Complexation of Ni (II) and Zn(II) ions by 3-(1-naphthyI)-2-mercaptopropenoic acid

The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H₂NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm^–3 in NaClO₄ as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP) ₂ ^2– , Zn(NMP) and Zn(NMP) ₂ ^2– , refined by the MINIGLASS program, are reported.     

Molecular dynamics simulations of the mononuclear zinc-beta-lactamase from Bacillus cereus complexed with benzylpenicillin and a quantum chemical study of the reaction mechanism

Herein, we present results from MD simulations of the Michaelis complex formed between the B. cereus zinc-beta-lactamase enzyme and benzylpenicillin. The structural and dynamical effects induced by substrate-binding, the specific role of the conserved residues, and the near attack conformers of the Michaelis complex are discussed. Quantum chemical methods (HF/6-31G* and B3LYP/6-31G*) are also applied to study the hydrolysis reaction of N-methylazetidinone catalyzed by a monozinc system consisting of the side chains of the histidine residues (His86, His88, and His149) complexed with Zn-OH and the side chains of Asp90 and His210. From this model system, we built molecular-mechanics representations of the prereactive complex and transition state configurations docked into the active site. Linear-scaling semiempirical calculations coupled with a continuum solvent model were then performed on these static models. We propose that the experimental rate data for the B. cereus enzyme is compatible with a one-step mechanism for the hydrolysis of beta-lactam substrates in which His210 acts as a proton donor.     

Enzyme catalysis in organic solvents: a promising field for optical biosensing

The ability of enzymes to work in non-aqueous media offers new and almost unexploited possibilities for the development of new optical biosensors. The advantages of performing biocatalytic reactions in non-aqueous media are discussed in relation to their possible application in optical biosensor design. Attention is focused on the factors that influence enzymatic catalysis in organic solvents, including the role of enzyme-associated water, criteria for solvent selection and the alteration of enzyme specificity. Recent examples of relevant applications and future prospects of organic-phase optical biosensing are discussed.     

Extraction of the (C4H9)4N+Co(II)SCN− ion-pair in chloroform and in isoamyl alcohol: Spectrophotometric determination of cobalt

When excesses of ammonium thiocyanate and tetrabutylammonium chloride are added to a cobalt(II) solution, a water-insoluble ion-pair is formed; this compound is soluble in chloroform, isoamyl alcohol, and other solvents. The variables which affect the extractions by these two solvents are studied in order to obtain the optimal conditions and two alternative extraction procedures are proposed. Thus, the separation of cobalt as a previous step for its spectrophotometric determination is studied.     

Nachweis von Peroxiden,Hydroperoxiden und Persäuren

Zusammenfassung Die Indikatorbase 4-Methoxyphenylazo--naphthylamin wird von p-Nitrobenzoylperoxid in neutralem oder saurem Medium ohne, von p-Nitrobenzopersäure unter Erwärmen oxydiert, gar nicht aber von p-Nitroäthylbenzol--hydroperoxid. Auf der Grundlage dieses Verhaltens können die drei Verbindungen unterschieden und p-Nitrobenzoylperoxid nachgewiesen werden. Die Indikatorsäure 4-Nitrophenylazo-2-amino-5-nitrobenzol wird von p-Nitroäthylbenzol--hydroperoxid oxydiert, nicht aber von p-Nitrobenzoylperoxid und p-Nitrobenzopersäure. Mit dieser Farbreaktion kann p-Nitroäthylbenzol--hydroperoxid nachgewiesen werden. p-Nitrobenzopersäure kann neben p-Nitroäthylbenzolhydroperoxid mit einer Farbreaktion von p- + m-Phenylendiamin nachgewiesen werden. Auch p-Nitrobenzoylperoxid gibt die Reaktion, aber p-Nitroäthylbenzol--hydroperoxid setzt sich nicht um.

---

Detection of peroxides, hydroperoxides, and peracids

Summary The indicator base 4-methoxyphenylazo--naphthylamine is oxidized in neutral medium without warming byp-nitrobenzoyl peroxide, and byp-nitrobenzoperacid with warming, but it is not oxidized at all byp-nitroethylbenzene--hydroperoxide. The three compounds may be differentiated on the basis of these behaviors and furthermore it is thus possible to detect and identifyp-nitrobenzoyl peroxide. The indicator acid 4-nitrophenylazo-2-amino-5-nitrobenzene is oxidized byp-nitroethylbenzene--hydroperoxide but not byp-nitrobenzoyl peroxide andp-nitrobenzoperacid.p-Nitroethylbenzene--hydroperoxide may be detected through this color reaction.p-Nitrobenzoperacid can be detected in the presence ofp-nitroethylbenzene--hydroperoxide by a color reaction withp + m-phenylenediamine but no reaction is given byp-nitroethylbenzene--hydroperoxide.

     

Mono- and diboronates derived from tridentate ONO ligands and arylboronic acids

The syntheses of eight [4.3.0] heterobicyclic boronates containing a N → B coordinative bond are described. The monomeric compounds were prepared by reaction of arylboronic acids with a tridentate ligand having the ONO donor set of atoms. It was shown that substituents at the para-position of the B-phenyl moiety transmit electronic effects to the CN bond which in turn is polarized by formation of the N → B coordination bond. At the same time, related tridentate ligands were also reacted with 1,4-benzenediboronic acid in order to prepare benzene diboron complexes. The structure of this type of compounds was confirmed by X-ray analysis for one of the derivatives.     

Cyclic Projections in Hadamard Spaces

Journal of Optimization Theory and Applications - We show that cyclic products of projections onto convex subsets of Hadamard spaces can behave in a more complicated way than in Hilbert spaces,...     

The crystal structure of eudesma-4(15),7(11)-dien-8α, 12-olide: a sesquiterpene lactone fromTrattinickia rhoifolia Willd

The title compound, formula C₁₅H₂₀O₂, is orthorhombic, P2₁2₁2₁ witha=8.747(2),b=12.025(3),c=12.554(3)Å,Z=4, andD _m =1.32(2)g/ml. The structural analysis shows that the compound corresponds to eudesma-4(15),7(11)-dien-8,12-olide, a sesquiterpene lactone previously isolated fromAster umbellatus but whose crystal structure was unknown.     

Individual extraction constants of some dicarbollylcobaltate anions in the water-nitrobenzene system

Individual extraction constants of nine dicarbollylcobaltate anions in the two-phase water-nitrobenzene system were determined radiometrically assuming that the changes of Gibbs energy of the transfer of the tetraphenylarsonium cation, Ph₄As⁺, and of the tetraphenylborate anion, BPh ₄ ^– , from the aqueous into the nitrobenzene phase are equal. The constants obtained by this method were correlated with Hansch's constants of hydrophobity.