Charge equilibria and pK values of 5-carboxypyranomalvidin-3-glucoside (vitisin A) by electrophoresis and absorption spectroscopy

Apparent pK values of the wine pigment, 5-carboxypyranomalvidin-3-glucoside (vitisin A), were determined using UV-vis spectroscopy, viz. pK_a1=0.98 (±0.10), pK_H1=4.51 (±0.03) and pK_H2=7.57 (±0.02). An additional ionisation constant at high pH (pK_a4=8.84±0.06) was established by high-voltage paper electrophoresis. These data in conjunction with previously published pK_a values determined by high-voltage electrophoresis suggest that in wine (pH 3.2-3.8), 5-carboxypyranomalvidin-3-glucoside exists as a complex mixture of hydrated and non-hydrated, partially ionised species with the predominant species being the quinonoidal base (λ_max 498 nm).     

The synthesis of thienocycloheptenoindoles

A synthesis of the methylthieno[3,2-c]cyclohepteno[b]indole 7 from 2-methylthieno[3,2-b]cycloheptanone 3 is described. Unsuccessful attempts to prepare the isomeric thienocycloheptenoindole system present in formula 2 , from the dihydrobenzothiophenone 8 , and from derivatives of 5-(2-thienyl)-4-oxopentanoic acid, 17 and 18 , and from N-benzylcycloheptindol-1-one 22 were unsuccessful. The preparation of 4,5-dihydro-2-phenyl-1-thienylmethyl-3H-pyridazin-3-one 20 and of the 5-aminopyrazole 21 are reported.     

Synthesis and near infrared luminescence of a tetrametallic Zn2Yb2 architecture from a trinuclear Zn3L2 Schiff base complex

Near infrared luminescence is observed in tetrametallic [Zn2Yb2L2(mu-OH)2Cl4].2MeCN which is obtained from the Zn3 Schiff-base complex [Zn3L2(NO3)2].MeOH, (H2L =N,N'-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine).     

The indirect spectrophotometric determination of the sulphate ion with 2-aminoperimidine

A new spectrophotometric determination of the sulphate ion is described which uses 2-aminoperimidine hydrochloride as a precipitating reagent. The excess of the reagent is measured at 305 nm. The procedure deals with sulphate in the range 4–120 p.p.m., and relies on simple calibration. The relative standard deviation for 50 p.p.m. of sulphate is 3.7%. The interference of 100 p.p.m. of phosphate, fluoride and nitrate is only slight in the determination of 50 p.p.m. of sulphate. The method is recommended for the determination of sulphate in rain and surface waters.     

Synthesis of luminescent gold(I) and gold(III) complexes with a triphosphine ligand

We have synthesized and characterized a series of trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine; X = Cl 1, Br 2, I 3, C(6)F(5) 4) and di- and trinuclear gold(III) complexes [[Au(C(6)F(5))(3)](n)(mu-triphos)] (n = 2 (5), 3 (6)). The crystal structure of 6 [[Au(C(6)F(5))(3)](3)(mu-triphos)] has been determined by X-ray diffraction studies, which show the triphosphine in a conformation resulting in very long gold-gold distances, probably associated with the steric requirements of the tris(pentafluorophenyl)gold(III) units. Complex 6 crystallizes in the triclinic space group P(-1) with a = 12.7746(16) A, b = 18.560(2) A, c = 21.750(3) A, alpha = 98.215(3) degrees, beta = 101.666(3) degrees, gamma = 96.640(3) degrees, and Z = 2. Chloride substitutions in complex 1 afford trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (X = Fmes (1,3,5-tris(trifluoromethyl)phenyl) 7, p-SC(6)H(4)Me 8, SCN 9) and [Au(3)Cl(3)(-)(n)()(S(2)CNR(2))(n)(mu-triphos)] (R = Me, n = 3 (10), 2 (12), 1 (14); R = CH(2)Ph, n = 3 (11), 2 (13), 1 (15)). The luminescence properties of these complexes in the solid state have been studied; at low temperature most of them are luminescent, including the gold(III) derivative 6, with the intensity and the emission maxima being clearly influenced by the nature and the number of the ligands bonded to the gold centers.     

The synthesis of the potent anti-herpes virus agent, E-5(2-bromovinyl)-2′-deoxyuridine and related compounds

The synthesis of $\text{E}$-5(2-bromovinyl)-2′-deoxyuridine in good yield from deoxyuridine $\text{via}$ an intermediate organopalladium derivative is described. The corresponding chloro and iodo compounds have also been made as have the corresponding bromo and iodo 2′-deoxycytidines.     

Phase-transfer catalysis-3: Acetylation of 2-acylcycloalkanones

With the exception of 2-formylcyclohexanone, which yields the E-exo-enol acetate, the phase-transfer catalysed acetylation of 2-acylcyclohexanones produces the 1-acetoxycyclohexene derivatives as the major products. The 1-acetoxy derivative is also obtained in good yield from the acetylation of 2-methoxycarbonylcyclopentanone but, generally, acetylation of 2-acylcyclopentanones yields the E-exo-enol acetates. 2-Acetylcyclopentanone, however, produces not only the E- and Z-exo-enol acetates, but also the endo-enol acetate, in a ratio of ca 2:2:1. The exo and endo-enol acetates were distinguished by ¹³CNMR spectroscopy and use of LIS reagents confirmed the configurational assignments of the exo-isomers     

Synthesis of s-triazolocycloalkyl-, s-triazolobenzocycloalkyl-, and s-triazolocycloalkylhydrothiadiazines

The reaction of cyclic-α-haloketones with 5-subslituted-4-amino-4H-1,2,4-triazole-3-lhiols gave s-triãzolocycloalkylhydrothiadiazines and s-triazolobenzocycloalkylthiadiazines. Reduetion of the 5,5a-imine bond of the s-triazoloeycloalkylthiadiazines gave s-triazolocycloalkylhydrothia-diazines.     

Détermination de traces de mercure dans les systèmes biologiques par activation de neutrons

Résumé Une méthode simple et rapide de détermination de traces de mercure est présentée utilisant l'activation de neutrons. Le mercure 197 sous forme de complexe (HgCl₄ ^2–) est retenu sur une résine échangeuse d'anion qui est comptée directement. La méthode est appliquée à des milieux biologiques très divers. Les échantillons contiennent des quantités de mercure allant de 10 p. p. b. à 200 p. p. m. La déviation standard dans ces cas est de ± 10%.

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Determination of traces of mercury in biological material by neutron activation

Summary A simple and rapid technique for the trace analysis of mercury by neutron activation is presented. The activated mercury, as an HgCl₄ ^2– complex, is retained on an anion exchange resin which is counted directly. Results obtained for biological samples containing 10 p. p. b. to 200 p. p. m. are given. In this range, results had a ± 10% standard deviation.

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Zusammenfassung Ein einfaches und rasches Verfahren zur Bestimmung von Spuren Quecksilber durch Neutronenaktivierung wurde beschrieben. Das aktivierte Quecksilber wird als HgCl₄ ^2– an einem Anionenaustauscherharz adsorbiert und seine Aktivität direkt gemessen. Biologische Proben mit 10 ppb bis 200 ppm Hg wurden analysiert. In diesem Bereich betrug die Standardabweichung ± 10%.