Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.     

Air-dispersion measurement by second-harmonic heterodyne interferometry

Interferometers with long optical paths in air usually require knowledge and control of air dispersion. In addition, the measurements at several wavelengths and the dispersion properties of air allow errors caused by air turbulence to be compensated for. An innovative technique for air-dispersion measurement is described for long-baseline ground-based stellar interferometers. The technique combines second-harmonic interferometry and heterodyne detection to permit high-resolution measurement even for low optical powers. Experimental results show measurements of air dispersion in good agreement with the values predicted from the Edlén equation.     

Description of pulse propagation in a dispersive medium by use of a pulse quality factor

We investigated how the duration of short laser pulses evolves in a dispersive material, using rms widths and a propagation law based on a pulse quality factor. Experiments were carried out with femtosecond pulses (10 to 25fs at the temporal waist) propagating in bulk fused silica. Excellent agreement was found between theory and experiment. This approach does not require complete characterization of laser pulses and eliminates the need for any assumption regarding the interpretation of autocorrelation traces. The method is of general validity, and it can be applied to pulses of arbitrary shape.     

Fission fragment mass yields of Th to Rf even-even nuclei

Fission properties of the actinide nuclei are deduced from theoretical analysis. We investigate potential energy surfaces and fission barriers and predict the fission fragment mass yields of actinide isotopes. The results are compared with experimental data where available. The calculations were performed in the macroscopic-microscopic approximation with the Lublin-Strasbourg Drop (LSD) for the macroscopic part, and the microscopic energy corrections were evaluated in the Yukawa-folded potential. The Fourier nuclear shape parametrization is used to describe the nuclear shape, including the non-axial degree of freedom. The fission fragment mass yields of the nuclei considered are evaluated within a 3D collective model using the Born-Oppenheimer approximation.     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Numerical study of the heat transfer and electro-thermo-convective flow patterns in dielectric liquid layer subjected to unipolar injection

In this article we study the electro-thermal convection in a dielectric liquid layer placed between two electrodes and subjected to the simultaneous action of an electric field and a thermal gradient. The full set of equations describing the electro-thermo-convective phenomena is directly solved using a finite volume method. We first heat the liquid from below at time t = 0, wait for the thermal steady state and then inject the electric charges by applying the electric potential. The development of the electro-convective motion is analysed in detail in two cases: 1) strong injection from the lower electrode, 2) strong injection from the upper one. We also study the heat transfer enhancement due to electro-convection. The evolution in time of the Nusselt number Nu for different combinations of the two usual non-dimensional parameters associated to the electro-thermo-convection phenomena (Rayleigh number Ra and the electrical parameter T) is also given and analysed.     

Sample Preparation for the Determination of Metals in Food Samples Using Spectroanalytical Methods—A Review

Abstract

The present article gives an overview of recent publications and modern techniques of sample preparation for food analysis employing atomic and inorganic mass spectrometric techniques, such as flame atomic absorption spectrometry, chemical vapor generation atomic absorption and atomic fluorescence spectrometry, graphite furnace atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry. Among the most frequently applied sample preparation techniques for food analysis are dry ashing, usually with the addition of an ashing aid, and acid digestion, preferably with the assistance of microwave energy. Slurry preparation, particularly with the assistance of ultrasound, is increasingly used to reduce acid consumption and sample preparation time. Direct analysis of solid samples is gaining importance in the field of food analysis as it offers the highest sensitivity, avoids the use of acids and other aggressive reagents, makes possible the analysis of micro‐samples, and can be applied for fast screening analysis, e.g., of fresh meat.     

Existence and invariance of twisted products on a symplectic manifold

It is now well-known [1] that the twisted product on the functions defined on a symplectic manifold, play a fundamental role in an invariant approach of quantum mechanics. We prove here a general existence theorem of such twisted products. If a Lie group G acts by symplectomorphisms on a symplectic manifold and if there is a G-invariant symplectic connection, the manifold admits G-invariant Vey twisted products. In particular, if a homogeneous space G/H admits an invariant linear connection, T ^*(G/H) admits a G-invariant Vey twisted product. For the connected Lie group G, the group T ^*G admits a symplectic structure, a symplectic connection and a Vey twisted product which are bi-invariant under G.     

Microwave spectrum,conformation, and dipole moment of 4-thiacyclohexanone

The microwave spectra of 4-thiacyclohexanone in the ground state and eight vibrationally excited states have been studied in the frequency region 18.0–40.0 GHz and the corresponding rotational constants have been determined. The following values of the ground-state rotational constants (MHz) were obtained from the analysis of the a-type transitions: A = 3935.149 (0.031), B = 1829.444 (0.001), and C = 1364.609 (0.001). Analysis of the Stark effect gives for the dipole components (in Debye units) μ_a = 1.409 (0.002), μ_c = 0.391 (0.064). These data are consistent with a chair conformation for the ring. A phisically reasonable set of structural parameters which reproduce the ground-state rotational constants has been derived. A qualitative estimate of the low-frequency vibrational modes was obtained from relative-intensity measurements. The lowest vibrational frequency is believed to be a ring-bending mode and it occurs at 77 ± 22 cm^?1 while the ring-twisting mode is at 204 ± 27 cm^?1.