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61.
62.
F. J. Arroyo F. J. Carmona I. García De La Fuente J. A. González J. C. Cobos 《Journal of solution chemistry》2000,29(8):743-756
Excess molar volumes V
E
m at 25°C and atmospheric pressure over the entirecomposition range for binary mixtures of 1-heptanol with 2,5-dioxahexane, 2,5,8-trioxanonane,5,8,11-trioxapentadecane, 2,5,8,11-tetraoxadodecane,or 2,5,8,11,14-pentaoxapentadecane, and mixtures of 1-nonanol with 2,5-dioxahexane,3,6-dioxaoctane, 2,5,8-trioxanonane, 3,6,9-trioxaundecane, 5,8,11-trioxapentadecane,2,5,8,11-tetraoxadodecane, or 2,5,8,11,14-pentaoxapentadecane are reportedfrom densities measured with a vibrating-tube densimeter.V
E
m curves are nearlysymmetrical at about 0.5 mole fraction. Excess molar volumes are usually positive,indicating predominance of positive contributions to V
E
m from the disruption ofH bonds of alcohols and from physical interactions. When chain lengths ofboth components of the mixture are increased, the contribution from interstitialaccommodation appears to be sufficiently negative, such that V
E
m becomes negative(e.g., l-nonanol + 5,8,11-tetraoxapentadecane). 相似文献
63.
D. Arroyo P. Chamorro J.M. Amigó F.B. Rodríguez P. Varona 《The European physical journal. Special topics》2013,222(2):457-472
In this work, we apply ordinal analysis of time series to the characterisation of neuronal activity. Automatic event detection is performed by means of the so-called permutation entropy, along with the quantification of the relative cardinality of forbidden patterns. In addition, multivariate time series are characterised using the joint permutation entropy. In order to illustrate the suitability of the ordinal analysis for characterising neurophysiological data, we have compared the measures based on ordinal patterns of time series to the tools typically used in the context of neurophysiology. 相似文献
64.
A micellar electrokinetic capillary chromatographic method is presented which enables quantification of dexamethasone, polymyxin B and trimethoprim in synthetic mixtures and pharmaceutical products. Separation was carried out at 25?°C and 30 kV, with 10 mmol L–1 borate–phosphate buffer adjusted to pH 8 as electrolyte, with 50 mmol L–1 sodium dodecyl sulfate. Under these conditions separations were performed in 10 min. The limits of detection and quantification were approximately 2 mg L–1 for each component, except for polymyxin B. The method was applied to different commercial formulations. 相似文献
65.
van Breemen AJ Herwig PT Chlon CH Sweelssen J Schoo HF Setayesh S Hardeman WM Martin CA de Leeuw DM Valeton JJ Bastiaansen CW Broer DJ Popa-Merticaru AR Meskers SC 《Journal of the American Chemical Society》2006,128(7):2336-2345
Butyl, hexyl, and decyl derivatives of the liquid-crystalline organic semiconductor 5,5' '-bis(5-alkyl-2-thienylethynyl)-2,2':5',2' '-terthiophene were synthesized and studied with respect to their structural, optical, and electrical properties. By means of an optimized thermal annealing scheme the hexyl and decyl compounds could be processed into self-assembled monodomain films of up to 150 mm in diameter. These were investigated with X-ray diffractometry, which revealed a clearly single-crystalline monoclinic morphology with lamellae parallel to the substrate. Within the lamellae the molecules were found to arrange with a tilt of about 50 degrees with the rubbing direction of the polyimide alignment layer. The resulting, close side-to-side packing was confirmed by measurements of the UV/vis absorption, which showed a dichroic ratio of 19 and indicated H-aggregation. AFM analyses revealed self-affinity in the surface roughness of the monodomain. The compounds showed bipolar charge transport in TOF measurements, with hole mobilities reaching up to 0.02 cm(2)/Vs and maximum electron mobilities around 0.002 cm(2)/Vs. The hexyl derivative was processed into large-area monodomain top-gate field-effect transistors, which were stable for months and showed anisotropic hole mobilities of up to 0.02 cm(2)/Vs. Compared to multidomain bottom-gate transistors the monodomain formation allowed for a mobility increase by 1 order of magnitude. 相似文献
66.
The reaction of fac-[ReBr(CO)3(NCMe)2] (1) with either pyrazole (Hpz) or 3,5-dimethylpyrazole (Hdmpz) in a 1:2 Re/pyrazole ratio affords the known complexes fac-[ReBr(CO)3(Hpz)2] (2) and [ReBr(CO)3(Hdmpz)2] (3). Using a 1:1 ratio, MeCN as solvent, and longer reaction times led to a mixture in which the major components are the pyrazolylamidino complexes fac-[ReBr(CO)3(HN=C(CH3)pz-kappa2N,N)] (4) and fac-[ReBr(CO)3(HN=C(CH3)dmpz-kappa2N,N)] (5). The complexes fac-[ReBr(CO)3(Hpz)(NCMe)] (6) and fac-[ReBr(CO)3(Hdmpz)(NCMe)] (7) (along with 2 and 3) were found to be minor components of these reactions. Analogous reactions of fac-[Re(OClO3)(CO)3(NCMe)2] yielded fac-[Re(NCCH3)(CO)3(HN=C(CH3)pz-kappa2N,N)]ClO4 (8), fac-[Re(NCCH3)(CO)3(HN=C(CH3)dmpz-kappa2N,N)]ClO4 (9), fac-[Re(Hpz)(CO)3(HN=C(CH3)pz-kappa2N,N)]ClO4 (10), and fac-[Re(Hdmpz)(CO)3(HN=C(CH3)dmpz-kappa2N,N)]ClO4 (11). The X-ray structure of 11 showed the perchlorate anion to be hydrogen-bonded by the N-H groups of the pyrazole and pyrazolylamidino ligands. The behavior of the compound fac-[Re(Hdmpz)(CO)3(HN=C(CH3)dmpz-kappa2N,N)]BAr'4 (13) (synthesized by reaction of [ReBr(CO)3(Hdmpz)2] (3) with (i) AgOTf and (ii) NaBAr'(4)/MeCN) as an anion receptor has been studied in CD3CN solution. In addition, the structure of the supramolecular adduct fac-[Re(CO)3(Hdmpz)(HN=C(CH3)dmpz-kappa2N,N)].Cl (14), featuring chloride binding by the two N-H groups, was determined by X-ray diffraction. 相似文献
67.
