Voltammetric characteristics and determination of clothianidin using a bismuth bulk annular band electrode regenerated in situ

Ionics - A new DP AdSV method was developed for the determination of the pesticide clothianidin (Clo) based on its nitro group reduction at the in situ renovated bismuth bulk annular band working...     

Novel Method for HPLC Analysis of Triterpenic Acids Using 9-Anthryldiazomethane Derivatization and Fluorescence Detection

Triterpenic acids are a group of secondary plant metabolites which are part of the cuticular waxes covering fruits, leaves, and flowers. To date, quantitative analysis of these compounds has often been conducted using high-performance liquid chromatography coupled with spectrophotometric detection or mass spectrometry; however, these methods have some major drawbacks. This paper reports a new method of analysis implementing derivatization with 9-anthryldiazomethane and fluorescence detection. The method consists of the extraction of analytes from a matrix, purification with anion exchanging SPE columns, and an optional step of the alkaline hydrolysis of triterpenic acid esters. The paper also describes a fast and easy method for the synthesis of the derivatization agent. The detection limits of the method presented are approximately 100-fold lower than in a similar method using ultraviolet spectrophotometry as the mode of detection. The recovery and repeatability of the method are at satisfactory levels.     

Bis(2-Chlorosulfonylphenyl) Diselenide—the Substrate for Organoselenium Sulfonamides

Abstract: Synthesis of bis(2-chlorosulfonylphenyl) diselenide (11) from 2-amino-benzenesulfonic acid was elaborated. It was shown that (11) is a good starting material for synthesis of the organoselenium sulfonamides, such as bis(2-sulfamoylphenyl) diselenides (3) and benz-2,3-azaselenathiophene 1,1-dioxides (4), being potential immunostimulants and oxidation catalysts.     

Structure and atropisomerisation of new diastereomeric gossypol Schiff bases with (R)-(+)-2-amino-3-benzyloxy-1-propanol studied by NMR,ECD and DFT methods

Gossypol Schiff base with (R)-(+)-2-amino-3-benzyloxy-1-propanol 1 was synthesised and resolved by HPLC method into diastereomers to study their atropisomerisation process. The spectroscopic analysis performed by one- and two-dimensional NMR, UV–vis and FT-IR methods indicated that the compound exists in solution as an enamine-oxo tautomer. The ECD measurements and TD-DFT calculations allowed us to unambiguously determine the configuration about the axially chiral biaryl moiety of 1. The conditions of the atropisomerisation processes of diastereopure gossypol Schiff bases (S_AX,R)-1 and (R_AX,R)-1 were determined on the basis of ECD and NMR measurements. Exposure of the diastereomers of 1 to sunlight and to the light at λ = 254 nm significantly accelerated the atropisomerisation when compared to its rate in the dark.     

The case of triethylammonium cation loss during purification of certain nucleotide analogues: a cautionary note

Nucleotides, their analogues, and other phosphate esters and phosphoramidates often contain the triethylammonium cation as a counterion. We found that this may be lost during chromatographic purification or concentration of solutions, yielding products in acidic forms or containing sub-stoichiometric amounts of the counterion. This in turn may be detrimental, e.g., due to possible decomposition of a compound or inaccurate sample preparation. Correlations between the structure of studied compounds and their susceptibility for cation loss were analyzed. Modifications in preparative techniques were developed to obtain the studied compounds with stoichiometric anion to cation ratios.

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Graphical Abstract Triethylammonium salts of phosphate esters and phosphoramidates may lose the cationic component during chromatography or evaporation of solvent

     

Reactions of thioquinanthrene with alcoholates

Reactions of thioquinanthrene (1) with primary and secondary sodium alcoholates yielded sodium 4-[1-alkyl-4(1 H)-quinolon-3-ylthio]-3-quinoline-thiolates (2), which were characterized by theirS-methyl derivatives (total yields 70–90%).     

Chlorination of 3,4-quinolinediyl bis-sulfides and 3-thiosubstituted 4-quinolinethiones with phosphoryl chloride

Transformation of some 4-quinolinyl sulfides 3 and 4 -quinolinethiones 4 into 4 -chloroquinolines 5 was performed in the reaction with phosphoryl chloride (alone or in N, N-dimethylformamide and ethanol). 3-Quinolinyl sulfides were stable in the reaction conditions.     

Determination of nikethamide by micellar electrokinetic chromatography

A simple, fast, sensitive and reproducible micellar electrokinetic chromatography (MEKC)–UV method for the determination of nikethamide (NKD) in human urine and pharmaceutical formulation has been developed and validated. The method exhibits high trueness, good precision, short analysis time and low reagent consumption. NKD is an organic compound belonging to the psychoactive stimulants used as an analeptic drugs. The proposed analytical procedure consists of few steps: dilution of urine or drug in distilled water, centrifugation for 2 min (12,000 g ), separation by MEKC and ultraviolet‐absorbance detection of NKD at 260 nm. The background electrolyte used was 0.035 mol/L pH 9 borate buffer with the addition of 0.05 mol/L sodium dodecyl sulfate and 6.5% ACN. Effective separation was achieved within 5.5 min under a voltage of 21 kV (~90 μA) using a standard fused‐silica capillary (effective length 51 cm, 75 μm i.d.). The determined limit of detection for NKD in urine was 1 μmol/L (0.18 μg/mL). The calibration curve obtained for NKD in urine showed linearity in the range 4–280 μmol/L (0.71–49.90 μg/mL), with R² 0.9998. The RSD of the points of the calibration curve varied from 5.4 to 9.5%. The analytical procedure was successfully applied to analysis of pharmaceutical formulation and spiked urine samples from healthy volunteers.     

X-ray structure of 2,6-dimethoxy-7-methylpurine

The title compound (C₈H₁₀N₄O₂) is monoclinic, with a = 7.740(2), b = 17.044(7), c = 6.992(3) Å, = 100.60(1)°, and space group P2₁/c. Two O-methyl groups are coplanar with the pyrimidine ring. Whereas, the O(6)-methyl group is directed away from the imidazole ring toward the N(1) atom, the O(2)-methyl is pointed away from the N(1) atom toward the N(3) atom. Two intermolecular hydrogen bonds H(8)···N(1) and H(711)···O(2) of 2.48(2) and 2.58(3) Å make a linear arrangement of the molecules. The conformation of the O-methyl groups explains some results of thermal rearrangement of 2,6-dialkoxy-7-methylpurines and differences in alkylations of 2,4-dialkoxypyrimidines and 2,6-dialkoxy-7-methylpurines.     

X-ray structure and NMR assignment of 4-methoxy-4′-methylthio-3,3′-diquinolinyl sulfidea

The title compound (C₂₀H₁₆N₂OS₂) is monoclinic, witha=7.786(3).,b=13.252(3),c=17.162(4) Å, =99.16(3)° and space groupP2₁/n. Two quinoline moieties are nearly perpendicular to each other (112.9(2)°). Both methoxy and methylthio groups are trans-orientated with the respect to the C(3)–S(1)–C(13) plane. Two pairs of the heteroatoms in ortho-positions are in very close contact. The conformation of the molecule explains an unusual¹H NMR spectrum