Pd-Xantphos-catalyzed direct arylation of nucleosides

Direct arylation of the exocyclic amino groups of nucleosides represents a simple approach to N-aryl nucleoside derivatives. To date, one limitation has been that only electron-deficient aryl bromides and triflates possessed adequate reactivity for efficient, direct N-arylation of nucleosides. We demonstrate herein that Pd-Xantphos catalytic systems lead to successful N-arylation of suitably protected 2'-deoxyadenosine and 2'-deoxyguanosine with a wide range of aryl bromides.     

Intact cell matrix-assisted laser desorption/ionization mass spectrometry as a tool to screen drugs in vivo for regulation of protein expression

Here we demonstrate for the first time the application of intact cell matrix-assisted laser desorption/ionization mass spectrometry (ICM-MS) to study the regulation of protein expression. This technique can be extended to screen the drugs that inhibit protein synthesis in various diseases. We have used Escherichia coli cells expressing a recombinant glutathione-S-transferase (GST) gene under an arabinose-inducible promoter as a model system. Using ICM-MS analysis, we have detected a 28 kDa peak corresponding to the production of recombinant GST under the arabinose-induced condition. Furthermore, recombinant GST protein was purified by a single-step affinity purification using a glutathione Sepharose 4B affinity column from arabinose-induced E. coli cells. The purified GST protein was found to be a 28 kDa protein by MALDI analysis suggesting the arabinose-induced protein is indeed GST. The regulation of protein expression was studied using glucose as an alternative metabolite. The glucose-mediated regulation of the ara-operon was followed using the ICM-MS technique. All the results obtained from ICM-MS data were validated using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) analysis. The present technique can be extended for in vivo screening of drugs and it holds tremendous potential to discover novel drugs against specific protein expressions in different diseases.     

Gelation of covalently edge-modified laponites in aqueous media. 1. rheology and nuclear magnetic resonance

We describe the covalent modification of the edges of laponite with organic groups and the influence of this modification on gelation behavior. We compare three materials: an unmodified laponite, a laponite edge modified with a trimethyl moiety (MLap), and an octyldimethyl moiety (OLap). Gelation is investigated using rheology and NMR T1 relaxation measurements and nuclear Overhauser enhancement spectroscopy (NOESY). MLap and OLap show qualitatively different gelation. Gelation of MLap is very similar to laponite: MLap gels over the same time scale as laponite and has about the same solid modulus, and the MLap gel is almost as transparent as laponite. In contrast, OLap gels rapidly relative to laponite and forms a weak, turbid gel. We believe that gelation in laponite and MLap results from the formation of a network of well-dispersed platelets (or a few platelets), while in OLap, gelation results from a network of stacks of several platelets. NMR relaxation measurements indicate that gelation does not affect the average relaxation of water protons. However, T1 increases marginally for the protons in the organic moieties in MLap and decreases for protons in the organic moieties in OLap. Relaxation measurements, analyses of line width, and NOESY taken together suggest that, in OLap, gelation is a consequence of association of the organic moieties on the laponite edges, and that this association strengthens with time. Thus, the time-dependent changes in NMR suggest a structural origin for the time-dependent changes in the rheological behavior.     

The mechanism of the reduction of [AnO2]2+ (An = U, Np, Pu) in aqueous solution, and by Fe(II) containing proteins and mineral surfaces, probed by DFT calculations

The fate of actinyl species in the environment is closely linked to oxidation state, since the reduction of An(VI) to An(IV) greatly decreases their mobility due to the precipitation of the relatively insoluble An(IV) species. Here we study the mechanism of the reduction of [AnO(2)](2+) (An = U, Np, Pu) both in aqueous solution and by Fe(II) containing proteins and mineral surfaces, using density functional theory calculations. We find a disproportionation mechanism involving a An(V)-An(V) cation-cation complex, and we have investigated how these complexes are formed in the different environments. We find that the behaviour of U and Pu complexes are similar, but the reduction of Np(V) to Np(IV) would seems to be more difficult, in line with the experimental finding that Np(V) is generally more stable than U(V) or Pu(V). Although the models we have used are somewhat idealised, our calculations suggest that there are strong similarities between the biotic and abiotic reduction pathways.     

