Nuclear spin quenching A new probe of exchange kinetics and droplet size in disperse systems

A new experimental technique, nuclear spin quenching (NSQ), is introduced, which can be used to measure droplet size and inter-droplet exchange rates of various intrinsic molecular species in disperse systems. The physical basis of the method is the quenching of the fine structure in spin-coupled N.M.R. spectra by intermolecular proton exchange, the rate of which is controlled by droplet exchange. The theoretical framework needed to interpret NSQ experiments is presented as well as an experimental case study on a water-in-oil microemulsion system. Being non-perturbing and having a large dynamic range, the NSQ technique should become a valuable complement to existing techniques for the study of structure and dynamics in disperse fluids.     

Dressed ion acoustic solitary waves in quantum plasmas with two polarity ions and relativistic electron beams

A theory for dressed quantum ion acoustic waves (QIAWs), which includes higher-order corrections when QIAWs are investigated by the reductive perturbation method, is presented for unmagnetized plasmas containing positive and negative ions and weakly relativistic electron beams. The properties of the QIAWs are investigated using a quantum hydrodynamic model, from which a Korteweg–de Vries equation is derived using the reductive perturbation method. An equation including higher-order dispersion and nonlinearity corrections is also derived, and the physical parameter space is discussed for the importance of these corrections.     

Synthesis of 2•,3•-Dideoxy-3•-<Emphasis Type="Italic">C</Emphasis>-hydroxymethylcytidine Phosphonomethyl Derivatives

Phosphonomethyl substituted 2?,3?-Dideoxy-3?-C-hydroxymethylcytidines have been synthesized and evaluated for their anti HIV-1 activities. The sugar moiety was synthesized starting from (S)-5-hydroxymethylfuran-2-(5H)-one using photocatalyzed addition of methanol. Reduction of the lactone, condensation with silylated 4-methoxy-2(1H)pyrimidinone, followed by phosphonomethylation and deprotection gave the title compounds. The compounds were tested for inhibition of HIV-1 activity but did not show any significant antiviral activity.     

The crystal structure of Hf3As

Hf₃As has a monoclinic unit cell of dimensions a = 15.3898(14) Å, b = 5.3795(5) Å, c = 15.330(14) Å, β = 90.291(6)°. A structure proposal based on space group $\text{C2}\text{c}$ (No. 15) has been refined by the least-squares method using a Rietveld-type fullprofile analysis of Guinier-Hägg X-ray powder film intensity data. The Hf₃As structure is an intermediate between the Fe₃P and the Ti₃P types. The atomic coordination follows rules formulated earlier for representatives of the Fe₃PTi₃PV₃S family of structures.     

Über die Verteilung organischer Verbindungen zwischen Wasser und organischen Lösungsmitteln

Zusammenfassung Verteilungskoeffizienten einer Anzahl von organischen Verbindungen zwischen Wasser und organischen Lösungsmitteln wurden bestimmt. Die Papierchromatographie aromatischer Verbindungen zeigte, daß der chromatographische Prozeß hauptsächlich ein Verteilungsvorgang ist und für die Schätzung von Verteilungskoeffizienten verwendet werden kann. Mit Hilfe von Papierchromatographie und Verteilungskoeffizienten sind Klassifizierungen von Lösungsmitteln und gelösten Verbindungen ausgeführt worden, welchen die wasserstoffbindenden Eigenschaften der erwähnten Stoffe zugrunde gelegt sind.     

Trace metal determinations in estuarine waters by electrothermal atomic absorption spectrometry after extraction of dithiocarbamate complexes into freon

Cadmium, copper, iron, lead, nickel and zinc are determined. The dithiocarbamate complexes of the metals are extracted into Freon-TF and back-extracted into dilute nitric acid solution. Portions of the back-extracts are injected into a graphite furnace. The method gives complete separation from the matrix irrespective of salinity. It is therefore useful throughout the full salinity range of an estuary, 0–35‰.The effect of high iron concentrations on the extraction is eliminated by using a mixed acetate buffercomplexing agent solution.     

Application of microbioreactors in fermentation process development: a review

Biotechnology process development involves strain testing and improvement steps aimed at increasing yields and productivity. This necessitates the high-throughput screening of many potential strain candidates, a task currently mainly performed in shake flasks or microtiter plates. However, these methods have some drawbacks, such as the low data density (usually only end-point measurements) and the lack of control over cultivation conditions in standard shake flasks. Microbioreactors can offer the flexibility and controllability of bench-scale reactors and thus deliver results that are more comparable to large-scale fermentations, but with the additional advantages of small size, availability of online cultivation data and the potential for automation. Current microbioreactor technology is analyzed in this review paper, focusing on its industrial applicability, and directions for future research are presented.     

Synthesis of a small library of non-symmetric cyclic sulfamide HIV-1 protease inhibitors

A set of 11 non-symmetric cyclic sulfamide HIV-1 protease inhibitors were synthesized and evaluated. The use of a key microwave-assisted silver(I) oxide mediated selective mono N-benzylation reaction enabled fast and straightforward synthesis. The K_i values of the new inhibitors ranged between 0.28 μM and >20 μM.     

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: Longitudinal relaxation dispersion for spin I = 1

The frequency dependence of the longitudinal relaxation rate, known as the magnetic relaxation dispersion (MRD), can provide a frequency-resolved characterization of molecular motions in complex biological and colloidal systems on time scales ranging from 1 ns to 100 μs. The conformational dynamics of immobilized proteins and other biopolymers can thus be probed in vitro or in vivo by exploiting internal water molecules or labile hydrogens that exchange with a dominant bulk water pool. Numerous water (1)H and (2)H MRD studies of such systems have been reported, but the widely different theoretical models currently used to analyze the MRD data have resulted in divergent views of the underlying molecular motions. We have argued that the essential mechanism responsible for the main dispersion is the exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings when internal water molecules or labile hydrogens escape from orientationally confining macromolecular sites. In the EMOR model, the exchange process is thus not just a means of mixing spin populations but it is also the direct cause of spin relaxation. Although the EMOR theory has been used in several studies to analyze water (2)H MRD data from immobilized biopolymers, the fully developed theory has not been described. Here, we present a comprehensive account of a generalized version of the EMOR theory for spin I = 1 nuclides like (2)H. As compared to a previously described version of the EMOR theory, the present version incorporates three generalizations that are all essential in applications to experimental data: (i) a biaxial (residual) electric field gradient tensor, (ii) direct and indirect effects of internal motions, and (iii) multiple sites with different exchange rates. In addition, we describe and assess different approximations to the exact EMOR theory that are useful in various regimes. In particular, we consider the experimentally important dilute regime, for which approximate analytical results are derived. As shown by the analytical expressions, and confirmed by exact numerical calculations, the dispersion is governed by the pure nuclear quadrupole resonance frequencies in the ultraslow-motion regime, where the relaxation rate also exhibits a much stronger dependence on the electric field gradient asymmetry than in the motional-narrowing regime.