Interaction of humic acid with plutonium/III/

The stability constants of the complex of Pu/III/ with a humic acid at pH 2.9 and 5.0 were measured using solvent-extraction technique. The organic extractant was dinonyl naphthalene sulphonic acid in sodium form /NaD/ in benzene while the humate aqueous phase had a constant ionic strength of 0.5M /NaClO₄/. The total carboxylate capacity of the humic acid was determined by direct potentiometric titration to be 6.201 Meq g^–1. The apparent pKa increased as the degree of ionization // increased. The 1g ₁ values of the complex of Pu/III/ with humic acid have been determined to be 2.8 and 3.11 at pH 2.9 and 5.0, respectively.     

Hybrid open-framework iron phosphate--oxalates demonstrating a dual role of the oxalate unit

New inorganic-organic hybrid open-framework materials of the phosphate-oxalate family, [Fe2(H2O)2-(HPO4)2(C2O4)].H2O (I), [Fe2(H2O)2-(HPO4)2(C2O4)].2H2O (II), [C3N2H12]-[Fe2(HPO4)2(C2O4)1.5]2 (III), and [C3N2OH12][Fe2(HPO4)2(C2O4)1.5]2 (IV) have been synthesized hydrothermally in the presence of structure-directing amines. The amine molecules are incorporated in III and IV, whereas I and II are devoid of them. The oxalate units act as a bridge between the layers in all the compounds. The layers in I and II are entirely inorganic, being formed by FeO6 and PO4 units, whereas in III and IV oxalate units constitute the inorganic layers and act as the bridge between these layers. Such a dual role of the oxalate unit is unique and noteworthy. The formation of two types of inorganic layers in I and II consisting of four-, six-, and eight-membered rings, indicates the interconversions between the various rings in the phosphate--oxalates to be facile. All the phosphate--oxalates show antiferromagnetic ordering at low temperatures.     

Optimization of ion-exchange displacement separations. II. Comparison of displacement separations on various ion-exchange resins

A variety of stationary-phase materials are currently available for the chromatographic purification of biomolecules. However, the effect of various resin characteristics on the performance of displacement chromatography has not been studied in depth. In Part I, a novel iterative scheme was presented for the rapid optimization of displacement separations in ion-exchange systems. In this article, the optimization scheme is employed to identify the optimum operating conditions for displacement separations on various ion-exchange resin materials. In addition, the effect of different classes of separation problems (e.g., diverging, converging or parallel affinity lines) on the performance of displacement separations is also presented. The solid film linear driving force model is employed in concert with the Steric Mass Action isotherm to describe the chromatographic behavior in these systems. The results presented in this article provide insight into the effects of resin capacity and efficiency as well as the type of separation problem on the performance of various ion-exchange displacement systems.     

Regioselective synthesis of mono- and bis-decahydrobenzocarbazoles via tandem reactions of α-diazo ketones

Regioselective intermolecular 1,3-dipolar cycloaddition reactions of rhodium generated carbonyl ylides with indoles are reported in this paper. Intermolecular 1,3-dipolar cycloaddition reactions of five-membered-ring cyclic carbonyl ylides with indole and substituted indoles afforded hexahydro-2H-carbazol-2-ones in a regioselective manner. Similarly, reactions of cyclic carbonyl ylides were carried out to afford decahydrobenzo[c]carbazoles or decahydrocyclopenta[c]carbazoles with high regioselectivity. Interestingly, the other possible regioisomer decahydrobenzo[a]carbazoles were also obtained by the reaction of cyclic carbonyl ylides and indoles having electron withdrawing substituents. The structure and stereochemistry of regioisomers 6,11c-epoxy-1,2,3,4,4a,5,6,6a,11b,11c-decahydro-4a-methyl-5-oxo-7H-benzo[c]carbazole and 11-benzenesulfonyl-6,11b-epoxy-2,3,4,4a,5,6,6a,11,11a,11b-decahydro-4a-methyl-5-oxo-1H-benzo[a]carbazole were unequivocally corroborated by single-crystal X-ray analyses. To advance this study, regioselective double 1,3-dipolar cycloaddition reaction of five-membered-ring cyclic carbonyl ylides has been demonstrated for the first time with biindoles having various aryl and alkyl spacers. This process constructed up to eight stereocenters, four carbon-carbon and two carbon-oxygen bonds in a single step with an excellent molecular complexity and stereoselectivity.     

