Novel calixarene hemisphere synthesized via pinacol rearrangement of [2.1.2.1]metacyclophane

[reaction: see text] Tetramethoxy[2.1.2.1]metacyclophane ([2.1.2.1]MCP) was prepared by the pinacol coupling reaction of diphenylmethane dialdehyde. The treatment of [2.1.2.1]MCP with trimethylsilyl chloride and sodium iodide yielded two unexpected calixarene derivatives, cone (hemisphere) and 1,2-alternate types, instead of octahydroxy[2.1.2.1]MCP. The X-ray structure of the cone-type derivative and its inclusion property with acetonitrile were also discussed.     

A highly practical instant catalyst for cyclotrimerization of alkynes to substituted benzenes

[reaction: see text] A 2-(2,6-diisopropylphenyl)iminomethylpyridine (1a)/CoCl(2).6H(2)O/Zn reagent has been developed as an effective instant catalyst for the intra- and intermolecular cyclotrimerization of alkynes to substituted benzenes, making the method extremely practical since the reagent, 1a/CoCl(2).6H(2)O/Zn, is inexpensive and easy to handle and the reaction is less sensitive to moisture and is reasonably general.     

Exact algorithms for the chance-constrained vehicle routing problem

We study the chance-constrained vehicle routing problem (CCVRP), a version of the vehicle routing problem (VRP) with stochastic demands, where a limit is imposed on the probability that each vehicle’s capacity is exceeded. A distinguishing feature of our proposed methodologies is that they allow correlation between random demands, whereas nearly all existing exact methods for the VRP with stochastic demands require independent demands. We first study an edge-based formulation for the CCVRP, in particular addressing the challenge of how to determine a lower bound on the number of vehicles required to serve a subset of customers. We then investigate the use of a branch-and-cut-and-price (BCP) algorithm. While BCP algorithms have been considered the state of the art in solving the deterministic VRP, few attempts have been made to extend this framework to the VRP with stochastic demands. In contrast to the deterministic VRP, we find that the pricing problem for the CCVRP problem is strongly \(\mathcal {NP}\)-hard, even when the routes being priced are allowed to have cycles. We therefore propose a further relaxation of the routes that enables pricing via dynamic programming. We also demonstrate how our proposed methodologies can be adapted to solve a distributionally robust CCVRP problem. Numerical results indicate that the proposed methods can solve instances of CCVRP having up to 55 vertices.     

Thiazolidinediones with thyroid hormone receptor agonistic activity.

Several thiazolidinedione derivatives (3-7) were designed and synthesized as candidate thyromimetic drugs. Among them, the dihydrogenated compounds, such as 5-2-[[4-(3-tert-butyl-4-hydroxyphenyl)oxy-3,5-diiodophenyl] ethyl]-2,4-thiazolidinedione (6b) and its 3-isopropyl analog (7b), exhibited potent thyroid hormone receptor alpha 1 (TR alpha 1) activation activity.     

Hydrogen bonding and mechanical properties of thin films of polyether-based polyurethane-silica nanocomposites

Two series of thin films of polyether-based polyurethane-silica nanocomposites having hard segment content of 51% and 34% and different concentrations of SiO₂ nanoparticles (0, 0.5, 1.0 and 3.0 vol.%) have been prepared. Infrared linear dichroic (LDIR) ratio, mechanical and differential scanning calorimetry (DSC) measurements were performed in order to determine the influence of hydrogen bonding on their mechanical and thermal properties. The degree of phase separation (DPS) and orientational functions in dependence on strain were calculated from the polarized IR spectra. The presence of silica nanoparticles gives rise to significant differences in the mechanical (stress-strain) properties of the nanocomposites with regard to the pure polymer. The nanocomposite thin films with lower hard segment content (HSC) displayed decreased stiffness and tensile and increased elongation at break in comparison to the nanocomposites with higher HSC. There was no distinctive influence of nanoparticles on the glass transition temperatures of soft segments. Nanosilica significantly affected the melting behavior of the hard phase only in samples with higher HSC.     

Solid-state fluorescence study of naphthalene adsorption on porous material

Naphthalene adsorption profile on porous materials was studied using solid-state fluorescence spectroscopy. When naphthalene crystals were simply mixed with porous crystalline cellulose (PCC), excimer emission of naphthalene was observed after 1 min of mixing, suggesting a drastic change in the naphthalene molecular environment during the mixing procedure. For the naphthalene-octadesyl silane (ODS)-80A or naphthalene-ODS-2 systems, the changes in adsorption profiles and fluorescence spectral pattern of naphthalene were similar to those of the naphthalene-PCC system. The final amounts of naphthalene adsorbed to ODS-80A and ODS-2 were 0.05 and 0.024 g/g adsorbent, respectively, even though the two materials had comparable values of specific surface area. The relative emission intensity (I(excimer)/I(monomer)) in the ODS-80A system was higher than that in the ODS-2 system when compared at the same amount of naphthalene adsorbed. It was concluded that the pore size of porous materials affected the naphthalene excimer formation on the surface.     

