On-line infrared detection in aqueous micro-volume systems

Mid infrared spectroscopy is a non-destructive technique that can provide detailed information on important, molecule-specific features such as the conformation and functional groups of a large range of compounds. Infrared spectroscopy is now an established and frequently used technique for qualitative analysis, i.e. the identification of chemical constituents in a sample. In addition, its use for quantitative purposes has grown dramatically in recent years. It is important to realise that the analytical problem defines the mode of operation and implementation of the FTIR technique. This Highlight article focuses on the advantages and scope of on-line FTIR detection strategies. However, in common with all techniques, on-line FTIR detection has a number of potential shortcomings, which are also discussed.     

Water wafers: structure and melting of a hydrate inclusion compound of a neutral Pt(IV) complex with 1-methylcytosinato ligands

The characterization by X-ray analysis of the trans,trans,trans-[bis(1-methylcytosinate,N4)bis(ammine)bis(hydroxo)platinum(IV)] octahydrate complex (I) reveals an unexpected crystal packing. The neutral complex molecule is hosted by layers, totally built up by water molecules which do not exhibit a direct coordination to metal ions. These corrugated layers are made by puckered eight- and planar four-membered rings of water molecules, held together by hydrogen bonds with an ordered proton arrangement.     

THE CONTROL OF METABOLISM BY BLUE LIGHT IN Acetabularia mediterranea—II. SELECTIVE TRANSLATIONAL CONTROL AND DIFFERENTIAL DEGRADATION OF ENZYMES

Abstract— During prolonged continuous irradiation with red light the specific activity of uridine 5'-diphosphoglucose (UDPG) pyrophosphorylase (uridine 5'-triphosphate: glucose 1-phosphate uridylyl-transferase EC 2.7.7.9) decreased in Acetabularia mediterranea Lamouroux (=A. acetabulum (L.) Silva). Subsequent blue light restored the original activity within a comparatively short period of 3 to 4 days. Computer-aided quantitative evaluation of density labelling experiments showed that the synthesis of the enzyme was accelerated about four-fold during the period of activation by blue light. A similar increase in the rate of synthesis was found for hydroxypyruvate reductase (EC 1.1.1.81), a control enzyme that showed no blue light-dependent changes in the specific activity under these conditions. The increase in the rate of enzyme synthesis was caused by an overall stimulation of the cytosolic translation. Degradation of UDPG pyrophosphorylase was unaffected by blue light, while the half life of hydroxypyruvate reductase was shortened about two-fold compared to continuous red light. Thus, degradation of proteins appears to be selectively light dependent in Acetabularia.
Model calculations for enzyme amount and enzyme synthesis were carried out using the measurements of enzyme activity, rates of cytosolic protein synthesis, and degradation constants of the enzymes. Assuming that activities represented amounts of the given enzymes, these calculations indicated a selective activation of UDPG pyrophosphorylase synthesis by blue light since it did not coincide with the overall stimulation of protein synthesis in the cytosol, in contrast to hydroxypyruvate reductase.     

Proton and antiproton impact ionization of atomic hydrogen and helium

Single ionization of helium and atomic hydrogen by the impact of protons and antiprotons is considered. Using a multiple scattering model, first proposed by Garibotti and Miraglia [1], angular and energy distributions of the ejected electrons are calculated. Structures arising in the cross section, especially the Coulomb density of states effect (CDS), are analysed. The contributions of various scattering amplitudes to the cross section are studied. It is concluded that multiple scattering together with the CDS-effect play an important role in determining the transition amplitude. Differences between particle and antiparticle impact are examined. In addition to the different behaviour of the CDS-effect, the interference of two scattering amplitudes turns out to be decisive in ionization by particle and antiparticle impact.     

