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101.
Mercedes Roncel José A. Navarro Francisco F. De la Rosa Miguel A. De la Rosa 《Photochemistry and photobiology》1984,40(3):395-398
A photoelectrochemical cell for hydrogen peroxide production using flavin photosystems is described. The anodic solution, which is kept free of oxygen by passing an Ar stream through it, contains the photoreceptor (flavin mononucleotide or lumiflavin) and the electron donor (EDTA, semicarbazide or hydroxylamine), while the peroxide is formed at the electrode of the cathodic solution, whose oxygen content is increased by bubbling with pure oxygen. Among several electrode metals that have been tested (Ag, Pt and Hg), Hg is the most efficient. The pH of the anodic and cathodic solutions should be adjusted to 14 and 1, respectively, for optimum results. 相似文献
102.
Zamudio-Rivera LS George-Tellez R López-Mendoza G Morales-Pacheco A Flores E Höpfl H Barba V Fernández FJ Cabirol N Beltrán HI 《Inorganic chemistry》2005,44(15):5370-5378
The one pot reaction of salicylaldehyde 1, beta-amino alcohols 2a-2c, and di-n-butyltin(IV) oxide 3a or diphenyltin(IV) oxide 3b produced five diorganotin(IV) compounds, 4a-4c, 5a, and 5c, in good yields. All compounds were characterized by IR, (1)H, (13)C, and (119)Sn NMR spectroscopy, and elemental analysis; furthermore, compounds 4b, 4c, 5a, and 5c were characterized by X-ray diffraction analysis. After the structural characterization, all of the compounds were tested in vitro against Bacillus subtilis (Gram-positive, strain ATCC 6633), Escherichia coli (Gram-negative, strain DH5alpha), Pseudomonas aeruginosa (Gram-negative, strain BH3), Desulfovibrio longus (strain DSM 6739), and Desulfomicrobium aspheronum (strain DSM 5918) to assess their antimicrobial activity. Compounds 4 and 5 demonstrated a wide range of bactericidal activities against the tested aerobic (one Gram-positive and two Gram-negative subtypes) and anaerobic bacteria (two sulfate-reducing bacteria, SRB). Compound 5 had better bactericidal performances than compound 4. For all of the compounds, the acute toxicity was measured using luminescent bacteria toxicity (LBT-Microtox) tests to track their further environmental impact. According to these results and in order to fulfill environmental regulations, the toxicity of the compounds studied herein can be modulated through the proper selection of the disubstituted tin(IV) moiety. 相似文献
103.
Francisco Palacios Ana M. Ochoa de Retana José I. Gil José M. Alonso 《Tetrahedron》2004,60(40):8937-8947
A simple and efficient regioselective synthesis of 4-oxazole-phosphine oxides 11 and -phosphonates 12 from 2H-azirine-phosphine oxides 1 and -phosphonates 6 is described. The key step for the synthesis of oxazoles 11 is a base-mediated ring closure of vinylogous α-aminophosphorus compounds derived from phosphine oxides 4 and from phosphonates 8. These derivatives 4 and 8 are obtained by reaction of functionalized azirines 1 and 6 with acyl chlorides 2 and subsequent acid-catalyzed ring opening of N-acylaziridine-phosphine oxides 3 and -phosphonates 7. Regioselective thermal ring cleavage of N-acylaziridine-phosphine oxides 3 leads α-chloro-β-(N-acylamido)-phosphine oxides 13 and their treatment with bases gives 5-oxazole-phosphine oxides 16. 相似文献
104.
Limited flexibility of lactose detected from residual dipolar couplings using molecular dynamics simulations and steric alignment methods 总被引:1,自引:0,他引:1
Martín-Pastor M Canales A Corzana F Asensio JL Jiménez-Barbero J 《Journal of the American Chemical Society》2005,127(10):3589-3595
The conformational flexibility of lactose in solution has been investigated by residual dipolar couplings (RDCs). One-bond carbon-proton and proton-proton coupling constants have been measured in two oriented media and interpreted in combination with molecular dynamics simulations (MD). Two different approaches, known as PALES (Zweckstetter et al., J. Am. Chem. Soc. 2000, 122, 3791-3792) and TRAMITE (Azurmendi et al., J. Am. Chem. Soc. 2002, 124, 2426-2427), have been used to determine the alignment tensor from a shape-induced alignment model with the oriented medium. The steric alignment of the structures from several MD trajectories has provided ensemble averaged RDCs that have been compared with the experimental ones. The obtained results reveal the almost exclusive presence of a major low energy region defined as syn-phi/syn-psi (> 97%), for which sampling occurs in a dynamic manner. This result satisfactorily agrees with that determined by standard NOE-based methods. 相似文献
105.
