<Emphasis Type="Italic">S,S,S</Emphasis>-Tris(2-ethylhexyl) phosphorotrithioate as an effective solvent mediator for a mexiletine-sensitive membrane electrode

S,S,S-Tris(2-ethylhexyl) phosphorotrithioate proved to be an effective solvent mediator for constructing a mexiletine-sensitive membrane electrode in combination with an ion-exchanger, sodium tetrakis[3,5-bis(2-methoxyhexafluoro-2-propyl)phenyl]borate. Among a series of phosphorus compounds containing phosphoryl (P=O) groups, this solvent mediator showed the highest sensitivity to mexiletine in phosphate-buffered physiological saline containing 0.15 mol L⁻¹ NaCl and 0.01 mol L⁻¹ NaH₂PO₄/Na₂HPO₄ (pH 7.4), giving a detection limit of 2 × 10⁻⁶ mol L⁻¹ with a slope of 58.8 mV decade⁻¹. This is the best reported detection limit of any mexiletine-sensitive electrode developed to date. Owing to its high selectivity toward inorganic cations, the electrode was used to determine the level of mexiletine in saliva, the monitoring of which is quite effective for controlling the dose of this drug noninvasively. The mexiletine concentrations determined with the mexiletine-sensitive electrode compared favorably with those determined by high-performance liquid chromatography.     

Pyrimidine dimer formation and oxidative damage in M13 bacteriophage inactivation by ultraviolet C irradiation

The mechanism by which UV-C irradiation inactivates M13 bacteriophage was studied by analyzing the M13 genome using agarose gel electrophoresis and South-Western blotting for pyrimidine dimers. The involvement of singlet oxygen (1O2) was also investigated using azide and deuterium oxide and under deoxygenated conditions. With a decrease in M13 infectivity on irradiation, single-stranded circular genomic DNA (sc-DNA) was converted to Form I and Form II, which had an electrophoretic mobility between that of sc-DNA and linear-form DNA. However, the amount of sc-DNA remaining was not correlated with the survival of M13. The formation of cyclobutane pyrimidine dimers (CPD) and pyrimidine (6-4) pyrimidone photoproducts ((6-4)PP) increased as a function of irradiation dose. The decrease in M13 infectivity was highly correlated with the increase in CPD and (6-4)PP, whereas no change was seen in M13 coat protein on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. 8-Oxo-7,8-dihydro-2'-deoxyguanosine did not form in the M13 genome after UV-C irradiation. Inactivation of M13 was neither enhanced by deuterium oxide nor inhibited by azide. Deoxygenation of the M13 suspension did not affect the inactivation, indicating that 1O2 did not participate in the inactivation of M13 by UV-C irradiation under these conditions. These results indicated that UV-C irradiation induced not only CPD and (6-4)PP formation but also additional tertiary structural change in DNA inside the M13 virions, resulting in primary damage and a loss of infectivity. The indirect effect of UV-C irradiation such as 1O2 production followed by oxidative damage to nucleic acids and proteins might have contributed less, if at all, to the inactivation of M13 than the direct effect of UV-C.     

Serum metabolomics as a novel diagnostic approach for gastrointestinal cancer

Conventional tumor markers are unsuitable for detecting carcinoma at an early stage and lack clinical efficacy and utility. In this study, we attempted to investigate the differences in serum metabolite profiles of gastrointestinal cancers and healthy volunteers using a metabolomic approach and searched for sensitive and specific metabolomic biomarker candidates. Human serum samples were obtained esophageal (n = 15), gastric (n = 11), and colorectal (n = 12) cancer patients and healthy volunteers (n = 12). A model for evaluating metabolomic biomarker candidates was constructed using multiple classification analysis, and the results were assessed with receiver operating characteristic curves. Among the 58 metabolites, the levels of nine, five and 12 metabolites were significantly changed in the esophageal, gastric and colorectal cancer patients, respectively, compared with the healthy volunteers. Multiple classification analysis revealed that the variations in the levels of malonic acid and l ‐serine largely contributed to the separation of esophageal cancer; gastric cancer was characterized by changes in the levels of 3‐hydroxypropionic acid and pyruvic acid; and l ‐alanine, glucuronoic lactone and l ‐glutamine contributed to the separation of colorectal cancer. Our approach revealed that some metabolites are more sensitive for detecting gastrointestinal cancer than conventional biomarkers. Our study supports the potential of metabolomics as an early diagnostic tool for cancer. Copyright © 2011 John Wiley & Sons, Ltd.     