Thermodynamic trans-Effects of the Nucleotide Base in the B12 Coenzymes

The thermodynamic effects of the nucleotide coordination on the Co-C bond strengths in the B ₁₂ coenzymes were analyzed. Methyl group transfer reactions from methylcob( III )inamides to cob( II )inamides and cob( I )inamides in neutral aqueous solution were used in equilibration experiments to determine the effect fo the intramolecular coordination of the nucleotide function on the Co-C bond dissociation energies of methylcob( III )alamin ( 4 ). In the equilibrium between 4 , cob( I )inamide ( 11 ), cob( I )alamin ( 10 ) and methylcob( III )inamide 6 (Scheme 2), 4 and 11 were found to predominate ( 4 + 11 ? 10 + 6 , equilibrium constant K_I/III≈0.004), while the equilibrium between 4 , cob( II )inamide 9 , cob( II )alamin ( 5 ), and 6 (Scheme 1) proved to be well balanced ( 4 + 9 ? 5 + 6 , equilibrium constant K_II/III=0.60). These equilibrium values indicate the nucleotide coordination to stabilize the Co–C bond in 4 both against homolysis (slight effect) and against nucleophilic heterolysis (considerable effect). They reflect a stabilization of the complete corrins 4 and 5 by the nucleotide coordination, which is also indicated for 4 and 5 by their (nucleotide) basicity. The latter information, where available for other organocobalamins, allows the analysis of the thermodynamicnucleotide trans effect there as well: e.g. in coenzyme B ₁₂ ( 1 ), the nucleotide coordination is found this way to weaken the Co–C bond towards homolysis by ca. 0.7 kcal/mol.     

Hexaphosphapentaprismane: a new gateway to organophosphorus cage compound chemistry

Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13.     

Synthesis,Characterization, and Crystal Structure of Thallium(I) Complex containing Monodeprotonated 2,6‐Pyridinedicarboxylic Acid

The reaction of an ethanolic solution 2,6‐pyridinedicarboxylic acid ( 1 , LH₂) with TlNO₃ in the presence of triethylamine led to the coordination polymer [Tl(LH)]_n ( 2 ). The complex was characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. Crystal data for 2 at –80 °C: monoclinic, space group I2/a, a = 696.1(1), b = 1190.6(2), c = 931.0(2) pm, β = 103.28(1)°, Z = 4, R₁ = 0.0256.     

Determination of arsenic in sediments, coal and fly ash slurries after ultrasonic treatment by hydride generation atomic absorption spectrometry and trapping in an iridium-treated graphite tube

A simple and reliable method for the determination of arsenic in sediment and in coal without sample digestion, based on hydride generation from slurry samples is proposed. After grinding the samples to a particle size of 50 μm, the sample powder was mixed with aqua regia and hydrofluoric acid in an ultrasonic bath for 30 min. After diluting the mixture with hydrochloric acid, the slurry was allowed to stand for 48 h, and an aliquot was used for hydride generation with sodium borohydride. More than 80% of the arsenic was leached to the aqueous phase under these conditions, except for one sediment sample with very high silica content. The generated arsine was collected in a graphite tube, treated with 0.5 mg of iridium as a permanent modifier, and the arsenic determination was carried out by electrothermal atomic absorption spectrometry. The same tube could be used for at least 160 cycles without any re-treatment. The greatest advantage of the method was that only a minimum of reagents and sample handling were required, reducing the risks of contamination and/or analyte loss. However, the addition calibration technique had to be used in order to obtain results within the 95% confidence level for 11 certified reference materials, 5 sediments, 5 coals and one coal fly ash. One certified sediment slurry was spiked with the analyte and the resulting addition calibration curve was used for the analysis of the certified sediments. Similarly, one certified coal was used to obtain the addition calibration curve for the coal and coal fly ash samples. The recoveries of the certified values, except for one sediment, were between 91 and 115%. The limits of detection in the samples were 0.54 and 0.7 μg g⁻¹ for the coal and sediment samples, respectively, obtained for 1 ml of slurry containing 1 mg of sample.