Homonuclear J-Coupling Spectroscopy at Low Magnetic Fields using Spin-Lock Induced Crossing**

Nuclear magnetic resonance (NMR) spectroscopy usually requires high magnetic fields to create spectral resolution among different proton species. Although proton signals can also be detected at low fields the spectrum exhibits a single line if J-coupling is stronger than chemical shift dispersion. In this work, we demonstrate that the spectra can nevertheless be acquired in this strong-coupling regime using a novel pulse sequence called spin-lock induced crossing (SLIC). This techniques probes energy level crossings induced by a weak spin-locking pulse and produces a unique J-coupling spectrum for most organic molecules. Unlike other forms of low-field J-coupling spectroscopy, our technique does not require the presence of heteronuclei and can be used for most compounds in their native state. We performed SLIC spectroscopy on a number of small molecules at 276 kHz and 20.8 MHZ and show that the simulated SLIC spectra agree well with measurements.     

CNN Pincer Ruthenium Catalysts for Hydrogenation and Transfer Hydrogenation of Ketones: Experimental and Computational Studies

Reaction of [RuCl(CNN)(dppb)] ( 1‐Cl ) (HCNN=2‐aminomethyl‐6‐(4‐methylphenyl)pyridine; dppb=Ph₂P(CH₂)₄PPh₂) with NaOCH₂CF₃ leads to the amine‐alkoxide [Ru(CNN)(OCH₂CF₃)(dppb)] ( 1‐OCH₂CF₃ ), whose neutron diffraction study reveals a short RuO ??? HN bond length. Treatment of 1‐Cl with NaOEt and EtOH affords the alkoxide [Ru(CNN)(OEt)(dppb)] ? (EtOH)_n ( 1‐OEt?n EtOH ), which equilibrates with the hydride [RuH(CNN)(dppb)] ( 1‐H ) and acetaldehyde. Compound 1‐OEt?n EtOH reacts reversibly with H₂ leading to 1‐H and EtOH through dihydrogen splitting. NMR spectroscopic studies on 1‐OEt?n EtOH and 1‐H reveal hydrogen bond interactions and exchange processes. The chloride 1‐Cl catalyzes the hydrogenation (5 atm of H₂) of ketones to alcohols (turnover frequency (TOF) up to 6.5×10⁴ h^?1, 40 °C). DFT calculations were performed on the reaction of [RuH(CNN′)(dmpb)] ( 2‐H ) (HCNN′=2‐aminomethyl‐6‐(phenyl)pyridine; dmpb=Me₂P(CH₂)₄PMe₂) with acetone and with one molecule of 2‐propanol, in alcohol, with the alkoxide complex being the most stable species. In the first step, the Ru‐hydride transfers one hydrogen atom to the carbon of the ketone, whereas the second hydrogen transfer from NH₂ is mediated by the alcohol and leads to the key “amide” intermediate. Regeneration of the hydride complex may occur by reaction with 2‐propanol or with H₂; both pathways have low barriers and are alcohol assisted.     

On a Model of Nonlocal Continuum Mechanics Part II: Structure, Asymptotics, and Computations

We consider the asymptotic behavior and local structure of solutions to the nonlocal variational problem developed in the companion article to this work, On a Model of Nonlocal Continuum Mechanics Part I: Existence and Regularity. After a brief review of the basic setup and results of Part I, we conduct a thorough analysis of the phase plane related to an integro-differential Euler--Lagrange equation and classify all admissible structures that arise as energy minimizing strain states. We find that for highly elastic materials with relatively weak particle-particle interactions, the maximum number of internal phase boundaries is two. Moreover, we also develop explicit bounds for the number of internal phase boundaries supported by any material and show that this bound is essentially inversely related to the particle size. To understand the question of asymptotics, we utilize the Young measure and show that in the sense of energetics and averages, minimizers of the full nonlocal problem converge to minimizers of two limiting problems corresponding to both the large and small particle limits. In fact, in the small particle limit, we find that the minimizing fields converge, up to a subsequence in strong-L^p, for 1 ≤ p < ∞, to fields that support either a single internal phase boundary, or two internal phase boundaries that are distributed symmetrically about the body midpoint. We close this work with some computations that illustrate these asymptotic limits and provide insight into the notion of nonlocal metastability. This revised version was published online in August 2006 with corrections to the Cover Date.     

