SEC–MALLS analysis of cellulose using LiCl/1,3-dimethyl-2-imidazolidinone as an eluent

The lithium chloride/1,3-dimethyl-2-imidazolidinone (LiCl/DMI) solvent system for cellulose was adopted as a mobile phase of size-exclusion chromatographic (SEC) analysis of cellulose, and the applicability of this system was examined using multi-angle laser light scattering and ¹³C-NMR analysis. The results indicate that 8% (w/v) LiCl/DMI ID a true solvent for cellulose, and that cellulose molecules dissolving ID 1% (w/v) LiCl/DMI are separated orderly depending on their molecular mass (MM) or root-mean-square (RMS) radius by the SEC system. Practically, no aggregates were detected ID the dilute cellulose/LiCl/DMI solutions. Furthermore, high stability of cellulose/LiCl/DMI solutions has been demonstrated; only a few percent of decline ID average MM was observed even after storage for 6 months at room temperature. Relationships between RMS radius and MM for hardwood bleached kraft pulp ID 1% LiCl/DMI was estimated as the following equation: _g^0.59, corresponding to a Mark–Houwink–Sakurada exponent of 0.77.     

Determination of empirical polarity parameters of the cellulose solvent N,N-dimethylacetamide/LiCl by means of the solvatochromic technique

Empirical solvatochromic polarity parameters (α-, β-, and $ \pi ^* $, AN and DN, as well as E_T(30)-values) for cellulose, N,N-dimethylacetamide (DMA)/LiCl and cellulose dissolved in DMA/LiCl are presented. The following solvent polarity indicators were applied: 2,6-diphenyl-4-(2,4,6-triphenyl-1- pyridinio)-1-phenolate ( 1 ), bis(4-N,N-dimethylamino)-benzophenone (MK, 2 ), iron(II)-di-cyano-bis(1,10)-phenanthroline, Fe(phen)₂(CN)₂, ( 3 ), and copper(II)-N,N,N′,N′-tetramethyl-ethylendiamine-acetylacetonate tetraphenylborate/chloride/bromide (Cu(tmen)(acac)⁺ X⁻ ( 4 )). The solvatochromic shifts (ν_max) of the indicators 1 , 2 , 3 , and 4 adsorbed to cellulose or dissolved in DMA/LiCl reflect the corresponding properties of the surrounding, the dipolarity/polarizability ($ \pi ^* $), the hydrogen bond donating ability or Lewis acidity (α), and the hydrogen bond accepting ability or Lewis basicity (β), respectively. Any indicator employed is well characterized (r > 0.97) by a linear solvation energy relationship (LSER) taking the Kamlet and Taft parameter into account: ν_max(indicator) = ν_max,0 + s$ \pi ^* $ + aα + bβ. Cellulose, DMA/LiCl, and the cellulose/DMA/LiCl solution approach a similar polarity with an E_T(30) parameter about 52 to 53 kcal mol⁻¹. The hypothetical interaction strength parameter (acid-base interactions, dipolar–dipolar interactions) between cellulose and DMA/LiCl are calculated by means of the individual Kamlet–Taft parameters α, β, and $ \pi ^* $ of cellulose and DMA/LiCl via a multiparameter equation. The specific chloride/cellulose interaction plays a dominant role in the cellulose solvent DMA/LiCl. Comparison of the polarity parameters of DMA/LiCl with the polarity parameters of other mixtures—such as N,N-dimethyl- formamide/LiCl, DMA/NaCl, or DMA/LiBr—are presented as well. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1945–1955, 1998     

LiCl／DMAc溶剂体系中长链脂肪酸纤维素酯的制备及其药物释放性能

在ＬｉＣｌ／ＤＭＡｃ溶剂体系中由纤维素与长链脂肪酸氯反应制备长链脂肪酸纤维素酯,并研究了反应条件对酯化反应取代度的影响。结果表明在适当的反应条件下,酯化聚代度可达到２．８５（９５％）。还研究了纤维酯作为药物控制释放载体对ＬＮＧ、Ａｓｐｉｒｉｎ、ＢＡＳ的释放性能。     

Chitin–cellulose blends: phase properties in dimethylacetamide–LiCl

Chitin–cellulose blends dissolved in dimethylacetamide containing LiCl (7% w/w) have been studied in a wide concentration range, from very dilute solutions to medium concentrations and up to solid films (absence of diluent). The intrinsic viscosities at various chitin–cellulose ratios, as well as the phase diagram behavior, imply a good compatibility between the components. The result is confirmed by the infrared measurements on solid films. The lack of anisotropic phase formation in chitin–diluent binary solutions and the anomalous trend of v′_CH–CE line on the phase diagram are both interpreted on the basis of aggregation phenomena.     

