Syntheses,characterizations, and redox behaviors of new self-assembled metal complexes with bridging ligands incorporating chalcogen sites

Three new complexes, [Zn(dbsf)₂(dmf)₂] · 5.5dmf (dbsf = 4,4′-sulfonyldibenzoate) (1β), [Cu(tdsa)(phen)₂] · 1.5EtOH (tdsa = 5,5′-thiodisalicylate, phen = 1,10-phenanthroline) (2), and [Cu(sdp)(phen) · Cu(Hsdp)(phen)(CH₃COO)] · 3EtOH (sdp = 4,4′-sulfonyldiphenolate) (3) were prepared and structurally characterized. Complex 1β shows a one-dimensional coordination framework constructed from bridges between Zn(II) centers with two ligands. Complex 2 is a monomeric complex, which assembles by π–π interactions. Complex 3 shows a unique two-dimensional coordination framework that is constructed from two Cu(II) centers, sdp, and Hsdp. The redox properties of these three complexes were characterized by solid-state cyclic voltammetry. Complexes 1β and 3 show irreversible reduction waves because of the reduction of their sulfone sites. Complex 2 shows an irreversible oxidation wave because of oxidation of the sulfide site.     

Characterization of acylmono-, mono-, di-, tri- and tetraglycosylsterol and saponin in Adzuki bean (Vigna angularis) seeds

Five sterylglycosides (acylmono-, mono-, di tri- and tetraglycosylsterol) and a saponin were isolated from Adzuki beans and characterized. In the glycosylsterols, the principal component sterols were sitosterol and stigmasterol; the major sugar component was glucose. The glucose units were shown to be linked by β1,6-bonds. The three oligoglycosylsterols were shown to be gentiobiosylsterol, gentiotriosylsterol and gentiotetraosylsterol; the latter two are novel sterylglycosides. The saponin was identified as glucopyranosyl-(β1→2)-glucopyranurosyl-(β1→3′)-soyasapogenol B (Azukisaponin I) which had previously been found in Adzuki beans.     

Novel polyion complex with interpenetrating polymer network of poly(acrylic acid) and partially protected poly(vinylamine) using N-vinylacetamide and N-vinylformamide

Poly(vinylamine), the simplest polycation with primary amines, was applied to interpenetrating polymer networks (IPN) with poly(acrylic acid). N-Vinylformamide (NVF) was employed for amino-protected monomers to control electrostatic balance. pH-responsivities of IPNs varied, depending on the hydrolysis conditions and acrylic acid (AAc) concentration of the second network. Poly(N-vinylacetamide)-co-poly(N-vinylformamide) (4/6, mol/mol) was employed for the first network, subsequently hydrolyzed with 50% amide groups, and the second network was polymerized with 0.25 mol L⁻¹ AAc, extremely shrunken hydrogels with polyion complex were formed at pH 7, showing that the controlled amount of highly active primary amines are available in IPN.     

Formation mechanism for hexagonal-structured self-assemblies of nanocrystalline titania templated by cetyltrimethylammonium bromide

Hexagonal-structured self-assemblies of nanocrystalline (anatase) titania templated by cetyltrimethylammonium bromide (C(16)H(33)N(CH(3))(3)Br; CTAB) (Hex-ncTiO(2)/CTAB Nanoskeleton) were formed after mixing of aqueous solutions containing CTAB spherical micelles and titanium oxysulfate acid hydrate (TiOSO(4).xH(2)SO(4).xH(2)O) as a titania precursor in the absence of any other additives. Formation mechanism of the Hex-ncTiO(2)/CTAB Nanoskeleton was examined in terms of the reaction temperature, titania precursor/CTAB mixing ratio, surfactant type, electrostatic interaction, micelle formation and molecular component. We found that crystal growth of crystalline (anatase) titania (polymorphic crystallization) was promoted with higher temperature and lower titania precursor content in aqueous solutions. In addition, we revealed that the crystalline (anatase) titania was formed in polycation, poly(allylamine hydrochloride ([CH(2)CH(CH(2)NH(2))HCl](n); PAH), and formamide (HCONH(2)) solutions. On the other hand, no titania formation was observed in anionic systems such as sodium dodecyl sulfate (CH(3)(CH(2))(11)OSO(3)Na; SDS) and poly(sodium 4-styrenesulfonate ([C(8)H(7)SO(3)Na](n); PSSS). This indicates that hydrolysis reaction of the titania precursor is initiated by not only cations but also nitrogen atoms in molecules and polymers. Hexagonally structure was formed in only cationic surfactant micellar solutions but not in polycation solutions and formamide.     

