Surface tension and viscosity of molten vanadium measured with an electrostatic levitation furnace

Surface tension and viscosity of molten vanadium were measured over a wide temperature range by the oscillating drop method in an electrostatic levitation furnace. Over the (2023 to 2517) K temperature range, the surface tension can be expressed as γ(T)/(10^?3 N/m) = 1935 ? 0.27 {(T ? T_m)/K} with T_m = 2183 K. Over the same temperature span, the viscosity can be expressed as η(T)/(10^?3 Pa · s) = 1.23exp[2.27 · 10⁴/(RTK^?1)], where R is the gas constant.     

Simultaneous determination of a pyridine-triphenylborane anti-fouling agent and its estimated degradation products using capillary zone electrophoresis

A commercial organoborane compound, pyridine-triphenylborane (PTPB), is often applied to ship hulls as an anti-fouling agent. We developed capillary zone electrophoresis (CZE) with direct UV detection for the simultaneous determination of PTPB and its estimated degradation products: diphenylborinic acid (DPB), phenylboronic acid (MPB), and phenol. The limits of detection (LODs) for PTPB, DPB, MPB, and phenol were, respectively, 25, 30, 50, and 29 μg/l at a signal-to-noise ratio of three. At concentrations of 0.5 mg/l, values of the relative standard deviation (RSD, n = 6, intra-day) of peak area were obtained, respectively, for PTPB, DPB, MPB, and phenol, as 4.1, 4.1, 4.7, and 3.4% for peak heights 3.6, 3.2, 1.7, and 1.4%, and for migration times 1.1, 1.1, 1.0, and 0.73%. The analytes were detected within 14 min. Simple photodegradation experiments were conducted to verify the usefulness of the proposed method for additional PTPB degradation investigations.     

Electrochemical Determination of Boric Acid Using the Boric Acid–Tiron Complexation System

For monitoring the boron concentration in reverse osmosis (RO) water produced by desalination plants, a voltammetric determination method for the amount of electrochemically inactive boron has been developed by using the complexation with 4,5‐dihydroxybenzene‐1,3‐disulfonic acid (Tiron). Cyclic voltammetric measurements showed the oxidation peak of boric acid–Tiron 1 : 1 complex at 920 mV. This peak was successfully applied to the determination of boron in RO water with the LOD of 0.1 mg B dm^?3 by using differential pulse voltammetry. The redox and acid–dissociation behaviors of Tiron and its boron complex are found to depend on the properties of pH buffer reagent.     

Scavenging effects of metal complexes of water-soluble thiacalix[4]arenetetrasulfonate on superoxide anion radicals

The scavenging effects of metal complexes of thiacalix[4]arenetetrasulfonate (Me-TCAS[4], Me=H?, Fe3(+), Mn3(+), Mn2(+), Cu2(+), and Zn2(+)) on superoxide anion radicals (O??) generated from the xanthine-xanthine oxidase system were investigated by the nitroblue tetrazolium (NBT) method and electron spin resonance (ESR) spin-trapping method using 5,5-dimethyl-1-pyrroline-N-oxide as a trapping reagent. As a reference, calix[4]arenetetrasulfonate (H?)-CAS[4]), calix[6]arenehexasulfonate (H?-CAS[6]) and calix[8]areneoctasulfonate (H?-CAS[8]) were also examined. The results by the NBT method indicated that Fe3(+)- and Mn3(+)-TCAS[4] exhibited the highest O?? scavenging activity among Me-TCAS[4] and H?-CAS[n] (n = 4, 6, 8) in this study. The IC?? values of Fe3(+)- and Mn3(+)-TCAS[4] for O?? scavenging activity were estimated to be 5.3 and 7.8 μM, respectively, and were almost the same as those of tannin acid, catechin and their derivatives, which are known as very effective scavengers of O??. Scavenging activities were in the order of Fe3(+)- and Mn3(+)-TCAS[4]>Mn2(+)-, Cu2(+)-, and Zn(2+)-TCAS[4]>H(2)-TCAS[4] and H?-CAS[n] (n=4, 6, 8). Each activity of Me-TCAS[4] (Me=Fe3(+), Mn3(+), Mn2(+), Cu2(+), and Zn2(+)) was higher than that of the corresponding metal ion, indicating that H?-TCAS[4] has the ability to raise the activity of the metal ion itself by forming a complex. Also, the ESR spin-trapping method revealed that Fe3(+)- and Mn3(+)-TCAS[4] showed high O?? scavenging activities, similarly to the results by the NBT method.     

