N-isobutyloxycarbonylation for improved detection of 3'-hydroxystanozolol and its 17-epimer in doping control

An improved screening method was developed for 3'-hydroxystanozolol and its 17-epimer in human urine involving gas chromatography-mass spectrometry (GC-MS) with N-isobutyloxycarbonyl (isoBOC) and O-trimethylsilyl (TMS) derivatization. A procedure was reported previously for the pentane extraction of many steroids from urine in doping control, but it was not suitable for the detection of stanozolol metabolites. Compared with the n-pentane extraction method, which gave a poor recovery (< 10%), isoBOC extraction resulted in a good recovery (> 80%). The sensitivity and specificity of mixed N-isoBOC-O-TMS derivatization were adequate for the detection of 3'-hydroxystanozolol and its 17-epimer when 3 ml of urine was used with spiking at a level of 2 ng ml-1. When applied to a stanozolol-positive urine sample, the proposed method allowed rapid and sensitive screening for the detection of 3'-hydroxystanozolol and its 17-epimer.     

Thermal properties of bio flour-filled polypropylene bio-composites with different pozzolan contents

In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric curve (DTG_max) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T _g), melting temperature (T _m) and percentage of crystallinity (X _c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X _c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was an effective method for enhancing the thermal stability and thermal expansion.     

Alcohol sensing membrane based on immobilized ruthenium(II) complex in carboxylated PVC and surface covalently bonded alcohol oxidase

Alcohol sensing membranes coated on overhead transparency films for the continuous monitoring of ethanol, propanol and butanol are presented. Alcohol oxidation catalyzed by alcohol oxidase in conjunction with the fluorescence quenching reaction of oxygen-sensitive dye ion-pair, tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) didodecylsulphate was chosen for the determination. Alcohol oxidase was immobilized covalently on a plasticized carboxylated poly(vinyl chloride) membrane and the oxygen-sensitive dye ion-pair was entrapped in the same membrane. The sensing membrane relates oxygen consumption, as a result of enzymatic oxidation, to alcohol concentration. Measurements have been performed in air-saturated alcohol standard solutions of pH 7.0. Storage stability, reproducibility and the effect of pH on sensing membrane performance have been studied in detail. The alcohol sensing membrane proposed here is simple to prepare and has a fairly rapid response time of <1 min. It has been successfully applied to the determination of the ethanol contents in various spirits.     

Determination of copper(II) in various samples by flame atomic absorption spectrophotometry after column preconcentration onto pulverized Amberlite XAD-4 loaded with N-benzoylphenylhydroxylamine

A sensitive technique for the determination of trace Cu(II) in various samples after column preconcentration by adsorbing onto pulverized Amberlite XAD-4 loaded with N-benzoylphenylhydroxylamine (BPHA) was developed. Several experimental conditions, such as the size of XAD-4, adsorption flow rate, pH of sample solution, and so forth, were optimized. The interfering effects of diverse concomitant ions were investigated. Al(III), Fe(III), Ni(II), and Co(II) interfered, but the interference by these ions was completely eliminated by adjusting the amount of XAD-4-BPHA resin to 0.30 g. The dynamic range, the correlation coefficient (R₂), and the detection limit obtained by the proposed technique were 1.0–60, 0.9953, and 0.83 ng/mL, respectively. For validating the technique, the aqueous samples (stream water, reservoir water, and wastewater), the diluted brass sample, and the plastic sample were used as real samples. Recovery yields of 94–102% were obtained. These measured data were not different from ICP-MS data at the 95% confidence level. This method was also validated by rice flour CRM (normal, fortified) samples. Based on the results of the experiment, it has been found that the proposed technique can be applied to the determination of Cu(II) in various real samples. The text was submitted by the authors in English.     

Tuning chirality of single-wall carbon nanotubes by selective etching with carbon dioxide

CO2 molecule chemisorbs selectively on the zigzag tube edge without an activation barrier, whereas it physisorbs on the armchair edge of nanotubes. In addition, carbon nanotubes can be etched by an adsorbed oxygen atom of CO2 molecule. From our results, we suggest a selective etching mechanism for tuning the chirality of the mass-produced carbon nanotubes.     

