Spectrophotometric determination of α-naphthol, β-naphthol,and oxine in aqueous solution

Diazotized orthanilic acid reagent has been devised as a novel chromogen for the trace determination of α-naphthol, β-naphthol, and oxine in aqueous solution. The developed method is characterized by simplicity and rapidness and does not resort to either temperature control or solvent extraction.     

Spectrophotometric determination of gold with phenyl-α-pyridyl ketoxime

A method is described for the spectrophotometric determination of gold in the concentration range of 2 to 16 p.p.m. using phenyl-α-pyridyl ketoxime as the reagent. The reagent permits to detect Iμ of gold in I ml of a solution. The method is particularly free from interference by the ions with which gold is frequently associated.     

A new potentiometric sensor for the determination of α-amylase activity

A platinum redox sensor for the direct potentiometric determination of α-amylase concentration has been described. The sensor measured the amount of triiodide released from a starch-triiodide complex, which was correlated with the α-amylase activity after biocatalytic starch degradation. The composition and stability of the potassium triiodide solution was optimized. The starch-triiodide complex was characterized potentiometrically at variable starch and triiodide concentrations. The response mechanism of the platinum redox sensor towards α-amylase was proposed and the appropriate theoretical model was elaborated. The results obtained using the redox sensor exhibited satisfactory accuracy and precision and good agreement with a standard spectrophotometric method and high-sensitive fully automated descret analyser method. The sensor was tested on pure α-amylase (EC 3.2.1.1, Fluka, Switzerland), industrial granulated α-amylase Duramyl 120 T and an industrial cogranulate of protease and α-amylase Everlase/Duramyl 8.0 T/60 T. The detection limit was found to be 1.944 mU for α-amylase in the range of 0-0.54 U (0-15 μg), 0.030 mKNU for Duramyl 120 T in the range of 0-9.6 mKNU (0-80 μg) and 0.032 mKNU for Everlase/Duramyl 8.0 T/60 T in the range of 0-9.24 mKNU (0-140 μg).     

pKa values in organic chemistry – Making maximum use of the available data

Acids and bases are ubiquitous. Sometimes, it is essential to know the accurate strength (pK_a values) of the acids/bases to work with, but sometimes just acidity/basicity order is enough. We often receive requests to measure pK_a values of different substances in different solvents for answering questions like “what acids can be used to protonate this substance” or “what base is able to deprotonate that compound?” Such questions can, in fact, often be answered using published pK_a data in different solvents. This digest/tutorial will give an overview of how to make efficient use of the existing pK_a data.     

A general and accurate nmr determination of the enantiomeric purity of α-aminoacids and α-aminoacid derivatives

Derivatization of α-aminoacids, α-aminoesters and α-aminolactones as N-acetyl derivatives allow the accurate NMR determination of the enantiomeric purity. In these conditions the major coordination site with a chiral shift reagent will correspond to the NMR observation site. Experimental factors leading to the highest ΔΔδ values are ascertained. No straightforward correlation with absolute configurations can be established.     

A reliable and efficient first principles-based method for predicting pKa values. III. Adding explicit water molecules: Can the theoretical slope be reproduced and pKa values predicted more accurately?

A popular method for predicting pK(a) values for organic molecules in aqueous solution is to establish empirical linear least-squares fits between calculated deprotonation energies and known experimental pK(a) values. In virtually all such calculations, the empirically observed slope of the pK(a) vs. ΔE fit is significantly less than the theoretical value, 1/(2.303RT) (which is 0.73 mol/kcal at room temperature). In our own continuum solvation calculations (Zhang et al., J Phys Chem A 2010, 114, 432), the empirical slope for carboxylic acids was only 0.23 mol/kcal, despite the excellent fit to the experimental pK(a) values. There has been much speculation about the reason for this phenomenon. Although the ΔE - pK(a) relation neglects entropic effects, these are expected to largely cancel. The most likely cause for the strange behavior of the fitted slope is explicit solute-solvent (water) interactions, especially involving the ions, which cannot be described accurately by continuum solvation models. We used our previously developed pK(a) protocol (OLYP/6-311+G(d,p)//3-21G(d) with the COSMO solvation model) to investigate the effect of adding one or two explicit water molecules to the system. The slopes for organic acids (especially carboxylic acids) are much closer to the theoretical value when explicit water molecules are added to both the neutral molecule and the anion. However, explicit water molecules have almost no effect on the slopes for organic bases. Adding explicit water molecules to the ions only produces intermediate results. Unfortunately, linear fits involving explicit water molecules have much larger errors than with continuum solvation models alone and are also much more expensive. Consequently, they are not suitable for large-scale pK(a) calculations. The results compared with literature values showed that our predicted pK(a) s are more accurate.     

Structure-activity relationship study of leucinostatin A,a modulator of tumor−stroma interaction

Structure-activity relationship study of leucinostatin A, a natural nonapeptide, was performed to gain insight into the structural requirements for leucinostatin A to exhibit antiproliferative activity against DU-145 prostate cancer cells under cocultured conditions with the corresponding stromal cells. Twenty truncated peptide analogs of leucinostatin A revealed that the nonapeptide structure as a whole is essential for the biological activity. Alanine scanning demonstrated the importance of some of the amino acid components, including hydroxyleucine and the second leucine from the N-terminus. Two of the three aminoisobutyric acids could be substituted with one of the enantiomers of alanine, clearly demonstrating that each methyl group in these portions has a distinct influence on the growth-inhibitory activity.     

