排序方式: 共有55条查询结果,搜索用时 296 毫秒
1.
Zabolotskii V. I. Manzanares J. A. Mafe S. Nikonenko V. V. Lebedev K. A. 《Russian Journal of Electrochemistry》2002,38(8):819-827
A relatively simple mathematical model based on the Poisson equation is considered. The model is intended for modeling transport through multilayered ion-exchange membranes operating at overlimiting currents. The boundary-value problem is solved by a numerical method of parallel shooting and by an approximate method based on the assumption that the charge density is distributed quasi-uniformly. Concentration profiles in diffusion layers and membranes, current–voltage curves, and dependences of effective transport numbers on the current density are examined. 相似文献
2.
den Brok MW Nuijen B Miranda E Floriano P Munt S Manzanares I Beijnen JH 《Journal of chromatography. A》2003,1020(2):251-258
ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] is a novel investigational anticancer agent, which has shown in vitro and in vivo cytotoxic activity against various tumor cell lines with selectivity for certain solid tumors. The pharmaceutical development of ES-285 x HCl warranted the availability of an assay for the quantification and purity determination of ES-285 x HCl active pharmaceutical ingredient (API) and its pharmaceutical dosage form. A liquid chromatographic method (LC) comprising of derivatisation of ES-285 x HCl with phenylisothiocyanate and UV-detection was developed. The method was found to be linear, precise and accurate. The assay also proved selectivity as determined by analysing ES-285 x HCl in combination with 15 analogues and in combination with hydroxypropyl-beta-cyclodextrin, the excipient used in the lyophilised pharmaceutical dosage form. Stress testing showed that the degradation products were separated from the parent compound, confirming its stability indicating capacity. The method was found robust as determined with design of experiments (DoE), which made it possible to predict system suitability responses in worst case experimental conditions and to define criteria for system suitability testing. 相似文献
3.
Ethanol production from steam-explosion pretreated wheat straw 总被引:1,自引:0,他引:1
Ignacio Ballesteros Ma José Negro José Miguel Oliva Araceli Cabañas Paloma Manzanares Mercedes Ballesteros 《Applied biochemistry and biotechnology》2006,130(1-3):496-508
Bioconversion of cereal straw to bioethanol is becoming an attractive alternative to conventional fuel ethanol production
from grains. In this work, the best operational conditions for steam-explosion pretreatment of wheat straw for ethanol production
by a simultaneous saccharification and fermentation process were studied, using diluted acid [H2SO4 0.9% (w/w)] and water as preimpregnation agents. Acid-or water-impregnated biomass was steam-exploded at different temperatures
(160–200°C) and residence times (5, 10, and 20 min). Composition of solid and filtrate obtained after pretreatment, enzymatic
digestibility and ethanol production of pretreated wheat straw at different experimental conditions was analyzed. The best
pretreatment conditions to obtain high conversion yield to ethanol (approx 80% of theoretical) of cellulose-rich residue after
steam-explosion were 190°C and 10 min or 200°C and 5 min, in acid-impregnated straw. However, 180°C for 10 min in acid-impregnated
biomass provided the highest ethanol yield referred to raw material (140 L/t wheat straw), and sugars recovery yield in the
filtrate (300 g/kg wheat straw). 相似文献
4.
Burt DP Cervera J Mandler D Macpherson JV Manzanares JA Unwin PR 《Physical chemistry chemical physics : PCCP》2005,7(15):2955-2964
A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple is reversible, the response is highly sensitive to local mass transfer of Ag+ away from the electrode, which, in turn, is governed by the interaction of Ag+ with the monolayer. The methodology has been used to determine the influence of surface pressure on the adsorption of Ag+ ions at a phospholipid (dipalmitoyl phosphatidic acid) Langmuir monolayer. It is shown that the capacity for metal ion adsorption at the monolayer increased as the density of surface adsorption sites increased (by increasing the surface pressure). A model for mass transport and adsorption in this geometry has been developed to explain and characterise the adsorption process. 相似文献
5.
Jingping Peng David L. Cedeo Carlos Manzanares I 《Journal of Molecular Structure》1998,440(1-3):265-288
The infrared spectra of cis-3-hexene and trans-3-hexene dissolved in liquid argon have been obtained at temperatures from 93 to 120 K. The absorptions were observed with a low-temperature cell and a Fourier transform infrared spectrophotometer. Ab initio molecular orbital calculations were performed to obtain the equilibrium geometry, vibrational frequencies, force fields, and infrared intensities. The calculations were done at the Hartree-Fock level using 6-31G basis set. The Cartesian force fields from ab initio calculations have been converted to the force field in symmetry coordinates. The scale factors of ab initio calculated force fields were determined. Normal coordinate calculations were performed using a scaled quantum mechanical (SQM) force field. Vibrational normal modes calculated for the lowest energy rotamers of cis- and trans-3-hexene have been assigned to infrared absorption bands observed in liquid argon solution. The assignments were based on calculated frequencies and potential energy distributions. The equilibrium geometries of the two lowest energy rotamers (symmetry C2 and Cs) of cis-3-hexene and of the three lowest energy rotamers (symmetry Ci, C2, and C1) of trans-3-hexene were calculated. Variable temperature studies of the infrared spectrum of cis- and trans-3-hexenes dissolved in liquid argon were done to obtain the ΔH of conversion between the rotamers C2 and Cs of cis-3-hexene and between the rotamers Ci, C2, and C1 of trans-3-hexene. 相似文献
6.
