was base catalysed. Simultaneously with the hydrolysis, condensation occurred at a rate which increased with increasing temperature, catalyst concentration, ETS40 concentration and, above all, with increasing initial water concentration. The condensation rate depended on the pH. The condensation was at its slowest for pH around 2.0. For pH below 2.0, the condensation increased with increasing hydrogen ion concentration; for pH above 2.0 the condensation increased with decreasing hydrogen ion concentration. Phosphoric acid and hydrofluoric acid increased the rate of condensation considerably. The reaction of ETS40 with water at pH around 2.0 gave rise during the hydrolysis to solutions of ethoxyhydroxysiloxanes with an average of 14–20 Si atoms in a molecule, which displayed long-term stability.     

SciFinder-guided rational design of fluorescent carbon dots for ratiometric monitoring intracellular pH fluctuations under heat shock

Intracellular pH plays a significant role in various biological processes, including cell proliferation, apoptosis, metabolism, enzyme activity and homeostasis. In this work, a novel design strategy for the preparation of pH responsive carbon dots (CDs-pH) for ratiometric intracellular imaging was reported. By using SciFinder database, fluorescent CDs-pH with the required pK_a value of 6.84 were rationally designed, which is vital important for precise sensing of intracellular pH. As a result, the synthesized CDs-pH demonstrated robust ability to test pH fluctuations within the physiological range of 5.4-7.4. The CDs-pH was further utilized for fluorescent ratiometric imaging of pH in living HeLa cells, effectively avoided the influence of autofluorescence from native cellular species. Moreover, real-time monitoring of intracellular pH fluctuation under heat shock was successfully realized. This SciFinder-guided design strategy is simple and flexible, which has a great potential to be used for the development of other types of CDs for various applications.     

Effect of the medium pH on the release of secondary metabolites from roots ofDatura stramonium,Catharanthus roseus,andTagetes patula cultured in vitro

The release of alkaloids from root culturesDatura stramonium andCatharanthus roseus and thiophenes from root cultures ofTagetes patula was found to increase when the pH of the culture media (ranging from 4.8 to 7.0) was reduced to 3.5. The extent of the effect was different in each type of culture. Increases ranged from 4- to 20-fold, which in some cases accounted for 75% of the total secondary metabolite pool produced per flask. When the release of individual metabolites was measured, even larger increases, were observed (nearly 400-fold for ajmalicine). Increased release of alkaloids fromC. roseus roots were also observed in cultures growing in a 14-L fermentor, when the medium pH was reduced. Reduction of the pH of the media did not affect growth of the root cultures in subsequent subcultures. The importance of this treatment as a stategy to improve the recovery of secondary metabolites from producing cultures is discussed.     

Computational Modelling of the Behaviour of Potentiometric Membrane Biosensors

This paper presents a mathematical model of a potentiometric biosensor based on a potentiometric electrode covered with an enzyme membrane. The model is based on the reaction–diffusion equations containing a non-linear term related to theMichaelis–Menten kinetics of the enzymatic reaction. Using computer simulation the influence of the thickness of the enzyme membrane on the biosensor response was investigated. The digital simulation was performed using the finite difference technique. Results of the numerical simulation were compared with known analytical solutions.      

溶液酸度在线检测装置的研制

研制了酸度在线检测装置，并应用于溶液酸度在线检测，溶液酸度在线检测装置，设有防污过滤器，自动采样器，蠕动泵，小型管道ｐＨ传感器和控制电路等，其特点为防污除油，随机自动采样，定时检测，全部管道化，可单独使用和计算机控制系统联网，适用于溶液酸在线分析，测定精度〈ｐＨ０．０５。     

Glass and polymeric membrane electrodes for the measurement of pH in milk and cheese

While there is a considerable interest in the food industry in determining various analytes using ion-selective electrodes (ISEs), only few reports describe their use for direct measurements in food. In this study, the suitability of glass electrodes and ionophore-based solvent polymeric ISEs for the determination of pH in Process cheese, Cheddar cheese and milk was investigated. The liquid junction potential between a 3 M KCl bridge electrolyte and diluted as well as undiluted Process cheese was found to be negligible. Reference electrodes with ceramic plug and sleeve-type junctions performed well, although precautions needed to be taken to prevent plugging at the junctions. While the protein rennet casein posed no problems in pH measurements, the extraction of neutral lipophilic compounds or hydrophobic peptides into solvent polymeric membranes was evident, resulting in some loss of selectivity for monovalent cations upon exposure to cheese. However, it was found that ISEs based on tridodecylamine (R₃N) as ionophore and o-nitrophenyl octyl ether (oNPOE) as plasticizer can be used to accurately measure the pH of milk and, after desensitization of the electrodes in a cheese emulsion, of diluted Process cheese. Since pH measurements with a glass electrode showed that emulsions of cheese moderately diluted to a cheese content of 70% have the same pH as undiluted cheeses, it is possible to determine the pH in cheese with ionophore-based ISEs. R₃N membranes also performed well in undiluted milk.     

铅笔芯修饰聚苯胺制作微型复合pH电极的性能

在0.3mm直径的铅笔芯上电修饰聚苯胺,封入玻璃毛细管中,并与Ag/AgCl电极组合成复合微型pH电极.经实验测试,该电极的pH响应特性良好,在pH1～11的线性范围内,能斯特斜率为(-56.4±0.5)mV/pH,线性相关系数不小于0.996.作为参比的Ag/AgCl电极性能稳定.由于电极是复合微型化的,所以可用于活体微区测定.