Palacios F Aparicio D Ochoa De Retana AM de los Santos JM Gil JI Alonso JM 《The Journal of organic chemistry》2002,67(21):7283-7288
A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. The key step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of beta-ketoxime tosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids 4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13. 相似文献
106.
[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11. 相似文献
107.
Alfonso Loaiza Dan Borchardt Francisco Zaera 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2481-2493
13C NMR at 125.76 MHz with 1H and 2H decoupling, 2H NMR at 76.77 MHz with 1H decoupling, and 1H NMR at 500.14 MHz with 2H decoupling were employed as analytical tools to study the complex mixtures of deuterated ethanes resulting from the catalytic H–D exchange of normal ethane with gas-phase deuterium in the presence of a platinum foil. Reference samples consisting of 1:1 binary mixtures of pure normal ethane and ethane-dn (n=1–6) were used to identify the peak positions in the 13C, 2H, and 1H NMR spectra due to each individual isotopomer, and the effect of isotopic substitution on the chemical shifts was determined in each case. While the NMR of all three nuclei worked well for the identification of the individual components of the 1:1 standard mixtures, both 1H and 2H NMR suffered from inadequate resolution when studying complex reaction mixtures because of the broadening of the lines due to 1H–1H (1H NMR) and 2H–2H (2H NMR) couplings. 13C NMR was therefore determined to be the method of choice for the quantitative analysis of the reaction mixtures. Using the 13C NMR results, a correlation that takes into account the primary and secondary isotope substitution effects on chemical shifts was deduced. This equation was used for the identification of the individual components of the mixtures, and integration of the individual observed resonances was then employed for quantification of their composition. This study shows that 13C NMR with 1H and 2H decoupling is a viable procedure for studying mixtures of deuterated ethanes. Furthermore, the additivity of the isotopic effects on chemical shifts and the transferability of the values obtained with ethane to other molecules makes this approach general for the analysis of other isotopomer mixtures. 相似文献
108.
Tenorio FJ Murray I Martinez A Klabunde KJ Ortiz JV 《The Journal of chemical physics》2004,120(17):7955-7962
Two stable products of reactions of water molecules with the Al3O3- cluster, Al3O4H2- and Al3O5H4-, are studied with electronic structure calculations. There are several minima with similar energies for both anions and the corresponding molecules. Dissociative absorption of a water molecule to produce an anionic cluster with hydroxide ions is thermodynamically favored over the formation of Al3O3-(H2O)n complexes. Vertical electron detachment energies of Al3O4H2- and Al3O5H4- calculated with ab initio electron propagator methods provide a quantitative interpretation of recent anion photoelectron spectra. Contrasts and similarities in these spectra may be explained in terms of the Dyson orbitals associated with each transition energy. 相似文献
109.
Combinatorial development of new catalysts with phosphodiesterase and esterase activities requires specific fluorescent probes for rapid visual detection of hydrolytic activity. Such fluorescent probes have been synthesized with special attention to solubility in water and stability towards spontaneous hydrolysis at a given pH. The probes reported here include compound 5 based on a fluorescein fluorophore, compound 12 for FRET-detection of phosphodiester hydrolysis and compound 25 based on a quinolinium fluorophore. 相似文献
110.
Lourenço JM Ribeiro PA Botelho do Rego AM Braz Fernandes FM Moutinho AM Raposo M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8103-8109
The amount of counterions in layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) has been determined with X-ray photoelectron spectroscopy (XPS) for films prepared from solutions with various NaCl concentrations. Sodium and chloride counterions are present in LBL films produced from salt solutions, which are located at the surface and in the bulk of the films. The percentage of bulk counterions increases with the ionic strength of the polyelectrolyte before reaching a constant value. The bulk sodium/sulfur percentage ratios tend to 0.8 for samples washed with pure water and for samples washed with NaCl aqueous solutions, while the bulk chlorine/nitrogen percentage ratios tend to 0.5 for the same samples. The ratio between the percentages of polyelectrolyte ionic groups lies close to unity for all samples, indicating that counterions do not contribute to charge compensation in the polyelectrolyte during the adsorption process. The presence of counterions in LBL films is explained by Manning condensation near the polyelectrolyte ionic groups, leading to inter-polyelectrolyte ionic bondings via ionic networks. It is believed that condensation leads to the formation of NaCl crystallites in these LBL films, which was confirmed by X-ray diffraction measurements. 相似文献