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41.
(15)N CP/MAS solid state NMR should be a method of choice to obtain essential structural information on organic materials containing nitrogen atoms. However, the technique is generally not selected for the characterization of non-labelled chemical compounds, which represents the most common situation encountered by chemists. Actually, due to the poor sensitivity of (15)N the method is time-consuming and a very fine calibration is often a prerequisite to reach a sufficient signal/noise. The main drawback comes from the weakness of (15)N-(1)H dipolar couplings which leads to a splitting of the static Hartman Hahn condition into very narrow sideband conditions under MAS. Practically, it is more difficult to obtain a high enough CP transfer level on (15)N for the entire spectrum than on other more conventional nuclei like (13)C. An experimental investigation of the CP efficiency using the ramp and adiabatic CP transfer experiments is here proposed. Preliminary adjustments of experimental settings were first made on an (15)N-labeled substituted heterocyclic model system, and then applied to several other organic compounds. Particular attention was paid to the detection of non-protonated nitrogen atoms with a significant chemical shift anisotropy, which represented the least favourable case. It was experimentally demonstrated that, for these atoms, the adiabatic passage provided a much higher transfer level than the more conventional ramp sequence leading to an enhancement factor of up to 3.5 at a MAS frequency of 30 kHz. The resulting sensitivity rendered possible the detection of non-protonated nitrogen atoms at natural abundance with 2.5-mm rotors at 9.4 T. 相似文献
42.
Quinton D Girard A Thi Kim LT Raimbault V Griscom L Razan F Griveau S Bedioui F 《Lab on a chip》2011,11(7):1342-1350
In this work we report on the design, microfabrication and analytical performances of a new electrochemical sensor array (ESA) which allows for the first time the simultaneous amperometric detection of nitric oxide (NO) and peroxynitrite (ONOO(-)), two biologically relevant molecules. The on-chip device includes individually addressable sets of gold ultramicroelectrodes (UMEs) of 50 μm diameter, Ag/AgCl reference electrode and gold counter electrode. The electrodes are separated into two groups; each has one reference electrode, one counter electrode and 110 UMEs specifically tailored to detect a specific analyte. The ESA is incorporated on a custom interface with a cell culture well and spring contact pins that can be easily interconnected to an external multichannel potentiostat. Each UME of the network dedicated to the detection of NO is electrochemically modified by electrodepositing thin layers of poly(eugenol) and poly(phenol). The detection of NO is performed amperometrically at 0.8 V vs. Ag/AgCl in phosphate buffer solution (PBS, pH = 7.4) and other buffers adapted to biological cell culture, using a NO-donor. The network of UMEs dedicated to the detection of ONOO(-) is used without further chemical modification of the surface and the uncoated gold electrodes operate at -0.1 V vs. Ag/AgCl to detect the reduction of ONOOH in PBS. The selectivity issue of both sensors against major biologically relevant interfering analytes is examined. Simultaneous detection of NO and ONOO(-) in PBS is also achieved. 相似文献
43.
Kellenbach E Sanders K Michiels PJ Girard FC 《Analytical and bioanalytical chemistry》2011,399(2):621-628
The recently revised European Pharmacopeia and US Pharmacopeia heparin sodium monographs include nuclear magnetic resonance
(NMR) tests on both identity and purity. In KMnO4-bleached heparin, an unidentified NMR signal is present at 2.10 ppm at a level of 15–20% of the mean of signal height of
the major glucosamine (GlcNAc/GlcNS,6S) anomeric proton signal at 5.42 ppm and of the major iduronic acid (IdoA2S) anomeric
proton signal at 5.21 ppm. According to the new monographs, no unidentified signals greater than 4% should be detected at
that position. Thus, the material did not meet the acceptance criterion. The signal at 2.10 ppm has been present at the same
level in all released MSD KMnO4-bleached heparin sodium batches analyzed over the past 10 years. The signal is a result of the KMnO4 bleaching. No (oversulfated) chondroitin sulfate or dermatan sulfate was detected in this material. A comprehensive NMR study
using long-range heteronuclear 2D techniques identifies this signal at 2.10 ppm as originating from the acetyl methyl group
of (6-sulfated) 2-N-acetyl-2-deoxy-glucono-1,5-lactone. This modified monosaccharide is formed by the KMnO4 oxidation of the reducing end of a terminal N-acetylglucosamine. 相似文献
44.