Isonitrosopropiophenone as an ambidentate chelating agent in some transition metal complexes

Summary Isonitrosopropiophenonates of cobalt(III), cobalt(II), nickel(II) and palladium(II) have been synthesised and characterised. Isonitrosopropiophenonatonickel(II) exists as green and brown varieties, the green forming mono- as well as bispyridine adducts. The brown variety is obtained after removal of base from the adducts. I.r. data of the metal chelates suggest atrans-asymmetric structure involving N and O bonding for one form and atrans-symmetric structure involving either N or O bonding of the oximino-group for the other. The former is observed exclusively with isonitrosopropiophenonates of nickel(II) while the latter is common among the other metal chelates. The low magnetic moment of the mono-adduct is ascribed to super-exchange interaction between two metal ions through oxo-bridges in the dimer. Acis-octahedral structure has been assigned to the tris(isonitrosopropiophenonato) cobalt(III) on the basis of¹H n.m.r. data. Isonitrosopropiophenone forms mixed-ligand complexes of cobalt(III) with tetradentate Schiff bases such as SALEN,N,N-ethylenebis(salicylaldimine), and SALPN,N,N-1,3-propylenebis-(salicylaldimine), where the isonitrose group bonds through the nitrogen atom. These complexes have a N,N,N,O,O,O ligand environment. The imino-nickel(II) and -palladium(II) complexes are assigned atrans-symmetric square planar structure. Characterisation of the complexes was based upon elemental analyses, conductivity and magnetic moment, and i.r.,¹H n.m.r., and electronic spectra.     

Electrochemical rectification at electrode surface modified with poly (acrylic acid) and decane thiol

Gold surface modified with a two-component system consisting of poly (acrylic acid) (PAA) by electropolymerizing acrylic acid (AA) and decane thiol (DT), further functionalized with ferrocene monocarboxylic acid (FMC) through covalent linkage, was used to demonstrate mediated electron transfer resulting in a unidirectional flow of current. The electrode surface was modified using two different configurations. In Configuration 1 (Config. 1), electrode surface modified with FMC showed rectification behavior when contacted with a solution containing methylene blue (MB). In Configuration 2, redox-active bilayer was constructed using polyvinyl pyrollidone (PVP) and hexaamineruthernium (II) chloride [Ru(NH₃)₆]²⁺ showed rectification characteristics. The continuous rectification property of the redox-active bilayer is achieved by releasing the trapped [Ru(NH₃)₆]³⁺ in the outer layer using a reductant (ascorbic acid). Spectroelectrochemical measurements were made to study the reduction property of the ascorbic acid. Atomic force microscopic images and impedance measurements were also made on the modified electrode surfaces to explore the compactness of the first layer (PAA and PAA/DT).     

Synthesis of a single four-ring (S4R) molecular zinc phosphate and its assembly to an extended polymeric structure: a single-crystal and in-situ MAS NMR investigation

A reaction of ZnO, HCl, H(3)PO(4), and 2-pyridylpiperazine in THF/H(2)O mixture at 75 degrees C for 72 h produces a new zinc phosphate, [(C(5)NH(5))(C(4)N(2)H(10))][Zn(H(2)PO(4))(2)(HPO(4))], I. Zinc phosphate I consists of single four-ring (S4R) units with terminal phosphoryl groups hanging from the Zn center. On reaction with zinc acetate dihydrate in the presence of water at 100 degrees C, I gave another new zinc phosphate, [(C(5)NH(5))(C(4)N(2)H(10))][Zn(2)(H(2)PO(4))(HPO(4))(PO(4))] x 2H(2)O, II. II has a layer structure with apertures formed by 4- and 8-T atoms (T = Zn, P). An examination of the two structures reveals that I and II are related, II being formed by the direct addition of Zn(2+) ions to I. Room-temperature (31)P MAS NMR studies show the presence of different phosphorus species in both compounds. An in-situ (31)P MAS NMR investigation on the formation of II from I in the presence of Zn(2+) ions and water reveals the transformation to be facile. What is noteworthy in this study is that the structural integrity of the S4Rs has been maintained during the formation of II. Donor-acceptor hydrogen bond interactions and pi-pi interactions involving the pyridyl groups also appear to play subtle roles in both phosphates. This study, the first attempt of its kind, combines the principles of supramolecular organic chemistry with inorganic building units and contributes to our understanding of the formation of framework solids.