Molecularly imprinted polymers with halogen bonding-based molecular recognition sites

Molecular recognition materials bearing halogen bonding-based binding sites were synthesized by a non-covalent imprinting technique using a 2,3,5,6-tetrafluoro-4-iodostyrene (TFIS) as the functional monomer. The binding sites were generated by co-polymerizing TFIS, styrene and divinylbenzene in the presence of the template molecule (4-dimethylaminopyridine—DMAP). The imprinted polymer preferentially adsorbed aminopyridine derivatives, suggesting that halogen bonding may play a role in the selective recognition of analytes by the synthesized synthetic receptor.     

Photocatalytic degradation of trichloroethylene on platinum ion-doped TiO<Subscript>2</Subscript> under visible light irradiation

Porous platinum ion-doped TiO₂ (Pt–TiO₂) was prepared by a sol–gel method and demonstrated to have superior photocatalytic activity for the photodegradation of gaseous trichloroethylene (TCE) under visible light (VL) irradiation from a xenon lamp equipped with 422-nm cut-off filter. Kinetic studies were performed to clarify the effect of the doping amounts, space times, VL intensity, and mole fractions of TCE, O₂, and H₂O on the degradation of TCE. Under ultraviolet (UV) irradiation, the photocatalytic activity of Pt–TiO₂ was the same as that of TiO₂, indicating that the doped Pt ion did not act as a recombination center for the photogenerated holes and electrons. Based on the kinetic data and reaction products, we conclude that the photocatalytic degradation of TCE on Pt–TiO₂ under VL irradiation proceeds similarly to TiO₂ under UV irradiation. We also performed the photocatalytic degradation of TCE at the space time of 7.5 × 10⁷ g s mol^?1 in a tubular reactor packed with the Pt–TiO₂ pellets which are more suitable than the Pt–TiO₂ powder for the practical remediation of the contaminated gas. TCE was completely degraded, i.e. 100% conversion was achieved under VL irradiation but only a small quantity of CO₂ was formed with the stoichiometric ratio of [CO₂]_formed/[TCE]_degraded of ca. 0.33. By switching the gas stream containing TCE to humid air, more CO₂ was formed, indicating that the dichloroacetates accumulated on the Pt–TiO₂ surface are photodegradable to CO₂ under VL irradiation.     

Stereoselective reduction of 2-butenolides to chiral butanolides by reductases from cultured cells of Glycine max

The stereoselective reduction of 2-butenolides by two reductases, p51 and p83, from cultured plant cells of Glycine max was investigated. The reduction of 2-methyl-2-butenolide by p51 reductase produced (R)-2-methylbutanolide, whereas the reduction by p83 reductase gave (S)-2-methylbutanolide. Both reductases reduced 3-methyl-2-butenolide to (R)-3-methylbutanolide. The reduction of 2,3-dimethyl-2-butenolide by p51 reductase gave (2R,3R)-2,3-dimethylbutanolide, whereas the reduction by p83 reductase produced (2S,3R)-2,3-dimethylbutanolide. The reduction of 4-alkyl-2-butenolides with these reductases was accompanied by resolution of chiral centers affording (R)-4-alkylbutanolides.     

Synthesis of unimolecular reversed micelle consisting of a poly(L‐lactide) shell and hyperbranched D‐mannan core

A novel biodegradable unimolecular reversed micelle consisting of a poly(L ‐lactide) (PLA) shell and a hyperbranched D ‐mannan (HBM) core, that is, a chestnut‐shaped polymer (PLA–HBM), was synthesized by the polymerization of L ‐lactide on HBM with 4‐(dimethylamino)pyridine (DMAP) as the catalyst. The obtained polymers were soluble in dimethyl sulfoxide, tetrahydrofuran, and chloroform but insoluble in H₂O. The molecular weights of the PLA chain on PLA–HBM tended to increase with increasing polymerization time. The number of PLA chains on PLA–HBM could be controlled by the ratio of DMAP to the sugar unit in HBM. The obtained copolymer, PLA–HBM, acted as a unimolecular reversed micelle with an encapsulation ability toward the hydrophilic molecule. In addition, the entrapped hydrophilic molecules were slowly released from the core of PLA–HBM, and the release rate was accelerated by the breaking of the PLA chains of the shell when proteinase K as a hydrolase of PLA was used. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 406–413, 2006     

Total synthesis and stereochemistry of the antitumor antibiotic PD 113,271

[Structure: see text] A total synthesis of PD 113,271, an antitumor fostriecin analogue isolated from Streptomyces pulveraceus, was achieved by the chiral pool approach starting with D-galactose and L-tartaric acid. The synthesis of PD 113,271 led to unambiguous assignment of the relative and absolute stereochemistry of its stereocenters.     

Precise retinal shape measurement by alignment error and eye model calibration

Optical Review - To evaluate the repeatability of the optical coherence tomography (OCT) retinal shape measurement with and without alignment correction in children and adults. 62 eyes of the 31...     

A theoretical study on the alkali metal carboxylate-promoted L-Lactide polymerization

Sodium acetate-catalyzed L-lactide polymerization reaction is a simple yet efficient reaction. It provides a robust system to produce poly(L-lactide) in industrial scale. In this study, the mechanism of this reaction has been studied by means of computational chemistry tools based on the experimental results. Basically, the mechanism consists of two steps: lactide coordination and ring opening through O-Acyl bond cleavage. Additionally, the effect of cation size and substituent on carboxylate moiety have been evaluated. The calculations indicate that the larger cation leads to faster reactions. Moreover, the stronger electron-donating group on carboxylate moiety accelerates the reaction rates. To obtain further insights, an orbital analysis has been also carried out. Our calculations are consistent with experimental findings and clarify underlying mechanistic features of the present reaction.     

Acoustic properties of aortic aneurysm obtained with scanning acoustic microscopy

In aortic aneurysm tissues, macrophages and their secretion of matrix metalloproteinases (MMPs) are playing important role for tissue degeneration. Some studies have shown that weakening of the mechanical properties of the degenerated tissues may progress the expansion of the aneurysm. However, actual measurement of the mechanical properties has not been investigated at microscopic level. The objective of the present study is to assess the mechanical properties of aortic aneurysm tissues by measuring acoustic properties by scanning acoustic microscopy (SAM). Twenty-one cases of aortic aneurysm including renal and common iliac aneurysm tissues were surgically excised. Each tissue was fixed by 4% formaldehyde and the specimens were treated as (1) picrosirius red staining for normal and polarized light microscopy, (2) CD68 staining for macrophage detection, and (3) no staining for acoustic microscopy. A specially developed SAM system operating in the frequency range of 100-200 MHz, was employed in the measurement. Images of amplitude and phase are obtained in a field of 2x2 mm. The intima was mainly consisted of degenerated collagen without polarization of picrosirius red staining. Macrophages stained by CD68 were observed near the degenerated collagen fibers. The sound speed was 1567 m/s in the intima, 1576 m/s in the media, 1640 m/s in the adventitia, respectively. Infiltration of macrophages showed higher values of attenuation and sound speed than the surrounding tissues. The sound speed of the intima was significantly lower than our previous measurement of atherosclerotic aorta without aneurismal change. As the tissue elasticity is closely correlated with the sound speed, the elasticity of the intima was considered to be lower in aneurysm tissues. This mechanical weakness may contribute to the expansion of the diameter of the aneurysm. Acoustic microscopy provided important data for assessing tissue mechanical properties of abdominal aneurysm.