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81.
Simon S. Jones Colin B. Reese Samson Sibanda Aiko Ubasawa 《Tetrahedron letters》1981,22(47):4755-4758
The protection of uracil and 2--acyl guanine residues with 4--phenyl [or 4--(2,4-dimethylphenyl)] and 6--(2-nitrophenyl) groups as in [or ] and , respectively, is described. These -aryl protecting groups, which appear to withstand the usual conditions of oligonucleotide synthesis, may readily be removed by treatment with 2-nitrobenzaldoximate ions. 相似文献
82.
Selectivity coefficients, K(H)(M), for the exchange of alkali metal ions and ammonium ions with the hydrogen form of ZeoKarb 225 cation-exchange resin have been determined in various organic solvent-water and organic solvent-water-phenol mixtures. There is an increase in K(H)(M) in passing from purely aqueous conditions to media of increasing organic solvent content, frequently with the effect of producing magnified differences and selectivity reversals between one ion and another. The results are discussed in terms of the relationship between K(H)(M) and the reciprocal of the dielectric constant of the medium and also in the light of free energies of transfer of cations between methanol-water systems. The effect of phenol giving a lowering of K(H)(Cs) in methanol-water, of K(H)(K) and K(H)(Na) in ethanol-water and of K(H)(Na) and K(H)(L1) in acetone-water systems cannot be fully reconciled with the mechanism involving bonding proposed by earlier workers. 相似文献
83.
The determination of sulphide at an electrochemically generated nickel oxide layer at glassy carbon and screen-printed electrodes in acidic media has been examined and appraised. The NiO layer was found to produce a stripping-like signal to sulphide and gave a linear peak current response from 20 to 90 μM. The response was further enhanced by repetitive cycling allowing accumulation of nickel sulphide at the electrode surface such that lower micromolar levels of sulphide (i.e. 5 μM) can be determined. The response at the NiO layer to sulphide is shown to be reproducible over a period of 24 h, thereby offering the development of a disposable amperometric sensor for sulphide. 相似文献
84.
Synthesis of an N-protected derivative of 2-amino-2'-deoxyadenosine (dA') from 2'-deoxyguanosine is reported. The syntheses of several oligodeoxynucleotides containing this modified nucleoside are described, together with physical characterization via melting studies and CD conformational analysis. As expected, the 2-amino group is seen to add to the duplex stability. Although the sequence d(TA')3 was found to undergo a salt-induced conformational transition, mixed sequences such as d(CGTA'CG) did not display this behavior. All guanine residues present in these sequences were O6 protected, either with the cyanoethyl group or the 4-nitrophenylethyl group, to eliminate guanine degradation during phosphorylation and condensation reactions. Procedures for the introduction and removal of these O6 protecting groups are described. 相似文献
85.
Axel Fischer Peter G. Jones Ion Neda Reinhard Schmutzler Igor V. Shevchenko 《无机化学与普通化学杂志》1994,620(5):908-913
Synthesis and Molecular Structure of new Ring Systems from 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1 reacts in two different ways to form new heterocycles. Partial oxidation of 1 with tetrachloroorthobenzoquinone furnishes the methylene-bridged λ3P, λ5P species 3 . Subsequent reactions with di- and triethylamine lead to the condensed ring system 6 with the P?C bonds connected to a central four-membered ring. Compound 6 displays crystallographic inversion symmetry, a short transannular P? P distance and an extremely distorted tetrahedral coordination geometry at the four-membered ring phosphorus atoms. 1 reacts with 7 to give the heterocycle 8 with a central eight-membered ring involving four phosphorus atoms. The eight – membered ring shows a ?bent”? crown conformation, the condensed five – membered rings display envelope conformation. 相似文献
86.
Oxidation reactions of an anionic gallium(I) N-heterocyclic carbene analogue with group 16 compounds
The reactivity of an anionic gallium(I) heterocycle, [K(tmeda)][:Ga([N(Ar)C(H)]2)], Ar = C6H3Pr(i)2-2,6, towards sources of elemental chalcogens and diorgano-dichalcogenides has been investigated and comparisons drawn with the reactivity of the valence isoelectronic N-heterocyclic carbene class of ligand. The reactions of the heterocycle with N2O or (Te)PEt3 yielded the dimeric, dianionic gallium(III) complexes, [K(L)]2[(mu-E)Ga([N(Ar)C(H)]2)]2, E = O, L = tmeda; E = Te, L = THF. Treatment of [K(tmeda)][:Ga([N(Ar)C(H)]2)] with the diphenyl dichalcogenides, PhEEPh, E = Se or Te, gave the one dimensional polymer, [K[(PhSe)2Ga([N(Ar)C(H)]2)]]infinity and the monomeric complex, [K(OEt2)3][(PhTe)2Ga([N(Ar)C(H)]2)], respectively. The X-ray crystal structures of the four complexes are reported. 相似文献
87.
Homocysteine is thought to be a risk factor for vascular disease and this has led to an increase in demand for its assay in clinical laboratories. An HPLC method, incorporating electrochemical detection, for measurement of plasma total homocysteine is presented. The method is simple to perform, precise and suitable for clinical applications. 相似文献
88.
Protein fold recognition 总被引:4,自引:0,他引:4
Summary An important, yet seemingly unattainable, goal in structural molecular biology is to be able to predict the native three-dimensional
structure of a protein entirely from its amino acid sequence. Prediction methods based on rigorous energy calculations have
not yet been successful, and best results have been obtained from homology modelling and statistical secondary structure prediction.
Homology modelling is limited to cases where significant sequence similarity is shared between a protein of known structure
and the unknown. Secondary structure prediction methods are not only unreliable, but also do not offer any obvious route to
the full tertiary structure. Recently, methods have been developed whereby entire protein folds are recognized from sequence,
even where little or no sequence similarity is shared between the proteins under consideration. In this paper we review the
current methods, including our own, and in particular offer a historical background to their development. In addition, we
also discuss the future of these methods and outline the developments under investigation in our laboratory. 相似文献
89.
Jochen Münchenberg Jens R. Goerlich Axel K. Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(2):348-354
Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 · Et2O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond. 相似文献
90.
Matthias Freytag Frank T. Edelmann Ludger Ernst Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》2004,630(3):377-383
The reaction of the symmetric diphosphene 2, 4, 6‐(CF3)3‐C6H2‐P=P‐C6H2‐2, 4, 6‐(CF3)3 4 with Ru3(CO)12 led to the 50‐electron Ru3P2 nido‐cluster Ru3(CO)9[μ‐P‐C6H2‐2, 4, 6‐(CF3)3]2 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru3P2 centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C6H2(CF3)3 groups is also appreciably distorted. Temperature‐dependent 19F NMR studies of the [A3M3X]2 spin system (A = M = CF3, X = 31P) of 5 indicated a rotational barrier ΔG≠ of 82.3 kJ mol‐1 at 141 °C. The same Ru3P2 core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru3(CO)12; hindered rotation about the C(aryl)—P bonds was also observed, in this case. 相似文献