Development and Characterization of Laccol Lacquer Blended with Urushiol Lacquer

A lacquer blending urushiol and laccol was investigated. The blended lacquer with 30wt.% urushiol and 100wt.% laccol has a good drying property and film hardness. 2-D-NMR and FD-MS measurements of the lacquer dimer showed that a transfer of radicals between urushiol and laccol occurred during the enzymatic polymerization, and 4-4′ biphenyl, 4-6′ (4′-6), and 6-6 (6-6′) dibenzofuran structures were obtained.     

Characterization of traditional Korean lacquers using surface analytical techniques

Traditional Korean lacquer films, such as Otchil and Hwangchil, are natural paints extracted from Rhus vernicifera and Dendropanax morbifera trees that grow in the eastern part and on the west and south coast of the Korean Peninsula, respectively. Rhus lacquer has a black color, and Hwangchil has a transparent gold color and a rich camphoric perfume (benzoin). These lacquers have been used since ancient times. In this study, analytical techniques, such as Fourier transform infrared (FT‐IR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), and time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), were used to study the traditional Rhus lacquer and Hwangchil films, avoiding time‐consuming and destructive extraction procedures. To compare the Rhus and Hwangchil lacquers, reference lacquer films were prepared using Rhus and Dendropanax saps. These films were then analyzed using FT‐IR, XPS, and TOF‐SIMS. After establishing the methodology using the reference lacquer films, surface analytical techniques were applied to two different plates painted by an artist. The results suggest that FT‐IR, XPS, and TOF‐SIMS are simple and complementary analytical techniques for the discrimination of old lacquer films. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of polysaccharides purified from Lacquer tree seed cakes and its antioxidant activity

Three polysaccharides, LTPS-1, LTPS-21 and LTPS-31 were isolated and purified from the seed cakes of lacquer tree using DEAE-52 cellulose and Sephadex G-200 column chromatography. The total sugar contents of LTPS-1, LTPS-21 and LTPS-31 were 931.8, 958.2 and 895.1 g kg^?1, respectively. LTPS-1 (3.48 kDa) was mainly composed of rhamnose, arabinose, glucose and galactose in a ratio of 35.36:5.06:1:2. LTPS-21 (11.4 kDa) was mainly composed of rhamnose, arabinose, mannose and galactose in a ratio of 41.93:21.8:1.01:9.24. LTPS-31 (19.49 kDa) was mainly composed of rhamnose, arabinose and mannose in a ratio of 38.31:16.44:1.1. IR analysis suggested they contained lower sulphuric acids, the LTPS-21 and LTPS-31 belonged to β-type polysaccharide. Among the three polysaccharides, LTPS-21 exhibited the strongest reducing power, scavenging activity on ABTS and hydroxyl radicals. These findings suggested that polysaccharides from the seed cakes could be potentially developed as natural functional ingredients in the food and cosmetic industry.     

添加改性松香对生漆漆膜性能的影响

通过添加松香、改性松香对生漆漆膜进行改性,研究结果表明,加入改性松香能改善生漆漆膜性能,在反应温度为80℃时,加入生漆质量5％的聚合松香效果最佳,附着力为1级,抗冲击力为35kg／cm,铅笔划痕为3H。反应温度对漆膜性能有很大影响,当加入生漆质量5％的聚合松香,反应温度从50℃升至80℃时,附着力从3级提高到1级,抗冲击力从10kg／cm提高到35kg／cm,铅笔划痕从H升至3H。红外光谱分析表明,天然松香对生漆性能的增强效果是由于与生漆发生了化学反应,而聚合松香对生漆性能的增强效果是协同作用造成的。     

高效液相色谱法分析生漆多糖中的单糖组成

采用μ－ＢｏｎｄａｐａｋＮＨ２ＴＭ色谱柱,以乙腈∶水∶甲醇（７０∶２５∶５,Ｖ／Ｖ）为流动相,利用示差折光检测器的高效液相色谱法对湖北毛坝大木、毛坝小木和建始３种生漆中漆多糖的单糖组成成分进行了直接分离分析,方法简便、快速、重现性好,回收率在９８．８％～１０３．６％之间,相对标准偏差在５％以下。     