Particle motions in non-Newtonian media

Summary An experimental study of the behaviour of rigid and deformable particles suspended in pseudoplastic and elasticoviscous liquids undergoing slowCouette flow was undertaken. The velocity profiles deviated slightly from those obtained forNewtonian fluids, but the measured angular velocities of rigid spheres showed that the rotation of the field was equal to half the velocity gradient. While the measured angular velocities of rods and discs were in accord with theory applicable toNewtonian liquids, in both non-Newtonian media there was a steady drift in the orbit towards an asymptotic value corresponding to minimum energy dissipation in the flow. Furthermore, discs in elasticoviscous solutions of polyacrylamide at higher shear stresses aligned themselves in the direction of the flow and ceased to rotate.Migration of rigid particles across the planes of shear in the annul us of theCouette was also observed. In pseudoplastic liquids, the migration was towards the region of higher shear, whereas the opposite was true in elasticoviscous liquids.The deformation, orientation and burst of pseudoplastic drops inNewtonian liquids and that ofNewtonian drops in pseudoplastic fluids were similar to those previously in completelyNewtonian systems. With elasticoviscous drops, however, the deformation was smaller than given by theory.As in elasticoviscous fluids, two-body collisions of rigid uniform spheres in the pseudoplastic liquids were unsymmetrical and irreversible, thus differing from collisions inNewtonian systems where complete reversibility is observed.While some of the observed phenomena in elasticoviscous suspensions could be qualitatively interpreted, particle behaviour in the pseudoplastic liquids could not be explained in terms of the known rheological properties of the fluids.

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Zusammenfassung Es wurde experimentell das Verhalten von festen und deformierbaren Teilchen untersucht, die bei der Suspension in strukturviskosen und viskoelastischen Flüssigkeiten einer langsamenCouette-Strömung ausgesetzt sind. Die Geschwindigkeitsprofile zeigten gewisse Abweichungen von denenNewtonscher Flüssigkeiten, aber die gemessenen Winkelgeschwindigkeiten der festen Kügelchen ergaben, daß die Drehung des Feldes gleich dem halben Geschwindigkeitsgradienten war. Die gemessenen Winkelgeschwindigkeiten der Stäbchen und Scheiben stimmten mit der Theorie, die auf Newtonsche Flüssigkeiten zutrifft, überein. In beiden nicht-Newtonschen Flüssigkeiten verschob sich jedoch die Kreisbahn stetig zu einem asymptotischen Wert, der einem Minimum der Dissipationsenergie der Strömung entsprach. Scheibchen in viskoelastischen Lösungen von Polyacrylamid richteten sich bei höherer Scherspannung in Strömungsrichtung aus und zeigten keine Drehung mehr.Es wurden auch Wanderungen von festen Teilchen über die Scherebene im Spalt derCouette-Anordnung beobachtet. In strukturviskosen Flüssigkeiten erfolgte die Wanderung in Richtung der höheren Scherung, während auf elastische Flüssigkeiten das Gegenteil zutraf.Die Deformation, Orientierung und das Aufbrechen strukturviskoser Tröpfchen inNewtonschen Flüssigkeiten und das Verhalten von Newtonschen Tröpfchen in strukturviskosen Flüssigkeiten waren den früher in rein-Newtonschen Systemen beobachteten Phänomenen ähnlich. Die Deformation der viskoelastischen Tröpfchen war jedoch kleiner als die von der Theorie vorhergesagt worden war.Zweikörper-Zusammenstöße zwischen festen gleichförmigen Kügelchen in strukturviskosen Flüssigkeiten waren unsymmetritch und irreversibel. Darin unterschieden sie sich von Zusammenstößen inNewtonschen Flüssigkeiten, in denen völlige Umkehrbarkeit beobachtet worden war.Während einige der beobachteten Phänomene in viskoelastischen Suspensionen qualitativ gedeutet werden konnten, ließ sich das Teilchenverhalten in strukturviskosen Flüssigkeiten nicht anhand der bekannten Theologischen Eigenschaften der Flüssigkeiten erklären.

