The impact of cellulose structure on binding interactions with hemicellulose and pectin

Four cellulose substrates including highly crystalline cellulose nanowhiskers (CNWs) from Gluconacetobacter xylinus (cellulose Iα) or cotton (cellulose Iβ) and amorphous cellulose derived from CNWs (phosphoric acid swollen cellulose nanowhiskers, PASCNWs) were used to explore the interaction between cellulose and well-defined xyloglucan, xylan, arabinogalactan and pectin. The binding behavior was characterized by adsorption isotherm and Langmuir models. The maximum adsorption and the binding constant of xyloglucan, xylan and pectin to any CNWs were always higher than to PASCNWs derived from the same source. The binding affinity of xyloglucan, xylan and pectin to G. xylinus cellulose was generally higher than to cotton cellulose, showing that binding interactions depended on the biological origin of cellulose and associated differences in its structure. The surface area, porosity, crystal plane and degree of order of cellulose substrate may all impact the interactions.     

Synthesis, Structure and H+/K+-ATPase Inhibitory Activity of Novel Triazolyl Substituted Tetrahydrobenzofuran Derivatives via One-pot Three-component Click Reaction

Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H⁺/K⁺‐ATPase inhibitor via one‐pot CuI‐catalyzed three‐component click reaction of azide, secondary amine and 3‐bromopropyne under mild conditions in water. Their structures were characterized by NMR, IR, ESI‐MS, elemental analysis and single‐crystal X‐ray diffraction analysis. Most of the target compounds exhibited better H⁺/K⁺‐ATPase inhibitory activity than commercial omeprazole with IC₅₀ values less than 15 µmol·L^?1. The initial structure‐activity analysis suggested that the triazole substituted by cycloalkyl, aromatic ring or O‐containing side‐chain seemed to be beneficial for enhancing the activity.     

Configuration Design Sensitivity Analysis of Kinematic Responses of Mechanical Systems∗

Abstract

A continuum-based configuration design sensitivity analysis method is presented for kinematically driven mechanical systems. Configuration design variable for mechanical systems are defined. The 3-1-3 Euler angle is used as the orientation design variable. The reassembly process for a mechanical system after a configuration design change is eliminated by imposing kinematic admissibility conditions of the velocity field. The direct differentiation method is used to derive design sensitivity equations. Numerical examples are presented to demonstrate the validity and effectiveness of the proposed method.     

Synthesis and characterization of thermally crosslinkable hole‐transporting polymers for PLEDs

Two new thermally crosslinkable hole‐transporting polymers, X‐PTPA and X‐PCz, were synthesized via Yamamoto coupling reactions. The number‐averaged molecular weights (M_n) of X‐PTPA and X‐PCz were found to be 45,000 and 48,000, respectively, and therewith, polydispersity indices were of 1.8 and 1.7, respectively. Thermally crosslinked X‐PTPA and X‐PCz exhibit excellent solvent resistance and stable optoelectronic properties. The UV–visible maximum absorption peaks of X‐PTPA and X‐PCz in the thin film state are at 389 and 322 nm, respectively. The HOMO levels of X‐PTPA and X‐PCz are estimated to be ?5.27 and ?5.39 eV, respectively. Multilayered devices (ITO/crosslinked X‐PTPA or X‐PCz/SY‐PPV/LiF/Al) were fabricated with SY (SuperYellow) as the emitting layer. The maximum efficiency of the multilayered device with a crosslinked X‐PTPA layer is approximately three times higher than that of the device without a crosslinked X‐PTPA layer and much higher than that of the crosslinked X‐PCz device. This result can be explained by the observations that crosslinked X‐PTPA produces increased electron accumulation within the emitter, SY, and also efficient exciton formation due to improved charge balance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5111–5117     

Phase Transfer Catalyzed Anomeric Nucleophilic Substitutions with D-Xylopyranosyl Halides

Abstract

Anomeric pairs of per-O-acetylated-D-xylopyranosyl halides were individually treated with a wide variety of nucleophiles under mild PTC conditions. Thus, 2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide 1 provided exclusively the β-D-xylopyranosyl anomers 2-11 in good to excellent yields (65-95%). Alternatively, under the same PTC conditions, 2,3,4-tri-O-acetyl-β-D-xylopyranosyl chloride 13 afforded solely the inverted α-D-anomers 15 (82%) and 16 (67%) upon treatment with thiophenol and sodium azide, respectively. Similarly, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 19 provided the analogous products 20 (63%) and 21 (31%) upon treatment with thiophenol and sodium azide. In the presence of tetrabutylammonium chloride as PTC catalyst, β-xylopyranosyl chloride 13 was shown to slowly equilibrate to the α-chloride 14. Therefore, care must be taken to avoid PTC catalyst for which counter anions can cause anomerization of the starting glycosyl halides.     

Multireference calculations on low-lying states and the X~3 Π_u -~3 Π_g absorption spectra of indium dimers

Multireference configuration interaction calculations are carried out on 11 Λ-S low-lying electronic states of indium dimers. The states are investigated with spin-orbit pseudopotentials via the state-interacting method, and characterized by fitted spectroscopic constants based on computed potential energy curves. The vibrational structures of the double-potential well 0+g (I) ( 3 Σ g ) state are also analyzed. The experimentally observed absorption spectrum centred at ～ 13000cm-1 is simulated and assigned to X 3 Πu (v=0)-3Πg transition according to the present ab initio calculations on transition energies and dipole moment functions.