A concise synthetic strategy to functionalized chromenones via [5+1] heteroannulation and facile C-N/C-S/C-O bond formation with various nucleophiles

A highly efficient strategy to 2,3-substituted chromen-4H-ones has been developed. The methodology involves unexpected intramolecular heteroannulation of readily accessible substituted 2-hydroxy-ω-nitroacetophenone with carbon disulfide in the presence K₂CO₃ followed by methylation with methyl iodide. These chromenones were further reacted with various nucleophiles such as amines, thiols, and alkoxide resulting in the facile C-N, C-S, and C-O bond formation. The scope and generality have been discussed.     

A new three-component reaction: green synthesis of novel isoindolo[2,1-a]quinazoline derivatives as potent inhibitors of TNF-α

Concurrent construction of five and six membered fused N-heretocyclic ring was achieved via a conceptually new three-component reaction affording 6,6a-dihydroisoindolo[2,1-a]quinazoline-5,11-diones as novel inhibitors of TNF-αin vitro. This represents one of the few examples of direct TNF-α inhibition by small molecules.     

Block copolymer containing poly(3‐hexylthiophene) and poly(4‐vinylpyridine): Synthesis and its interaction with CdSe quantum dots for hybrid organic applications

Poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer was synthesized by RAFT polymerization of 4‐vinyl pyridine using a trithiocarbonate‐terminated poly(3‐hexylthiophene) macro‐RAFT agent. The optoelectronic properties and the morphology of the block copolymer blends with CdSe quantum dots were investigated. UV‐vis and fluorescence experiments were performed to prove the charge transfer between CdSe and poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Enhancement of OFET performance of semiconducting polymers containing benzodithiophene upon surface treatment with organic silanes

Poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene} ( P1 ) homopolymer and poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene ‐alt‐thiophene} ( P2 ) alternating copolymer have been synthesized by Stille coupling polymerization. The field‐effect mobilities of both polymers were measured on both untreated and silane‐treated OFET devices. Various silanes were selected to allow an incremental increase in the hydrophobicity of the silicon dioxide dielectric. A direct correlation was observed between the hydrophobicity of the silicon dioxide dielectric surface and the enhancement of the field‐effect mobilities. The highest mobilities for both polymers were measured on the OFET devices treated with heptadecafluoro‐1,1,2,2‐tetrahydro‐decyl‐1‐trimethoxysilane (FS) which generated the most hydrophobic surface. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of cobalt doped γ-Fe2O3 and Mn-Zn ferrites by the thermal decomposition of the hydrazine precursors

Fine particle cobalt doped-Fe₂O₃ and Mn-Zn ferrites have been prepared by the thermal decomposition of N₂H₅Co _x Fe_1–x (N₂H₃COO)₃.H₂O wherex=1–10 atom% and (N₂H₅)₃Mn_xZn_1–x Fe₂(N₂H₃COO)₉· 3H₂O wherex=0.2–0.8, respectively. Formation of these oxide materials has been confirmed by thermogravimetry and X-ray powder diffraction patterns. The fine particle nature of these oxide materials is evident from particle size analysis and surface area measurements.

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Zusammenfassung Mit fein verteiltem Kobalt versetztes-Fe₂O₃ sowie Mn-Zn Ferrite wurden durch thermische Zersetzung von N₂H₅Co _x Fe_1–x (N₂H₃COO)₃·H₂O mit jc=1–10 Atomprozent bzw. (N₂H₅)₃Mn _x Zn_1–x Fe₂(N₂H₃COO)₉·3H₂O mitx=0,2–0,8 hergestellt. Die Bildung dieser Oxidstoffe wurde durch Thermogravimetrie und Pulverdiffraktionsmethoden bekräftigt. Die Feinkornstruktur dieser Oxidstoffe wird durch Korngrößenverteilungs- und Oberflächenmessungen augenscheinlich.

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N₂H₅Co _x Fe_1–x (N₂H₃COO)₃·H₂O, x-1–10 %, (N₂H₅)₃Mn _x Zn_1–x Fe₂(N₂H₃COO)₉ · 3H₂O, x=0,2–0,8, , , -Fe₂O₃ Mn-Zn . . .