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631.
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633.
Abdulbaset M. Alayat Elena Echeverria David N. Mcllroy Armando G. McDonald 《燃料化学学报》2018,46(8):957-966
The effect of ethylene diamine tetraacetic acid(EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings(NS) supported cobalt(Co) catalyst was investigated in the conversion of syngas(H~(2+) CO) to hydrocarbons by Fischer-Tropsch synthesis(FTS). The unmodified Co/NS and modified Co/NS-EDTA catalysts were synthesized via an impregnation method. The prepared Co/NS and Co/NS-EDTA catalysts were characterized before the FTS reaction by BET surface area,X-ray diffraction(XRD),transmission electron microscopy(TEM),temperature programmed reduction(TPR),X-ray photoelectron spectroscopy(XPS),differential thermal analysis(DTA) and thermogravimetric analysis(TGA) in order to find correlations between physico-chemical properties of catalysts and catalytic performance. FTS was carried out in a quartz fixedbed microreactor(H_2/CO of 2 ∶1,230 ℃ and atmospheric pressure) and the products trapped and analyzed by GC-TCD and GC-MS to determine CO conversion and reaction selectivity. The experimental results indicated that the modified Co/NS-EDTA catalyst displayed a more-dispersed phase of Co_3O_4 nanoparticles(10.9%) and the Co_3O_4 average crystallite size was about 12.4 nm. The EDTA modified catalyst showed relatively higher CO conversion(70.3%) and selectivity toward C_(6-18)(JP-8,Jet A and diesel) than the Co/NS catalyst(C_(6-14))(JP-4). 相似文献
634.
Nurul Hamizah Hamidon Siti Suraiya Maria E. Sarmiento Armando Acosta Mohd Nor Norazmi Theam Soon Lim 《Applied biochemistry and biotechnology》2018,184(3):852-868
B cells and in particular antibodies has always played second fiddle to cellular immunity in regard to tuberculosis (TB). However, recent studies has helped position humoral immunity especially antibodies back into the foray in relation to TB immunity. Therefore, the ability to correlate the natural antibody responses of infected individuals toward TB antigens would help strengthen this concept. Phage display is an intriguing approach that can be utilized to study antibody-mediated responses against a particular infection via harvesting the B cell repertoire from infected individuals. The development of disease-specific antibody libraries or immune libraries is useful to better understand antibody-mediated immune responses against specific disease antigens. This study describes the generation of an immune single-chain variable fragment (scFv) library derived from TB-infected individuals. The immune library with an estimated diversity of 109 independent clones was then applied for the identification of monoclonal antibodies against Mycobacterium tuberculosis α-crystalline as a model antigen. Biopanning of the library isolated three monoclonal antibodies with unique gene usage. This strengthens the role of antibodies in TB immunity in addition to the role played by cellular immunity. The developed library can be applied against other TB antigens and aid antibody-derived TB immunity studies in the future. 相似文献
635.
Isse AA Gottardello S Durante C Gennaro A 《Physical chemistry chemical physics : PCCP》2008,10(17):2409-2416
The reductive cleavage of a series of organic chlorides, including chloroaromatics, benzyl chlorides, activated chloroalkanes and polychloromethanes, was investigated at Ag, Cu, Pd and glassy carbon (GC) electrodes in CH(3)CN + 0.1 M (C(2)H(5))(4)NClO(4). The silver cathode was either a 2-mm diameter disc, fabricated from Ag wire, or nanoclusters of average diameter d = 304 nm, prepared by electrodeposition on GC. Ag, Cu and Pd electrodes have shown remarkable electrocatalytic properties for the reduction of several compounds. The peak potentials recorded at these electrodes, for example, at upsilon = 0.1 V s(-1) are positively shifted by 0.3-0.8 V with respect to the reduction potentials measured at a non catalytic electrode such as GC. Electrocatalysis is strictly related to the concerted nature of the dissociative electron transfer to the carbon-chlorine bond. No catalysis is observed when the dissociative electron transfer to RCl occurs according to a stepwise mechanism involving the intermediate formation of a radical anion. The catalytic surfaces affect the reaction scheme, offering a more favourable route possibly through the formation of strongly adsorbed activated complexes. 相似文献
636.
