Reactions of ketenes with ethoxyalkynes: Synthesis of 2,2,4-trialkylcyclobutane-1,3-diones

Treatment of dimethyl ketene with ethoxyacetylene 1a, 1-ethoxyoct-1-yne 1b, and 1-ethoxytetrade-1-yne 1c afforded the 3-ethoxycyclobutenones 2a–c. Hydrolysis of 2a–c with dilute hydrochloric acid gave the cyclobutane-1,3-diones 3a–c. The ¹H NMR spectra of these compounds indicate that in CDCl₃ solution 2,2-dimethylcyclobutane-1,3-dione 3a exists as the diketone, whereas the 2,2,4-trialkylcyclobutane-1,3-diones 3b and 3c exist as the monoenols.     

Charge stabilization in nonpolar solvents

While the important role of electrostatic interactions in aqueous colloidal suspensions is widely known and reasonably well-understood, their relevance to nonpolar suspensions remains mysterious. We measure the interaction potentials of colloidal particles in a nonpolar solvent with reverse micelles. We find surprisingly strong electrostatic interactions characterized by surface potentials, |ezeta|, from 2.0 to 4.4 k(B)T and screening lengths, kappa(-1), from 0.2 to 1.4 microm. Interactions depend on the concentration of reverse micelles and the degree of confinement. Furthermore, when the particles are weakly confined, the values of |ezeta| and kappa extracted from interaction measurements are consistent with bulk measurements of conductivity and electrophoretic mobility. A simple thermodynamic model, relating the structure of the micelles to the equilibrium ionic strength, is in good agreement with both conductivity and interaction measurements. Since dissociated ions are solubilized by reverse micelles, the entropic incentive to charge a particle surface is qualitatively changed from aqueous systems, and surface entropy plays an important role.     

Effect of dose on radiation-induced conductivity in polymers

Numerical simulation of radiation-induced conductivity in polymers upon long-term irradiation on the basis of the generalized Rose-Fowler-Vaisberg model, which allows for both dipolar carrier transport and generation of radiation traps during irradiation, was performed. The unusual properties of radiation-induced conductivity, such as the appearance of a maximum on current transients, the absence of a steady state, and a substantial difference between these curves for the first and subsequent irradiation, are rationalized in terms of the formation of free radicals, the major feature of radiolysis in the chemical aspect. This interpretation does not require the involvement of degradation or crosslinking processes, unlike other interpretations that appear in the literature. With the use of low-density polyethylene as an example, it was shown that radiation-induced conductivity both upon pulse and continuous irradiation can satisfactorily be described with the unified set of parameters of the generalized Rose-Fowler-Vaisberg model.     

Amorphous-amorphous transition in glassy polymers subjected to cold rolling studied by means of positron annihilation lifetime spectroscopy

In this study, polycarbonate (PC) and polystyrene (PS) are subjected to plastic deformation by means of cold rolling and the resulting variation of the free volume and its subsequent time evolution after rolling is investigated by means of positron annihilation lifetime spectroscopy (PALS). The value of the long lifetime component that is attributed to the decay of ortho-positronium (tau(o-Ps)) and its intensity (I(o-Ps)) are used to characterize, respectively, the size and the concentration of the free-volume holes. In addition to the PALS experiments, the effect of plastic deformation on the dynamic tensile modulus is investigated. The PALS results show that both for well-aged PC and PS an increase of tau(o-Ps) and a decrease of I(o-Ps) occur upon plastic deformation. During the subsequent aging, tau(o-Ps) tends to return to the value assumed before plastic deformation, while I(o-Ps) remains constant with time. These results corroborate the idea of an amorphous-amorphous transition, rather than that of a "mechanical rejuvenation" as proposed in the past to explain the ability of plastic deformation to reinitiate physical aging. Finally, a linear relation between the size of the free-volume holes and the dynamic tensile modulus is found, which suggests that the stiffness of amorphous glassy polymers is fully determined by their nanoscopic structure.     