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This work was supported by the Defence Research Board of Canada (DRB Grant 9530-47).     

Sonovoltammetric studies on copper in buffered alkaline solution

The effect of ultrasound on the voltammetry of copper in alkaline solution is reported. At pH 7 the electrode surface remains active after scanning to ca. +1.0 V (vs. SCE) and the effects of ultrasound show the expected substantial enhancement in limiting current due to improved mass transport under ultrasound. However at pH 9, whereas the silent scan is only slightly altered in gross detail from that obtained at pH 7, the sonicated scan is significantly different. This shows the expected current increase only up until ca. +0.6 V (vs. SCE), where there is a substantial loss of current showing a passivation phenomenon that is enhanced by ultrasound. In addition, during the reverse (reduction) scan under ultrasound an anodic peak appears. This suggests reactivation of the electrode during the cathodic sweep, possibly by reductive removal of a transient species from the electrode/(hydr)oxide interface at a potential where oxidation still occurs. Increasing the pH to 11 further shifts the cathodic peaks in the silent voltammogram.     

The sonoelectrooxidation of thiophene S-oxides

Thiophene-S-oxides (thiophene monoxides) are relatively new compounds, less stable than the better-known thiophene-S-dioxides. They are useful as synthons for a range of applications, including in the production of pharmaceuticals. They have interesting photochemical properties, but in this presentation we contrast the electro-oxidative voltammetry of differently substituted derivatives. We also compare carbocyclic compounds such as tetracyclone, the electro-oxidation of which at relatively high potentials has never been reported in silent or insonated conditions.     

Potential uses of ultrasound in the biological decontamination of water

In the past there was a prevailing feeling in industry that power ultrasound would be too expensive to use for water treatment on an industrial scale. This was based on calculations involving the direct scale up of power consumption in small-scale (generally batch) laboratory experiments. In recent times this attitude has changed somewhat as a result of the installation of a number of ultrasonic devices in operational water or sewage treatment plants. In our laboratories we have investigated the decontamination of water under the influence of ultrasound alone and in conjunction with other treatments. The results, particularly when applied to flowing systems, indicate a real future for sonochemistry in water treatment.     

Sonochemistry and sonoprocessing: the link,the trends and (probably) the future

Traditionally the community of scientists involved with ultrasound has been divided broadly into those who use it as a measurement device with no effect on the medium (high frequency low power ultrasound e.g. non-destructive testing) and those who use it to produce physical or chemical effects in a medium (higher power low frequency ultrasound e.g. sonochemistry). Divisions also exist within the broad spectrum of those involved with the latter. In the early days of sonochemistry this did not prove to be a major problem, the subject was new and the field was expanding within the chemistry community. However at a point some years ago Jean-Louis Luche made the very important observation that sonochemistry applications could be subdivided into reactions which were the result of "true" and "false" effects [Synthetic Organic Chemistry by J.-L. Luche, 1998, p. 376]. Essentially these terms referred to real chemical effects induced by cavitation and those effects that could be mainly ascribed to the mechanical impact of bubble collapse. These mechanical effects have not held the interest of synthetic chemists as much as the so-called true ones but nevertheless they are certainly important in areas such as processing. In this paper I will attempt to show that there are links that can be made across many of the ultrasound "disciplines" and that these links can only serve to strengthen research in the general area of power ultrasound. If research on power ultrasound is strong then research into "pure" sonochemistry will also flourish and "false" sonochemistry will be born again as a significant research area.     

Diffusion coefficients of gases from the rate of approach to the steady state in thermal diffusion

The rate of approach to the steady state in a convection-free two-bulb thermal diffusion experiment is treated in a more rigorous manner than previously available, in order that reliable ordinary diffusion coefficients may be derived from thermal diffusion measurements. The final results are of the same form as in the original simplified Jones and Furry treatment, but the parameters are now interpreted somewhat differently and a new correction term appears. Application to Nettley's measurements on H₂-N₂ mixtures removes an apparent discrepancy with the kinetic theory prediction of the composition dependence of the diffusion coefficient for this system.