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81.
Fernando Sartillo-Piscil Silvano CruzMario Sánchez Herbert HöpflCecilia Anaya de Parrodi Leticia Quintero 《Tetrahedron》2003,59(23):4077-4083
Twelve 2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes fused with a 1,2-O-isopropylidene-α-d-xylofuranose moiety in cis orientation and substituted at the C′5 position were prepared in two steps from commercially available diacetone-α-d-glucose. Their conformations, and configurations were determined by 1H and 31P NMR and X-ray crystallographic techniques. Both, chair-twisted-chair and chair-boat equilibria were observed in solution. We observed that the strong anisotropic shielding effect of the benzene ring in the phenoxy group generates an upfield shift of the H1 hydrogen atom, when the cyclic phosphates adopt a boat conformation. This is due to a relative cis-orientation of the P-phenoxy group and the H1 proton of the 1,2-O-isopropylidene-α-d-xylofuranose moiety. Therefore, the configuration of the phosphorus center (SP or RP) can be determined by 1H NMR spectroscopy. Interestingly, the crystal structure of one of the cyclic phosphates exhibits two independent molecules in the asymmetric unit, one with a chair and the other one with a boat conformation. 相似文献
82.
Roberta Galeazzi Silvano Geremia Giovanna Mobbili Mario Orena 《Tetrahedron: Asymmetry》1996,7(12):3573-3584
(R)- and (S)-N-allyl-N-(1-phenylethyl)methoxycarbonylacetamide, 5 and 6, underwent oxidative cyclisation mediated by Mn(III), to give easily separable diastereomeric mixtures of 3-aza-2-oxobicyclo[3.1.0]hexanes 8a,b and 9a,b, respectively, whose structures were assigned on the basis of 1H NMR spectra and then confirmed by X-ray diffraction analysis of the derivatives 11b and 14. 相似文献
83.
Fernanda Ricchelli Silvano Gobbo Giulio Jori Giuliana Moreno Françoise Vinzens Christian Salet 《Photochemistry and photobiology》1993,58(1):53-58
We have compared the photodynamic activities of hematoporphyrin (HP) and protoporphyrin (PP) on isolated rat liver mitochondria by measuring the decline of the respiratory control ratio (RCR) after irradiation at 365 nm. Before addition to the respiratory mcdium, the dyes were dissolved in phosphate-buffered saline (PBS) or incorporated into unilamellar liposomes of dipalmitoyl-phosphatidylcholine (DPPC), sometimes enriched with cholesterol (Chol) or cardiolipin (Card), which are naturally present in mitochondrial membranes. Chol and especially Card strongly increase the porphyrin uptake by mitochondria. In all experimental conditions, PP is taken up by mitochondria to a higher extent than HP. Nevertheless, under conditions giving the same amount of mitochondriabound dye, HP is a morc efficient photosensitizer than PP. As the efficiency of singlet oxygen production has been shown to be equivalent for the two porphyrins in monomeric state, the resulting photobiological effects are explained in terms of different localization of HP and PP in the mitochondrial membrancs. In particular, HP preferentially localizes in the protein-rich polar domains of the inner mitochondrial membrane, whereas PP dissolvcs in the lipid regions of the mcmbrancs. 相似文献
84.
Králik M Kratky V De Rosso M Tonelli M Lora S Corain B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):209-214
The polymer framework of a resin-based catalyst built up with Pd nanoclusters (ca. 3 nm) dispersed inside the nanoporous domains of a thermally stable gel-type polyacrylic resin exhibits a good chemical stability under 5 bar H(2) at 40 degrees C for reasonable contact times. Chemical and physico-chemical integrity of the polymer framework are checked with a variety of instrumental analytical methods. Catalyst reusability turns out to be quite good. 相似文献
85.