Application of ACC method to synchronous luminiscence: determination of α-tocopherol and α-tocopheryl acetate in beverages

A new method based on the Q parameter, that permits the determination of the C_{compound A} /C_{compound B} ratio without preparing calibration graphs of the two compounds, is proposed. This method has been applied to signals obtained by synchronous luminiscence. Simultaneous determination of α-tocopherol and α-tocopheryl acetate in beverages using synchronous fluorescence has been carried out. To isolate the compounds from samples, liquid extraction with n-hexane as the organic phase was employed. The presence of interferences was tested using the apparent content curves (ACC) method and the C_{α-tocopherol}/¶C_{α-tocopheryl acetate} ratio was calculated using the Q parameter. The reproducibility and detection limit for the determination of α-tocopherol and α-tocopheryl acetate were 6.6% and 0.016 mg/L and 1.8% and 0.017 mg/L, respectively.     

Voltammetric determination of α-tocopherol in the presence of surfactants

As established, α-tocopherol is electrochemically active on glassy carbon electrode in the available range of anodic potentials in acetonitrile and its aqueous mixtures. However, an increase in the water percentage up to 50% and beyond leads to a substantial decrease and then the total disappearance of the analytical signal. A scheme of electrode reaction responsible for the signal formation is proposed. The effect of surfactants on the oxidation of α-tocopherol in aqueous acetonitrile is estimated. As found, surfactants (N-dodecylpyridinium bromide, Triton X-100 and N-cetylpyridinium bromide) enhance the current of α-tocopherol oxidation. The surfactants reduce the detection limit and extend the analytical range. Analytical methods for the voltammetric quantification of α-tocopherol in drugs in the presence of surfactants are elaborated and may be recommended for the control of pharmaceuticals.     

Application of hydroxyproline derivatives in enantioselective α-amination reactions in organic and aqueous environments: a structure-activity relationship study

We examined the activity of a series of L-hydroxyproline derivatives in enantioselective α-amination reaction between diethyl azodicarboxylate and propanal both in organic and aqueous media. In organic media most of the catalysts showed high activity and enantioselectivities comparable to that accessible with L-proline that is among the best catalysts in the reaction. The catalysts showed good activity under aqueous conditions as well; however, only low enantioselectivities were obtained in this case, primarily due to the racemisation of the product under the reaction conditions. Thus, the attempted achiral acid/base additive-driven stereocontrol was not feasible on a practical level.     

Conformational study of α-phenylthiocarbonyl compounds

Electrical and electrooptical characteristics of-phenylthioacetone,-phenylthiocyclohexanone, and-phenylthio-4-caranone have been determined and used in establishing the structure of the compounds in solution. It has been shown that the preferred conformer with respect to the bond , is the ac-conformer [(O=C-C-S)>90°], in which the gauche conformer with respect to the C-S bond is realized, with a 1,3-parallel position of the C=O and S-Ph bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2483–2488, November, 1991.     

The photometric determination of silicon as α-silicomolybdic acid

A photometric method for the determination of silicon based on the yellow color of α-silicomolybdic acid is described. The pH must be kept within the range 3.0–3.7, and the equilibrium state is established by beating the solution. Since the color of this modification is remarkably stable and reproducible, a high degree of precision can be attained.     

Micro-heterometric determination of molybdic acid with α-benzoin oxime

1 mg of molybdenum as molybdic acid in 20 ml solution can be titrated heterornetrically with a-benzoin oxime in the presence of ~ 99% of most bivalent or tri valent cations as well as in excesses of tungstic or vanadic acids. Error: 0–2%.     

Relative silver(I) ion binding energies of α-amino acids: A determination by means of the kinetic method

The relative silver(I) ion binding energies of 19 α-amino acids have been measured by means of the kinetic method. In general, they are similar to the relative copper(I) ion binding energies of corresponding amino acids although there are differences that can be accounted for by differences in silver(I) and copper(I) chemistry. The correlation with proton basicities is comparatively poorer. Again, the differences between silver(I) and proton binding can be attributed to differences in silver(I) and proton chemistry. The relative silver(I) binding energies measured are best described as relative basicities or ΔΔG _Ag ^° ’s. The observed internal consistency during construction of a silver(I) ion basicity ladder implies that ΔΔS _Ag ^° is approximately zero except when histidine and lysine are involved. For 16 α-amino acids, their relative silver(I) ion basicities ≈ relative silver(I) ion affinities or ΔΔG° _Ag ≈ ΔΔH _Ag ^° .     

Spectrophotometric studies on oxidation of some primary alcohols by 2,2′-bipyridinium chromate. A kinetic study

Some primary alcohols were oxidized by 2,2-bipyridinium chromate (BPC) in the presence of oxalic acid and TsOH giving aldehyde as major product. The reactions were carried out in 80% MeCN-DMF (v/v) medium under varied experimental conditions. The rate depends on the first power of the concentration of BPC and fractional power on the concentrations of alcohol, oxalic acid and TsOH.