Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

Dielectric,electro-optical and thermodynamic investigation of binary mixtures formed by pyridine with hydrocarbons and chlorobenzene

The dielectric constant, Kerr constant, excess enthalpy, and excess Gibbs energy of binary systems formed by pyridine with cyclohexane, benzene, ethylbenzene and chlorobenzene were experimentally determined. Complex analysis of the data obtained was carried out.The results obtained exhibit a different degree of association of the pyridine molecules, depending on the second component present in the mixture investigated. The structure and properties of the mixtures are discussed in detail.     

Determination of sulfur forms in wine including free and total sulfur dioxide based on molecular absorption of carbon monosulfide in the air–acetylene flame

A new method for the determination of sulfur forms in wine, i.e., free SO₂, total SO₂, bound SO₂, total S, and sulfate, is presented. The method is based on the measurement of the carbon monosulfide (CS) molecular absorption produced in a conventional air–acetylene flame using high-resolution continuum source absorption spectrometry. Individual sulfur forms can be distinguished because of the different sensitivities of the corresponding CS molecular absorption. The sensitivity of free SO₂ is about three times higher than the value for bound SO₂ and sulfate. The method makes use of procedures similar to those used in classic reference methods. Its performance is verified by analyzing six wine samples. Relative standard deviations are between 5 and 13% for free SO₂ and between 1 and 3% for total SO₂. For the validation of the accuracy of the new method, the results are compared with those of reference methods. The agreement of the values for total SO₂ with values of the classic method is satisfactory: five out of six samples show deviations less than 16%. Due to the instability of free SO₂ in wine and the known problems of the used reference method, serious deviations of the free SO₂ results are found for three samples. The evaluation of the limits of detection focuses on the value for free SO₂, which is the sulfur form having by far the lowest concentration in wine. Here, the achievable limit of detection is 1.8 mg L⁻¹. Figure Detection of non-metal elements using continuum source flame absorption spectrometry     

Selective synthesis and derivatization of alkali metal silanides MSi(SiH3)3

Greetings from silicon valley: Alkali metal silanides (H(3)Si)(3)Si(-)M(+) were shown to be selectively accessible for the first time by the reaction of neopentasilane Si(SiH(3))(4) with tBuOM or iPr(2)NLi. The method allows the convenient derivatization of higher silicon hydrides and provides a simple access for unprecedented systematic studies on the chemical behavior of hydropolysilanes (see scheme).     

Spin-lock techniques and CPMG imaging sequences: a critical appraisal of T1p contrast at 0.15 T

The addition of a spin-lock preparatory sequence to a Carr-Purcell-Meiboom-Gill (CPMG) imaging sequence provides a method which allows an accurate and simple comparison of T1p and T2 contrast. Sagittal and axial brain images, produced with the application of a three pulse preparatory spin-lock sequence prior to a sixteen-echo CPMG imaging sequence, are compared with images acquired without the spin-lock sequence. The CPMG sequence uses non-selective refocusing pulses. Therefore, observed echo signals accurately reflect T2 relaxation. This allows a convenient method for assessing the degree to which T1p and T2 contrast differ. The spin-lock CPMG (SL-CPMG) images were acquired with a spin-locking field amplitude of 0.4 G and resemble heavily T2-weighted images at 0.15 T. Quantitative analyses of signal intensities from edema and normal brain tissue confirm the qualitative observations. This in vivo method should prove useful for determining when the additional RF power deposition associated with spin-locking techniques will provide an alternate form of tissue contrast than that available from additional echo collection.     

Scales of Nucleophilicity and Electrophilicity: A System for Ordering Polar Organic and Organometallic Reactions

Contrary to widely held opinion, for many reactions in organic and organometallic chemistry it is possible to define nucleophilicity and electrophilicity parameters that are independent of the reaction partners. This phenomenon, discovered by Ritchie during the early 1970s for reactions of highly stabilized carbenium and diazonium ions with n-nucleophiles, also occurs with reactions of carbenium ions with aliphatic and aromatic π-electron systems and in hydride transfer reactions. With the aid of the scales of nucleophilicity and electrophilicity set out here, which extend over eighteen orders of magnitude, forecasts can be made about the feasibility and rate of a given CC bond formation, ionic reduction, or diazo coupling. Linkage with the reactivity scales of Ritchie and Sweigart/Kane-Maguire enables a unified treatment of a large number of polar reactions.     

Clinical experience with rapid 2DFT SSFP imaging at low field strength

A retrospective analysis of clinical imaging using 2DFT SSFP at 0.14 T is presented. The technique's potential for tissue characterization and its utility for clinical diagnosis were tested by both in vitro measurements of various tissues and in vivo clinical images. Different pulse angles not only influenced image contrast, but also helped characterize lesions, particularly those containing fat. In addition, the pulse angle changed the signal from venous flow perpendicular to the imaged slice. The slow flow sensitivity of the 2DFT SSFP technique was demonstrated in the detection of CSF motion. Rapid SSFP offers flow sensitivity and adequate lesion detecting ability, along with high patient throughput.