Characterization of Chinese Lacquer in Historical Artwork by On-Line Methylation Pyrolysis-Gas Chromatography/Mass Spectrometry

An effective method for characterizing Chinese lacquer as binding medium in historical artwork has been developed by on-line methylation pyrolysis-gas chromatography–mass spectrometry (pyrolysis GC–MS). The characteristic pyrolytic components of Chinese lacquer were identified in artificially aged pure and pigmented lacquer. Methylation of urushiol (mainly composed of catechol derivatives) was performed by adding tetramethyl ammonium hydroxide to convert phenolic hydroxyl groups into methylated derivatives to improve the resolution of catechol derivatives and urushiol monomers. The mechanism of formation of small molecular components was proposed, and the influence of different mineral pigments (azurite, malachite, ochre, and cinnabar) on the determination of characteristic components was discussed. Aliphatic hydrocarbon components, benzene derivatives, catechol derivatives, and urushiol monomers were proposed as characteristic pyrolytic components. In addition to 3-pentadecene-catechol, 3-pentadecane-catechol, and 3-heptadecene-catechol, 3-pentadecene-phenol was also identified as an urushiol monomer in Chinese lacquer. Four pigments slightly reduced the detection of aliphatic hydrocarbon components, but were unconspicuous for the detection of benzene derivatives. Azurite, malachite, and cinnabar decreased the measurement of urushiol monomers, but ochre significantly increased their relative abundance. The established on-line methylation pyrolysis GC–MS procedure and summarized data were successfully applied to the identification of samples collected from Terra-Cotta Warriors and Horses of Qin Dynasty (221–207 BC), Han Yang Mausoleum of Han Dynasty (206 BC–24 AD), and Dazu Grotto of Tang Dynasty (618–907 AD).     

螺噁嗪化合物在丙烯酸聚氨酯清漆膜中的光致变色性能

制备了含有螺噁嗪(SO)化合物的紫外光固化丙烯酸聚氨酯清漆(UV-PUA)膜, 研究了SO在该清漆中的光致变色性能, 并与其在聚甲基丙烯酸甲酯(PMMA)中的光致变色性能进行了比较. 结果发现, 紫外光固化螺噁嗪丙烯酸聚氨酯清漆(UV-SO-PUA)膜在紫外光固化过程中逐渐由无色变为蓝色和紫色, 撤去紫外光源, 漆膜退色至粉色, 且固化后的漆膜在粉色和紫色之间可逆变化; 而SO-PMMA膜在无色和蓝色之间可逆变化. 紫外光激发的UV-SO-PUA膜的紫外-可见吸收光谱可见光区出现了明显的双重吸收峰(520和600 nm), 而在PMMA中仅出现单峰. SO开环体在UV-PUA 中室温稳定性优于其在ＰＭＭＡ中的稳定性. SO在UV-PUA膜中的抗疲劳性能与其在PMMA中相比显著提高, 紫外光照射16 h, UV-SO-PUA漆膜未出现疲劳现象. SO在UV-PUA膜中表现出了优良的光致变色行为.     

汽车漆皮的气相色谱指纹图谱比对方法及应用研究

采用在线热解吸/毛细管气相色谱联用方法建立了对汽车漆皮指纹图谱进行比对的方法,并将该方法应用于实际样品的鉴定。该方法通过将一定大小和质量的漆皮样品置于热解吸炉中进行加热解吸,自漆皮中解吸出来的挥发性有机物在色谱仪上得到分离检测。通过直观比较两张漆皮图谱的峰形轮廓是否一致进行初步判断,对外形相似的图谱进一步计算二者谱峰的重叠率,并以相对保留时间比值rt2/rt1和相对峰面积比值rA2/rA1来考察待比较图谱的相似度。当谱峰重叠率大于90%,rt2/rt1和rA2/rA1的相似度分别大于99%和70%时,可认定待比较的两个漆皮样品来自同一辆车。该方法操作简便,谱峰识别能力强,实现了对指纹图谱的定量表征描述,使漆皮的仪器分析数据成为法律上可采信的有力物证之一。     

