Facile synthesis of O6-alkyl-, O6-aryl-, and diaminopurine nucleosides from 2'-deoxyguanosine

The 3',5'-bis-O-TBDMS derivative of 2'-deoxyguanosine can be converted to its O6-alkyl and O6-aryl ethers as well as to N6-substituted diaminopurine nucleosides in two simple steps. Also described is a novel, nonaqueous, one-step O6-desulfonylation method that leads to deprotection of the carbonyl moiety of 2'-deoxyguanosine.     

Synthesis of pyrene and benzo[a]pyrene adducts at the exocyclic amino groups of 2'-deoxyadenosine and 2'-deoxyguanosine by a palladium-mediated C-N bond-formation strategy

Single-electron oxidation of the carcinogenic hydrocarbon benzo[a]pyrene (BaP) is thought to result in a radical cation intermediate and this species has been proposed to cause alkylation at the nitrogens of the purine nucleobases. Although several different nucleoside adducts have been isolated as arising from this mode of metabolic activation, there are no selective, total syntheses of the stable exocyclic amino group adducts formed by the single-electron oxidation of any hydrocarbon with the purine 2'-deoxynucleosides to date. In this paper we disclose the synthesis of the model adducts N(6)-(1-pyrenyl)-2'-deoxyadenosine and N(2)-(1-pyrenyl)-2'-deoxyguanosine as well as the first synthesis of the carcinogen-linked nucleoside derivatives N(6)-(6-benzo[a]pyrenyl)-2'-deoxyadenosine and N(2)-(6-benzo[a]pyrenyl)-2'-deoxyguanosine via a palladium-mediated C-N bond formation. Two different coupling strategies were attempted: coupling of an aryl bromide with a suitably protected nucleoside and the coupling of an arylamine with a suitable halonucleoside. The former had somewhat limited applicability in that only N(6)-(1-pyrenyl)-2'-deoxyadenosine was prepared by this method; on the other hand, the latter was more general. However, there are noteworthy differences in the amination reactions at the C-6 and C-2 positions. Reactions at the C-6 resulted in the competing formation of a 1:2 amine-nucleoside adduct in addition to the desired monoaryl nucleoside. Such a dimer formation was not observed at the C-2. The C-2 adducts, however, displayed an interesting conformational behavior.     

Gold Decorated Graphene by Laser Ablation for Efficient Electrocatalytic Oxidation of Methanol and Ethanol

A well‐known limitation in the fabrication of metal‐graphene composite has been the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. We demonstrate here a novel one‐pot synthesis of gold nanoparticles by laser ablation of gold strip and in‐situ decoration on graphene substrate. Not only the impregnation of nanoparticles was linker free, but also the synthesis by itself was surfactant‐free. The composite materials were well characterized morphologically and functionally using electron microscopy, X‐ray and electron diffraction, Raman spectroscopy, Zeta potential, electrochemical measurements and UV‐Visible spectroscopic techniques. This linker‐free gold‐graphene based composite has been employed for catalytic applications pertaining to electrooxidation. We have explored the use of this composite as a binder‐free electrode in electrocatalytic oxidation of methanol and ethanol in alkaline medium. Additionally, the onset potential for ethanol oxidation was found to be more negative, ?100 mV, an indication of its promising application in direct ethanol fuel cells.     

Kinetics of thermal decomposition of a synthetic K–H3O jarosite analog

The thermal decomposition kinetics of a synthetic K–H₃O jarosite analog was determined from thermogravimetric analysis at various heating rates in air. A thermal decomposition mechanism was proposed based on X-ray analysis of partially decomposed material and distinct features observed during thermal decomposition analysis. The decomposition path is complex. The material was treated as a composite of K-jarosite, H₃O-jarosite, and a “vacancy component”. The evolution of (OH)^? and SO₃ from these individual components was modeled. The decomposition is broken into subreactions according to distinct features in the thermoanalytical measurements. The subreactions are arranged sequentially and in parallel according to the evolution of the participating phases. A set of associated apparent activation energies was determined using isoconversion analysis. Kinetic triplets were assigned to each subreaction. A reasonable match with the observed decomposition was achieved by varying pre-exponential factors.     

