Simultaneous spectrophotometric and liquid chromatographic determination of dextromethorphan hydrobromide,phenylephrine hydrochloride,and carbinoxamine maleate in pharmaceutical preparations

Simultaneous determination of dextromethorphan hydrobromide (DEX), phenylephrine hydrochloride (PHEN), and carbinoxamine maleate (CAR) in pharmaceutical preparations was performed by using liquid chromatograpy (LC) and spectrophotometry. In LC, the separation was achieved on a C18 column and the optimal mobile phase for satisfactory separation in a gradient elution program was found to be acetonitrile-sodium perchlorate solution (5: 95, v/v) initially, then a linear gradient up to 60% acetonitrile in 8 min. In spectrophotometric method, a chemometric technique, principal component regression (PCR), was used. In the method, the absorbance data matrix corresponding to the concentration data matrix was obtained by the measurement of absorbances in their zero order spectra by Δλ = 1 nm in the 210–300 nm range. Then, the calibration was obtained by using this data matrix for the prediction of unknown concentrations of DEX, PHEN, and CAR in their ternary mixture. The methods proposed were validated and successfully applied to a pharmaceutical preparation, capsule, and the results were compared.     

Single-step fabrication of patterned gold film array by an engineered multi-functional peptide

This study constitutes a demonstration of the biological route to controlled nano-fabrication via modular multi-functional inorganic-binding peptides. Specifically, we use gold- and silica-binding peptide sequences, fused into a single molecule via a structural peptide spacer, to assemble pre-synthesized gold nanoparticles on silica surface, as well as to synthesize nanometallic particles in situ on the peptide-patterned regions. The resulting film-like gold nanoparticle arrays with controlled spatial organization are characterized by various microscopy and spectroscopy techniques. The described bio-enabled, single-step synthetic process offers many advantages over conventional approaches for surface modifications, self-assembly and device fabrication due to the peptides' modularity, inherent biocompatibility, material specificity and catalytic activity in aqueous environments. Our results showcase the potential of artificially-derived peptides to play a key role in simplifying the assembly and synthesis of multi-material nano-systems in environmentally benign processes.     

Controlling the surface chemistry of graphite by engineered self-assembled peptides

The systematic control over surface chemistry is a long-standing challenge in biomedical and nanotechnological applications for graphitic materials. As a novel approach, we utilize graphite-binding dodecapeptides that self-assemble into dense domains to form monolayer-thick long-range-ordered films on graphite. Specifically, the peptides are rationally designed through their amino acid sequences to predictably display hydrophilic and hydrophobic characteristics while maintaining their self-assembly capabilities on the solid substrate. The peptides are observed to maintain a high tolerance for sequence modification, allowing control over surface chemistry via their amino acid sequence. Furthermore, through a single-step coassembly of two differently designed peptides, we predictably and precisely tune the wettability of the resulting functionalized graphite surfaces from 44° to 83°. The modular molecular structures and predictable behavior of short peptides demonstrated here give rise to a novel platform for functionalizing graphitic materials that offers numerous advantages, including noninvasive modification of the substrate, biocompatible processing in an aqueous environment, and simple fusion with other functional biological molecules.     

Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions

Safe and efficient hydrogen storage is a major obstacle for using hydrogen as an energy carrier. Therefore, intensive efforts have been focused on the development of new materials for chemical hydrogen storage. Of particular importance, hydrazine borane (N(2)H(4)BH(3)) is emerging as one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (15.4 wt%) and low molecular weight. Herein, we report metal catalyzed methanolysis of hydrazine borane (N(2)H(4)BH(3), HB) as a fast hydrogen generation system under mild conditions. When trace amounts of nickel(ii) chloride (NiCl(2)) is added to the methanol solution of hydrazine borane ([HB]/[Ni] ≥ 200) the reaction solution releases 3 equiv. of H(2) with a rate of 24 mol H(2) (mol Ni min)(-1) at room temperature. The results reported here also includes (i) identification of the reaction products by using ATR-IR, DP-MS, (1)H and (11)B NMR spectroscopic techniques and the establishment of the reaction stoichiometry, (ii) investigation of the effect of substrate and catalyst concentrations on the hydrogen generation rate to determine the rate law for the catalytic methanolysis of hydrazine borane, (iii) determination of the activation parameters (E(a), ΔH(#), and ΔS(#)) for the catalytic methanolysis of hydrazine borane by using the temperature dependent rate data of the hydrogen generation.     