Liquid crystalline cellulose derivative elastomer films under uniaxial strain

Mesogenic cellulose derivative chains cross-linked into free-standing thin films were prepared by a shear-casting technique from anisotropic precursor solutions of thermotropic (acetoxypropyl)cellulose. After shear cessation a macroscopically oriented serpentine structure with the director in average along the shear direction is locked resulting in anisotropic optical and mechanical properties of the material. These films were submitted to an external uniaxial mechanical field perpendicular and parallel to the shear direction. Stretching perpendicular to the shear direction produced significant director rotations and a reset of order of the director order parameter for a deformation in the range 2–3 as detected by X-rays and optical microscopy. The different response found for strains imposed parallel and perpendicular to the initial average director orientation indicates that even though our system shows a serpentine director modulation that is either attenuated or reinforced by deformations parallel or perpendicular to the shear direction, its behaviour is similar to theoretical predictions for monodomain nematic elastomers described in the literature.     

Enthalpies of formation of some phases present in the Y−Ba−Cu−O system by solution calorimetry

Enthalpies of some of the phases in the Y–Ba–Cu–O system were determined by solution calorimetry using a Calvet microcalorimeter. The standard enthalpies of formation for the phases were found to be YBa₂Cu₃O_6.60, –2627.9; YBa₂Cu₃O_6.77, –2641.8; YBa₂Cu₃O_6.90, –2652.0; YBa₂Cu₃O_6.99, –2659.3; Y₂Cu₂O₅, –2198.6; Y₂BaCuO₅, –2656.4; BaCuO_2.33, –788.6; and BaCuO_2.42, –796.2 kJ-mol^–1.     

Functionalized diacetylenes for nonlinear optical applications: Synthesis,characterization, and the properties of their monolayers

Synthesis and characterization of DA(8/1)OMe (14-{4′-[(methoxy)methoxy] biphenyl}-10,12-tetradecadiynoic acid) and DA(8/1)NBP (14-{4′-[(nitro)methoxy] biphenyl}-10,12-tetradecadiynoic acid ) are presented. Monolayers of DA(8/1)OMe at gas-water interface were investigated. It does not form a stable monolayer nor does it undergo polymerization at the gas-water interface. However, the Ba²⁺ and Cd²⁺ salts formed stable monolayer that polymerized. Polymerization was confirmed by Raman spectroscopy. The diacetylene analog with the more polar tail group, DA(8/1)NBP, does not form a monolayer and undergo polymerization regardless of the subphase condition. A mixed monolayer of DA(8/1)OMe and DA(8/1)NBP forms a true monolayer if the composition of DA(8/1)NBP is 50% or less. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1771–1779, 1999     

Preparation of liquid–crystal thermosets: In situ photopolymerization of oriented liquid–crystal diacrylates

The photoinitiated polymerization of 2-chloro-1,4-phenylene bis[4-[6-(acryloyloxy)hexyloxy]benzoate] (1M) was studied. The monomer 1M exhibited a broad nematic phase between 24.9 and 113.7 °C on a DSC cooling scan. It was oriented in its nematic phase at a substrate coated with polyimide and unidirectionally rubbed with a nylon cloth. During polymerization, the ordering of the liquid–crystal molecules was fixed, yielding a uniaxially crosslinked network. The clear liquid–crystal networks (LCNs) exhibited a birefringence between 0.14 and 0.19, depending on the polymerization temperature. Finally, a nonmesogenic diluent, tetra(ethylene glycol)diacrylate, was mixed with 1M, subsequently decreasing the birefringence of the obtained LCNs. The LCNs containing nonmesogenic diluent exhibited not only a smaller birefringence but also a weaker birefringence dispersion in the visible region. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3929–3935, 1999     

基于印刷电子的透明导电薄膜研究进展

透明导电薄膜是一种在可见光范围内透光率较高、导电性优良的薄膜材料.近年来随着智能手机、平板电脑等电子产品日益普及,透明导电薄膜受到越来越多的关注.本文分析了目前占据市场统治地位的掺锡氧化铟透明导电薄膜的缺点以及近年来国内外对透明导电薄膜开展的研究工作,总结了目前在印刷电子领域透明导电薄膜的主要研究方向,一方面是在传统金属氧化物薄膜基础上的改进;另一方面是寻找新型透明导电薄膜材料,并分别综述了各个研究方向的最新进展.     

溶剂热法制备铝掺杂的氧化锌透明导电薄膜

采用溶剂热法在玻璃基片上沉积铝掺杂的氧化锌透明导电膜(AZO)。研究了前驱溶液中Al3+与Zn2+的物质的量的比nAl3+/nZn2+、溶剂热反应温度和反应时间对薄膜物相、形貌、可见光透过率和电阻率的影响。结果表明,溶剂热法所制备的AZO薄膜具有六方纤锌矿结构,Al3+不仅改善薄膜的导电性而且起矿化剂的作用促进薄膜生长,溶剂热反应时间的增加没有使薄膜显著增厚。采用溶剂热法可制备出可见光平均透过率大于80%、方块电阻小于500Ω的AZO薄膜。