Partial crystalline transformation of solvated cellulose IIII crystals, reproduced by theoretical calculations

In hot-water molecular dynamics simulation at 370 K, four cellulose III_I crystal models, with different lattice planes and dimensions, exhibited partial crystalline transformations of (1 ?1 0) chain sheets, in which hydroxymethyl groups were irreversibly rotated from gt into tg conformations, accompanied by hydrogen-bond exchange from the original O3–O6 to cellulose-I-like O2–O6 bonds. The final hydrogen-bond exchange ratio was about 95 % for some of the crystal models after 50 ns simulation. The corrugated (1 ?1 0) chain sheet was converted to a cellulose-I-like flat chain sheet with a slightly right-handed twist. The 3D structures of the three types of isolated chain sheet models were optimized using density functional theory calculations to compare their stabilities without crystal packing forces. The cellulose Iβ (1 0 0) models were more stable than the cellulose III_I (1 ?1 0) models. The optimized structure of cellulose III_I (1 0 0) models deviated largely from the initial sheet form. It was proposed to the crystalline transformation from cellulose III_I to Iβ that conversion of the chain sheet structure first take place, followed by sliding of the chain sheet along the fiber axis.     

Tandyukisin,a novel ketoaldehyde decalin derivative,produced by a marine sponge-derived Trichoderma harzianum

Tandyukisin (1), a novel decalin derivative with an enolic β-ketoaldehyde, has been isolated from a strain of Trichoderma harzianum OUPS-111D-4 originally derived from the marine sponge Halichondria okadai, and its structure has been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques. In addition, the absolute configuration for 1 was established by the application of CD spectrum to the tribenzoate derivative. This compounds exhibited moderate cytotoxicity against human cancer cell lines.     

A Tray‐Shaped,PdII‐Clipped Au3 Complex as a Scaffold for the Modular Assembly of [3×n] Au Ion Clusters

A tray‐shaped Pd^II₃Au^I₃ complex ( 1 ) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with Au^I followed by Pd^II clipping. Tray 1 is an efficient scaffold for the modular assembly of [3×n] Au^I clusters. Treatment of 1 with the Au^I₃ tricyclic guest 2 in H₂O/CH₃CN (7:3) or H₂O results in the selective formation of a [3×2] cluster ( 1 ⋅ 2 ) or a [3×3] cluster ( 1 ⋅ 2 ⋅ 1 ), respectively. Upon subsequent addition of Ag^I ions, these complexes are converted to an unprecedented Au₃–Au₃–Ag–Au₃–Au₃ metal ion cluster.     

Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions

Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.     

4-Ketozeinoxanthin,a novel carotenoid produced in Escherichia coli through metabolic engineering using carotenogenic genes of bacterium and liverwort

In order to produce a novel keto-carotenoid in Escherichia coli, we introduced the marine bacterial carotenoid ketolase gene (crtW) into pathway-engineered E. coli producing carotenoids of plant origin, which carried the lycopene biosynthesis genes (crtE, crtB, and crtI) from soil bacterium Pantoea ananatis and the liverwort Marchantia polymorpha genes that encode lycopene β-cyclase (MpLCYb), lycopene ε-cyclase (MpLCYe), and β-carotenoid hydroxylase (MpBHY). A novel keto-carotenoid (1) was produced by these carotenoid biosynthesis genes in E. coli along with α-echinenone, adonirubin, and adonixanthin. The structure of 1 was determined as (3S,6′R)-3-hydroxy-β,ε-caroten-4-one based on Uv–vis, MS, ¹H NMR, and CD spectral data. This compound was named 4-ketozeinoxanthin and showed anti-tumor-promoting activity.     

Preparation of Molecule‐Responsive Microsized Hydrogels via Photopolymerization for Smart Microchannel Microvalves

Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.

     

Quantification of Intracellular Thiols by HPLC-Fluorescence Detection

Biothiols, such as cysteine and glutathione, play important roles in various intracellular reactions represented by the redox equilibrium against oxidative stress. In this study, a method for intracellular thiol quantification using HPLC-fluorescence detection was developed. Thiols were derivatized with a thiol-specific fluorescence derivatization reagent, viz. ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), followed by reversed-phase separation on an InertSustain AQ-C18 column. Six different SBD-thiols (homocysteine, cysteine, cysteinylglycine, γ-glutamylcysteine, glutathione, and N-acetylcysteine as an internal standard) were separated within 30 min using a citric buffer (pH 3.0)/MeOH mobile phase. The calibration curves of all the SBD-thiols had strong linearity (R² > 0.999). Using this developed method, the thiol concentrations of human chronic myelogenous leukemia K562 cell samples were found to be 5.5–153 pmol/1 × 10⁶ cells. The time-dependent effect of a thiol scavenger, viz. N-ethyl maleimide, on intracellular thiol concentrations was also quantified. This method is useful for elucidating the role of intracellular sulfur metabolism.     

Dispersion of Carbon Nanotubes with “Green” Detergents

Solubilization of carbon nanotubes (CNTs) is a fundamental technique for the use of CNTs and their conjugates as nanodevices and nanobiodevices. In this work, we demonstrate the preparation of CNT suspensions with “green” detergents made from coconuts and bamboo as fundamental research in CNT nanotechnology. Single-walled CNTs (SWNTs) with a few carboxylic acid groups (3–5%) and pristine multi-walled CNTs (MWNTs) were mixed in each detergent solution and sonicated with a bath-type sonicator. The prepared suspensions were characterized using absorbance spectroscopy, scanning electron microscopy, and Raman spectroscopy. Among the eight combinations of CNTs and detergents (two types of CNTs and four detergents, including sodium dodecyl sulfate (SDS) as the standard), SWNTs/MWNTs were well dispersed in all combinations except the combination of the MWNTs and the bamboo detergent. The stability of the suspensions prepared with coconut detergents was better than that prepared with SDS. Because the efficiency of the bamboo detergents against the MWNTs differed significantly from that against the SWNTs, the natural detergent might be useful for separating CNTs. Our results revealed that the use of the “green” detergents had the advantage of dispersing CNTs as well as SDS.