Shabi Abbas Zaidi Seung Mi Lee Zeid A. AL Othman Abdullah M. AL Majid Won Jo Cheong 《Chromatographia》2011,73(5-6):517-525
Some acidic chiral templates were used to prepare open tubular (OT) molecule imprinted polymer (MIP) capillary columns to explore the effects of molecular structures of templates on chiral recognition capabilities and to verify the feasibility of the general MIP preparation protocol introduced in the previous study. The templates are phenyl carboxylic acids and their derivatives. Optimization was carried out for chiral separation of template enantiomers for each MIP column through varying pH and composition of eluent. It was found that the preparation protocol can be successfully applied for the appropriate templates with functional groups fulfilling the three-points interaction rule. The chiral separation performances were quite satisfactory for MIPs of such templates although they are yet inferior to the separation performances of the MIP columns fabricated with the templates of profen drugs (2-arylpropionic acids with a large substituent on the phenyl ring). Subtle variations of the template molecular structures have been found to be critical to enhance chiral recognition ability of the resultant MIP column. 相似文献
45.
Askari MS Girard B Murugesu M Ottenwaelder X 《Chemical communications (Cambridge, England)》2011,47(28):8055-8057
The reaction of nitrosobenzene with copper(I) complexes of a tetradentate ligand led to two novel species that are best described as copper(II) complexes of an O-bonded nitrosobenzyl radical anion, in either the singlet or the triplet spin-state. Both states were characterized by crystal structures, magnetic measurements and DFT calculations. 相似文献
46.
F. Girard M.-G. Lee L. A. Agrofoglio A. Fridland 《Journal of heterocyclic chemistry》1998,35(4):911-913
A stereoselective five-step total synthesis of the hitherto unknown carbocyclic alpha-L-dideoxyhomonu-cleosides starting from readily available (1R,5S)-2-oxabicyclo[3.3.0]oct-6-en-3-one is described. 相似文献
47.
M.A. Bouchene V. Blanchet C. Nicole N. Melikechi B. Girard H. Ruppe S. Rutz E. Schreiber L. Wöste 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》1998,2(2):131-141
The interaction of a sequence of two identical ultrashort laser pulses with an atomic system results in quantum interferences
as in Ramsey fringes experiments. These interferences allow achievement of temporal coherent control of the excitation probability.
We present the results of a temporal coherent control experiment on two different atomic systems: one-photon absorption in
K (4s-4p) and two-photon absorption in Cs (6s-7d). In K, the quantum interferences between the two excitation paths associated with the laser pulses are revealed through
rapid oscillations of the excitation probability as a function of the time delay between the two pulses. These oscillations
take place at the transition frequency (period T = 2.56 fs). The interferences are modulated by beats (at about 580 fs) resulting from the doublet structure of the excited
state (4p (2
P
1/2
, 2
P
3/2
)). Three complementary interpretations of this experiment are presented: in terms of beats of quantum interferences, of variation
in the spectrum intensity, and of wave packet interferences. Whenever the two laser pulses are temporally overlapped, optical
interferences are superimposed on to the quantum interferences. The distinction between these two types of interference is
clearly revealed in the two-photon excitation scheme performed on Cs (6s-7d (2
D
3/2
, 2
D
5/2
)) because quantum interferences occur at twice the frequency of the optical interferences.
Received: 30 December 1997 / Revised: 28 February 1998 / Accepted: 4 March 1998 相似文献
48.
Q. Liu B. Poumellec C. Haut D. Dragoe R. Blum G. Girard J.-E. Bourée A. Kudlinski Y. Quiquempois G. Blaise 《Applied Physics A: Materials Science & Processing》2005,81(6):1213-1219
Amorphous N- or Ge-doped H:SiO2 films deposited on silica by the matrix distributed electron cyclotron resonance-PECVD method were irradiated by an electron-beam with different doses in order to pole the material and induce second harmonic generation (SHG). SHG was measured using the Maker-fringe method. When irradiated at an acceleration voltage of 25 kV, an incident current of 5 nA during 480 s, the N-doped H:SiO2 films exhibited a maximum second harmonic signal in the order of 0.003 pm/V, but when irradiated with an acceleration voltage of 30 kV, at 5 nA during 240 s, the films exhibited a maximum second harmonic signal of 0.006 pm/V. With a smaller current of 0.5 nA during 25 s and 25 kV acceleration voltage, the Ge-doped H:SiO2 films (3.8 at. % Ge) showed a maximum second-order nonlinearity of 0.0005 pm/V. But an H:SiO2 films with a smaller Ge content (1.0 at. % Ge), showed a large SHG: d33=0.09 pm/V when irradiated at 25 kV, 0.5 nA during 15 s. PACS 78.66.J; 42.65.K; 68.60.D 相似文献
49.
We study a first-order identification problem in a Banach space. We discuss the nondegenerate and mainly the degenerate case. As a first step, suitable hypotheses on the involved closed linear operators are made in order to obtain unique solvability after reduction to a nondegenerate case; the general case is then handled with the help of new results on convolutions. Some applications to partial differential equations motivate this abstract approach.Communicated by I. GalliganiWork partially supported by MIUR (Ministero dell’ Istruzione, dell’ Università e dalla Ricerca), Project PRIN 2004011204 “Analisi Matematica nei Problemi Inversi,” and by the University of Bologna Funds for Selected Research Topics. 相似文献
50.