侧链液晶高分子的非线性光学特征及其应用

阐述了侧链高分子液晶非线性光学的基本原理,着重讨论了影响非线性光学特征的几个基本因素,说明了双折射与外场强度、双折射与序参数之间的定量关系,展望了侧链高分子液晶非线性光学特征在一些领域中的应用前景。     

Systematic and efficient side chain optimization for molecular docking using a cheapest‐path procedure

Molecular docking of small‐molecules is an important procedure for computer‐aided drug design. Modeling receptor side chain flexibility is often important or even crucial, as it allows the receptor to adopt new conformations as induced by ligand binding. However, the accurate and efficient incorporation of receptor side chain flexibility has proven to be a challenge due to the huge computational complexity required to adequately address this problem. Here we describe a new docking approach with a very fast, graph‐based optimization algorithm for assignment of the near‐optimal set of residue rotamers. We extensively validate our approach using the 40 DUD target benchmarks commonly used to assess virtual screening performance and demonstrate a large improvement using the developed side chain optimization over rigid receptor docking (average ROC AUC of 0.693 vs. 0.623). Compared to numerous benchmarks, the overall performance is better than nearly all other commonly used procedures. Furthermore, we provide a detailed analysis of the level of receptor flexibility observed in docking results for different classes of residues and elucidate potential avenues for further improvement. © 2013 Wiley Periodicals, Inc.     

Comprehensive Characterization of Chain End Groups of Vinylidene Fluoride Based Polymers

Summary: In this work an investigation of the chain end groups produced in the free radical copolymerization of vinilydene fluoride (VDF) and hexafluoropropylene (HFP) is performed. Type and amount of chain end groups are evaluated by a meticulous analytical characterization of VDF/HFP copolymer. At first pulsed gradient spin-echo nuclear magnetic resonance (spin-echo NMR) is used to identify all the chain end groups also at very low concentration (equal to 0.1 mmol · Kg⁻¹). The instrument sensitivity is increased of an order of magnitude in comparison with the traditional NMR. Moreover potentiometric titration and ion chromatography (IC) are also used to study the chain end groups and, as a consequence, the nature and the amount of the acidity showed by the polymer chains. In details two intensity of acidity are detected by potentiometric titration, namely strong and weak. The strong acidity is associated to the presence of residual surfactant and can be removed washing the polymer, while the weak acidity is due to free molecules of fluoride acid (HF). The standard ion chromatography facility is properly modified to quantify the fluoride in the polymer matrix without any pre extraction in water. Thanks to this the HF concentration in the polymer is evaluated with high accuracy. A detailed kinetic scheme for the VDF/HFP polymerization is also proposed taking into account all the findings obtained studying the chain end groups.     

具有圆偏振光特性的卟啉衍生物的合成、表征和CD光谱研究

合成了一组不同碳链的胆甾醇酯侧链卟啉配体和金属Zn配合物. 研究了它们的吸收光谱和发射光谱. 将这些卟啉配体以一定浓度掺杂在聚甲基丙烯酸甲酯(PMMA)中制成固体薄膜, 发现由于在卟啉环上引入了手性的胆甾醇酯侧链, 卟啉化合物在soret带和Q带均有较强的CD吸收, 这种现象可能是卟啉环上的四个手性胆甾醇酯侧链与四苯基卟啉环发生偶合作用. 进一步还发现这些卟啉化合物的圆偏振吸收性质与在PMMA中的浓度有关.     