Wrightiamines A and B,two new cytotoxic pregnane alkaloids from Wrightia javanica

Two new pregnane alkaloids, wrightiamines A (1) and B (2), were isolated from the extract of the tropical Apocynaceous plant Wrightia javanica collected in Thailand, and their structures were elucidated by spectral data. Wrightiamine B (2) was preparaed from 3beta-hydroxy-5alpha-pregnan-20-one to establish the configuration of the C-20 position as S. Wrightiamine A (1) exhibited cytotoxic activity against vincristine-resistant murine leukemia P388 cells.     

Intermediate-range order in glassy GexSe1−x around the stiffness transition composition

X-ray scattering measurements on glassy Ge_xSe_1−x were performed in a concentration range x=0.07-0.333 in fine steps of 0.005-0.05, in order to explore the relation between the intermediate-range order (IRO) and the stiffness transition in this glassy system. The oscillations beyond the first peak around 20.5 nm⁻¹ in the structure factor, S(Q), remain almost unchanged or damp very slowly with decreasing the Ge concentration x, suggesting the preserve of the short-range order. On the other hand, the pre-peak around 10-12 nm⁻¹, indicating the existence of IRO, systematically changes with decreasing x; its Q position shifts towards the higher Q values and its area decreases. Especially near the onset of the stiffness transition, x=0.20, the peak position starts to deviate from the linear relation. The origin of the pre-peak is discussed in connection with results of a recent anomalous X-ray scattering measurement indicating two contributions of Ge-Ge and Se-Se correlations. Around the onset composition of the stiffness transition, the area of the pre-peak associated with the Ge-Ge correlation has a plateau-like gradual decrease with x followed by a rapid decrease at x<0.18, which is in good agreement with Raman data.     

Bioaccumulation of Antimony by Chlorella vulgaris and the Association Mode of Antimony in the Cell

The bioaccumulation and excretion of antimony by the freshwater alga Chlorella vulgaris , which had been isolated from an arsenic-polluted environment, are described. When this alga was cultured in a medium containing 50 μg cm⁻³ of antimony(III) for 14 days, it was found that Chlorella vulgaris bioaccumulated antimony at concentrations up to 12 000 μg Sb g⁻¹ dry wt after six days' incubation. The antimony concentration in Chlorella vulgaris decreased from 2570 to 1610 μg Sb g⁻¹ dry wt after the cells were transferred to an antimony-free medium. We found that the excreted antimony consists of 40% antimony(V) and 60% antimony(III). This means that the highly toxic antimony(III) was converted to the less toxic antimony (V) by the living organism. Antimony accumulated in living Chlorella vulgaris cells was solvent-fractionated with chloroform/methanol (2:1), and the extract residue was fractionated with 1% sodium dodecyl sulfate (SDS). Gel-filtration chromatography of the solubilized part showed that antimony was combined with proteins whose molecular weight was around 4×10⁴ in the antimony-accumulated living cells. © 1997 by John Wiley & Sons, Ltd.     

Behavior of nitroxyl radical in the polymerization process forming copolymers bearing diarylnitrone pendants and photocontrol of refractive indices for these copolymers

To establish the reaction condition under which the radical copolymerization of methyl methacrylate (MMA) with α‐(2‐hydroxy‐4‐methacryloyloxyphenyl)‐N‐(2,6‐dimethylphenyl)nitrone (HMDN) proceeds smoothly to give photoreactive copolymers, the effects of the nitrone chromophore on the extent to which the radical polymerization of MMA is inhibited were investigated. It was found that the reversible addition of initiating radical to the CH?N⁺(? O^?) moiety in the nitrone chromophore readily occurs to give the nitroxyl radical. It was also found that the latter radical undergoes an efficient coupling reaction with propagating radical to inhibit the radical copolymerization of MMA with HMDN. However, on raising the reaction temperature and the radical concentration, the copolymerization was successfully carried out. This polymerization condition allowed us to prepare the HMDN/MMA, HMDN/styrene, and HMDN/cyclohexyl acrylate copolymers in good yields. The photoirradiation of the copolymer film prepared on a silicon wafer lowered its refractive index by 0.003–0.023, depending on the relative composition of the diarylnitrone chromophore in these copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 88–97, 2006