A fluorimetric determination of lecithin-cholesterol acyltransferase in blood plasma

A fluorimetric assay for lecithin-cholesterol acyltransferase in human plasma (normal and pathological) is described. The lowered cholesterol concentration in the enzyme reaction is determined fluorimetrically by using the cholesterol oxidase—peroxidase —tyramine system. The assay requires only 10 μl of plasma.     

A new synthetic method: Direct replacement of the nitro group by hydrogen or deuterium

The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively.     

Effects of hydrophobic chain length on the characteristics of the micelles of octaoxyethylene tetradecyl C(14)E(8), hexadecyl C(16)E(8), and octadecyl C(18)E(8) ethers

Size, shape, and flexibility of micelles of octaoxyethylene tetradecyl C(14)E(8), hexadecyl C(16)E(8), and octadecyl C(18)E(8) ethers in dilute aqueous solutions were determined at finite surfactant concentrations c by static light scattering (SLS) and dynamic light scattering experiments at several temperatures T below the critical points. The SLS results were successfully analyzed with the aid of the thermodynamic theory formulated with wormlike spherocylinder model for SLS of micelle solutions. The analysis yielded the molar mass M(w) of the micelles as a function of c and the cross-sectional diameter d. The hydrodynamic radius R(H) and the radius of gyration S(2)(1/2) of the micelles as functions of M(w) were found to be also well-described by the corresponding theories for the wormlike spherocylinder or wormlike chain models. The results of the stiffness parameter lambda(-1) have revealed that the micelles are far from rigid rods but rather stiff compared with typical flexible polymers and they grow in size with increasing T to greater length for longer hydrophobic chains, i.e., alkyl groups of the surfactants. As the alkyl group becomes longer, the d value increased, while the spacings s between adjacent hexaoxyethylene chains on the micellar surface were found to remain substantially constant.     

On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III).The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 μg l⁻¹, respectively. The total analysis time was about 9.4 min.The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results.     

Formulation of Aluminum Chloride Phthalocyanine in Pluronic™ P‐123 and F‐127 Block Copolymer Micelles: Photophysical properties and Photodynamic Inactivation of Microorganisms

Aluminum Chloride Phthalocyanine (AlPcCl) can be used as a photosensitizer (PS) for Photodynamic Inactivation of Microorganisms (PDI). The AlPcCl showed favorable characteristics for PDI due to high quantum yield of singlet oxygen (Φ_Δ) and photostability. Physicochemical properties and photodynamic inactivation of AlPcCl incorporated in polymeric micelles of tri‐block copolymer (P‐123 and F‐127) against microorganisms Staphylococcus aureus, Escherichia coli and Candida albicans were investigated in this work. Previously, it was observed that the AlPcCl undergoes self‐aggregation in F‐127, while in P‐123 the PS is in a monomeric form suitable for PDI. Due to the self‐aggregation of AlPcCl in F‐127, this formulation did not show any effect on these microorganisms. On the other hand, AlPcCl formulated in P‐123 was effective against S. aureus and C. albicans and the death of microorganisms was dependent on the PS concentration and illumination time. Additionally, it was found that the values of PS concentration and illumination time to eradicate 90% of the initial population of microorganisms (IC₉₀ and D₉₀, respectively) were small for the AlPcCl in P‐123, showing the effectiveness of this formulation for PDI.     

Changes of electrochemical responses of the bulk solution species by thermotropic permeability of liquid crystalline membranes coated on electrodes

Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)^3?₆ ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)^—₆ at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)^3?₆ in a bulk solution was examined in order to understand the transport process of Fe(CN)^?3₆ through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)^3?₆ within the membrane was found to obey Fick's Law.     

