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871.
The formula of a new compound isolated in the LaOsO system has been established by means of crystal structure determination. There are two La3Os2O10 units in a face-centered monoclinic unit cell (S.G. ); a = 7.911(2) Å, b = 7.963(2) Å, c = 6.966(2)Å, β = 115.76(2)°;. For 1082 intensities, collected on an automated single-crystal diffractometer, the final R value was 0.025 after absorption corrections. The structure consists of isolated Os2O10 clusters composed of two edge-shared OsO6 octahedra. These dimeric units are connected together by two types of La3+ ions in eightfold coordination. In view of the OsOs distance inside the pair (2.462 Å), La3Os2O10 provides an example of metal-metal bonding involving a transition metal in a half-integral formal oxidation state of 5.5. 相似文献
872.
873.
George S Nangia A Lam CK Mak TC Nicoud JF 《Chemical communications (Cambridge, England)》2004,(10):1202-1203
Crystalline nitrodiphenyl ureas adopt the N-H...O tape alpha-network only when stabilization accrues from the I...O(2)N or C[triple bond]C-H...O(2)N synthon, otherwise the ureanitro motif is preferred; soft, weak interactions can direct polar self-assembly in strong N-HO hydrogen-bonded crystals. 相似文献
874.
Skander M Humbert N Collot J Gradinaru J Klein G Loosli A Sauser J Zocchi A Gilardoni F Ward TR 《Journal of the American Chemical Society》2004,126(44):14411-14418
We report on the generation of artificial metalloenzymes based on the noncovalent incorporation of biotinylated rhodium-diphosphine complexes in (strept)avidin as host proteins. A chemogenetic optimization procedure allows one to optimize the enantioselectivity for the reduction of acetamidoacrylic acid (up to 96% ee (R) in streptavidin S112G and up to 80% ee (S) in WT avidin). The association constant between a prototypical cationic biotinylated rhodium-diphosphine catalyst precursor and the host proteins was determined at neutral pH: log K(a) = 7.7 for avidin (pI = 10.4) and log K(a) = 7.1 for streptavidin (pI = 6.4). It is shown that the optimal operating conditions for the enantioselective reduction are 5 bar at 30 degrees C with a 1% catalyst loading. 相似文献
875.
Gray TG Rudzinski CM Meyer EE Holm RH Nocera DG 《Journal of the American Chemical Society》2003,125(16):4755-4770
The electronic, vibrational, and excited-state properties of hexanuclear rhenium(III) chalcogenide clusters based on the [Re(6)(mu(3)-Q)(8)](2+) (Q = S, Se) core have been investigated by spectroscopic and theoretical methods. Ultraviolet or visible excitation of [Re(6)Q(8)](2+) clusters produces luminescence with ranges in maxima of 12 500-15 100 cm(-)(1), emission quantum yields of 1-24%, and emission lifetimes of 2.6-22.4 microseconds. Nonradiative decay rate constants and the luminescence maxima follow the trend predicted by the energy gap law (EGL). Examination of 24 clusters in solution and 14 in the solid phase establish that exocluster ligands engender the observed EGL behavior; clusters with oxygen- or nitrogen-based apical ligands achieve maximal quantum yields and the longest lifetimes. The excited-state decay mechanism was investigated by applying nonradiative decay models to temperature-dependent emission experiments. Solid-state Raman spectra were recorded to identify vibrational contributions to excited-state deactivation; spectral assignments were enabled by normal coordinate analysis afforded from Hartree-Fock and DFT calculations. Excited-state decay is interpreted with a model where normal modes largely centered on the [Re(6)Q(8)](2+) core induce nonradiative relaxation. Hartree-Fock and DFT calculations of the electronic structure of the hexarhenium family of compounds support such a model. These experimental and theoretical studies of [Re(6)Q(8)](2+) luminescence provide a framework for elaborating a variety of luminescence-based applications of the largest series of isoelectronic clusters yet discovered. 相似文献
876.