Molecular paramagnetic semiconductor: crystal structures and magnetic and conducting properties of the Ni(dmit)(2) salts of 6-oxoverdazyl radical cations (dmit = 1,3-dithiol-2-thione-4,5-dithiolate)

Four kinds of 1:1 and 1:3 salts of 3-[4-(trimethylammonio)phenyl]-1,5-diphenyl-6-oxoverdazyl radical cation ([1](+)) and its mono- and dimethyl derivatives ([2](+) and [3](+)) with Ni(dmit)(2) anions (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) ([1](+)[Ni(dmit)(2)](-) (4), [2](+)[Ni(dmit)(2)](-) (5), [3](+)[Ni(dmit)(2)](-) (6), and [1](+)[Ni(dmit)(2)](3)(-) (7)) have been prepared, and the magnetic susceptibilities (chi(M)) have been measured between 1.8 and 300 K. The chi(M) values of salts 5 and 7 can be well reproduced by the sum of the contributions from (i). a Curie-Weiss system with a Curie constant of 0.376 (K emu)/mol and negative Weiss constants (THETAV;) of -0.4 and -1.7 K and (ii). a dimer system with strong negative exchange interactions of 2J/k(B) = -354 and -258 K, respectively. The dimer formations in Ni(dmit)(2) anions have been ascertained by the crystal structure analyses of salts 4-6. In salts 4 and 6, Ni(dmit)(2) dimer molecules are sandwiched between two verdazyl cations, indicating the formation of a linear tetramer in 4 and 6. The magnetic susceptibility data for salts 4 and 6 have been fitted to a linear tetramer model using an end exchange interaction of 2J(1)/k(B) = -600 K and a central interaction of 2J(2)/k(B) = -280 K for 4 and 2J(1)/k(B) = -30 K and 2J(2)/k(B) = -580 K for 6, respectively. The results of the temperature dependence of the g(T) value in salts 4-6 obtained by ESR measurement also support the above analyses. The 1:1 salts 4-6 are insulators. On the other hand, the conductivity of the 1:3 salt 7 at 20 degrees C was sigma = 0.10 S cm(-)(1) with an activation energy E(A) = 0.099 eV, showing the semiconductor property. Salt 7 is a new molecular paramagnetic semiconductor.     

Low-dimensional ferromagnetic properties of SrCuV2O7 and BaCuV2O7

The crystal structure of isostructural SrCuV(2)O(7) and BaCuV(2)O(7) consists of one-dimensional (1D) zigzag chains of Cu atoms with next-nearest-neighbor interaction. The main intrachain interaction was found to be ferromagnetic and estimated at 4.6 K (Hamiltonian H approximately -2J). SrCuV(2)O(7) and BaCuV(2)O(7) are new examples in the scanty family of 1D ferromagnets. Isothermal magnetization measurements at 0.08 K and specific heat data showed that MCuV(2)O(7) exhibits antiferromagnetic long-range ordering at T(N) = 1.36 K for SrCuV(2)O(7) and T(N) = 1.47 K for BaCuV(2)O(7). Spin-flop transitions were observed in the antiferromagnetic state at 0.08 K near 0.5 kOe in SrCuV(2)O(7) and 2 kOe in BaCuV(2)O(7). In air, SrCuV(2)O(7) and BaCuV(2)O(7) melted incongruently above 983 and 1018 K, respectively.     