Surface reaction of alkynes and alkenes with H-Si(111): a density functional theory study

Recent experiments on the addition of alkene and alkyne molecules to H-terminated silicon surfaces have provided evidence for a surface chain reaction initiated at isolated Si dangling bonds and involving an intermediate carbon radical state, which, after abstraction of a hydrogen atom from a neighboring Si-H unit, transforms into a stable adsorbed species plus a new Si dangling bond. Using periodic density functional theory (DFT) calculations, together with an efficient method for determining reaction pathways, we have studied the initial steps of this chain reaction for a few different terminal alkynes and alkenes interacting with an isolated Si dangling bond on an otherwise H-saturated Si(111) surface. Calculated minimum energy pathways (MEPs) indicate that the chain mechanism is viable in the case of C(2)H(2), whereas for C(2)H(4) the stabilization of the intermediate state is so small and the barrier for H-abstraction so (relatively) large that the molecule is more likely to desorb than to form a stable adsorbed species. For phenylacetylene and styrene, stabilization of the intermediate state and decrease of the H-abstraction barrier take place. While a stable adsorbed species exists in both cases, the overall heat of adsorption is larger for the alkyne molecules.     

Multiplex amplified product-length polymorphism analysis of 36 mitochondrial single-nucleotide polymorphisms for haplogrouping of East Asian populations

We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations.     

Synthesis and photophysical properties of luminescent mononuclear and dinuclear gold(I) complexes with ethynyl-substituted phenanthrolines

A novel asymmetric dinuclear gold(I) complex with 3,6-diethynylphenanthroline, 3,6-bis{(PPh₃)–Au–C≡C}₂-phen, has been synthesized from Au(PPh₃)Cl (PPh₃ = triphenylphosphine) and 3,6-diethynyl-1,10-phenanthroline. The asymmetrical dinuclear gold(I) complex, 3,6-bis{(PPh₃)–Au–C≡C}₂-phen, demonstrated a weak phosphorescence assignable to the metal-perturbed ³ π–π* transition in the long wavelength region compared to an intense emission of the symmetrical dinuclear complex with 3,8-diethynylphenanthroline, 3,8-bis{(PPh₃)–Au–C≡C}₂-phen. A similar tendency of phosphorescent bands for the mononuclear gold(I) complexes with 5-ethynylphenanthroline, 5-{(PPh₃)–Au–C≡C}-phen, and 3-ethynylphenanthroline, 3-{(PPh₃)–Au–C≡C}-phen was observed. The absorption bands assignable to the π–π*(C≡Cphen) transition and phosphorescent emission assignable to the metal-perturbed ³ π–π* transition for these four gold(I) complexes were reasonably consistent with the results calculated by DFT and TD-DFT.     

Chromatographic determination of sulfasalazine and its active metabolites: greenness assessment and application to spiked human plasma

Green TLC-densitometric and RP-HPLC methods were developed and validated for the determination of the active prodrug sulfasalazine (SZ), its active metabolite mesalazine (MZ) and the major active metabolite of mesalazine, N-acetyl-5-aminosalicylic acid (AS). In the developed TLC-densitometric method, chromatographic separation was carried out on TLC silica gel plates 60 F₂₅₄ using a developing system consisting of ethyl acetate–methanol–ammonia solution 33% (8:2.5:0.3, by volume) and then scanning the separated bands at 215 nm using hydrochlorothiazide as an internal standard with linearity ranges of 0.4–3, 0.4–2.4 and 0.3–2 for SZ, MZ and AS, respectively. The developed RP-HPLC method depended on chromatographic separation using a C₁₈ column with a solvent mixture of methanol–aqueous acetic acid solution (pH 5) as a mobile phase with gradient elution mode and UV scanning at 243 nm using pyrazinamide as internal standard with linearity ranges of 5–50, 5–40, and 3–20 for SZ, MZ and AS, respectively. US Food and Drug Administration guidelines were followed during validation of the methods. The greenness of the developed methods was estimated using the greenness profile and the Eco-Scale approach. Both methods passed the four quadrants of the greenness profile and had Eco-Scale score ˃75, thus they were considered to be green according to these approaches.