Relativistic calculations on the ground and excited states of AgH and AuH in cylindrical harmonic confinement

The relativistic ground and low-lying excited state potential energy curves of AgH and AuH in the presence of a cylindrical harmonic confining potential were calculated using the multi-state multi-reference perturbation theory with the spin-free no-pair Hamiltonian obtained via the third-order Douglas–Kroll transformation, incorporated with the full two-electron Breit–Pauli spin–orbit operator. The spectroscopic parameters were obtained for both the scalar- and quasi-relativistic potentials. The spin–orbit coupling constants were calculated for several strengths of the confining potential, and the effects of the applied potential on the coupling constants were analyzed using configuration interaction. This paper is dedicated to Serafín Fraga—colleague, mentor, and friend.     

Drag on two nonuniformly structured flocs moving along the axis of a cylindrical tube

The boundary effect on the drag on two identical, nonuniformly structured flocs moving along the axis of a cylindrical tube filled with a Newtonian fluid is investigated at a small to medium larger Reynolds number. A two-layer model is adopted to simulate various possible structures of a floc, and the flow field inside is described by Darcy–Brinkman model. The results of numerical simulation reveal that a convective flow is present in the rear region of a floc when Reynolds number is on the order of 40. The presence of the tube wall and/or the porous structure of a floc has the effect of reducing that convective flow. For a fixed level of the volume-average permeability of a floc, the influence of the tube wall on the drag depends upon floc structure; the influence on a nonuniformly structured floc is more significant than that on a uniformly structured floc. The more nonuniform the floc structure, the more appreciable the deviation of the drag coefficient–Reynolds number curve from a Stokes’-law-like relation becomes. The smaller the volume-average permeability of a floc and/or the smaller the separation distance between the two flocs, the greater is the deviation, but the presence of the tube wall has the effect of reducing that deviation.     

Energy migration and transfer in poly(phenylacetylene)

Studies have been made of energy migration and transfer in dilute solutions of poly(phenylacetylene). In fluid media, “down-chain” energy migration is very efficient (being limited only by chain length in the system studied); however, in a rigid matrix, the energy migration rate is significantly lower. It is suggested that segmental rotation in a fluid environment brings neighbouring chain units into conformations suitable for resonance energy transfer and also breaks conjugated sequences functioning as exciton “traps”. The broad absorption spectrum (and relatively high extinction coefficients) coupled with the efficient transfer of the energy make these substances very efficient energy transfer additives in polymer systems.     

Electrochemical monitoring of indigo preparation using Maya’s ancient procedures

The preparation of indigo from Indigofera suffruticosa following the procedures attributed to ancient Mayas was electrochemically monitored using the voltammetry-of-microparticles approach. The mechanism formation of indigotin and indirubin from its precursors, indican and isatan, is discussed. Comparison of voltammetric profiles for differently prepared and commercial indigos and genuine Maya Blue samples suggests that the preparation procedure of indigo changed during the Late Classical Maya period. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Elemental analysis of Korean women’s blood serums using instrumental neutron activation analysis

Instrumental neutron activation analysis was used to assess the concentration of the inorganic trace elements in Korean women’s blood serums. It was found that a high concentration of Na and Cl incurs an analytical interference, but the 12 elements such as Br, Ca, Cl, Co, Cr, Cs, Fe, K, Na, Rb, Se and Zn could be determined under the condition of an interference minimization. Serum samples collected from 63 women were analyzed and the concentration level and range of the elements were evaluated. NIST SRMs were analyzed simultaneously for quality control. The average values of the Na and Cl determined in the serum samples were 3,365 and 3,533 mg/l, Ca was 96.4 mg/l and K was 191 mg/l. Besides, Br, Se and Zn have a concentration level of 6.46, 0.13 and 0.98 mg/l, respectively. It was found that there is no significant difference between the present values and the reported values.     

