Raman and SERS study of metoclopramide at different pH values

Conjugate acid–base forms of the drug metoclopramide were investigated by Raman spectroscopy in aqueous solutions and by surface‐enhanced Raman scattering (SERS), when the molecules were adsorbed on colloidal silver surfaces. Raman spectra were recorded at pH values below 8, metoclopramide being poorly water soluble at higher pH values. The SERS spectra of metoclopramide were recorded in the 3–11 pH range, even in spite of its low solubility at basic pH values. The Raman and SERS spectra were assigned by means of density functional theory (DFT) calculations. By monitoring several SERS marker bands, the protonated, neutral or the coexistence of both molecular species adsorbed on the colloidal silver particles could be evidenced. The adsorbate orientation was deduced to be perpendicular to the metal surface for the protonated molecular species and tilted for the neutral metoclopramide molecular species. Copyright © 2009 John Wiley & Sons, Ltd.     

Modeling phase transition for compressible two-phase flows applied to metastable liquids

The seven-equation model for two-phase flows is a full non-equilibrium model, each phase has its own pressure, velocity, temperature, etc. A single value for each property, an equilibrium value, can be achieved by relaxation methods. This model has better features than other reduced models of equilibrium pressure for the numerical approximations in the presence of non-conservative terms. In this paper we modify this model to include the heat and mass transfer. We insert the heat and mass transfer through temperature and Gibbs free energy relaxation effects. New relaxation terms are modeled and new procedures for the instantaneous temperature and Gibbs free energy relaxation toward equilibrium is proposed. For modeling such relaxation terms, our idea is to make use of the assumptions that the mechanical properties, the pressure and the velocity, relax much faster than the thermal properties, the temperature and the Gibbs free energy, and the ratio of the Gibbs free energy relaxation time to the temperature relaxation time is extremely high. All relaxation processes are assumed to be instantaneous, i.e. the relaxation times are very close to zero. The temperature and the Gibbs free energy relaxation are used only at the interfaces. By these modifications we get a new model which is able to deal with transition fronts, evaporation fronts, where heat and mass transfer occur. These fronts appear as extra waves in the system. We use the same test problems on metastable liquids as in Saurel et al. [R. Saurel, F. Petitpas, R. Abgrall, Modeling phase transition in metastable liquids: application to cavitating and flashing flows, J. Fluid Mech. 607 (2008) 313–350]. We have almost similar results. Computed results are compared to the experimental ones of Simões-Moreira and Shepherd [J.R. Simões-Moreira, J.E. Shepherd, Evaporation waves in superheated dodecane, J. Fluid Mech. 382 (1999) 63–86]. A reasonable agreement is achieved. In addition we consider the six-equation model with a single velocity which is obtained from the seven-equation model in the asymptotic limit of zero velocity relaxation time. The same procedure for the heat and mass transfer is used with the six-equation model and a comparison is made between the results of this model with the results of the seven-equation model.     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo‐outcomes presents an even more formidable challenge. Described herein is a simple iron‐based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2‐ and 2,2‐subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.     

Zinc Substitution of Cobalt in Vitamin B12: Zincobyric acid and Zincobalamin as Luminescent Structural B12‐Mimics

Replacing the central cobalt ion of vitamin B₁₂ by other metals has been a long‐held aspiration within the B₁₂‐field. Herein, we describe the synthesis from hydrogenobyric acid of zincobyric acid ( Znby ) and zincobalamin ( Znbl ), the Zn‐analogues of the natural cobalt‐corrins cobyric acid and vitamin B₁₂, respectively. The solution structures of Znby and Znbl were studied by NMR‐spectroscopy. Single crystals of Znby were produced, providing the first X‐ray crystallographic structure of a zinc corrin. The structures of Znby and of computationally generated Znbl were found to resemble the corresponding Co^II‐corrins, making such Zn‐corrins potentially useful for investigations of B₁₂‐dependent processes. The singlet excited state of Znby had a short life‐time, limited by rapid intersystem crossing to the triplet state. Znby allowed the unprecedented observation of a corrin triplet (E^T=190 kJ mol^?1) and was found to be an excellent photo‐sensitizer for ¹O₂ (Φ_Δ=0.70).     

LC–ELISA as a contribution to the assessment of matrix effects with environmental water samples in an immunoassay for estrone (E1)

Accreditation and Quality Assurance - Estrone (E1), a metabolite of the estrogenic hormones 17β-estradiol (β-E2) and 17α-estradiol (α-E2), is itself a potent estrogen which can...     

Invariance of the Spectrum for Hypoelliptic Operators

We show that the spectra of the -realizations for a class of hypoelliptic (pseudo-)differential operators are independent of in an interval around depending on the growth properties of the symbol. For elliptic operators we obtain the classical boundedness interval of Fefferman; in the general case we obtain a smaller interval which is as large as one can possibly expect it to be.