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42.
S. Ravi Kanth D. Maitraie P. Shanthan Rao B. Sridhar 《Journal of fluorine chemistry》2006,127(9):1211-1221
Three-component Grieco condensation reaction of 3-aminopyrazolo[3,4-b]pyridine, formaldehyde/benzaldehyde and electron rich alkenes in presence of iron(III) chloride gave tetrahydropyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidines/quinazolines in single pot. The sequence of reactions is formation of di-azadiene in situ and the subsequent regioselective addition of alkenes in aza-Diels Alder type reaction. The structure and stereochemistry of the products were confirmed by spectral data and single crystal X-ray crystallography. 相似文献
43.
The kinetics of decomposition of hydrogen peroxide have been studied on mixed Fe(III)–Al(III) hydroxide and oxide catalysts. While iron hydroxide possesses considerable catalytic activity, aluminium hydroxide has very little activity. The rate of decomposition on mixed hydroxides increases with increasing concentration of aluminium hydroxide up to about 1.5 mol% and decreases thereafter. The mixed oxides possess negligible activity compared to the corresponding hydroxides. The energy of activation, as calculated from the Arrhenius equation, is 10.1 kcal/mol for sample S4, containing 1.52 mol% of alumina. The rate of decomposition of S4 increases with increasing pH up to 6.8 and decreases thereafter. The rate is first order in all these cases. A suitable mechanism is suggested.
Fe(III)–Al(III). , . , 1,5 , . . , , 10,1 / S4, 1,52 . S4 pH 6,8, . . .相似文献
44.
Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors 总被引:10,自引:0,他引:10
Singh R Pantarotto D McCarthy D Chaloin O Hoebeke J Partidos CD Briand JP Prato M Bianco A Kostarelos K 《Journal of the American Chemical Society》2005,127(12):4388-4396
Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems. 相似文献
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46.
Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures. 相似文献
47.
Kumar MR Prabhakar S Kumar MK Reddy TJ Vairamani M 《Rapid communications in mass spectrometry : RCM》2004,18(10):1109-1115
The negative ion electrospray ionization (ESI) mass spectra of a series of dicarboxylic acids, a pair of isomeric (cis/trans) dicarboxylic acids and two pairs of isomeric (positional) substituted benzoic acids, including a pair of hydroxybenzoic acids, were recorded in the presence of halide ions (F(-), Cl(-), Br(-) and I(-)). The ESI mass spectra contained [M--H](-) and [M+X](-) ions, and formation of these ions is found to be characteristic of both the analyte and the halide ion used. The analytes showed a greater tendency to form adduct ions with Cl(-) under ESI conditions compared with the other halide ions used. The isomeric compounds yielded distinct spectra by which the isomers could be easily distinguished. The collision-induced dissociation mass spectra of [M+X](-) ions reflected the gas-phase basicities of both the halide ion and [M--H](-) ion of the analyte. However, the relative ordering of gas-phase basicities of all analyte [M--H](-) and halide ions could not account for the dominance of chloride ion adducts in ESI mass spectra of the analytes mixed with equimolar quantities of the four halides. 相似文献
48.
Pinacol Formation and Reduction of Aromatic Carbonyls with Magnesium–Methanol at Ambient Temperature
Jitender M. Khurana Geeti Bansal Gagan Kukreja Ravi R. Pandey 《Monatshefte für Chemie / Chemical Monthly》2003,421(5):1365-1371
A simple and inexpensive procedure for the pinacol formation of aromatic aldehydes and reduction of aromatic ketones to the corresponding alcohols with magnesium in dry methanol at ambient temperature is reported. The pinacol formation and reduction are proposed to be proceeding by SET from magnesium. 相似文献
49.
Raghuraman K Katti KK Barbour LJ Pillarsetty N Barnes CL Katti KV 《Journal of the American Chemical Society》2003,125(23):6955-6961
Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A). 相似文献
50.
Ravi Shankar Anubhav Saxena Ajaib S. Brar 《Journal of organometallic chemistry》2002,650(1-2):223-230
New functional polysilanes [R2R1Si(CH2)2SiH]n (R=Me, R1=H (1); R=R1=Et (2); R=Me, R1=Ph (3)) bearing carbosilyl side chains have been synthesized by catalytic dehydropolymerization of precursor carbosilanes R2R1SiCH2CH2SiH3 using Cp2TiCl2–BuLi as a catalyst. These polymers are characterized by 1H, 13C, 29Si, {1H–29Si} HSQC NMR spectroscopy, GPC and TGA. Attempts to delineate the tacticity from the analysis of deconvoluted 29Si{1H}-NMR signals associated with the side chain silicon atoms reveal that the triad concentration ratio follows a Bernoullian statistical model for polymers 1 and 2 only. 相似文献