7.
J M Caba I M Rodriguez I Manzanares E Giralt F Albericio 《The Journal of organic chemistry》2001,66(23):7568-7574
Marine organisms are a rich source of novel, biologically active compounds. Herein, the solid-phase total synthesis of trunkamide A, currently in preclinical trials, is presented. Trunkamide A contains a thiazoline heterocycle and two residues of Ser and Thr with the hydroxy function modified as reverse prenyl (rPr). Cornerstones of the synthesis are as follows: (i) solid-phase peptide chain elongation using a quasi-orthogonal protecting scheme with tert-butyl and fluorenyl based groups, on a chlorotrityl resin; (ii) concourse of HOAt-based coupling reagents; and (iii) cyclizations in solution. Furthermore, the following synthetic steps are discussed: (i) preparation of the reverse prenyl derivatives of Ser and Thr; (ii) introduction of precursor of thiazoline as a protected amino thionoacid derivative; and (iii) formation of the thiazoline ring with DAST. All these features make this strategy particularly suitable for the large-scale synthesis of trunkamide A and other peptides containing the same motifs. 相似文献
8.
We present some novel thermodynamic ideas based on the Maupertuis principle. By considering Hamiltonians written in terms of appropriate action-angle variables we show that thermal states can be characterized by the action variables and by their evolution in time when the system is nonintegrable. We propose dynamical definitions for the equilibrium temperature and entropy as well as an expression for the nonequilibrium entropy valid for isolated systems with many degrees of freedom. This entropy is shown to increase in the relaxation to equilibrium of macroscopic systems with short-range interactions, which constitutes a dynamical justification of the Second Law of Thermodynamics. Several examples are worked out to show that this formalism yields the right microcanonical (equilibrium) quantities. The relevance of this approach to nonequilibrium situations is illustrated with an application to a network of coupled oscillators (Kuramoto model). We provide an expression for the entropy production in this system finding that its positive value is directly related to dissipation at the steady state in attaining order through synchronization. 相似文献
9.
This article presents a collection of vibrational overtone spectra of hydrocarbons in cryogenic solutions. Vibrational overtone spectra of ethane and propane dissolved in liquid argon and n-butane and isobutane dissolved in liquid krypton were recorded between 5000 and 14,000 cm(-1). Spectral regions for the first four overtones were measured using a Fourier transform spectrophotometer. The fifth overtone (Deltaupsilon = 6) spectra were recorded with a double beam (pump-probe) thermal lens technique using concentrations as low as 10-3 mole fraction. We obtained the C-H (Deltaupsilon = 6) spectra of (a) liquid ethane at 100 K and ethane in solutions in liquid Ar at 92 K and liquid N2 at 85 K, (b) liquid propane at 148 K and propane in liquid Ar at 93 K, (c) n-butane in liquid Kr at 129 K, (d) n-pentane in liquid Xe at 160 K, and (e) isobutane liquid at 135 K and isobutane in liquid Kr at 130 K. Local-mode parameters were calculated for primary, secondary, and tertiary C-H oscillators in solution and compared with gas-phase local-mode parameters. The peak frequency shift (Deltaomega) from gas phase to solution is explained by the change in harmonic frequency and anharmonicity in solution with respect to the gas-phase values. The bandwidth (Deltaomega1/2) of the (Deltaupsilon = 6) C-H absorption bands of ethane in solution can be explained in terms of collisions with the solvent molecules. 相似文献
10.
Perez-Delgado Y Barroso JZ Garofalo LA Manzanares CE 《The journal of physical chemistry. A》2012,116(9):2071-2079
The vibrational overtone spectra of the acetylenic (Δυ = 4, 5) and methyl (Δυ = 5, 6) C-H stretch transitions of tert-butyl acetylene [(CH(3))(3)C-C≡C-H] were obtained using the phase shift cavity ring down (PS-CRD) technique at 295 K. The C-H stretch fundamental and overtone absorptions of the acetylenic (Δυ = 2 and 3) and methyl (Δυ = 2-4) C-H bonds have been obtained using a Fourier transform infrared and near-infrared spectrophotometer. Harmonic frequency ω(ν(1)) and anharmonicities x(ν(1)) and x(ν(1), ν(24)) are reported for the acetylenic C-H bond. Molecular orbital calculations of geometry and vibrational frequencies were performed. A harmonically coupled anharmonic oscillator (HCAO) model was used to determine the overtone energy levels and assign the absorption bands to vibrational transitions of methyl C-H bonds. Band strength values were obtained experimentally and compared with intensities calculated in terms of the HCAO model where only the C-H modes are considered. No adjustable parameters were used to get order of magnitude agreement with experimental intensities for all pure local mode C-H transitions. 相似文献