NiFe alloy particles doping effect of Gd–Ba–Cu–O bulks processed by a new cold-seeding technology

The process of cold seeding melt growth of GdBa₂Cu₃O_y (Gd123) bulk superconductors using NdBa₂Cu₃O_y (Nd123) thin films was reported. In addition, a novel cold seeding concept of combining MgO crystal and buffer pellet was also introduced. The misorientation caused by the lattice mismatch between MgO and Gd123 melt was overcome by choosing suitable heat treatment program and Gd₂BaCuO₅ (Gd211) content of the buffer pellet. The doping effect of soft ferromagnetic NiFe alloy particles was also reported. The bulk sample with 0.4% (mole fraction) doping amount shows the best performance on the flux trapping. The critical current density is largely enhanced under the external field of 1–2 T, which is promising for large-scale applications. This effect is originated from the substitution of Fe and Ni ions for the Cu sites contributing to magnetic flux pinning.     

Applications of hydrothermal electrolysis for conversion of 1-butanol in wastewater treatment

Hydrothermal electrolysis of organic compound in the presence of electrolyte was conducted for a woody biomass model compound. The reaction behavior of 1-butanol as a woody biomass model compound was studied in subcritical conditions at 200-250 °C and 8-12 MPa with a batch autoclave. The autoclave volume was 500 mL and equipped system with agitation stirrer, electric current control, electric heating and temperature control and a pressure gauge. The chemical species in aqueous products were identified by gas chromatography mass spectrometry (GC-MS) and quantified using gas chromatography flame ionization detector (GC-FID). The gaseous products were analyzed by gas chromatography with a thermal conductivity detector (GC-TCD). The effects of reaction temperature, pressure and applied constant current on the conversion process of 1-butanol were presented. The main products from the conversion of 1-butanol were butanal, butyric acid, hydrogen and carbon dioxide. Additionally, the values of reaction rate constant for butanal and butyric acid formation were calculated at 200 and 250 °C by kinetic study.     

Molecular Targeted Therapy for the Bone Loss Secondary to Pyogenic Spondylodiscitis Using Medications for Osteoporosis: A Literature Review

Pyogenic spondylodiscitis can cause severe osteolytic and destructive lesions in the spine. Elderly or immunocompromised individuals are particularly susceptible to infectious diseases; specifically, infections in the spine can impair the ability of the spine to support the trunk, causing patients to be bedridden, which can also severely affect the physical condition of patients. Although treatments for osteoporosis have been well studied, treatments for bone loss secondary to infection remain to be elucidated because they have pathological manifestations that are similar to but distinct from those of osteoporosis. Recently, we encountered a patient with severely osteolytic pyogenic spondylodiscitis who was treated with romosozumab and exhibited enhanced bone formation. Romosozumab stimulated canonical Wnt/β-catenin signaling, causing robust bone formation and the inhibition of bone resorption, which exceeded the bone loss secondary to infection. Bone loss due to infections involves the suppression of osteoblastogenesis by osteoblast apoptosis, which is induced by the nuclear factor-κB and mitogen-activated protein kinase pathways, and osteoclastogenesis with the receptor activator of the nuclear factor-κB ligand-receptor combination and subsequent activation of the nuclear factor of activated T cells cytoplasmic 1 and c-Fos. In this study, we review and discuss the molecular mechanisms of bone loss secondary to infection and analyze the efficacy of the medications for osteoporosis, focusing on romosozumab, teriparatide, denosumab, and bisphosphonates, in treating this pathological condition.     

Effect of proton irradiation on electrical properties of CuInSe2 thin films

High-energy proton irradiation (380 keV and 1 MeV) on the electrical properties of CuInSe₂ (CIS) thin films has been investigated. The samples were epitaxially grown on GaAs (0 0 1) substrates by Radio Frequency sputtering. As the proton fluence exceeded 1×10¹³ cm⁻², the carrier concentration and mobility of the CIS thin films were decreased. The carrier removal rate with proton fluence was estimated to be about 1000 cm⁻¹. The electrical properties of CIS thin films before and after irradiation were studied between 80 and 300 K. From the temperature dependence of the carrier concentration in CIS thin films, we found N_D=9.5×10¹⁶ cm⁻³, N_A=3.7×10¹⁶ cm⁻³ and E_D=21 meV from the fitting to the experimental data on the basis of the charge balance equation. After irradiation, a defect level was created, and N_T=1×10¹⁷ cm⁻³ for a fluence of 3×10¹³ cm⁻², N_T=5.7×10¹⁷ cm⁻³ for a fluence of 1×10¹⁴ cm⁻² and E_T=95 meV were also obtained from the same fitting. The new defect, which acted as an electron trap, was due to proton irradiation, and the defect density was increased with proton fluence.     

Beneficial effect of carbon–PVA colloid additives for lead–acid batteries

Based on the previous success of adding ultra-fine carbon–PVA (polyvinyl alcohol) colloid solution to restore performance of weak batteries, a large scale test programme of practical batteries including those used in forklift, golf cart, taxi cab, truck and bus applications from 150 companies was carried out. More than 95% of the tested batteries exhibited excellent recovery in performance parameters including the specific gravity (S.G.), voltage and operation time (Ah capacity). The work reported here includes basic research studies to understand better the beneficial action of the carbon–PVA colloid additive.