Reddy PM Jindra PT Satz AL Bruice TC 《Journal of the American Chemical Society》2003,125(26):7843-7848
A series of pyrrole, imidazole-substituted bis-benzimidazole conjugates, Py-Py-Im-gamma-biBenz, Py-Py-gamma-biBenz, Py-Im-gamma-biBenz, and Im-Py-gamma-biBenz (1-4), were prepared in an attempt to target dsDNA sequences possessing both A/T and G/C bps. The dsDNA interactions and sequence specificity of the conjugates have been characterized via spectrofluorometric titrations and thermal melting studies. All conjugates form 1:1 complexes with dsDNA at subnanomolar concentrations. The Im moiety selectively recognizes a G/C bp embedded in the A/T-rich binding site. This represents the first clear example of sequence selective recognition in a 1:1 motif.(1) The equilibrium association constant (K(1)) for complexation of a specific nine-bp dsDNA site, 5'-gcggTATGAAATTcgacg-3', by conjugate 1 is approximately 2.6 x 10(9) M(-1). Displacement of the G/C position or G/C-->A/T substitution within the nine-bp site decreases the K(1) by approximately 8-fold, whereas two continuous G/C bps decrease the K(1) by approximately 50-fold magnitude. The K(1) values for seven-bp dsDNA, 5'-gcggtaTGAAATTcgacg-3' and 5'-gcggtaCAAAATTcgacg-3', binding sites by conjugates Py-Im-gamma-biBenz (3) and Im-Py-gamma-biBenz (4) are approximately 2.3 x 10(9) and approximately 1.2 x 10(9) M(-1), respectively. However, the conjugates with no Im moiety, Py-Py-gamma-biBenz (2) and Py-Py-Py-gamma-biBenz (5 and 6), are specific for seven- to nine-bp A/T-rich sites and single A/T-->G/C bp substitution within the binding site decreases the K(1) values by 1-2 orders of magnitude. 相似文献
877.
Manikandan P Muthukumaran R Thomas KR Varghese B Chandramouli GV Manoharan PT 《Inorganic chemistry》2001,40(10):2378-2389
Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy. 相似文献
878.
Following the strategy of using polyfunctional phosphonic acids for the synthesis of open-framework metal phosphonates, the phosphonocarboxylic acid (H2O3PCH2)2NCH2C6H4COOH was used in the hydrothermal synthesis of new Ba phosphonates. Its decomposition led to the first open-framework barium phosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O. The synthesis was also successfully performed using iminobis(methylphosphonic acid), (H2O3PCH2)2NH, as a starting material, and the synthesis was optimized to obtain as a pure material. The reaction setup as well as the pH are the dominant parameters, and only a diffusion-controlled reaction led to the desired compound. The crystal structure was solved from single-crystal data: monoclinic; C2/c; a=2328.7(2), b=1359.95(7), and c=718.62(6) pm; beta=98.732(10) degrees ; V=2249.5(3)x10(6) pm3; Z=4; R1=0.036; and wR2=0.072 (all data). The structure of [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O is built up from BaO8 and BaO10 polyhedra forming BaO chains and layers, respectively. These are connected to a three-dimensional metal-oxygen-metal framework with the iminobis(methylphosphonic acid) formally coating the inner walls of the pores. The one-dimensional pores (3.6x4 A) are filled with H2O molecules that can be thermally removed. Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 240 degrees C. The uptake of N,N-dimethylformamide and H2O by dehydrated samples is demonstrated. Furthermore, IR, Raman, and 31P magic-angle-spinning NMR data are also presented. 相似文献
879.
Thomas H Pate 《Journal of Differential Equations》1979,34(2):261-272
If m and n are positive integers then let S(m, n) denote the linear space over R whose elements are the real-valued symmetric n-linear functions on Em with operations defined in the usual way. If is a function from some sphere S in Em to R then let (i)(x) denote the ith Frechet derivative of at x. In general (i)(x)∈S(m,i). In the paper “An Iterative Method for Solving Nonlinear Partial Differential Equations” [Advances in Math. 19 (1976), 245–265] Neuberger presents an iterative procedure for solving a partial differential equation of the form , where k > n, is the unknown from some sphere in Em to R, A is a linear functional on S(m, n), and F is analytic. The defect in the theory presented there was that in order to prove that the iterates converged to a solution the condition was needed. In this paper an iteration procedure that is a slight variation on Neuberger's procedure is considered. Although the condition cannot as yet be eliminated, it is shown that in a broad class of cases depending upon the nature of the functional A the restriction may be replaced by the restriction . 相似文献
880.