Development of sensitive derivatization method for aldosterone in liquid chromatography-electrospray ionization tandem mass spectrometry of corticosteroids

A highly sensitive quantification method of aldosterone by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was investigated in a positive mode using recently developed picolinyl derivatization. Aldosterone was smoothly and quantitatively converted to the ethyl ether-picolinyl derivative by treatment with HCl-ethanol followed by the esterification with picolinic acid in the presence of 2-methyl-6-nitrobenzoic anhydride and 4-dimethylaminopyridine. The positive ion-ESI mass spectrum of the ethyl ether-picolinyl derivative was characterized by an appearance of protonated molecule ([M+H](+)) as a base peak. The ethyl ether-picolinyl derivatization gave a successful result in a separation of aldosterone from corticosterone, dehydrocorticosterone and cortexolone, and also provided an approximately 10-fold higher ESI response in the positive-LC-ESI-MS/MS (selected reaction monitoring; SRM) when compared to that of underivatized molecule (negative mode). The limit of quantification of aldosterone by SRM using ethyl ether-picolinyl derivatization (m/z 494-->m/z 448) was 1 pg/0.2 ml serum with accuracy and precision of 92.6% and 5.6%, respectively.     

Synthesis of diphenylmethyl analogues and their affinity for the melanocortin-4 receptor and the serotonin transporter

While examining antagonists of the melanocortin-4 receptor (MC4 receptor), we found that compound 12b, containing a diphenylmethyl moiety, had a relatively high affinity for the MC4 receptor. When diphenylmethyl analogues were further examined, compounds 12c and 18 were also found to exhibit a high affinity for the MC4 receptor (IC(50)=46.7 nM and 33.2 nM, respectively). Furthermore, compound 12c was also found to show a high affinity for the serotonin transporter (IC(50)=10.7 nM). Here, we describe the synthesis and biological evaluation of various diphenylmethyl analogues in relation to their actions on the MC4 receptor and the serotonin transporter.     

Direct and Indirect Bactericidal Effects of Cold Atmospheric-Pressure Microplasma and Plasma Jet

The direct and indirect bactericidal effects of dielectric barrier discharge (DBD) cold atmospheric-pressure microplasma in an air and plasma jet generated in an argon-oxygen gas mixture was investigated on Staphylococcus aureus and Cutibacterium acnes. An AC power supply was used to generate plasma at relatively low discharge voltages (0.9–2.4 kV) and frequency (27–30 kHz). Cultured bacteria were cultivated at a serial dilution of 10⁻⁵, then exposed to direct microplasma treatment and indirect treatment through plasma-activated water (PAW). The obtained results revealed that these methods of bacterial inactivation showed a 2 and 1 log reduction in the number of survived CFU/mL with direct treatment being the most effective means of treatment at just 3 min using air. UV–Vis spectroscopy confirmed that an increase in treatment time at 1.2% O₂, 98.8% Ar caused a decrease in O₂ concentration in the water as well as a decrease in absorbance of the peaks at 210 nm, which are attributed NO₂⁻ and NO₃⁻ concentration in the water, termed denitratification and denitritification in the treated water, respectively.     

Adsorption and valence electronic states of nitric oxide on metal surfaces

Among fundamental diatomic molecules, the adsorption of carbon monoxide (CO) and nitric oxide (NO) on metal surfaces has been a subject of intensive research in the surface science community, partly owing to its relevance to heterogeneous catalysis used for environmental control. Compared to the rather well-defined adsorption mechanism of CO, that of NO is less understood because the adsorption results in much more complex reactions. The complexity is ascribed to the open-shell structure of valence electrons, making the molecule readily interact with the metal surface itself as well as with co-adsorbed molecules. Furthermore, the interaction crucially depends on the local structure of the surface. Therefore, to elucidate the interaction at the molecular scale, it is essential to study the valence state as well as the bonding geometry for individual NO molecules placed in a well-defined environment on the surface. Scanning tunneling microscopy (STM) is suitable for this purpose. In this review, we summarize the knowledge about the interaction of NO with metal surfaces, mainly focused on the valence electronic states, followed by recent studies using STM and atomic force microscopy (AFM) at the level of individual molecules.     

Effective enhancement of the performance of black dye based dye-sensitized solar cells by metal oxide surface modification of the TiO2 photoelectrode

Effective enhancement of the performance of black dye based dye-sensitized solar cells has been achieved by MgO or Al(2)O(3) surface modification of the TiO(2) photoelectrode. The conversion efficiency was improved from 10.4% to 10.8% due to the blocking effect of the thin overlayer at the TiO(2) surface.     

Bilayered Super-Structures of Antiferroelectric Mesogens

Abstract

Crystal structures of two antiferroelectric mesogens, TFMHPBC and MHPBC-10, were analysed by an X-ray diffraction method. In both crystals, mesogen molecules formed a herringbone structure which was essentially the same as that proposed for the antiferroelectric liquid crystal phase. Because of the crystallographic 2₁-symmetry along the b-axis, only the b-axis component of the dipole moment remains in a smectic layer. Since the dipole moment in the next layer has the same magnitude but the opposite direction, both crystals show no dipole moment as a whole. These structural features observed in their crystal states seem to be conserved in their antiferroelectric liquid crystal phases which are just above their crystal phases.     

Structures of Complex Crystals of Alkylammonium Salts with Aromatic Molecules

Abstract

The complex crystal structures of dodecyltrimethylammonium chloride (DTAC) with catechol and hydroquinone were analysed by an X-ray diffraction method. Both complexes have isomorphous layered structures. The guest molecules locate between the interdigitated host molecules. Crystal structures are stabilized by mainly hydrogen bonds including water molecules. A cross-section balance between hydrophilic and hydrophobic parts is important for an energetically stable packing. DTAC can form the crystalline complexes with catechol and hydroquinone by both crystallizing from the solution and mixing host and guest powders in a mortar. In addition, DTAC can also make a complex with resorcinol. Powder diffraction pattern indicates that this complex has similar layered structure with complexes of DTAC / catechol and DTAC / hydroquinone. However, it is unstable in atmospheric condition.     

Fekete configuration, quantitative equidistribution and wandering critical orbits in non-archimedean dynamics

Let f be a rational function of degree d > 1 on the projective line over a possibly non-archimedean algebraically closed field. A well-known process initiated by Brolin considers the pullbacks of points under iterates of f, and produces an important equilibrium measure. We define the asymptotic Fekete property of pullbacks of points, which means that they mirror the equilibrium measure appropriately. As application, we obtain an error estimate of equidistribution of pullbacks of points for C ¹-test functions in terms of the proximity of wandering critical orbits to the initial points, and show that the order is ${O(\sqrt{kd^{-k}})}$ upto a specific exceptional set of capacity 0 of initial points, which is contained in the set of superattracting periodic points and the omega-limit set of wandering critical points from the Julia set or the presingular domains of f. As an application in arithmetic dynamics, together with a dynamical Diophantine approximation, these estimates recover Favre and Rivera-Letelier’s quantitative equidistribution in a purely local manner.