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51.
Summary A simple, sensitive, accurate and reliable method for morphine determination in biological samples has been developed. It uses reverse-phase HPLC on a polymeric column with an eluent (0.05 mol/L dibasic sodium phosphate: acetonitrile, 8515) at pH 9.5, allowing both the suppression of ionization of morphine amine and the promotion of oxidation of the phenolic group. Amperometric detection at mild oxidizing potential (350 mV) proves very selective, and, therefore, only a simple and rapid one-step liquid-liquid sample preparation is required. Under these conditions clean chromatograms are obtained even with complex biological matrices such as cadaveric blood, urine and hair.Minimum detectable amount of morphine is about 200 pg injected. A calibration line with a correlation coefficient of 0.99996 has been produced over the range 7.5–250 ng/mL. Precision results comparable to other HPLC methods.A preliminary report was presented at the 25th T.I.A.F.T. Meeting 1988, Groningen (NL), June 27–30 1988. 相似文献
52.
53.
M'Hamed Ali Hamza Guy Serratrice Jean-Jacques Delpuech 《Magnetic resonance in chemistry : MRC》1981,16(2):98-102
Carbon-13 chemical shifts, spin-lattice relaxation times and nuclear Overhauser enhancement factors are reported for five polyfluoroaromatic compounds at 28°C. In all cases the relaxation of the fluorine bearing carbon is predominantly dipolar. Effective correlation times are smaller than those of the analogous benzene derivatives by a factor of 3–4, in qualitative agreement with predictions from the Stokes–Einstein diffusion theory. The T1 values for the para-carbon of monosubstituted fluorobenzenes is clearly shorter than the T1 values for the ortho- and meta-carbons. This phenomenon was traced to anisotropic tumbling, and D∥ and D⊥ diffusion coefficients were computed using Woessner's equations for molecules assumed to behave like symmetric rotors about their C2 in-plane principal symmetry axis. Equal tumbling ratios, D∥/D⊥, were found in this way for toluene and perfluorotoluene. 相似文献
54.
Cheikh?L? Jean-Jacques?Aaron Václav?Kozmík Ji?í?Svoboda Jean-Claude?Brochon Li?Na 《Journal of fluorescence》2010,20(5):1037-1047
The synthesis, electrochemical and optical properties of three fluorescent substituted thieno[3,2-b][1]benzothiophenes (TBT)
derivatives, including 3-methoxythieno[3,2-b][1]benzothiophene (3-MeO-TBT), 2,3-dimethylthieno[3,2-b][1]benzothiophene (2,3-diMe-TBT),
and 6-methoxythieno[3,2-b][1]benzothiophene-2-carboxylate (6-MeO-TBT-2-COOMe), were investigated. The oxidation potential
values varied between 1.40 and 1.20 V/SCE according to the electronic substituent effect, and electropolymerization attempts,
performed in 0.1 M LiClO4 acetonitrile solution, led to the formation of very thin films of poly(3-MeO-TBT) and poly(2,3-di-Me-TBT). Electronic absorption
spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) , lifetimes (τF), and other photophysical parameters of the three new TBT derivatives were measured in DMSO solutions at room temperature.
For the methyl-and methoxy-substituted TBT derivatives, the fluorescence emission peak were slightly red shifted relative
to that of unsubstituted TBT (Δλem = 1–12 nm) whereas, in the case of 6-MeO-TBT-2-COOMe, a rather strong red-shift (Δλem = 73 nm) was attributed to the existence of a “push-pull” electronic interaction of the MeO and COOMe groups. All ΦF values were rather high, varying between 0.11 and 0.35, according to the substituent effect. Fluorescence decays were mono-exponential
and τF values were very short, ranging between 0.11 and 0.30 ns for the substituted TBT derivatives until study. 相似文献
55.
SELEX (for Systematic Evolution of Ligands by Exponential enrichment) has proven to be extraordinarily powerful for the isolation of DNA or RNA aptamers that bind with high affinity and specificity to a wide range of molecular targets. However, the modest chemical functionality of nucleic acids poses some limits on the versatility of aptamers as binders and catalysts. To further improve the properties of aptamers, additional chemical diversity must be introduced. The design of chemical modifications is not a trivial task. Recently, dynamic combinatorial chemistry (DCC) has been introduced as an alternative to traditional combinatorial chemistry. DCC employs equilibrium shifting to effect molecular evolution of a dynamic combinatorial library of molecules. Herein, we describe an original process that combines DCC and SELEX for the in vitro selection of modified aptamers which are conjugated to chemically diverse small-molecules. Its successful application for the selection of small-molecule conjugated RNA aptamers that bind tightly to the transactivation-response (TAR) element of HIV-1 is presented. 相似文献
56.
Emmanuel Rousseau Marine Laroche Jean-Jacques Greffet 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(7-8):1005-1014
Radiative heat transfer at the nanoscale is becoming an important technological issue with the development of nano electromechanical systems (NEMS). In this article, we derive asymptotic expressions to compute near-field radiative heat transfer between two planes of silicon. We identify two physical mechanisms that give the dominant contribution at small gaps. For intrinsic and low-doped silicon, the main contribution is due to evanescent waves coming from propagating waves undergoing frustrated total internal reflections at the interfaces. For doping levels larger than Ne=1016 cm?3 surface mode coupling contributes to the heat transfer. Asymptotic expressions are also given in that case. In all cases, we compare analytical formulas with exact numerical calculations when varying the temperature and the doping concentration. We also give their range of validity. 相似文献
57.
Raffaele Marigo 《Israel Journal of Mathematics》2010,178(1):107-112
The main step in the proof of Hartogs’ theorem on separate analyticity (see [3], [4], [5]) consists in showing that if a function f defined in Δ × Δ is holomorphic for |z
2| < ε and separately holomorphic in z
2 when z
1 is kept fixed, then it is jointly holomorphic; the normal convergence of the Taylor series of f is obtained through the celebrated Hartogs’ lemma on subharmonic functions. 相似文献
58.
An efficient method for preparation of 4,6 or 5,6 disubstituted 3-aminopyridazines was easily carried out starting from easily available 4-bromo-pyridazine-3,6-dione, and using combination of both amination and Pd(0) cross-coupling reactions under microwave irradiation. 相似文献
59.
Jean-Jacques Bonnet Patrick Cassoux Paule Castan Jean-Pierre Laurent Regis Soules 《Molecular Crystals and Liquid Crystals》2013,570(1-4):113-125
Abstract Potassium bis(1,2-cyclobutenedione 3,4-dithiolato) palladate (Pd(dithiosquarato)2K2) crystallizes in the monolinic system, space group P21/c, a = 8.046(2), b = 15.235(4), c = 6.289(1). The dithiosquarate entities are stacked in parallel columns separated by potassium cations and water molecules. π-interactions within a stack are evidenced by the short stacking distance (3.51 Å). Further interstack interactions involve close S…O or O…O interstack contacts. (~3.5 Å). As a result, the structural arrangement is nearly two-dimensional. Conductivity measurements carried out on pressed pellets show a semi-conductive behavior (σ = 2 × 10?5 Ω?1 cm1). 相似文献
60.
Abstract We present a numerical simulation of scattering by one-dimensional randomly rough surfaces. It is based on the use of plane-wave expansions to describe the Melds on the surface (i.e. Rayleigh hypothesis). Accuracy and convergence properties of two different numerical implementations are studied. Some examples of results for a dielectric and a metallic Gaussian rough surface are shown to be in good agreement with calculations by a rigorous numerical method. The Rayleigh method appears to be a fast computation tool for dielectric surfaces with slopes of less than 0.2. 相似文献