Optical absorption spectrum of Co2+ in ammonium perchlorate single crystal

Single crystals of cobalt — doped ammonium perchlorate were grown at room temperature. The electronic absorption bands observed at room and liquid air temperatures have been assigned transitions from the ground⁴T₁(F) state to the excited⁴T₂(F),⁴A₂(F),²T₁(G) and⁴T₁(P) states. The crystal parameters derived areDq=880 cm^–1,B=865 cm^–1 andC= 4·63B.The authors wish to express their thanks to the authorities of the Indian Institute of Science, Bangalore for kind permission to use their spectrophotometer. Two of the authors (B. C. V.Reddy and J. L.Rao) express their greatful thanks to the council of scientific and Industrial Research (New Delhi) for financial assistance.     

Optical absorption spectrum of Ni2+ doped in ammonium zinc sulphate

The optical absorption spectrum of Ni²⁺ ion doped in ammonium zinc sulphate has been studied at room and liquid air temperatures. From the nature and the positions of the bands a successful interpretation of all the bands could be made assumingO _h symmetry for the Ni²⁺ ion in the crystal. The fine splitting of the³ T ₁ ¹ band at liquid air temperature has been successfully interpreted to be due to spin-orbit interaction. The crystal field and spin-orbit parameters derived areDq=1000 cm⁻¹;B=750 cm⁻¹;C=3.45B andξ=600 cm⁻¹.     

Absorption spectra of Cu2+ in shattuckite and plancheite

Optical and EPR measurements are carried out on shattuckite, a copper bearing silicate. The EPR spectrum observed at 120 K reveales hyperfine structure for parallel and perpendicular components. The measured values are g6 = 2.402, g⊥ = 2.038, A6 = 112 × 10^-4 cm^-1 and A⊥ = 49.5 × 10^-4 cm^-1 and they indicate a tetragonal distortion for the Cu²⁺ion. Further, the constants P and K are evaluated and found to be 0.014 cm^-1 and 0.0112 respectively. The bands observed at 8160, 13330 and 16125 cm^-1 are assigned to the electronic states of Cu²⁺, in a crystal field subjected to tetragonal (C_4V) distortion. The crystal field parameters evaluated are Dq = -1333, Ds = -1565 and Dt = -380 cm^-1. Correlating the EPR and optical data, the orbital reduction factors are calculated as k6 = 0.89 and k⊥ = 0.59. It is confirmed from EPR and optical studies that the Cu²⁺ion in shattuckite is sited in an elongated octahedron. Similar studies are carried out for plancheite. The observed optical absorption spectrum of plancheite is attributed to Cu²⁺ sited in an elongated octahedron and tetragonal field parameters are evaluated.     

Racah and Judd-Ofelt parameters for Pr3+, Nd3+, and Er3+ ions in a laser liquid

The values of the Slater-Condon (F₂, F₄, F₆), Racah (E¹, E², E³) and Lande ξ₄f coefficients the nephelauxetic ratio (β), the bonding parameter (σ), and the Judd-Ofelt intensity (T_λ) parameters have been calculated from the reported absorption spectra of Pr³⁺, Nd³⁺, and Er³⁺ ions in an aprotic solvent SeOCl₂ acidified with antimony pentachloride. The nature of the bonding is suggested to be covalent for praseodymium, neodymium and erbium ions in the laser liquid in view of the magnitude of the respective bonding parameters.     

Evaluation of the enantiomeric resolution of 7,8-dihydroxy-7,8-dihydrobenzo[a]-pyrene and its 6-fluoro and 6-bromo derivatives on polysaccharide-derived stationary phases

The enantiomeric resolution and the elution order of (+/-)-trans-7,8-dihydrodiols of benzo[a]pyrene and its 6-fluoro and 6-bromo derivatives were analyzed on three polysaccharide-based columns: Daicel Chiralcel CA-I (cellulose triacetate), OF, and OG [cellulose tris(4-chloro- and 4-methylphenylcarbamate)]. For comparison, the separation of (+/-)-1,1'-bi-2-naphthol was evaluated on the OG and OF columns. Possibly similar interactions of (S)-1,1'-bi-2-naphthol and (7S,8S)-isomers of 6-halo-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene with the chiral sorbent are suggested.