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1.
The effects of amine structure on the montmorillonite-catalyzed oligomerization of the 5'-phosphoramidates of adenosine are investigated. 4-Aminopyridine derivatives yielded oligoadenylates as long as dodecamers with a regioselectivity for 3',5'-phosphodiester bond formation averaging 88%. Linear and cyclic oligomers are obtained and no A5'ppA-containing products are detected. Oligomers as long as the hexanucleotide are obtained using 2-aminobenzimidazole as the activating group. A predominance of pA2'pA is detected in the dimer fraction along with cyclic 3',5'-trimer; no A5'ppA-containing oligomers were detected. Little or no oligomer formation was observed when morpholine, piperidine, pyrazole, 1,2,4-triazole, and 2-pyridone are used as phosphate-activating groups. The effects of the structure of the phosphate activating group on the oligomer structure and chain lengths are discussed. 相似文献
2.
Methyladenine and adenine N-phosphoryl derivatives of adenosine 5'-monophosphate (5'-AMP) and uridine 5'-monophosphate (5'-UMP) are synthesized, and their structures are elucidated. The oligomerization reactions of the adenine derivatives of 5'-phosphoramidates of adenosine on montmorillonite are investigated. 1-Methyladenine and 3-methyladenine derivatives on montmorillonite yielded oligoadenylates as long as undecamer, and the 2-methyladenine and adenine derivatives on montmorillonite yielded oligomers up to hexamers and pentamers, respectively. The 1-methyladenine derivative yielded linear, cyclic, and A5'ppA-derived oligonucleotides with a regioselectivity for the 3',5'-phosphodiester linkages averaging 84%. The effect of pKa and amine structure of phosphate-activating groups on the montmorillonite-catalyzed oligomerization of the 5'-phosphoramidate of adenosine are discussed. The binding and reaction of methyladenine and adenine N-phosphoryl derivatives of adenosine are described. 相似文献
3.
Dr. Dominika Bednarczyk Dr. Orly Dym Dr. Vadivel Prabahar Dr. Yoav Peleg Douglas H. Pike Dr. Dror Noy 《Angewandte Chemie (International ed. in English)》2016,55(24):6901-6905
The ability to tune the light‐absorption properties of chlorophylls by their protein environment is the key to the robustness and high efficiency of photosynthetic light‐harvesting proteins. Unfortunately, the intricacy of the natural complexes makes it very difficult to identify and isolate specific protein–pigment interactions that underlie the spectral‐tuning mechanisms. Herein we identify and demonstrate the tuning mechanism of chlorophyll spectra in type II water‐soluble chlorophyll binding proteins from Brassicaceae (WSCPs). By comparing the molecular structures of two natural WSCPs we correlate a shift in the chlorophyll red absorption band with deformation of its tetrapyrrole macrocycle that is induced by changing the position of a nearby tryptophan residue. We show by a set of reciprocal point mutations that this change accounts for up to 2/3 of the observed spectral shift between the two natural variants. 相似文献
4.
A simple and efficient synthesis of 2-arachidonoyl glycerol, an endogenous agonist for cannabinoid receptors was achieved using Novozym 435, immobilized lipase from Candida antarctica. 相似文献
5.
Al-Salhi M Masilamani V Vijmasi T Al-Nachawati H VijayaRaghavan AP 《Journal of fluorescence》2011,21(2):637-645
Lung cancer takes a heavy toll every year, since the survival rate is not more than 15%. In this paper, we present results
of a novel technique based on the autofluorescence of body fluids like blood plasma, acetone extract of cellular components,
sputa and urine of lung cancer patients (N = 27). A set of ratio parameters based on the fluorescence peaks of tryptophan and elastin, in plasma and sputum; flavin,
NADH (reduced nicotinamide adenine dinucleotide) and porphyrin in urine; porphyrin alone in acetone extract of formed elements,
were all evaluated. Similar sets of ratios were obtained for age adjusted normal controls (N = 27) and all these ratios were given as inputs to multivariate (principle component and discriminant) analyses, which showed
that the two groups could be classified with an accuracy of about 90%. Since the instrumentation involved was an ordinary
steady state Xe lamp based spectrofluorometer, the technique is of significant advantage in screening and early detection
of lung cancer in high risk population such as heavy smokers. 相似文献
6.
A concise stereoselective synthesis of 3-spiro-α-methylene-γ-butyrolactone oxindoles from Morita-Baylis-Hillman adducts of isatin in excellent yield has been achieved following a three-step reaction sequences viz. (1) Isomerisation of the Morita-Baylis-Hillman adducts of isatin with trimethyl orthoformate and montmorillonite K10 clay catalyst, (2) a second Morita-Baylis-Hillman reaction with formaldehyde, and (3) an acid catalysed lactonization. The structure and stereochemistry of the products were assigned by X-ray crystallographic and NMR spectroscopic studies. Formation and mechanism of the minor product spirofuran oxindoles and a one-pot base promoted second Morita-Baylis-Hillman adduct formation-lactonization reaction have also been achieved. 相似文献
7.
8.
Nickel nanoparticles have been synthesized by chemical reduction method. By the analysis of X-ray diffraction, the resultant particles are characterized and found to be pure crystalline nickel with a face-centered cubic (FCC) structure. The morphology and size of the nanoparticles are studied by scanning electron microscopy (SEM) and micrographs reveal that the nanoparticles are mostly spherical. The compositional analysis has been carried out by using EDAX. The quantum size confinement of the crystallites is evident from the blue-shift of the absorption edge in the UV–vis absorption spectrum. 相似文献
9.
Solvent-free films of poly (ethylene oxide)–silver triflate (PEO–AgCF3SO3)/MgO-based nanocomposite polymer electrolytes (PEO)50AgCF3SO3–x wt.% MgO (x = 1, 3, 5, 7, and 10) obtained using solution casting technique were found to exhibit an appreciably good complexation of
MgO nanofiller within the polymer electrolyte system and non-Debye type of relaxation as revealed by Fourier transform infrared
and complex impedance analyses. Optimized filler (5 wt.% MgO) when incorporated into the polymer electrolyte resulted in a
maximum electrical conductivity of 2 × 10−6 S cm−1 in conjunction with a silver ionic transference number (t
Ag+) of 0.23 at room temperature (298 K). Detailed structural, thermal, and surface morphological investigation indicated a slight
reduction in the degree of crystallinity owing to the addition of MgO nanofiller. 相似文献
10.
Ponnusamy Shanmugam Vadivel Vaithiyanathan Baby Viswambharan Suchithra Madhavan 《Tetrahedron letters》2007,48(52):9190-9194
The reaction of the Baylis–Hillman adduct 2 of ferrocenealdehyde with various oxygen and carbon nucleophiles in the presence of montmorillonite K10 clay catalyst furnished highly functionalised trisubstituted alkene derivatives of ferrocenealdehyde in excellent yield. Synthetic use of one of products 7 has been demonstrated with the synthesis of a 1,3-diyne ether derivative of ferrocene 16 via an Eglinton coupling reaction. 相似文献