New general sulfinylating process for asymmetric synthesis of enantiopure sulfinates and sulfoxides

[reaction: see text] A general process for the efficient synthesis of sulfinyl transfer agents has been developed using cinchona alkaloids quinine and quinidine as chiral auxiliaries. The importance of these new and unique sulfinyl transfer agents is exemplified by the expedient synthesis of several sulfoxides in excellent enantiopurities and high yields.     

Untersuchungen über den Einfluß der Infektion mit Tabakmosaikvirus auf den Nucleinsäuregehalt von Nicotiana tabacum

Zusammenfassung Junge Pflanzen von Nicotiana tabacum wurden mit Tabakmosaikvirus (TMV) infiziert und die Konzentration an pufferlöslicher und an pufferunlöslicher Pflanzen-Nucleinsäure zu verschiedenen Zeiten nach der Infektion bestimmt.In der Fraktion der pufferlöslichen Pflanzen-Nucleinsäure (DNS und RNS) konnten keine mit der TMV-Infektion zusammenhängenden Konzentrationsänderungen festgestellt werden. Hingegen wird in der pufferunlöslichen Fraktion eine beträchtliche Verminderung an RNS gefunden. In dieser Fraktion bleibt die Konzentration an DNS mit der Dauer der Virusinfektion annähernd konstant. Es ist daher wahrscheinlich, daß die pufferunlösliche RNS zumindest einen Teil des für die Synthese der Virusnucleinsäure notwendigen Materials liefert.     

The adsorption of silver on potassium cyanocobalt(II)ferrate(II)

A procedure is described for recovering silver from industrial sewage (mining and photo-industry etc) with the aid of the ion-exchanger potassium cyanocobalt(II)ferrate(II) (KCFC). Silver is easily removed by simple mixing with KCFC, even from solutions containing less than 1 g of silver per ton of solution. The process is performed at room temperature at pH < 7. There is no interference from a 600-fold amount of Ca, Cu(II), Zn, Cd, Pb, and Fe(II). Pure silver may be obtained by dissolution of the ion-exchanger in potassium cyanide solution, subsequent precipitation as sulphide, and roasting, or by melting it out of the ion-exchanger after heat treatment in a high-frequency furnace. With 1 kg of KCFC, 1.25 kg of silver may be extracted from solution. The process is simple and economic.     

1,3-Dipolar cycloaddition of azomethine ylide with ethene and 2-butene: a computational study

B3LYP/6-311 + G(d,p) has been used to calculate the relative energies and geometrical parameters of the respective reactants, transition states, and cycloadducts from the cycloadditions of azomethine ylide and ethene, (Z)-2-butene, and (E)-2-butene. The half-chair (envelope) transition state structures are consistent with a synchronous concerted cycloaddition mechanism.     

Analysis by desorption of volatile impurities from an ionic liquid solution in an unmodified gas chromatograph inlet

A procedure for using ionic liquids to determine volatile impurities in compounds or matrices that are soluble in an ionic liquid is described. Using a conventional autosampler a droplet of ionic liquid solution is suspended in the inlet of the gas chromatograph and analytes are desorbed onto a GC column using splitless injection conditions. Results are presented for 1,2-propanediol, nonane, N,N-dimethylacetamide, and mesitylene in two different compounds in the ionic liquids trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide and trihexyltetradecylphosphonium dicyanamide.     

Heating in the MRI environment due to superparamagnetic fluid suspensions in a rotating magnetic field

In the presence of alternating-sinusoidal or rotating magnetic fields, magnetic nanoparticles will act to realign their magnetic moment with the applied magnetic field. The realignment is characterized by the nanoparticle's time constant, τ. As the magnetic field frequency is increased, the nanoparticle's magnetic moment lags the applied magnetic field at a constant angle for a given frequency, Ω, in rad/s. Associated with this misalignment is a power dissipation that increases the bulk magnetic fluid's temperature which has been utilized as a method of magnetic nanoparticle hyperthermia, particularly suited for cancer in low-perfusion tissue (e.g., breast) where temperature increases of between 4 and 7 degree Centigrade above the ambient in vivo temperature cause tumor hyperthermia. This work examines the rise in the magnetic fluid's temperature in the MRI environment which is characterized by a large DC field, B₀. Theoretical analysis and simulation is used to predict the effect of both alternating-sinusoidal and rotating magnetic fields transverse to B₀. Results are presented for the expected temperature increase in small tumors (approximately 1 cm radius) over an appropriate range of magnetic fluid concentrations (0.002-0.01 solid volume fraction) and nanoparticle radii (1-10 nm). The results indicate that significant heating can take place, even in low-field MRI systems where magnetic fluid saturation is not significant, with careful selection of the rotating or sinusoidal field parameters (field frequency and amplitude). The work indicates that it may be feasible to combine low-field MRI with a magnetic hyperthermia system using superparamagnetic iron oxide nanoparticles.     