Oxidation of guanosine derivatives by a platinum(IV) complex: internal electron transfer through cyclization

Many transition-metal complexes mediate DNA oxidation in the presence of oxidizing radiation, photosensitizers, or oxidants. The DNA oxidation products depend on the nature of the metal complex and the structure of the DNA. Earlier we reported trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum (trans-Pt(d,l)(1,2-(NH(2))(2)C(6)H(10))Cl(4), [Pt(IV)Cl(4)(dach)]; dach = diaminocyclohexane) oxidizes 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) to 7,8-dihydro-8-oxo-2'-deoxyguanosine 5'-monophosphate (8-oxo-5'-dGMP) stoichiometrically. In this paper we report that [Pt(IV)Cl(4)(dach)] also oxidizes 2'-deoxyguanosine 3'-monophosphate (3'-dGMP) stoichiometrically. The final oxidation product is not 8-oxo-3'-dGMP, but cyclic (5'-O-C8)-3'-dGMP. The reaction was studied by high-performance liquid chromatography, (1)H and (31)P nuclear magnetic resonance, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The proposed mechanism involves Pt(IV) binding to N7 of 3'-dGMP followed by nucleophilic attack of a 5'-hydroxyl oxygen to C8 of G and an inner-sphere, 2e(-) transfer to produce cyclic (5'-O-C8)-3'-dGMP and [Pt(II)Cl(2)(dach)]. The same mechanism applies to 5'-d[GTTTT]-3', where the 5'-dG is oxidized to cyclic (5'-O-C8)-dG. The Pt(IV) complex binds to N7 of guanine in cGMP, 9-Mxan, 5'-d[TTGTT]-3', and 5'-d[TTTTG]-3', but no subsequent transfer of electrons occurs in these. The results indicate that a good nucleophilic group at the 5' position is required for the redox reaction between guanosine and the Pt(IV) complex.     

Isolation of a potent anti-MRSA sesquiterpenoid quinone from Ulmus davidiana var. japonica

A highly potent anti-MRSA sesquiterpenoid has been isolated from Ulmus davidiana var. japonica, which has been traditionally used to treat infectious diseases in Korea. This naturally occurring antibiotic was identified as mansonone F (1). This compound has been found to be highly active specifically against MRSA and showed an MIC range of 0.39-3.13 microg/ml which is comparable to that of vancomycin.     

Analysis of an ancient bronze statue by external beam pixe

A quantitative analysis of an ancient Buddha statue was performed by external beam Proton Induced X-ray Emission for the purpose of identifying its originality. It is shown how the PIXE method can be applied for archeological study. The elemental composition of the statue is compared with that of several samples with definite ages. The experiment was performed by extracting 2.4 MeV proton beam through a 2 mm diameter collimator and 7.6 m kapton foil to the He atmosphere. X-rays were measured by a Si(Li) detector. The analysed elements were Fe, Cu, Ag, Au and Hg for gold coating and Fe, Ni, Cu, Zn, As, Ag, Sn, Au, Pb and Bi for bronze body.     

Imidazole-based excited-state intramolecular proton-transfer materials: synthesis and amplified spontaneous emission from a large single crystal

We have synthesized a novel class of imidazole-based excited-state intramolecular proton-transfer (ESIPT) materials, i.e., hydroxy-substituted tetraphenylimidazole (HPI) and its derivative HPI-Ac, which formed large single crystals exhibiting intense blue fluorescence and amplified spontaneous emission (ASE). Transparent, clear, and well-defined fluorescent single crystals of HPI-Ac as large as 20 mm x 25 mm x 5 mm were easily grown from its dilute solution. From the X-ray crystallographic analysis and semiempirical molecular orbital calculation, it was deduced that the four phenyl groups substituted into the imidazole ring of HPI and HPI-Ac allowed the crystals free from concentration quenching of fluorescence by limiting the excessive tight-stacking responsible for intermolecular vibrational coupling and relevant nonradiative relaxation. Fluorescence spectral narrowing and efficient ASE were observed in the HPI-Ac single crystal even at low excitation levels attributed to the intrinsic four-level ESIPT photocycle.     

Characterization and epitope mapping of two monoclonal antibodies against human CD99

CD99 plays a critical role in the diapedesis of monocytes, T cell differentiation, and the transport of MHC molecules. Engagement of CD99 by agonistic monoclonal antibodies has been reported to trigger multifactorial events including T cell activation as well as cell-cell adhesion during hematopoietic cell differentiation. In this study, to identify the functional domains participating in the cellular events, we mapped the epitopes of CD99, which are recognized by two agonistic CD99 monoclonal antibodies, DN16 and YG32. Using recombinant fusion proteins of GST with whole or parts of CD99, we found that both antibodies interact with CD99 molecules independently of sugar moieties. DN16 mAb detected a linear epitope located in the amino terminal region of CD99 while YG32 mAb bound another linear epitope in the center of the extracellular domain. To confirm that the identified epitopes of CD99 are actually recognized by the two mAbs, we showed the presence of physical interaction between the mAbs and the fusion proteins or synthetic peptides containing the corresponding epitopes using surface plasmon resonance analyses. The dissociation constants of DN16 and YG32 mAbs for the antigen were calculated as 1.27 x 10(-7) and 7.08 x 10(-9) M, respectively. These studies will help understand the functional domains and the subsequent signaling mechanism of CD99.