Cuquejo J Jiménez ML Delgado AV Arroyo FJ Carrique F 《The journal of physical chemistry. B》2006,110(12):6179-6189
In the past few years, different models and analytical approximations have been developed facing the problem of the electrical conductivity of a concentrated colloidal suspension, according to the cell-model concept. Most of them make use of the Kuwabara cell model to account for hydrodynamic particle-particle interactions, but they differ in the choice of electrostatic boundary conditions at the outer surface of the cell. Most analytical and numerical studies have been developed using two different sets of boundary conditions of the Neumann or Dirichlet type for the electrical potential, ionic concentrations or electrochemical potentials at that outer surface. In this contribution, we study and compare numerical conductivity predictions with results obtained using different analytical formulas valid for arbitrary zeta potentials and thin double layers for each of the two common sets of boundary conditions referred to above. The conductivity will be analyzed as a function of particle volume fraction, phi, zeta potential, zeta, and electrokinetic radius, kappaa (kappa(-1) is the double layer thickness, and a is the radius of the particle). A comparison with some experimental conductivity results in the literature is also given. We demonstrate in this work that the two analytical conductivity formulas, which are mainly based on Neumann- and Dirichlet-type boundary conditions for the electrochemical potential, predict values of the conductivity very close to their corresponding numerical results for the same boundary conditions, whatever the suspension or solution parameters, under the assumption of thin double layers where these approximations are valid. Furthermore, both analytical conductivity equations fulfill the Maxwell limit for uncharged nonconductive spheres, which coincides with the limit kappaa --> infinity. However, some experimental data will show that the Neumann, either numerical or analytical, approach is unable to make predictions in agreement with experiments, unlike the Dirichlet approach which correctly predicts the experimental conductivity results. In consequence, a deeper study has been performed with numerical and analytical predictions based on Dirichlet-type boundary conditions. 相似文献
68.
69.
Four spectrophotometric methods are described and applied to resolve binary mixtures of the corticosteroid hydrocortisone
and the antibacterial polypeptide Zn-Bacitracin. The simultaneous determination of the two compounds was accomplished by means
of derivative methods, which were satisfactory used to determine synthetic mixtures of these compounds in different ratios
and in pharmaceutical preparations (only for hydrocortisone). Direct absorption spectra of compounds were used to optimise
the spectral data set performs the calibration by PLS-1, PLS-2 and PCR algorithms. These calibration models were evaluated
through internal validation (prediction of compounds in its own designed training set of calibration), cross-validation (obtaining
statistical parameters that show the efficiency for a calibration fit model) and external validation over synthetic and pharmaceutical
mixtures. The four described procedures do not require any separation step. Precision studies were achieved over two series
of ten standards for each compound showing no significant differences at 95% confidence level in the two spectrophotometric
methods. The results found in commercial products were compared with those obtained by means of MEKC method and similar values
were found.
Correspondence: Department of Analytical Chemistry and Food Technology, Universidad de Castilla-La Mancha, 13071 Ciudad Real,
Spain. e-mail: JoseMaria.Lemus@uclm.es
Received January 25, 2002; accepted October 22, 2002 相似文献
70.
Capitán-Vallvey LF Avidad R Fernández-Ramos MD Ariza-Avidad A Arroyo E 《Analytical and bioanalytical chemistry》2002,373(4-5):289-294
A disposable test strip is proposed for the determination of nitrite in waters. The strip is an inert rectangular strip of polyester with a 6 mm o.d. circular, transparent and colorless film attached to its surface. This film contains the chemicals required for reaction and fixation of the dye formed, sulfanilamide, N-(1-naphthyl)ethylenediamine on Nafion. When the test strip is placed in an acidified (pH 2.0) sample solution containing nitrite a red-violet color develops; the absorbance of this is measured at 536 nm. The linear range of the method depends on the time of equilibration of the test strip with the sample solution. When the equilibration time was 45 min, the linear range was 8.9-500 microg L(-1) whereas for an equilibration time of 60 min it was 4.7-200 microg L(-1). The detection limit was 1.4 microg L(-1) for an equilibration time of 60 min. The precision of the method, expressed as RSD, was 8.8 % at 100.0 microg L(-1). The method was applied, and validated chemometrically, for the determination of nitrite in different types of water (spring, mineral, tap, well, and sea). 相似文献