2—氯苯甲醛缩氨基硫脲合Cu(Ⅰ)、Fe(Ⅱ)、Sn(Ⅱ)、Pb(Ⅱ)配合物的直接电化学合成

以往含硫希夫碱金属配合物的合成,大都是配体和相应金属的盐在乙醇溶液中完成［１,２］,而用金属阳极在含配体的非水溶剂中的电化学氧化直接合成金属配合物尚未见报道。为此,本文作者首次用金属阳极电化学氧化合成了２—氯苯甲醛缩氨基硫脲（ＨＬ）与Ｃｕ（Ⅰ）、Ｆｅ...     

An ab initio CI study on the rotational barrier of the allyl anion

All-electron and pseudopotential non-empirical calculations have been performed on C _2v and C _s (syn, anti) allyl anion conformations. Using a double-zeta valence-shell basis set within the Epstein-Nesbet definition of the unperturbed Hamiltonian, a value about 19 kcal/mol is found for the barrier to rotation of the allyl anion. This value is the theoretical value obtained with greater accuracy, and the lowest one for the rotational barrier.     

Synthesis of ribonucleosides of 4(5)-cyano-5(4)-methylimidazole and related 4-substituted-5-methylimidazole ribosides

4-Cyano-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-5-methylimidazole ( 4 ) and its corresponding 5-cyano-4-methyl substituted isomer ( 5 ) have been obtained by ribosylation of 4(5)-cyano-5(4)-methylimidazole ( 3 ) via the mercuric cyanide method or by ribosylation of the trimethylsilyl derivative of 3 . Treatment of 4 with methanolic ammonia, ammonium chloride in liquid ammonia and potassium hydrosulfide provided 4-cyano-1-β-D-ribofuranosyl-5-methylimidazole ( 6 ), 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamide ( 2 ) and 1-β-D-ribofuranosyl-5-methylimidazole-4-thiocarboxamide ( 11 ) respectively. Reaction of 6 with hydroxylamine afforded the corresponding 4-carboxamidoxime substituted nucleoside ( 13 ) which on catalytic reduction in the presence of ammonium chloride, was transformed into 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamidine ( 14 ) as hydrochloride salt.     

Chromogenic and fluorogenic reagents for chemical warfare nerve agents' detection

The ease of production, the extreme toxicity of organophosphorus-containing nerve agents, and their facile use in terrorism attacks underscores the need to develop accurate systems to detect these chemicals. Among different technologies we review here recent advances in the design of chromo-fluorogenic methods for the specific detection of nerve agents. Optical sensing (especially colorimetric detection) requires usually low-cost and widely used instrumentation and offers the possibility of so-called "naked eye detection". Recent reported examples suggest that the application of chromo-fluorogenic supramolecular concepts for the chromogenic or fluorogenic sensing of nerve agents might be an area of increasing interest that would allow developing systems able to overcome some of the limitations shown by classical analytical methods.     

Facile Formation of Redox‐Active Totally Organic Nanoparticles in Water by In Situ Reduction of Organic Precursors Stabilized through Aromatic–Aromatic Interactions by Aromatic Polyelectrolytes

The formation of redox‐active, totally organic nanoparticles in water is achieved following a strategy similar to that used to form metal nanoparticles. It is based on two fundamental concepts: i) complexation through aromatic–aromatic interactions of a water‐soluble precursor aromatic molecule with polyelectrolytes bearing complementary charged aromatic rings, and ii) reduction of the precursor molecule to achieve stabilized nanoparticles. Thus, formazan nanoparticles are synthesized by reduction of a tetrazolium salt with ascorbic acid using polyelectrolytes bearing benzene sulfonate residues of high linear aromatic density, but cannot be formed in the presence of nonaromatic polyelectrolytes. The red colored nanoparticles are efficiently encapsulated in calcium alginate beads, showing macroscopic homogeneity. Bleaching kinetics with chlorine show linear rates on the order of tenths of milli­meters per minute. A linear behavior of the dependence of the rate of bleaching on the chlorine concentration is found, showing the potential of the nanoparticles for chlorine sensing.

     

Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I) centers

The monohapto neutral 2-(diphenylphosphino)aniline (PNH(2)) complexes [Au(C(6)F(5))(2)X(PNH(2))] (X = C(6)F(5) (1), Cl (2)) have been obtained from [Au(C(6)F(5))(3)(tht)] or [Au(C(6)F(5))(2)(micro-Cl)](2) and PNH(2), and the cationic [Au(C(6)F(5))(2)(PNH(2))]ClO(4) (3) has been similarly prepared from [Au(C(6)F(5))(2)(OEt(2))(2)]ClO(4) and PNH(2) or from 2 and AgClO(4). The neutral amido complex [Au(C(6)F(5))(2)(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac = acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO(3))(PPh(3))] or [Au(OClO(3))(PPh(3))] to give the dinuclear species [Au(C(6)F(5))(2)[PNH(MPPh(3))]]ClO(4) (M = Ag (5), Au (6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh(3))]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C(6)F(5))(2)[PN(AuPPh(3))(2)]]ClO(4) (7) is obtained. The crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)-Au(III) interaction.     

Visible light mediated photocatalytic oxidative coupling reaction of N-phenyl tetrahydroisoquinoline with β-keto acids

A visible light mediated photocatalytic oxidative coupling reaction of N-phenyl tetrahydroisoquinoline with β-keto acids has been developed. This approach provides a mild and operationally simple access to the synthesis of C1-acylmethylated tetrahydroisoquinolines.     

Determination and quantification of phenolic compounds in methanolic extracts of Solanum ferrugineum (Solanaceae) fruits by HPLC-DAD and HPLC/ESI-MS/TOF

Solanum ferrugineum Jacq. is a wild species that in previous analysis reported a significant antioxidant capacity. The aim of our research was to determine total phenolic content (TPC) and total flavonoid content (TFC), and the phenolic composition by HPLC-DAD and HPLC/ESI-MS/TOF of methanolic extracts of S. ferrugineum fruits, collected from Paredones, Jiquilpan, and Fray Dominguez, Pajuacarán in the Mexican state of Michoacán. TPC and TFC were determined by the spectrophotometric Folin–Ciocalteu reagent and the AlCl₃ method, respectively. TPC in S. ferrugineum fruit [31.41?±?0.91?mg gallic acid equivalent/g dry tissue (DT)] was similar to those reported for Turkey berry (Solanum torvum Sw.) and eggplant (Solanum melongena L.) fruits. The TFC values of S. ferrugineum fruits (29.14?±?4.99?mg catechin equivalent /g DT) corresponded to 80.24% of the TPC. Eight phenolic compounds (PC) were identified by HPLC analysis. The main PC identified in S. ferrugineum fruits were chlorogenic acid, caffeic acid, p-coumaric acid, gallic acid, quercetin, and kaempferol. S. ferrugineum fruits could be used as a starting material for the extraction of high-value PC with potential applications.