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921.
Giovanni Minghetti Angelino Doppiu Antonio Zucca Sergio Stoccoro Maria Agostina Cinellu Mario Manassero Mirella Sansoni 《Chemistry of Heterocyclic Compounds》1999,35(8):992-1000
Reaction of Pd(OAc)2 with HL1 and HL2 (HL1=6-iso-propyl-2,2-bipyridine; HL2=6-neo-pentyl-2,2-bipyridine), followed by treatment with LiCl or KI, gives [PdCl(L1)]2, (1), [PdCl(L2)]2 (2), and [PdI(L2)]2 (3), respectively. The chloride bridge in complexes1 and2 is split by PPh3 to give the mononuclear species PdCl(L1)(PPh3) (4) and PdCl(L2)(PPh3) (5). Spectroscopic data provide evidence for coordination of the deprotonated ligands through a nitrogen and the C(3) atom of the 6-substituted pyridine. An analogous platinum complex PtCl(L3)(SMe2) (6) (HL3=6-tert-butyl-2,2-bipyridine) was obtained from trans-PtClMe(SMe2)2 and HL3. The crystal structures of compounds1 and6 have been solved by X-ray diffraction analysis.Dipartimento di Chimica, Universita di Sassari, via Vienna 2, I-07100 Sassari, Italy; Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Universita di Milano, Centro CNR, I-20133 Milano, Italy; Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1127–1137, August, 1999. 相似文献
922.
Kinzie SD Thevis M Ngo K Whitelegge J Loo JA Abu-Omar MM 《Journal of the American Chemical Society》2003,125(16):4710-4711
Phenylalanine hydroxylase, a mononuclear non-heme iron enzyme, catalyzes the hydroxylation of phenylalanine to tyrosine in the presence of oxygen and reduced pterin cofactor. X-ray structural studies have established the coordination around the iron metal center and point to significant interactions within the second coordination sphere. One such interaction involves Tyr325 in human phenylalanine hydroxylase (hPAH), which forms a hydrogen-bonding network with an aqua ligand on iron and the pterin cofactor. The full-length tetramer (1-452) and truncated dimer (117-424) Tyr325Phe hPAH mutant enzymes showed similar kinetics, thermal stabilities, and oligomerization profiles as their corresponding wild-type proteins. The possibility of in vivo posttranslational hydroxylation that would restore the activity of hPAH was examined by mass spectrometry on the trypsin digested full-length (1-452) hPAH Tyr325Phe point mutant. The amino acid tags obtained by ESI-MS/MS confirmed the presence of a Phe325 in the peptide corresponding to the doubly charged precursor ion at m/z 916.4 (L A T I F W F T V E F G L C K), and its hydroxylated counterpart in the peptide corresponding to the m/z 924.4 (L A T I F-OH W F T V E F G L C K) byproduct ion series comprising the fragments y(5)-y(12). Furthermore, the point mutation Tyr325Ala resulted in an enzyme that was totally inactive and did not display any evidence of hydroxylation. These results demonstrate the importance of Tyr325 for proper conformation of the active site, substrate binding, and catalysis. The rescue of the Tyr325Phe mutant in hPAH via self-hydroxylation presents a novel example of oxidative repair on the molecular level. 相似文献
923.
The kinetics and mechanism of the substitution of coordinated water in nitrilotriacetate complexes of iron(III) (Fe(NTA)(OH(2))(2) and Fe(NTA)(OH(2))(OH)(-)) by phosphate (H(2)PO(4)(-) and HPO(4)(2)(-)) and acetohydroxamic acid (CH(3)C(O)N(OH)H) were investigated. The phosphate reactions were found to be pH dependent in the range of 4-8. Phosphate substitution rates are independent of the degree of phosphate protonation, and pH dependence is due to the difference in reactivity of Fe(NTA)(OH(2))(2) (k = 3.6 x 10(5) M(-)(1) s(-)(1)) and Fe(NTA)(OH(2))(OH)(-) (k = 2.4 x 10(4) M(-)(1) s(-)(1)). Substitution by acetohydroxamic acid is insensitive to pH in the range of 4-5.2, and Fe(NTA)(OH(2))(2) and Fe(NTA)(OH(2))(OH)(-) react at equivalent rates (k = 4.2 x 10(4) and 3.8 x 10(4) M(-)(1) s(-)(1), respectively). Evidence for acid-dependent and acid-independent back-reactions was obtained for both the phosphate and acetohydroxamate complexes. Reactivity patterns were analyzed in the context of NTA labilization of coordinated water, and outer-sphere electrostatic and H-bonding influences were analyzed in the precursor complex (K(os)). 相似文献
924.
