Metalation reactions. : IV. Metalation of o-alkyl- and o,o′-dialkyl-substituted alkylthiobenzenes

Metalation of o-alkyl- and o,o′-dialkylsubstituted alkylthiobenzenes with n-butyllithium, in the presence and absence of TMEDA, has been investigated. The results showed that metalation at the thioalkyl carbon probably occurs by direct attack of the organolithium reagent, although a transmetalation reaction cannot be excluded in some cases. It has also been found that benzylic, thio-methylic, and ring metalation occurs in ether alone, whereas mainly thio-methylic or ring metalation occurs in the presence of TMEDA.     

BIPHASIC ENERGY CONVERSION KINETICS AND ABSORBANCE DIFFERENCE SPECTRA OF PHOTOSYSTEM II OF CHLOROPLASTS. EVIDENCE FOR TWO DIFFERENT PHOTOSYSTEM II REACTION CENTERS

Abstract— The continuous illumination induced kinetics of photochemical energy conversion at system II have been measured with isolated and 3-(3, 4-dichlorophenyl)-l, l-dimethylurea (DCMU) poisoned chloroplasts by means of absorbance difference spectroscopy in the UV and by the area growth over the fluorescence induction curve at room temperature. An optimal set of conditions was found in order to isolate absorbance changes caused by the reduction of the primary electron acceptor Q of PS II by suppressing other electron transfer processes. The light induced kinetics of Q- accumulation in the absorbance change measurements were found to be biphasic and strictly correlated with the kinetics of the area growth measured under the same conditions. From the resolution of the biphasic kinetics at different wavelengths in the UV region of the spectrum, it was found that both kinetic components in the system II photochemistry involve the reduction of a plastoquinone molecule to its plastosemiquinone anion. From the two kinetic components one was fast and non-exponential and the other relatively slow with an exponential time course. The initial rate difference in the kinetics of the two components was by a factor of approximately 3. A difference by a factor of about three was also found in the flash saturation curves of the two kinetic components.
The results are explained by the hypothesis that in higher plant chloroplasts there are system II reaction centers embedded in a large pigment matrix with statistical energy transfer, and system II reaction centers embedded in separate, in terms of excitation energy transfer, units. The effective absorption cross section per reaction center for the centers in the statistical pigment bed is approximately 3 times larger than that of the reaction centers in the separate system II units. The two types of system II reaction centers have different yields of excitation trapping and charge stabilization properties.     

Low viscosity DNA sieving matrices for capillary electrophoresis

The rapid development of DNA capillary electrophoresis (CE) technology has increased the demand of new low viscosity sieving matrices with high separation capacity. The high throughput, resolution and automatic operation of CE systems have stimulated the application of the technique to different kinds of DNA analysis, including DNA sequencing, separation of restriction fragments, PCR products and synthetic oligonucleotides. In addition specific methods for PCR-based mutation assays for the study of known and unknown point mutations have been developed for use in CE. The key component for a large scale application of CE to DNA analysis is the availability of appropriate sieving matrices. This article gives an overview of the linear polymers used as DNA separation matrices with particular emphasis on the polymers that combine high sieving capacity, low viscosity and chemical resistance.     

Design and use of electrochemical sensors in enantioselective high throughput screening of drugs. A minireview

The importance of reliable detection systems for enantiomeric assays increases with the necessity of high throughput screening analysis of raw materials for the pharmaceutical industry. The utilization of electrochemical sensors in enantioselective analysis is an accurate and precise alternative to chromatographic techniques. The reliability of the response characteristics as well as of the analytical information obtained by using electrochemical sensors is strictly correlated with the design of the sensors. The designs evaluated for sensors have been based on PVC, imprinting polymers and carbon paste matrices. Among these, carbon paste sensors have been the most reliable and have been utilized for the construction of potentiometric, enantioselective membrane electrodes as well as for amperometric biosensors, and immunosensors. There are two ways to use the electrochemical sensors in enantioselective screening analysis: selective binding and catalyst selectivity. A molecule with a special chemical architecture is required for selective binding: a lock for a key. The high reliability of analytical information obtained using these sensors has made possible the automation of potentiometric and amperometric techniques by integration of enantioselective sensors as detectors in flow injection analysis and sequential injection analysis techniques.     

Sivers effect for pion and kaon production in semi-inclusive deep inelastic scattering

We study the Sivers effect in the transverse single spin asymmetries (SSA) for pion and kaon production in semi-inclusive deep inelastic scattering (SIDIS) processes. We perform a fit of which, by including recent high-statistics experimental data for pion and kaon production from HERMES and COMPASS Collaborations, allows a new determination of the Sivers distribution functions for quarks and antiquarks with u , d and s flavours. Estimates for forthcoming SIDIS experiments at COMPASS and JLab are given.     

On the origin of some red soils from Sardinia (Italy): A neutron activation analysis investigation

In Sardinia, the Italian island in the middle of the MediterraneanSea, there are many red soils developed on limestone or dolomite. Soil andunderlying bedrock samples from 5 different sites have been submitted to chemicaland mineralogical characterization, by using standard X-ray diffraction analysis,spectrochemical methods and instrumental neutron activation analysis. Obtainedresults are presented and discussed in terms of precision and accuracy. Traceelement concentration variation with depth is discussed as well as the enrichment/depletionratios between soils and rocks, and the rare-earth element distribution. Dataanalysis suggests for some soils a formation process based on the evolutionof the underlying bedrock, and for the other soils a formation process partlybased on the evolution of the local rock but with meaningful contributionsof external sources, both eolian and/or alluvial.     

X-ray structural investigation on a series of polyesteramides

The crystal structures of three polyesteramides of the type conventionally referred to as nNTm, i.e. 6NT6, 12NT6 and 12NT12, were investigated by X-ray diffraction methods. The copolymers crystallize with triclinic symmetry and the repeat distances along the chain axis are 31.78(8), 39.27(20) and 46.77(15) Å, respectively. In 6NT6, the crystal structure of which was studied in more detail, the conformation of the molecular chain displays some departure from the fully extended form, particularly by rotation of the amide and the ester groups (about 26 and 15°, respectively) away from the plane of the benzene ring. Layers of chains, linked together by intermolecular hydrogen bonds, are formed. For the other two copolymers. evidence was obtained for a rather close isomorphism. A model of a structural disorder is proposed and discussed for the 6NT6 copolymer.