The amino acid catalyzed aldol condensation is of great interest in organic synthesis and natural environments such as atmospheric particles. However, kinetic and mechanistic information on these reactions is limited. In this work the kinetics of the aldol condensation of acetaldehyde in water and aqueous salt solutions (NaCl, CaCl2, Na2SO4, MgSO4) catalyzed by five amino acids (glycine, alanine, serine, arginine, and proline) at room temperature (295 +/- 2 K) has been studied. Monitoring the formation of three products, crotonaldehyde, 2,4-hexadienal, and 2,4,6-octatrienal, by UV-vis absorption over 200-1100 nm revealed two distinct kinetic regimes: at low amino acid concentrations (in all cases, below 0.1 M), the overall reaction was first-order with respect to acetaldehyde and kinetically limited by the formation of the enamine intermediate. At larger amino acid concentrations (at least 0.3 M), the kinetics was second order and controlled by the C-C bond-forming step. The first-order rate constants increased linearly with amino acid concentration consistent with the enamine formation. Inorganic salts further accelerated the enamine formation according to their pKb plausibly by facilitating the iminium or enamine formation. The rate constant of the C-C bond-forming step varied with the square of amino acid concentration suggesting the involvement of two amino acid molecules. Thus, the reaction proceeded via a Mannich pathway. However, the contribution of an aldol pathway, first-order in amino acid, could not be excluded. Our results show that the rate constant for the self-condensation of acetaldehyde in aqueous atmospheric aerosols (up to 10 mM of amino acids) is identical to that in sulfuric acid 10-15 M (kI approximately 10-7-10-6 s-1) clearly illustrating the potential importance of amino acid catalysis in natural environments. This work also demonstrates that under usual laboratory conditions and in natural environments aldol condensation is likely to be kinetically controlled by the enamine formation. Notably, kinetic investigations of the C-C bond-forming addition step would only be possible with high concentrations of amino acids. 相似文献
637.
Luzyanin KV Kukushkin VY Kuznetsov ML Ryabov AD Galanski M Haukka M Tretyakov EV Ovcharenko VI Kopylovich MN Pombeiro AJ 《Inorganic chemistry》2006,45(5):2296-2306
The coupling between coordinated propiononitriles in trans-[PtCln(EtCN)2] (n = 2, 4) and the 1,2-hydroxylaminooximes HON(H)CMe2C(R)=NOH (R = Ph 1, Me 2) proceeds smoothly in CHCl(3) at ca. 40-45 degrees C and gives trans-[PtCln{NH=C(Et)ON(H)CMe2C(R)=NOH}2] (n = 2, R = Ph 5, Me 6; n = 4, R = Ph 7, Me 8) in 80-85% isolated yields. The reaction is highly regioselective, and both spectroscopic (IR; FAB+-MS; 1D 1H, 13C{1H}, and 195Pt NMR; and 2D 1H,13C HMQC, 1H,13C HMBC, and 1H,15N HMQC NMR) and X-ray data for 6-8 suggest that the addition proceeds exclusively via the hydroxylamine moiety of the 1,2-hydroxylaminooxime species; the existence of an oxime group remote from the nucleophile was also confirmed. Heating of 6 in air leads to its conversion to the unusual nitrosoalkane complex [PtCl2{HON=C(Me)C(Me)2N=O}] (9), whereas in the case of 5, only the metal-free salt [H3NC(Me)2C(Ph)=NOH]2(NO3)Cl.H2O (10) was isolated. To compare the kinetic aspects and trends in the addition of both types of nucleophiles (oximes and hydroxylamines; for the latter, see our recent work: Inorg. Chem. 2005, 44, 2944) to coordinated nitriles, a kinetic study of the addition of HON=C(CH2Ph)2 to [Ph3PCH2Ph][PtCl5(EtCN)] (11) to give [Ph(3)PCH(2)Ph][PtCl(5){NH=C(Et)ON=C(CH2Ph)2}] (12) was performed. The calculated rate constant k2 of 3.9 x 10(-6) M(-1) s(-1) at -20 degrees C for the addition of the oxime indicates that the hydroxylamine is, by a factor 1.7 x 10(4), more reactive toward the addition to nitriles than the oxime. Results of the synthetic, kinetic, and theoretical (at the B3LYP level of theory) studies have demonstrated that the high regioselectivity of the reactions of the 1,2-hydroxylaminooximes with ligated nitriles is both kinetically and thermodynamically controlled. 相似文献
638.