Belletête M Durocher G Hamel S Côte M Wakim S Leclerc M 《The Journal of chemical physics》2005,122(10):104303
The molecular structure of three ladder oligo(p-aniline)s, 5,11-diethyl-6,12-dimethylindolo[3,2-b]carbazole (DIMER 2P), 14-ethyl-5,8-dihydro-diindolo[3,2-b:2',3'-h]carbazole (TRIMER 2P), and 5,8,14-triethyl-diindolo[3,2-b:2',3'-h]carbazole (TRIMER 3P) were investigated by first principles calculations at the Hartree-Fock (HF6-31G*) and density functional theory (DFTB3LYP6-31G*) levels. It is found that the agreement between theoretical and x-ray geometrical parameters is good and rather similar for both theoretical methods. The nature and the energy of the first two singlet-singlet electronic transitions have been obtained by Zerner intermediate neglect of differential overlap/spectroscopy semiempirical calculations performed on the HF6-31G* and DFTB3LYP6-31G* optimized geometries, as well as time-dependent density functional theory (TDDFT) calculations performed on the DFTB3LYP6-31G* optimized structures. For all the compounds and for all the theoretical approaches, it is observed that the S(1)<--S(0) electronic transition (pipi*) is weakly allowed and polarized along the short axis (y) of the molecule. On the other hand, the S(2)<--S(0) electronic transition of each oligomer possesses a much larger oscillator strength and is polarized along the long (x) molecular axis. It is found that TDDFT calculations provide the best overall agreement between the energies and the corresponding optical transitions obtained from the absorption bands (0-0 peaks) measured in dichloromethane as well as providing a good evaluation of the bathochromic shifts caused by the increase in the conjugation length or by the presence of extra alkyl chains on the nitrogen atoms in TRIMER 3P compared to TRIMER 2P. 相似文献
925.
Szczepina MG Johnston BD Yuan Y Svensson B Pinto BM 《Journal of the American Chemical Society》2004,126(39):12458-12469
The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the least hindered primary center afforded the desired ammonium salt. In aqueous solution, these salts were configurationally labile at the ammonium center. Sulfonium and/or selenonium analogues of the ammonium salts were prepared by analogous reactions. The chalcogen salts were obtained as mixtures of diastereomers, separable in some cases, differing only in the stereochemistry at the configurationally stable sulfur or selenium atoms. Proof of configuration and conformation of each compound was obtained by detailed NMR experiments. The compounds are six-membered ring analogues of salacinol, a known sulfonium-salt glucosidase inhibitor. Evaluation of the target compounds for enzyme inhibition of the glucosidase enzyme glucoamylase G2 indicated that these compounds were either inactive or, at best, only weak inhibitors of maltose hydrolysis. 相似文献
926.
Paolo Cabella Massimo Barbeni Marcella Conterno Daniela Talarico Emilio Marengo Mario Marsili 《Analytica chimica acta》1990
Computer-assisted methods for improving research and production in a food-flavour company are described. Methods of experimental design are used in planning experiments. Special programs are used for identification of components through correlation of mass spectra and gas chromatographic retention indices, and for the design of new synthetic routes. In flavour creation, a data base containing qualitative and quantitative information on flavours, relevant legislation and organoleptic properties of components, can be searched selectively in attempts to improve flavours and to identify better combinations of substances. A computer-assisted production system is described which ensures complete qualitative and quantitative control. 相似文献
927.
Mario Castagnino 《General Relativity and Gravitation》1978,9(2):101-121
It is demonstrated that (1) there exist infiniteG
1 that satisfy Lichnerowicz's conditions (L conditions) in a globally hyperbolic manifold; and, (2) there is noG
1 in an expanding universe that would satisfy those conditions and that would behave as the ordinary 1 of flat space whenx x. The author thinks that these results present a serious problem for finding a semiclassical theory of scalar field in curved space-time. 相似文献
928.
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
929.
Giampiero Pagani Zecchini Mario Paglialunga Paradisi 《Journal of heterocyclic chemistry》1979,16(8):1589-1597
Treatment of protected dipeptides containing 1,2,3,4-tetrahydroquinoline-2-carboxylic acid with acetic anhydride affords only 1H,3H,5H-oxazolo[3,4-a]quinolin-3-one derivatives. The formation of a-acylaminomethylketones, arising from the competitive Dakin-West reaction, was generally observed when the cyclization procedure was extended to some amides of the cyclic imino acid. The preferential stabilization of one of two probable mesoionic intermediates seems to determine the preferred pathway. 相似文献
930.
Calorimetric and dielectric results for crystallizable poly(n-alkyl methacrylates) (PnAMA) with C=12, 16 and 18 alkyl carbons per side chain are presented. Degree of crystallization Dcal and melting peak temperature TM are estimated from conventional DSC measurements. For poly(n-hexadecyl methacrylate) (C=16) the influence of isothermal crystallization is studied by DSC as well as TMDSC. Changes in dielectric relaxation strength Δε and α peak shape during crystallization are investigated. Effects of side chain crystallization on the complex dynamics of PnAMA are discussed. The results are related to the relaxation behavior of lower nanophase-separated PnAMA with two co-existing glass transitions, the conventional glass transition (a or α) and the polyethylene-like glass transition (αPE) within alkyl nanodomains formed by aggregated alkyl rests. It is shown that amorphous as well as semicrystalline PnAMA can be understood as nanophase-separated polymers with alkyl nanodomains having a typical dimension of 1-2 nm. The results are compared with the predictions of simple morphological pictures for side chain polymers. X-ray scattering data for the amorphous and semicrystalline PnAMA are included in the discussion. Common aspects of nanophase-separated systems in both states as well as differences caused by crystallization are discussed. Indications for the existence of rigid amorphous regions are compiled. Different approaches to explain a similar increase of Tg(αPE)—the glass temperature of the amorphous alkyl nanodomains—and TM—the melting temperature of crystalline alkyl nanodomains—with side chain length are considered. Pros and cons of both approaches, based on increasing order within the alkyl nanodomains and confinement effects in nanophase-separated systems, are discussed. Main trends concerning crystallization and cooperative dynamics are compared with those in other systems with self-assembled nanometer confinements like microphase-separated blockcopolymers or semicrystalline main chain polymers. 相似文献