Simultaneous determination of N-butylscopolamine and oxazepam in pharmaceutical formulations by first-order digital derivative spectrophotometry

A simple method has been developed for the simultaneous determination of N-butylscopolamine bromide and oxazepam in pharmaceutical formulations using first-order digital derivative spectrophotometry. Acetonitrile was selected as the solvent in which both compounds showed well-defined bands. Both analytes showed good stability in this solvent when solutions of the analytes were exposed to light and temperatures between 20 degrees and 80 degrees C. The simultaneous determination of both drugs was performed by the zero-crossing method at 226.0 and 257.0 nm for N-butylscopolamine and oxazepam, respectively. The linear range of determination was found to be 2.5 x 10(-7) to 8.0 x 10(-5) mol/L for N-butylscopolamine and 7.1 x 10(-8) to 8.0 x 10(-5) mol/L for oxazepam. A very good level of repeatability (relative standard deviation) of 0.2% was observed for N-butylscopolamine and oxazepam. The ingredients commonly found in pharmaceutical formulations do not interfere. The proposed method was applied to the determination of these drugs in pharmaceutical formulations (capsules).     

Synthesis and characterization of hybrid borosiloxane gels as precursors for Si–B–O–C fibers

The sol–gel method has been used for the synthesis of borosilicate gels from mixtures of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) and boric acid. The use of boric acid, B(OH)₃ allows the hydrolysis and condensation of hybrid silicon alkoxides without further addition of water or catalyst. The use of difunctional silicon units, –(CH₃)₂SiO– promote the formation, during the sol–gel process, of linear oligomers which facilitate fiber drawing before gelation. Gel characterization performed by FT-IR, XRD, TG-DTA and DCS analysis indicates the formation of a mixed network with incorporation of the boron units via =B-O-Si≡ bridges. The formation of borosiloxane bonds seems favored by the presence of DMDES. SiBOC glasses were obtained after pyrolysis of the borosilicate gels in argon atmosphere at 1000 °C. TG-DTA study indicates that the ceramic yield decreases by increasing the amount of DMDES. Gel fibers were successfully prepared from convenient partially-aged solutions by hand drawing. Pyrolysis of the obtained gel fibers under argon atmosphere at 1000 °C open the possibility to produce SiBOC homogeneous glass fibers with diameter as low as 10 μm.     

Excess volumes of binary mixtures of (p-xylene+an n-alkane)

A semi-continuous dilatometer for measuring excess volume is described. Excess volumes of p-xylene +n-hexane + n-octane, +n-decane, +n-dodecane, +n-tetradecane, and +n-hexadecane have been measured at 298.15 K as a function of composition.     

The site of protonation of bifunctional bases with competing basic centers. I. Aromatic nitriles

The experimental values of the gas-phase proton affinities for a variety of 4-substituted benzonitriles, 4-substitutedN, N-dimethylanilines, and 4-substituted benzaldehydes have been examined by means of correlation analysis techniques and by ab initio quantum mechanical methods (MP2/ 6-31G(d) level). From this study it is concluded that in the gas phase, 4-(dimethylamino)-benzonitrile essentially protonates on the dimethylamino group, while protonated 4-cyanobenzaldehyde is very nearly a 21 mixture of the carbonyl- and cyano-protonated forms.This work is dedicatedin memoriam to Professor Robert W. Taft.     

High yield synthesis and reactivity of a phosphinidene bridged dimolybdenum complex

Protonation of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] (Cp = eta5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4.OEt2 gives the hydridophosphinidene complex [Mo2Cp2(mu-H)(mu-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(mu-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(mu-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(mu-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(mu-PR*)(mu-CO)2] and the hydridophosphido derivative [Mo2Cp2(mu-H){mu-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HCC(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{mu-eta1:eta2,kappa-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Intramolecular "Aryl-metal chelate ring" pi,pi-interactions as structural evidence for metalloaromaticity in (aromatic alpha,alpha'-diimine)-copper(II) chelates: molecular and crystal structure of aqua(1,10-phenanthroline)(2-benzylmalonato)copper(II) three-hydrate

By reaction of Cu(2)CO(3)(OH)(2), 2-benzylmalonic acid (H(2)Bzmal), and 1,10-phenanthroline (phen), [Cu(Bzmal)(phen)(H(2)O)] x 3H(2)O (compound 1) has been obtained and characterized by thermal, spectral, magnetic, and X-ray diffraction methods. The molecular structure of 1 is remarkably similar to that of [Cu(Bzmal)(bipy)(H(2)O)] x 2H(2)O (compound 2, bipy = 2,2'-bipyridine). In both complexes, the aryl(Bzmal) ring produces an unexpected pi,pi-stacking interaction with the Cu(II)-(aromatic alpha,alpha'-diimine) chelate ring, at an average distance d(pi)(-)(pi) of 3.40 A, involving roughly parallel and smoothly slipped rings. This insight is discussed as new structural evidence for metalloaromaticity of Cu(II)-(aromatic alpha,alpha'-diimine) chelate rings. Interestingly, 1 recognizes itself by a weak intermolecular pi,pi-stacking interaction between aryl(Bzmal) ligands to give pairs of complex molecules. In contrast, there is an intermolecular pyridyl-pyridyl pi,pi-stacking interaction also forming pairs of complex molecules in 2.     

Setting up of recovery profiles: A tool to perform the compliance with recovery requirements for residue analysis

The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜ^C, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure.     

Unexpected valence bond isomerization of [1,2,4]triazolo[3,4-c][1,2,4]benzotriazines under flash vacuum pyrolytic (fvp) conditions

Flash vacuum pyrolysis (fvp) of some substituted [1,2,4]triazolo[3,4-c][1,2,4]benzotriazine derivatives (1a-d) has been studied between 450 and 600 °C. The only transformation observed up to 525 °C was the unexpected valence bond isomerization of the angularly fused starting compounds to the isomeric linearly fused [1,2,4]triazolo[4,3-b][1,2,4]benzotriazine derivatives (9a-d), whereas at higher temperatures fragmentation products such as aromatic nitriles were also formed. Kinetic measurements revealed negative entropies of activation in the isomerization process, which suggest a concerted ring closure reaction to an intermediate antiaromatic diazirine. Reversibiblity of the title isomerization reaction was also proved by FVP experiments.     

Optimization of chromatographic parameters for the determination of biogenic amines in wines by reversed-phase high-performance liquid chromatography

A method suitable for the determination of eight biogenic amines (histamine, tyramine, phenylethylamine, tryptamine, cadaverine, putrescine, spermidine and spermine) in wines has been developed. The method involves derivatization of the amines by treatment with dabsyl chloride, after which the derivates were analysed by reversed-phase liquid chromatography with gradient elution and spectrophotometric detection at 446 nm. Different variables affecting separation were optimized. Validation of the method included calibration experiments, the addition of standards amines for the determination of recovery and repeatability tests. Good linearity of the responses was obtained up to 500 microg l(-1), except for putrescine (up to 2100 microg l(-1)). The detection limits ranged between 10 and 60 microg l(-1) for standard solutions. The method was successfully applied to the analysis of five Spanish wines.