Novel solid-phase refolding method for preparation of scFv-immobilized polystyrene plates with high-antigen-binding activity

In the present study, we demonstrated site-specific immobilization and solid-phase refolding of single-chain Fv antibodies on hydrophilic polystyrene (phi-PS) plates that was mediated by novel polystyrene binding peptides (PS-tags: RIIIRRIRR), which were originally isolated and optimized in previous studies. Three PS-tag-fused scFvs, namely scFv-PS, scFv-(PS), and scFv-PSII, which were over-expressed in the insoluble fraction of Escherichia coli cells were denatured and site-specifically immobilized onto hydrophilic PS plates in the presence of 0.5~4 M urea and 0.1% Tween 20. The antigen-binding activity of the scFvs was efficiently recovered by washing the surface of the plate with PBS that contained 0.1% Tween 20 (PBST). The solid-phase refolding mediated by PS-tag was successfully applied to several scFvs such as mouse anti-CRP antibodies and an anti-RNase antibody, although further investigation of the versatility of scFv-PSII is needed. The maximal density of PS-tag-fused scFvs was increased more than 15-fold compared with a whole monoclonal antibody (mAb) immobilized on Maxisorp™ and, consequently, the sensitivity of PS-tag-fused scFvs for CRP in a sandwich ELISA was increased 25-fold. Thus, the novel, solid-phase, refolding method mediated by a PS-tag will be very useful for preparation of solid supports coated with recombinant antibody fragments, which can be used in immunoassays and immuno-separation.     

Stereocontrolled synthesis of carbocyclic compounds with a quaternary carbon atom based on SN2' alkylation of γ,δ-epoxy-α,β-unsaturated ketones

We developed a new method for stereoselective construction of an all-carbon quaternary stereogenic center on a carbocyclic ring based on regio- and stereoselective S(N)2' alkylation reactions of γ,δ-epoxy-α,β-unsaturated cyclic ketones. Treatment of the ketones, which were readily prepared in enantiomerically pure form by means of aldol condensations between 3-ethoxy-2-cycloalkenones and α,β-epoxy aldehydes, with a R(2)Zn-CuCN reagent afforded anti-S(N)2' products stereoselectively. Conversely, the corresponding syn-S(N)2' products were stereoselectively obtained through two-step transformations of the same γ,δ-epoxy-α,β-unsaturated cyclic ketones: (1) conversion of the epoxide moiety to a chlorohydrin by treatment with MgCl(2) and (2) subsequent S(N)2' substitution of the chlorohydrin with a R(2)Zn-CuCN reagent. These substitution products with their chiral trans-allylic alcohol moieties are promising precursors for complex molecules. For example, Eschenmoser-Claisen rearrangement of one of the substitution products resulted in stereoselective formation of a keto amide having contiguous quaternary and tertiary stereogenic centers.     

Temperature-responsive ionic liquid/water interfaces: relation between hydrophilicity of ions and dynamic phase change

Phase separation between ionic liquids (ILs) and molecular liquids is of interest physico-chemically, and also has industrial relevance. IL/water mixtures are of great interest in many fields. Unlike static phase separation between IL and water, dynamic shifts of IL/water mixtures between a homogeneous mixture and separate phases have a wide variety of applications. The miscibility of ILs with water generally increases upon heating, and a few ILs undergo a lower critical solution temperature (LCST)-type phase transition with water in which the separated biphases become miscible upon cooling. As the phase transition is controlled by changing the temperature by a few degrees, the LCST-type phase response of IL/water mixtures makes it possible to use ILs as solvents in various energy-saving processes. Since many hydrophilic ILs do not undergo phase separation with water, we aim to determine the necessary conditions under which hydrophobic ILs undergo the phase transition. Based on physico-chemical analysis of many hydrophobic ILs that undergo a phase separation after mixing with water, we find there is a particular range of "hydrophilicity" of these hydrophobic ILs within which the LCST-type phase transition is possible. Accordingly, a hydrophilicity index (HI) of ILs is proposed, in terms of the number of water molecules in the separated IL phase. The HI value proves to be a good indicator of the phase behaviour of IL/water mixtures, as well as their phase transition temperature. Potential application of the LCST-type phase change to the selective extraction of water-soluble proteins is also summarised.     

Selective construction of Pd2Pt and PdPt2 triangles in a sandwich framework: carbocyclic ligands as scaffolds for a mixed-metal system

Sandwich time! The mixed-metal triangular-trinuclear sandwich complexes of Pd(2)Pt and PdPt(2) were selectively synthesized. The Pd(2)Pt and PdPt(2) triangles in a cycloheptatrienyl sandwich framework were identified by (31)P?NMR analyses of the tris-triphenylphosphine complexes (see scheme).     

Polystyrene-based blend nanorods with gradient composition distribution

The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6-dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices.