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91.
Two new zinc ion dependent oligonucleotide based artificial nucleases (OBAN's) have been synthesized. These consist of 2'-O-methyl modified RNA oligomers conjugated to 5-amino-2,9-dimethylphenanthroline (neocuproine)via a urea linker. OBAN 4 carries the catalytic group on a linker extending from the C-4 of an internal cytosine moiety. OBAN 5 has two neocuproine units attached, each to linkers extending from the C-5 position of uridine moieties, one placed internally and the other at the at the 5'-end of the oligonucleotide. The key step in the synthesis of the OBAN systems is conjugation of the catalytic group to the respective amino linkers of the modified oligonucleotides. This is achieved by first converting the 5-amino-2,9-dimethylphenanthroline to the phenylcarbamate. The reaction of this neocuproine phenylcarbamate with the oligonucleotide carrying one or two primary aliphatic amines in aqueous buffer (at pH 8.5) leads to nearly quantitative formation of the urea-linked conjugates. Both OBAN systems were found to cleave RNA in the bulged out regions formed from the non-complementary part of the target sequences, in the presence of Zn(II) ions. Differences in efficiency between these and previously reported systems are discussed. 相似文献
92.
The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes. 相似文献
93.
Thorsten Oldag Thomas Aussieker Hans‐Lothar Keller Christian Preitschaft Arno Pfitzner 《无机化学与普通化学杂志》2005,631(4):677-682
Solvothermal Synthesis and Crystal Structure Determination of AgBiI4 and Ag3BiI6 AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag3BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order. 相似文献
94.
Gasphase Reactions. 92 Thermal Elimination of HCl from Alkyldichlorophosphanes (H3C/H)3C? PCl2 to Phosphaalkenes (H3C/H)2C?PCl and Phosphaalkines (H3C/H)C≡P The alkyldichlorophosphanes H3C? PCl2, ClH2? PCl2, (H3C)H2C? PCl2 and (H3C)2HC? PCl2 split off HCl on heating in a gasflow under reduced pressure. PE spectroscopic gas analysis proves that under these conditions the short-lived phosphaalkenes H2C?PCl, (H3C)H2C?PCl and – catalyzed by [MgCl2? MgO/SiO2]∞ – (H3C)2C?PCl as well as the phosphaalkines HC≡P and (H3C)C≡P are formed, all of which can be isolated by low temperature condensation. Based on the PES ionization patterns recorded and on the MNDO calculations for their assignment, the πCP multiple bonds are discussed. The presumable pathway of the HCl elimination is rationalized for (H3C)H2C? PCl2 by an approximate MNDO energy hypersurface. 相似文献
95.
A series of β-ketoselenenic acids was generated at low temperature ( - 20° to - 50°) by selenoxide syn elimination of appropriate selenoxides (13-ox, 16-ox, 35-ox, 38-ox, and 39-ox). No evidence for the buildup of significant concentrations of selenenic acid was obtained. A selenolseleninate (15, 2,2' - diseleno - bis(1 - phenyl - 2 - methyl -1 - propanone) - Se - oxide) was detected as an intermediate in the decomposition of 13-ox and 16-ox. This compound, which is stable in solution below - 50° was charaeterized by NMR spectroscopy (1H, 13C,77Se) and by its thermal decomposition and reactions with phosphite (reduction to diselenide 6) and dialkylamines (formation of selenenamide 11). Decomposition of 15 in the presence of dibenzylamine resulted in trapping of a selenenic acid-like species (RSeSeOH) to give RSeSeN(CH2Ph)2 (R = PhC(O)C(CH3)2). Although 15 could not be prepared by oxidation of diselenide 6, it was possible to prepare a cyclic selenolseleninate (4,4-dimethyl-1,2-diselenolane monoxide, 20) by oxidation of the related diselenide (19). Attempts to prepare more stable aliphatic selenenic acids by blocking the principal decomposition pathway of 15 were not successful. Thus 1 - benzoyl -1 - cyclopropaneselenenic acid was generated from 35-ox and 38-ox and 1 - benzoyl - 2,2 - dimethylcyclopropaneselenenic from 39-ox. The former underwent normal disproportionation (to 36 and 37) even when prepared at -49°. The latter gave what appeared to be a selenolseleninate (40) which again disproportionated at -17°. 相似文献
96.