Anisotropic muon Knight shift in the HCP single crystals of Cd,Zn and Be

In single crystal samples of Zn, Cd and Be (hcp structure) stroboscopicSR measurements successfully revealed anisotropies in the muon Knight shift (K). An anisotropic K can provide information on the amount of non s-electrons screening the charge of the muon implanted in these metals as a light hydrogen isotope. In Cd, the anisotropic part depends strongly on the temperature and shows a change in sign at roughly 110 K. In Zn, the anisotropic part below 10 K turns out to comprise 4th order contributions in the direction cosines of the external field. This can be understood on the basis of an anisotropicg-factor of the conduction electrons or spin-orbit coupling, respectively.     

Nontrivial fixed points in three-dimensional Abelian Higgs models with fermions

Exact expressions (in the limit N) for the renormalization group functions of the general class of three-dimensional Abelian Higgs models with fermions are obtained. They are shown to possess several nontrivial infrared and ultraviolet stable fixed points corresponding to models with nonlinear constraints.     

In vitro high throughput screening of compounds for favorable metabolic properties in drug discovery

Drug metabolism can have profound effects on the pharmacological and toxicological profile of therapeutic agents. In the pharmaceutical industry, many in vitro techniques are in place or under development to screen and optimize compounds for favorable metabolic properties in the drug discovery phase. These in vitro technologies are meant to address important issues such as: (1) is the compound a potent inhibitor of drug metabolising enzymes (DMEs)? (2) does the compound induce the expression of DMEs? (3) how labile is the compound to metabolic degradation? (4) which specific enzyme(s) is responsible for the compound's biotransformation? and (5) to which metabolites is the compound metabolized? Answers to these questions provide a basis for judging whether a compound is likely to have acceptable pharmacokinetic properties in vivo. To address these issues on the increasing number of compounds inundating the drug discovery programs, high throughput assays are essential. A combination of biochemical advances in the understanding of the function and regulation of DMEs (in particular, cytochromes P450, CYPs) and automated analytical technologies are revolutionizing drug metabolism research. Automated LC-MS based metabolic stability, fluorescence, radiometric and LC-MS based CYP inhibition assays are now in routine use. Automatible models for studying CYP induction based on enzyme activity, quantitative RT-PCR and reporter gene systems are being developed. We will review the utility and limitations of these HTS approaches and highlight on-going developments and emerging technologies to answer metabolism questions at the different stages of the drug discovery process.     

On-line preconcentration of inorganic mercury and methylmercury in sea-water by sorbent-extraction and total mercury determination by cold vapour atomic absorption spectrometry

A comparative study of three mercury chelate forming reagents [diethyldithiocarbamate, pyrrolidin-1-yldithioformate and diphenylthiocarbazone (dithizone)] has been carried out for the preconcentration of ultratrace amounts of inorganic mercury and methylmercury in silica C(18) minicolumns as the solid sorbent. Sample flow injection in-line sorbent extraction was coupled with continuous cold vapour atomic absorption spectrometry (CVAAS) for detection. Results showed the superiority of the carbamate type reagents over the dithizone for the on-line formation and preconcentration of the corresponding mercury chelates. Using diethyldithiocarbamate (DDC) as reagent, aqueous sample volumes of 100 ml can be preconcentrated with 100% efficiency for both inorganic mercury and methylmercury. Quantitative release of the retained DDC chelates was obtained for volumes of eluent (ethanol) of 50 microl. Following the proposed procedure, detection limits of 16 ng/l. of mercury were achieved for sample volumes of 25 ml. The relative standard deviation was +/- 3.4% at 0.5 microg/l. Hg(II) levels. The method has been successfully applied to the determination of low levels of mercury in sea-water.     

Direct determination of the enantiomeric purity of oxyphenonium using chiral HPLC with post-column extraction detection

Summary A method is described for the determination of the enantiomeric purity (enantiomeric excess) of the anticholinergic drug oxyphenonium. The method for this quaternary ammonium compound is based on the direct HPLC analysis with a chiral stationary phase. Two kinds of 1-acid glycoprotein-bonded phases were used.For the detection a post-column extraction with fluorescence detection of the ion-pair counter ion dimethoxyantracene sulphonate was used.