Simulating magnetic nanoparticle behavior in low-field MRI under transverse rotating fields and imposed fluid flow

In the presence of alternating-sinusoidal or rotating magnetic fields, magnetic nanoparticles will act to realign their magnetic moment with the applied magnetic field. The realignment is characterized by the nanoparticle's time constant, τ. As the magnetic field frequency is increased, the nanoparticle's magnetic moment lags the applied magnetic field at a constant angle for a given frequency, Ω, in rad s⁻¹. Associated with this misalignment is a power dissipation that increases the bulk magnetic fluid's temperature which has been utilized as a method of magnetic nanoparticle hyperthermia, particularly suited for cancer in low-perfusion tissue (e.g., breast) where temperature increases of between 4 and 7 °C above the ambient in vivo temperature cause tumor hyperthermia. This work examines the rise in the magnetic fluid's temperature in the MRI environment which is characterized by a large DC field, B₀. Theoretical analysis and simulation is used to predict the effect of both alternating-sinusoidal and rotating magnetic fields transverse to B₀. Results are presented for the expected temperature increase in small tumors ( radius) over an appropriate range of magnetic fluid concentrations (0.002-0.01 solid volume fraction) and nanoparticle radii (1-10 nm). The results indicate that significant heating can take place, even in low-field MRI systems where magnetic fluid saturation is not significant, with careful the goal of this work is to examine, by means of analysis and simulation, the concept of interactive fluid magnetization using the dynamic behavior of superparamagnetic iron oxide nanoparticle suspensions in the MRI environment. In addition to the usual magnetic fields associated with MRI, a rotating magnetic field is applied transverse to the main B₀ field of the MRI. Additional or modified magnetic fields have been previously proposed for hyperthermia and targeted drug delivery within MRI. Analytical predictions and numerical simulations of the transverse rotating magnetic field in the presence of B₀ are investigated to demonstrate the effect of Ω, the rotating field frequency, and the magnetic field amplitude on the fluid suspension magnetization. The transverse magnetization due to the rotating transverse field shows strong dependence on the characteristic time constant of the fluid suspension, τ. The analysis shows that as the rotating field frequency increases so that Ωτ approaches unity, the transverse fluid magnetization vector is significantly non-aligned with the applied rotating field and the magnetization's magnitude is a strong function of the field frequency. In this frequency range, the fluid's transverse magnetization is controlled by the applied field which is determined by the operator. The phenomenon, which is due to the physical rotation of the magnetic nanoparticles in the suspension, is demonstrated analytically when the nanoparticles are present in high concentrations (1-3% solid volume fractions) more typical of hyperthermia rather than in clinical imaging applications, and in low MRI field strengths (such as open MRI systems), where the magnetic nanoparticles are not magnetically saturated. The effect of imposed Poiseuille flow in a planar channel geometry and changing nanoparticle concentration is examined. The work represents the first known attempt to analyze the dynamic behavior of magnetic nanoparticles in the MRI environment including the effects of the magnetic nanoparticle spin-velocity. It is shown that the magnitude of the transverse magnetization is a strong function of the rotating transverse field frequency. Interactive fluid magnetization effects are predicted due to non-uniform fluid magnetization in planar Poiseuille flow with high nanoparticle concentrations.     

Existence of Local Covariant Time Ordered Products of Quantum Fields in Curved Spacetime

 We establish the existence of local, covariant time ordered products of local Wick polynomials for a free scalar field in curved spacetime. Our time ordered products satisfy all of the hypotheses of our previous uniqueness theorem, so our construction essentially completes the analysis of the existence, uniqueness, and renormalizability of the perturbative expansion for nonlinear quantum field theories in curved spacetime. As a byproduct of our analysis, we derive a scaling expansion of the time ordered products about the total diagonal that expresses them as a sum of products of polynomials in the curvature times Lorentz invariant distributions, plus a remainder term of arbitrarily low scaling degree. Received: 6 December 2001 / Accepted: 10 June 2002 Published online: 21 October 2002