Growth and reactivity of silver clusters in amino polycarboxylic acid solutions

Reduction and subsequent aggregation of silver ions in the presence of various chelating agents such as trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) 1,2-propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraaminehexaacetic acid (TTHA) have been studied by pulse radiolysis. Rate constants of formation and transient absorption spectra for the ligand-complexed Ag(0) and Ag(2)(+) have been determined. The redox potential of Ag(+)(L)/Ag(0)(L) becomes more negative than that of Ag(+)/Ag(0). Growth and reactivity of silver clusters were also studied in the presence of methyl viologen (MV(2+)). The kinetics of formation of the MV(+*) radical, produced by the same pulse as in the case of silver atoms, confirms the catalytic electron transfer toward super critical silver clusters in the presence of ligands. The results suggest that catalytic electron transfer activity of silver clusters depends on the ligand.     

Transition metal complexes with bidentate ligands spanning trans-positions. XII. The preparation and properties of complexes trans-[MX2 (1)] and trans-[PtHCl (1)] (M = Ni,Pd and Pt; X = Cl and NCS; 1 = ditertiary phosphine)

Complexes [MX₂(1)] (M = Ni, Pd and Pt; X=Cl and NCS; 1 = 2,11-bis(dialkyl-[or diaryl]phosphinomethyl)benzo[c]phenanthrene; alkyl = cyclohexyl t-butyl; aryl = m-tolyl, p-anisyl and m-CF₃ C₆H₄) have been synthesized. An NMR. study of the t-butyl complexes provides evidence for a “fan-like” motion of the benzo[c]phenanthrene moiety over the plane of the complex.     

Recovery of plutonium and americium from laboratory acidic waste solutions using tri-n-octylamine and octylphenyl-N-N- diisobutylcarbamoylmethylphosphine oxide

Plutonium from acidic waste solutions has been recovered quantitatively using tri-n-octylamine (TnOA) in xylene and americium using a mixture of octylphenyl-N-N- diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane by extraction and extraction chromatographic methods. The Pu ( IV ) TnOA species extracted into the organic phase from higher nitric acid concentrations has been confirmed as (R(3)NH)(2)Pu(NO(3))(6) (where R(3)N = TnOA by employing slope analysis as well as spectrophotometric studies.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Efficient transesterification/acylation reactions mediated by N-heterocyclic carbene catalysts

Imidazol-2-ylidenes, a family of N-heterocyclic carbenes (NHC), are efficient catalysts in the transesterification involving numerous esters and alcohols. Low catalyst loadings of aryl- or alkyl-substituted NHC catalysts mediate the acylation of alcohols with enol acetates in short reaction times at room temperature. Commercially available and more difficult to cleave methyl esters react with primary alcohols in the presence of alkyl-substituted NHC to efficiently form the corresponding esters. While primary alcohols are selectively acylated over secondary alcohols with use of enol esters as acylating agents, methyl and ethyl esters can be employed as protective agents for secondary alcohols in the presence of the more active alkyl-substituted NHC catalysts. The NHC-catalyzed transesterification protocol was simplified by generating the imidazol-2-ylidene catalysts in situ.     

Studies on adsorption of 5-amino tetrazole on silver nanoparticles by SERS and DFT calculations

The surface-enhanced Raman scattering (SERS) studies of 5-amino tetrazole (5AT), a tetrazole derivative, in aqueous silver sol at pH approximately 9 and on deposited colloidal silver films were carried out and compared with the normal Raman spectrum of the molecule. The experimentally observed Raman bands along with their corresponding infrared bands were assigned based on the results of density functional theory (DFT) calculations. The significant changes evidenced between the SERS and the normal Raman spectra combined with the theoretical data obtained for Ag-5AT system demonstrated that the molecule is adsorbed on colloidal Ag particles through the lone pair of electrons of the nitrogen atom. The contribution of the chemical mechanism for the SERS enhancement was proved by the behavior of the electronic absorption spectrum of the Ag colloid upon addition of 5AT. This is further supported by the theoretical calculations that show that the favorable interaction of the frontier orbitals localized on Ag(+) and the negatively charged nitrogen from the tetrazole ring leads to the formation of the stable (up to 130 kJ mol(-1)) charge-transfer complex. The orientation of the adsorbed species with respect to the metal surface was also predicted by applying the "surface selection rule". In addition, the feasibility of the formation of the polymeric species has also been discussed.     

On-chip electrochromatography using sol-gel immobilized stationary phase with UV absorbance detection

A chromatography column on a chip was fabricated by immobilizing reversed-phase stationary phase particles (5 microm, C4) using sol-gel technology. Channels were fabricated in quartz using photolithography and wet etching. Localization of the stationary phase was achieved by immobilizing the stationary phase at the desired location in the separation channel prior to bonding of the cover plate. Cross channel design was employed for gated injection. An optical fiber setup was developed for carrying out on-chip UV absorbance detection. The effective optical path length was theoretically determined for the trapezoidal shaped channel and the result was shown to match closely with the experimentally determined value. The effect of applied voltage on velocity was evaluated using thiourea as an unretained marker. Separation performance of the stationary phase was demonstrated by separation of three peptides (Trp-Ala, Leu-Trp and Trp-Trp) under isocratic chromatographic conditions.     

Photophysical characteristics and density functional theory calculations of indole 2-carboxylic acid in the presence of mercurous ions

Many photo-physical studies have been reported for the detection of Hg²⁺ ions. Here we present the effect of Hg ₂ ²⁺ ions on the absorption and fluorescence of indole-2-carboxylic acid (I2C). Experimental evidence, supported by density functional theory B3LYP/LANL2DZ/PCM, for the formation of a I2C-Hg ₂ ²⁺ complex, is reported for the first time. It was observed that I2C forms a ground-state complex with Hg ₂ ²⁺ ions in a ratio of 3:1. The possibility of I2C to be used as a selective novel chemical sensor for the spectrophotometric detection of mercurous ions is described.     

Near-barrier fission of the system12C+232Th

The fission fragment angular distributions for the system¹²C +²³²Th have been measured in the energy range 0.97<>_c.m./V_B<1.22. the=" measured=" anisotropies=" have=" been=" compared=" with=" the=" predictions=" of=" the=" standard=" saddle=" point=" statistical=" model,=" using=" the=" second=" moment=" of=" the=" compound=" nucleus=" spin=" distribution=">l² deduced from a Wong model fit to the fission excitation function. While the measured anisotropies agree with the standard saddle point statistical model for E_c.m./V_B>1.05, they are abnormally large at lower energies. This is also true for the existing measurements of¹⁶O and¹⁹F +²³²Th systems. Since for this system pre-equilibrium fission contributions are not expected, this anomaly indicates strong channel coupling effects leading to an increase in l² at sub-barrier energies.The authors thank Drs. R.K. Choudhury and A. Saxena for useful discussions, Dr. R.J. Singh for making the thorium target and the Pellectron operation staff for excellent operation of the machine.