Design, synthesis, and biological activities of some branched carbasugars: construction of a substituted 6-oxabicyclo[3.2.1]nonane skeleton

Transformation of cyclohexa-2,4-diene-1,2-diylbis(methylene) diacetate to various carbasugars is described. Photooxygenation of a cyclohexadiene derivative gave a bicyclicendoperoxide, which was reduced with thiourea to [2-[(acetyloxy)methyl]cyclohexa-2,4-dien-1-yl]methyl acetate. Epoxidation of the remaining double bond followed by epoxide ring-opening and hydrolysis of the acetate groups gave one of the target hexols. The bicyclic endoperoxide was rearranged to a diepoxide with CoTPP. The diepoxide was reacted with sulfamic acid in acetic anhydride, resulting in the formation of a new branched carbasugar as well as in the formation of cyclitols with a 6-oxabicyclo[3.2.1]nonane skeleton. The mechanism of the formation of the products is discussed. The inhibition activity of six cyclitol derivatives was tested against α-glycosidase.     

Manganese(III) acetate mediated synthesis of 3-trifluoroacetyl-4,5-dihydrofurans and 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones by free radical cyclization. Part 1

2-Trifluoroacetyl-4,5-dihydrofurans were obtained by manganese(III) acetate mediated radical cyclization of trifluoromethyl-1,3-dicarbonyl compounds (1a-c) with conjugated alkenes (2a-h). The reaction of 1,1,1-trifluoropentane-2,4-dione (1a) with propenylbenzene and 1,1-diphenyl-1-butene surprisingly yielded 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones besides 3-trifluoroacetyl-4,5-dihydrofurans.     

Investigation of spectroscopic studies and DFT calculations on glucofuranose derivatives of dithiophosphonates

Abstract

2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson’s reagent: LR) was reacted with 1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose and 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose in toluene and gave rise to crude dithiophosphonic acids. The crude dithiophosphonic acids were treated with excess triethylamine and the triethylammonium salts of dithiophosphonic acids (1) and (2) were isolated by crystallization method. Compounds 1 and 2 were characterized by elemental analysis, IR, and NMR (¹H-, ¹³C- and ³¹P-) spectroscopies and mass spectrometry. In addition, NMR spectra, the electronic properties (the electronic chemical potential, electronegativity, chemical hardness and the global electrophilicity index) and NBO analysis of compound 2 have been calculated by using the Gaussian 16?W program. The electronic properties were calculated using Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energies by density functional method (DFT/B3LYP) at 6-31G(d,p) level. The HOMO and LUMO energies are ?5.9 and ?0.72?eV, respectively. The HOMO–LUMO energy difference is 5.18?eV and this value shows that compound 2 has a high stability and low reactivity.     

A Grafting Study on Partially Dehydrochlorinated Poly(vinyl chloride) by Atom Transfer Radical Polymerization

HCl elimination in low ratio was first carried out from poly(vinyl chloride) to increase allylic chlorines. Partially dehydrochlorinated poly(vinyl chloride), having a macroinitiator effect, was grafted with tert‐butyl methacrylate via atom transfer radical polymerization in the presence of CuBr/2,2′‐bipyridine at 64°C in tetrahydrofuran. Original poly(vinyl chloride) was also grafted with tert‐butyl methacrylate under the same conditions to compare with that of partially dehydrochlorinated poly(vinyl chloride). The graft copolymers were characterized by elemental analysis, FTIR, ¹H and ¹³C‐NMR, differential scanning calorimetry, and gel permeation chromatography (GPC). Thermal stabilities of the graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators.     

Synthesis and Properties of Thiophene and Dithiin Functionalized Tetrathiafulvalenes

Abstract

Syntheses of two analogues of tetrathiafulvalene (TTF), fused to 1,4-dithiin and thiophene rings, substituted with thiophene moieties, have been illustrated. The syntheses were accomplished through the reaction of a 1,8-diketone with phosphorus pentasulfide or Lawesson's reagent in boiling dry toluene. Conversion of the thioketones to their the oxo forms with mercury (II) acetate, was followed by self-coupling in freshly distilled boiling triethyl phosphite. Attempts for their electro-polymerizations through the thiophene groups at the peripherals were unsuccessful. Computational chemistry studies revealed that the thiophene groups did not exhibit enough spin densities to perform polymerization.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Complexation and transport of amino acid esters and their salts with synthesised chiral novel aza crown ether derivatives

The syntheses of four aza-15-crown-5 ethers bearing phenyl and phenoxymethyl moieties attached to a stereogenic centre on the crown ring were achieved. Macrocycles have exhibited strong binding ability (K_a = 5364–12,969 M^? 1) and modest enantiomeric discrimination towards the enantiomers of amino acid methyl ester salts by UV titration method in CHCl₃ at 25°C. Computer modelling results supported experimental data providing a detailed understanding of the molecular recognition mode between hosts and guests and the likely binding sites involved. Macrocycles were used for chiral discrimination of amino acids in their zwitterionic forms or as potassium and sodium salts in transport experiments across a bulk chloroform membrane with satisfactory selectivity.