Geremia S Di Costanzo L Randaccio L Engel DE Lombardi A Nastri F DeGrado WF 《Journal of the American Chemical Society》2005,127(49):17266-17276
The de novo protein DF1 is a minimal model for diiron and dimanganese metalloproteins, such as soluble methane monooxygenase. DF1 is a homodimeric four-helix bundle whose dinuclear center is formed by two bridging Glu side chains, two chelating Glu side chains, and two monodentate His ligands. Here, we report the di-Mn(II) and di-Co(II) derivatives of variants of this protein. Together with previously solved structures, 23 crystallographically independent four-helix bundle structures of DF1 variants have been determined, which differ in the bound metal ions and size of the active site cavity. For the di-Mn(II) derivatives, as the size of the cavity increases, the number and polarity of exogenous ligands increases. This collection of structures was analyzed to determine the relationship between protein conformation and the geometry of the active site. The primary mode of backbone movement involves a coordinated tilting and sliding of the first helix in the helix-loop-helix motif. Sliding depends on crystal-packing forces, the steric bulk of a critical residue that determines the dimensions of the active site access cavity, and the intermetal distance. Additionally, a torsional motion of the bridging carboxylates modulates the intermetal distance. This analysis provides a critical evaluation of how conformation, flexibility, and active site accessibility affect the geometry and ligand-binding properties of a metal center. The geometric parameters defining the DF structures were compared to natural diiron proteins; DF proteins have a restricted active site cavity, which may have implications for substrate recognition and chemical stability. 相似文献
86.
A new way of computing the upper bound for the zero-one knapsack problem is presented, substantially improving on Dantzig's approach. A branch and bound algorithm is proposed, based on the above mentioned upper bound and on original backtracking and forward schemes. Extensive computational experiences indicate this new algorithm to be superior to the fastest algorithms known at present. 相似文献
87.
Given a set ofn positive integers and another positive integerW, the Subset-Sum Problem is to find that subset whose sum is closest to, without exceeding,W. We present a polynomial approximation scheme for this problem and prove that its worst-case performance dominates that of
Johnson's well-known scheme.
Research supported by Ministero Pubblica Istruzion, Italy. 相似文献
88.
We prove that the worst-case performance ratio of the Karmarkar-Karp differencing method for the Partition Problem is 7/6 相似文献
89.
Sensitization of nanocrystalline TiO2 with black absorbers based on Os and Ru polypyridine complexes
Altobello S Argazzi R Caramori S Contado C Da Fré S Rubino P Choné C Larramona G Bignozzi CA 《Journal of the American Chemical Society》2005,127(44):15342-15343
New metal complexes of the type [M(H3tcterpy)LY]+ (where M = Os(II) or Ru(II), L = substituted or unsubstituted bipyridine or pyridylquinoline, and Y = Cl-, I-, or SCN-) have been designed, synthesized, and characterized in view of their application for dye-sensitized solar cells (DSSCs). The Os dyes show a very broad absorption, and correspondingly, the DSSCs show an unprecedented spectral response in the NIR, with an onset at 1100 nm, reaching values of about 50% at 900 nm. The integrated photocurrent of some of such Os dyes is similar to that of the well-known [Ru(Htcterpy)(NCS)3](TBA) and superior to that of the [Ru(Hdcbpy)2(NCS)2](TBA)2 sensitizer. The Ru dyes show absorption and DSSC spectral response between those of the red and black dyes. Their advantage is their potential superior stability due to the reversible oxidative electrochemistry. 相似文献
90.
Corbellini F Di Costanzo L Crego-Calama M Geremia S Reinhoudt DN 《Journal of the American Chemical Society》2003,125(33):9946-9947
We report on the synthesis and characterization of a water-soluble molecular capsule based on multiple ionic interactions. The assembly has been studied by means of 1H NMR, ESI-MS spectroscopy, and isothermal titration calorimetry (ITC), showing an association constant in water, Ka, of 3.3 x 104 M-1. The achieved water solubility of the system opens the possibility of using this supramolecular assembly for molecular recognition in pure water. Encapsulation studies have been performed and are reported in this Communication. 相似文献