Designed ferromagnetic, ferroelectric Bi(2)NiMnO(6)

A newly designed ferromagnetic, ferroelectric compound, Bi(2)NiMnO(6), was prepared by high-pressure synthesis at 6 GPa. The crystal structure, as determined by synchrotron X-ray powder diffraction, is a heavily distorted double perovskite with Ni(2+) and Mn(4+) ions ordered in a rock-salt configuration. The presence of 6s(2) lone pairs of Bi(3+) ions and the covalent Bi-O bonds give ferroelectric properties with T(CE) of 485 K, while -Ni(2+)-O-Mn(4+)-O-Ni(2+)- magnetic paths lead to a ferromagnetism with T(CM) of 140 K. This simple material design to distribute two magnetic elements with and without e(g) electrons on B sites of Bi- and Pb-based perovkites can be applied to other Bi(2)M(2+)M'(4+)O(6) and Pb(2)M(3+)M'(5+)O(6) systems to search for newer ferromagnetic ferroelectrics.     

MR signal change in venous thrombus relates organizing process and thrombolytic response in rabbit

Venous thrombus is subsequently organized and replaced by fibrous connective tissue. However, the sequential changes in venous thrombi are not reliably detected by current noninvasive diagnostic techniques. The purpose of this study is to reveal whether magnetic resonance (MR) can detect venous thrombus, define thrombus age and predict thrombolytic responses. Thrombus in the rabbit jugular vein was imaged with a 1.5-T MR system at 4 h and at 1, 2 and 4 weeks using three-dimensional (3D) fast asymmetric spin echo T2-weighted (T2W) and 3D-gradient echo T1-weighted (T1W) sequences. The jugular veins were histologically assessed at each time point. Magnetic resonance imaging (MRI) was also performed in vivo before and 30 min after tissue plasminogen activator (t-PA) administration. The thrombi in MRI were comparable in size to histological sections. The signal intensity (SI) of thrombi at 4 h was heterogeneously high or low on T2W or T1W images, respectively. The SI of thrombi on T2W images decreased time-dependently, but increased on T1W images at 1 and 2 weeks. Morphological analysis showed time-dependent decreases in erythrocyte, platelet and fibrin areas and time-dependent increases in smooth muscle cell, macrophage, collagen and iron areas. The t-PA administration significantly decreased thrombus volume at 4 h but not at 1, 2 and 4 weeks. Venous thrombosis can be reliably and noninvasively detected by MRI. Measurement of SI might support assessments of thrombus age and thrombolytic response.     

Total synthesis of benzo[c]phenanthridine alkaloids based on a microwave-assisted electrocyclic reaction of the aza 6π-electron system and structural revision of broussonpapyrine

Total syntheses of the des-N-methyl (nor) type of benzo[c]phenanthridine alkaloids 1a-f and 19 and benzo[c]phenanthridine alkaloids, chelerythrine (2d), and broussonpapyrine (2f) were achieved. The key step was the construction of tetracyclic 10,11-dihydrobenzo[c]phenanthridines using a microwave-assisted electrocyclic reaction of the 2-cycloalkenylbenzaldoxime methyl ether 4 as an aza 6π-electron system, which was derived in two steps from a Suzuki-Miyaura cross-coupling reaction of 2-bromobenzaldehyde 6 with 2-(3,4-dihydro-6,7-methylenedioxynaphthyl)boronic acid pinacol ester 7. In addition, the exact structure of broussonpapyrine (2f) (2,3,9,10-tetraoxygenated type) was determined to be chelerythrine (2d).     

Partial crystallization of silicon by high intensity laser irradiation

Commercial single crystal silicon wafers and amorphous silicon films piled on single crystal silicon wafers were irradiated with a femtosecond pulsed laser and a nanosecond pulsed laser at irradiation intensities between 10¹⁷ W/cm² and 10⁹ W/cm². In the single crystal silicon substrate, the irradiated area was changed to polycrystalline silicon and the piled silicon around the irradiated area has spindly column structures constructed of polycrystalline and amorphous silicon. In particular, in the case of the higher irradiation intensity of 10¹⁶ W/cm², the irradiated area was oriented to the same crystal direction as the substrate. In the case of the lower irradiation intensity of 10⁸ W/cm², only amorphous silicon was observed around the irradiated area, even when the target was single crystal silicon. In contrast, only amorphous silicon particles were found to be piled on the amorphous silicon film, irrespective of the intensity and pulse duration.Three-dimensional thermal diffusion equation for the piled particles on the substrate was solved by using the finite difference methods. The results of our heat-flow simulation of the piled particles almost agree with the experimental results.