Hansen MR Madsen GK Jakobsen HJ Skibsted J 《The journal of physical chemistry. A》2005,109(9):1989-1997
The refinement of borate structures using DFT calculations combined with experimental (11)B quadrupole coupling parameters from solid-state NMR spectroscopy is presented. The (11)B electric field gradient (EFG) tensors, calculated using the WIEN2k software for trigonal and tetrahedral boron sites in a series of model compounds, exhibit a convincing linear correlation with the quadrupole coupling tensor elements, determined from (11)B MAS NMR spectra of the central or satellite transitions. The model compounds include Li(2)B(4)O(7), Mg(2)B(2)O(5), Mg(3)B(2)O(6), NH(4)B(C(6)H(5))(4), and colemanite (CaB(3)O(4)(OH)(3).H(2)O). The (11)B quadrupole moment, Q = 0.0409 +/- 0.0002 barn, derived from the linear correlation, is in excellent agreement with the accepted value for Q((11)B). This demonstrates that DFT (WIEN2k) calculations can provide precise (11)B quadrupole coupling parameters on an absolute scale. On the other hand, DFT calculations based on the reported crystal structures for datolite (CaBSiO(4)(OH)) and danburite (CaB(2)Si(2)O(8)) cannot reproduce the experimental (11)B quadrupole coupling parameters to the same high precision. However, optimization of these structures by minimization of the forces between the atoms (obtained by DFT) results in a significant improvement between the calculated and experimental (11)B quadrupole coupling parameters, which indicates that reliable refinements of the borate structures are obtained by this method. Finally, the DFT calculations also provide important structural information about the sign and orientation of the EFG tensor elements in the crystal frame, a kind of information that cannot be achieved from (11)B NMR experiments on powdered samples. 相似文献
97.
98.
The so-called “Bergmann oxide” 4a and the related compounds 4b-i dissociate reversibly to the corresponding radicals 5 at elevated temperatures. Analysis of the ESR spectra reveals that in 5a-f the unpaired electron is delocalized over the entire molecule. On the other hand the strongly reduced spin density at the β-carbon atom in 5h-i as well as in 7 indicates a twisting about the N,N-bond in these radicals, whereas m 5g the bond between the β-carbon atom and the group Ar1 is twisted. The results of spin density calculations for radicals 5 are in agreement with the experimentally estimated spin densities. In spin trap experiments with nitrosobenzene or nitrones respectively, 5a reacts at the β-carbon atom, indicating this position as the most reactive one. 相似文献
99.
Hans‐Ruedi Mürner Rosario Scopelliti Jean‐Claude G. Bünzli 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(8):m434-m435
In the title compound, [TbCl(C27H35N3)2(H2O)](ClO4)2·2C2H6O, the TbIII ion has a coordination number of eight, composed of two tridentate substituted‐terpyridine ligands, a water molecule and a bound Cl? anion. The first coordination shell can be described as a distorted bicapped trigonal prism. The dihedral angles between pyridine rings belonging to the same tpy ligand range from 5.2 (5) to 16.8 (5)°. 相似文献
100.
The collision-induced dissociation (CID) spectra of five alkylmethyleneimmonium ions (H2C-N+R1R2, (a) R1 = R2 = C2H5, (b) R1 = n-C3H7, R2 = H, (c) R1 = n-C3H7, R2 = CH3, (d) R1 = n-C3H7, R2 = C2H5, (e) R1 = R2 = n-C3H7) are reported and discussed in terms of the mechanism of alkane loss. The most abundant alkane losses result from 2-azaallylic bond cleavages within R1 and R2 leading to daughter ions of m/z 84. Ion d (R1 = n-C3H7, R2 = C2H5) was chosen for a deuterium-labelling study because it exhibited methane loss nearly free from interferences with other fragmentations. The methane lost consists to a great extent (95%) of the methyl moiety of R2. Whereas the methyl moiety obviously stays intact during the fragmentation process, the hydrogen additionally needed originates from all positions of R1 and the double-bonded methylene in an approximately random distribution, suggesting extensive hydrogen migrations preceding the transfer step. 相似文献