Kuznetsov ML Kukushkin VY Pombeiro AJ 《Dalton transactions (Cambridge, England : 2003)》2008,(10):1312-1322
Reactions of the nitrone CH3CH=N(CH3)O and the nitrile oxide CH3C[triple bond]NO with the nitrile complexes trans-[MCl2(N[triple bond]CCH3)2] (M = Pt, 1; Pd, 2) were investigated by theoretical methods at B3LYP and, for some processes, CCSD(T) levels of theory. The mechanisms of substitutions and cycloadditions were studied in detail. The former occur via a concerted asynchronous mechanism of dissociative type. The calculations of the metal-ligand bond energies in the starting complexes and substitution products and the analysis of structural features of the transition states indicate that the M-N bond dissociation (rather than M-O bond formation) is the step, which controls the reactivity of and in substitutions. The different chemical behaviours of the Pt and Pd complexes towards the 1,3-dipoles were investigated. The exclusive isolation of cycloaddition rather than substitution products in any solvents in the case of is both kinetically and thermodynamically controlled.The switch of the reaction mode from cycloaddition to substitution for 2 in CH2Cl2 solution is caused by the significantly lower Pd-N bond energy in comparison with the Pt-N bond energy, consistent with the higher lability of the Pd complexes. The different chemical behaviour of 2 in CH3CN and CH2Cl2 solvents is accounted for by the great excess of acetonitrile in the CH3CN solution rather than a different solvation character. The relative variation of Wiberg bond indices along the reaction path is proposed as a quantitative criterion for the classification of the reaction mechanism. 相似文献
639.
Kirillov AM Karabach YY Haukka M Guedes da Silva MF Sanchiz J Kopylovich MN Pombeiro AJ 《Inorganic chemistry》2008,47(1):162-175
The new copper(II) or copper(II)/sodium(I) 1D coordination polymers [Cu2(Hmdea)2(mu-H2O)(mu2-tpa)]n.2nH2O (1), [Cu2(H2tipa)2(mu2-ipa)]n.4nH2O (2), [Cu2(H2tea)2Na(H2O)2(mu2-tma)]n.6nH2O (3), [Cu2(H2tea)2(mu2-ipa)]n.nH2O (4a), and [Cu2(H2tea)2{mu3-Na(H2O)3}(mu3-ipa)]n(NO3)n.0.5nH2O (4b) have been prepared in aqueous medium by self-assembly from copper(II) nitrate, aminopolyalcohols [methyldiethanolamine (H2mdea), triisopropanolamine (H3tipa), and triethanolamine (H3tea)] as main chelating ligands and benzenepolycarboxylic acids [terephthalic (H2tpa), isophthalic (H2ipa), and trimesic (H3tma) acid] as spacers. They have been characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses, the latter indicating the formation of unusual multinuclear metal cores interconnected by various benzenepolycarboxylate spacers, leading to distinct wavelike, zigzag, or linear 1D polymeric metal-organic chains. These are further extended to 2D or 3D hydrogen-bonded supramolecular networks via extensive interactions with the intercalated crystallization water molecules. The latter are associated, also with aqua ligands, by hydrogen bonds resulting in acyclic (H2O)3 clusters in 1, (H2O)8 clusters in 2, infinite 1D water chains in 3, and disordered water-nitrate associates in 4b, all playing a key role in the structure stabilization and its extension to further dimensions. Variable-temperature magnetic susceptibility measurements have shown that 1-4 exhibit a moderately strong ferromagnetic coupling through the alkoxo bridge. The small Cu-O-Cu bridging angle and the large out-of-plane displacement of the carbon atom of the alkoxo group accounts for this behavior. The magnetic data have been analyzed by means of a dinuclear and a 1D chain model, and the magnetic parameters have been determined. The magnetic exchange coupling in 3, to our knowledge, is the highest found in alkoxo-bridged copper(II) complexes. 相似文献
640.
Liliana López-Garrido Angel E. Bañuelos-Hernández Elizabeth Pérez-Hernández Romeo Tecualt-Gómez Jorge Quiroz-Williams Armando Ariza-Castolo Elvia Becerra-Martínez Nury Pérez-Hernández 《Magnetic resonance in chemistry : MRC》2020,58(1):65-76
Cartilage-forming lesions include tumours that can vary in severity from benign enchondromas to high-grade malignant chondrosarcomas. Chondrosarcoma is the second most frequent malignant bone tumour, accounting for 20–30% of all malignant bone neoplasms. Surgery is the standard treatment for cartilage tumours (CTs); however, their incidental diagnosis and the difficult differentiation of low-grade lesions like chondrosarcoma grade I from benign entities like enchondroma are challenges for clinical management. In this sense, the search for circulating biomarkers for early detection and prognosis is an ongoing interest. Targeted metabolomics is a powerful tool that can propose potential biomarkers in biological fluids as well as help to discover disturbed metabolic pathways to reveal tumour pathogenesis. In this context, the aim of this study was to investigate the 1H nuclear magnetic resonance metabolomic serum profile of patients with CTs contrasted with healthy controls. Forty-one metabolites were identified and quantified; the multivariate statistical methods principal component analysis and partial least squares discriminant analysis reveal a clear separation of the CT group, that is, the differential metabolites that were involved in two main metabolic pathways: the taurine and hypotaurine metabolism and synthesis and degradation of ketone bodies. Our results represent preliminary work for emergent serum-based diagnostics or prognostic methods for patients with chondrogenic tumours. 相似文献