Determination of cyclosporin A in the serum of kidney transplant patients by rapid-flow fractionation and normal-phase high-performance liquid chromatography

High-performance liquid chromatography was used to determine cyclosporin A (CsA) concentrations in the serum of kidney transplant patients by rapid-flow fractionation (RFF) followed by silica gel normal-phase high-performance liquid chromatography (HPLC). The extraction of CsA from serum was achieved by RFF using a short diatomaceous earth column eluted with diethyl ether-n-hexane (50:50, v/v). The recovery was more than 80% at concentrations of 50-150 micrograms/l. The concentration of this compound was determined by HPLC using a conventional silica gel column with 3.3 M ammonia solution-ethanol-n-hexane (0.31:10.69:89, v/v) as eluent. Concentration calibration was made on the basis of the peak-height ratio of CsA to CsD as the internal standard. The coefficient of variation of this assay was less than 6.5% and the results were used for the therapeutic drug monitoring of CsA administered to kidney transplant patients. Measurements of the CsA concentrations in 160 serum specimens were also made by conventional radioimmunoassay (RIA) using commercial kits. The data obtained by RIA were on average 2.5 times those obtained by HPLC. Higher values in RIA were observed characteristically with patients with severe disfunction resulting from CsA hepatotoxicity. From the results, it appeared that HPLC rather than RIA provides more precise and reliable values for the concentration of this drug.     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

The control of very low oxygen partial pressures with stabilized zirconia cell

Control of very low oxygen partial pressures was performed in the range of 10⁻²¹-10⁻²⁴ Pa at 750°C by pumping oxygen into the purified hydrogen stream with a stabilized zirconia cell. The oxygen partial pressures were monitored by a stabilized zirconia sensor. The stabilized zirconia oxygen sensor was calibrated by H₂-CO₂ gas buffer mixture in the range of oxygen pressure from 10⁻¹⁷ to 10⁻²¹ Pa, and oxygen partial pressures below 10⁻²¹ Pa were measured by extrapolating the calibration line to very low oxygen partial pressures. The lowest oxygen partial pressure controlled was 10⁻²⁴ Pa at 750°C, which was limited by gas leaks in the system and also by the reduction of the ionic transference number in solid electrolyte used as the oxygen pump.     

Preparation, properties, and reduction of a novel TCNQ-type thienoquinoid

[Structure: see text] TCNQ-type bithienoquinoid condensed with a alpha-dicarbonyl group was synthesized. The compound revealed a reversible reduction wave at +0.32 V vs SCE. The radical anion species was cleanly generated by a reduction with Na-Hg and characterized: lambdamax=1027 nm in vis-NIR and a large spin density of the beta-carbon atoms on the fused ring by EPR spectroscopy. The radical anion salts were isolated by a reduction with iodide and showed moderate conductivity.     

Redox-Induced Modulation of Exchange Interaction in a High-Spin Ground-State Diradical/Triradical System

A triplet ground-state diradical molecule, bis(nitronyl nitroxide)-substituted diphenyldihydrophenazine ( 1 ^..), that can be converted into a one-electron oxidized species, 1 ^{… +} , in the quartet ground state has been developed. Surprisingly, these species, 1 ^.. and 1 ^{… +} , can be used under ambient conditions because they are reasonably stable under aerobic conditions, even in solution. The temperature-dependent magnetic susceptibilities reveal that 1 ^.. and 1 ^{… +} are in the triplet state, with a weak exchange interaction (J₁/k_B = +3.1 K) and quartet ground state with a strong exchange interaction (J₂/k_B = +160 K), respectively. The interconversion between the neutral and one-electron oxidized species can be realized through electrochemical reactions. Significantly different absorption bands in the near-IR region newly appeared in the electronic spectra acquired during electrochemical oxidation/reduction.     

Chemical Stimulus‐responsive Folding and Unfolding of a Dendrimeric Assembly

A dendrimeric trimer undergoes folding and unfolding in response to a chemical stimulus. The trimer of interest contains a central dendrimer with a butadiyne‐linked zinc porphyrin dimer ((ZnP)₂) core, in addition to two terminal dendrimers with zinc porphyrin (ZnP) cores. The obtained absorption spectra indicate that the unfolded form is the exclusive conformer in chloroform, while the addition of 1,4‐diazabicyclo[2.2.2]octane (DABCO) in chloroform leads to transformation from the unfolded to the folded structure containing two DABCO units per trimer; the folded structure originates from the cross‐linking of (ZnP)₂ and ZnP with DABCO. Moreover, the addition of excess DABCO promotes the generation of the unfolded structure containing four DABCO units.     

Stepwise construction of a cross-shaped covalent assembly of dendrimers

A methodology for the stepwise construction of shape-persistent assemblies using snowflake-shaped dendrimers as the key modular building blocks was described. The Sonogashira coupling reaction of A₃B-type Zn-porphyrin with A₄-type free-base porphyrin afforded a cross-shaped covalent assembly. Intramolecular singlet energy transfer from peripheral Zn-porphyrin core to a free-base porphyrin core was observed.