Improved high-performance liquid chromatographic method for the simultaneous determination of caffeine and its N-demethylated metabolites in plasma using solid-phase extraction

An improved high-performance liquid chromatographic method for the simultaneous determination of caffeine and its N-demethylated metabolites in plasma is described. Excellent resolution of all components is provided by reversed-phase chromatography using a mobile phase consisting of 1% acetic acid-methanol (83:17) at a flow-rate of 2.7 ml/min, in conjunction with a Waters Assoc. Nova-Pak C18 column which was protected by a Waters Assoc. Guard-Pak precolumn module containing a Guard-Pak CN cartridge. Rapid extraction of caffeine and the dimethylxanthines from plasma was achieved using reversed-phase octadecylsilane bonded-silica columns (Bond-Elut C18). With only 100 microliters of sample, plasma levels in the region of 50 ng/ml for the dimethylxanthines and 100 ng/ml for caffeine can be determined using ultraviolet detection at 273 nm. The method has been used for measuring umbilical cord plasma samples to provide information regarding foetal exposure to caffeine and its metabolites and is also suitable for therapeutic drug monitoring of caffeine and theophylline levels in the treatment of neonatal apnoea.     

Composition and thermal stability of SiO2-based hybrid materials TEOS-MTEOS system

Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS (tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties. To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of the gels is rather influenced by their composition than the conditions of the gelation process. This revised version was published online in July 2006 with corrections to the Cover Date.     

On simple periodic linear groups— Dense subgroups,permutation representations,and induced modules

We determine the Zariski-dense subgroups of Chevalley groups and their twisted analogues over infinite algebraic extensions of finite fields. It turns out that these are essentially forms of the same group (possibly becoming twisted) over smaller infinite fields. It follows from our classification that if is a simple algebraic group over the algebraic closure of a finite field, then a dense subgroup of can never be maximal, and so the maximal subgroups of are necessarily closed. It follows that Seitz’s determination of the closed maximal subgroups of actually gives all the maximal subgroups. It also enables us to prove that ifG is a simple Chevalley group or twisted type over an infinite algebraic extension of a finite field, then in every non-trivial permutation representation ofG, every finite subgroup has a regular orbit. It follows that every non-trivial permutation module forG over a fieldk iskG-faithful. This is relevant to a programme of studying ideals in group rings of simple locally finite groups. To John Thompson in recognition of his many outstanding contributions to group theory     

Evaluation and validation of the ABI 3700, ABI 3100, and the MegaBACE 1000 capillary array electrophoresis instruments for use with short tandem repeat microsatellite typing in a forensic environment

The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer.     

Detection of chiral perturbations in ferroelectric liquid crystals induced by an atropisomeric biphenyl dopant

The atropisomeric dopant 2,2',6,6'-tetramethyl-3,3'-dinitro-4,4'-bis[(4-nonyloxybenzoyl)oxy]biphenyl (1) induces a ferroelectric SmC phase when doped into the SmC liquid crystal hosts 2-(4-butyloxyphenyl)-5-octyloxypyrimidine (PhP1) and (+/-)-4-[(4-methylhexyl)oxy]phenyl 4-decyloxybenzoate (PhB). The propensity of dopant 1 to induce a spontaneous polarization (polarization power) is much higher in PhP1 than in PhB (1555 nC/cm(2) vs <35 nC/cm(2)), which is attributed to a greater propensity of 1 to undergo chirality transfer via core-core interactions with PhP1. In previous work, we postulated that a chiral perturbation exerted by 1 in PhP1 amplifies the polarization power of the dopant by causing a chiral distortion of the mean field potential (binding site) constraining the dopant in the SmC host, as described by the Chirality Transfer Feedback (CTF) model. To test the validity of the CTF model, and to provide a more direct assessment of the chiral perturbation exerted by dopant 1 on surrounding host molecules, we measured the effect of 1 on the polarization power of other chiral dopants acting as probes. In one series of experiments, (S,S)-5-(2,3-difluorooctyl)-2-(4-octylphenyl)pyridine (MDW950) and (S)-4-(1-methylheptyloxy)phenyl 4-decyloxybenzoate (4), which mimic the structures of PhP1 and PhB, were used as probes. In another series of experiments, the atropisomeric dopant 2,2',3,3',6,6'-hexamethyl-4,4'-bis[(4-nonyloxybenzoyl)oxy]biphenyl (2) was used as probe in PhP1. The results of the probe experiments suggest that dopant 1 exerts a much stronger chiral perturbation in PhP1 than in PhB. More significantly, the results of experiments using 2 as probe show that the chiral perturbation exerted by 1 can amplify the polarization power of another atropisomeric dopant, thus providing the first experimental evidence of the CTF effect.     

Radiation dose contribution from coal-slags used as structural building material

A significant dose contribution on the population could be derived from coal slags used as isolation material. Extremely high natural activities are measured in the coal slag, derived from the region of the settlement Ajka, Hungary. In some buildings monitored, the elevated -doses were nearly 5–10 times higher than the world average ones. The annual average indoor radon concentrations from the slag exceeded 400 Bq/m³ and in some cases up to 1200 Bq/m³. Due to the elevated exposure and the radon concentrations in the dwellings the annual dose was estimated to 8–24 mSv/y more than 5–10 times of the world average one.     

Synthesis of 2-substituted benzofurans and indoles using functionalized titanium benzylidene reagents on solid phase

Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride. The titanium benzylidenes converted Merrifield and Wang resin-bound esters into enol ethers. The oxygen nucleophile was masked as a TMS ether, and when the resin-bound enol ethers bearing this ortho substituent were treated with 1% TFA in dichloromethane, benzofurans were released from resin in high yields. The chameleon catch strategy ensured excellent purity. In a similar way, N-alkylated and N-silylated tert-butyl carbamates were used for the synthesis of N-alkyl and N-Boc indoles, respectively. These traceless solid-phase syntheses of heterocycles are believed to involve postcleavage modification rather than cyclative termination.     

Entanglement for the masses

Circular electron accelerators are extensively used as wide spectrum sources of photons for research in several fields of science. The basic principles and methods underlying the applications of synchrotron radiation are outlined, and its unique potential illustrated with selected examples.