Characterisation of poly(neutral red) modified carbon film electrodes; application as a redox mediator for biosensors

The polymer redox mediator, poly(neutral red) (PNR), has been synthesised and characterised electrochemically to investigate the best electropolymerisation and mediation conditions for application in enzyme biosensors and to clarify the mechanism of action. Neutral red was electropolymerised by potential cycling on carbon film electrode substrates by allowing the monomer to be oxidised during the full 20 cycles of polymerisation or reducing the positive limit of the potential window after the first 2 cycles to impede monomer oxidation with a view to obtaining longer polymer chains and a lesser degree of branching. Comparison was made with glassy carbon substrates. The PNR films on carbon film electrodes were characterised using cyclic voltammetry and electrochemical impedance spectroscopy, as well as in glucose biosensors prepared with PNR. Glucose oxidase enzyme was immobilised by encapsulation in silica sol-gel and compared with that obtained by cross-linking with glutaraldehyde. The biosensors were evaluated by chronoamperometry in 0.1 M phosphate buffer saline solution, pH 7.0, and showed evidence of electron transfer between the enzyme cofactor flavin adenine dinucleotide and PNR dissolved in the enzyme layer competing with PNR-mediated electrochemical degradation of H₂O₂ formed during the enzymatic process. This paper is dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday.     

On the structure of histidine and its role in enzyme active sites

A structural refinement is proposed for the mechanistic details of the action of the serine proteases. The proposal involves ring flipping of the imidazole function of the histidine side chain as a vehicle for proton transfer. The geometric feasibility of this motion is established by molecular graphics analysis of the crystal structure of-chymotrypsin. It is suggested that the shape of histidine is as important as its pK _a for its function at the active sites of enzymes.     

Technological quality determination of pharmaceutical disintegrant by DSC cooling and DSC photovisual

A number of disintegrants are available on the market. They improve tablets’ disintegration. The objective of this work is the comparison of the technological quality parameters of disintegrants using different analytical techniques. Three batches of disintegrants and their binary mixtures (water:disintegrants) were investigated. Cooling experiments were used from –30 up to 200°C. The data obtained showed calorimetric differences between the samples. In the binary mixtures water showed different crystallization behaviour from the one found in the literature. According to the results DSC technique helped the quality control of different disintegrants.     

Thermodynamic characterization of different actin isoforms

Summary The thermodynamic properties of the cardiac and skeletal a-actin isoforms were studied to characterize the molecular bases of the functional differences between them with the method of differential scanning calorimetry (DSC). The thermal properties of the actin filaments were described in the presence of calcium and magnesium ions as well. Based on the calculated free energy changes the α-cardiac actin filaments appeared to be more stable in its physiologically more relevant, magnesium saturated form. The magnesium saturated form of the α-cardiac actin filaments seemed to be more stable compared to the calcium saturated form of it. The enthalpy and entropy changes could differentiate between the α-cardiac and α-skeletal actin isoforms and between the calcium and magnesium saturated cardiac actin isoforms as well. Our results can demonstrate that the few differences between the amino acid sequences of the α-actin isoforms have an influence on the thermal properties and maybe on the function of these proteins as well.     

Determination of malachite green and leucomalachite green in a variety of aquacultured products by liquid chromatography with tandem mass spectrometry detection

A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for determining the residues of malachite green (MG) and leucomalachite green (LMG) in a number of aquatic species. MG and its metabolite were extracted from homogenized tissues with a perchloric acid-acetonitrile solution; the extract was centrifuged; and an aliquot was taken, concentrated, and passed through a chemically bonded octadecyl C18 solid-phase extraction column. The compounds of interest were eluted with acetonitrile, and the eluate was evaporated to dryness. The residue was dissolved in acetonitrile and diluted with water in preparation for analysis by LC/MS/MS. MG and its metabolite were determined by reversed-phase LC using a Luna C18 column with an ammonium hydroxide-formic acid buffer in acetonitrile gradient and MS/MS detection using multiple reaction monitoring. Calibration curves were linear for all analyses between 5 and 500 pg injected for both analytes, with recoveries ranging from 81% for LMG to 98% for MG in salmon spiked at the 1 ng/g level. Detection limits of 0.1 ng/g for both MG and LMG were easily obtainable using the recommended method. The operational errors, interferences, and recoveries for spiked samples compared favorably with those obtained by established methodology. The recommended method is simple, rapid, and specific for monitoring residues of MG and LMG in a number of aquatic species.