用混合乳化剂UE20/PVA制备的水包油型生漆乳液的性能

以漆酚基乳化剂(UE20)和聚乙烯醇(PVA)为混合乳化剂制备了水包油(O/W)型生漆乳液(RLE), 研究了UE20与PVA的质量比、混合乳化剂质量分数(wME)、水与天然生漆(RL)的质量比、温度和贮存时间对RLE性能的影响, 并用透射电镜观察了wME对RLE粒子的大小及形态的影响. 结果表明, RLE的黏度随着PVA的增加而增大; 当wME≤6.7%时, RLE表现出假塑性流体的特征, 其黏度随着wME的增大而增大, 乳液的稳定性增强; 而当wME≥10.0%时, RLE则表现出膨胀型流体的特征, 乳液的黏度较低; 随着温度的升高及水的用量增加, RLE粒子间相互作用减弱, 乳液的稳定性降低. 正交实验结果表明, 影响RLE的黏度及稳定性的顺序为wME＞mH2O∶mRL＞mUE20∶mPVA＞乳化温度. 随着wME的增大, RLE粒子的粒径减小, 其形态也由不规则的形状转变为球形粒子.     

Dimer Structures and Laccase-Catalyzed Polymerization Mechanism of Laccol in Fresh Rhus Succedanea Lacquer Sap

Laccase-catalyzed polymerization of laccol was promoted by a kneading process, and the molecular weight distribution and drying properties were examined. The laccol dimers were separated and purified by HPLC, and the chemical structures were characterized by IR, GC-MS, and NMR spectroscopy involving two-dimensional NMR measurements. Two sorts of C-C coupling, nuclear-nuclear (C-C) and nuclear-side chain (C-C), were found in the laccol dimer, which differ from the nuclear-side chain (C-O-C) couplings of urushiol and the only nuclear-nuclear (C-C) couplings of thitsiol. Based on these results, the properties of laccol lacquer film and the laccase-catalyzed polymerization mechanism of laccol are discussed.     

Composite spectral density functions for the interpretation of the 13C NMR relaxation behavior of polymers containing hydrocarbon side chains. Free and restricted side chain motion

¹³C NMR NT₁ and NOE have been calculated by using composite spectral density functions describing polymer chain segmental motion and internal rotation of a hydrocarbon side chain attached to the polymer backbone. Numerical results at two magnetic fields are presented as a function of the various motional parameters characterizing the various models. NT₁ and NOE relaxation parameters are well behaved and appear to have practical value for describing the dynamics of these systems. The models have been applied to the relaxation data of poly(n-butyl methacrylate) and poly(n-hexyl methacrylate) in toluene solutions. The dynamics of the two polymers are characterized by a very localized backbone motion and restricted internal rotation about successive C? C bonds of the side chains. © 1995 John Wiley & Sons, Inc.     

Characterization of mechanically sheared ethylene–propylene copolymers by high resolution NMR

We report high-resolution solution-state NMR experiments on chain ends generated in ethylene–propylene copolymers by mechanical shearing in an extruder. The use of the higher resolution of the ¹³C-NMR spectrum, in a two-dimensional ¹H-¹³C chemical shift correlation experiment, has allowed the complete resolution and assignment of the olefinic chain-end region of the ¹H-NMR spectrum. Simultaneously, the assignments of the ¹³C olefinic resonances, previously identified [A. C. Kolbert, J. G. Didier, and L. Xu, Macromolecules, 29 , 8591 (1996)] are confirmed. An iterative method for calculating the average molecular weight, based on quantitative measurements of the olefinic ¹H-NMR peak intensities is introduced and these results are compared with measurements from ¹³C-NMR and size exclusion chromatography and correlated to reduced viscosities. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1955–1961, 1997     

新型不饱和聚磷酸酯的合成、表征及性能

通过溶液聚合制备了一种新型不饱和聚磷酸酯(Polymer Ⅰ), 经季铵化得到了侧基含季铵基的不饱和聚磷酸酯(PolymerⅡ). 对聚合物的结构和热性能进行了表征. 研究了PolymerⅡ与聚丁二酸丁二醇酯(PBS)的共混片基(Polymer Ⅱ的质量分数分别为5%, 10%和20%)在pH=7.4的磷酸缓冲溶液中的溶胀和降解性能. 结果表明, 以纯三甲胺为季铵化试剂, 在V(氯仿): V(异丙醇): V(DMF)=3: 5: 5的混合溶剂中, 于60℃反应24 h可得到季铵化率高达48%的PolymerⅡ. 在PBS中PolymerⅡ的含量越多, 达到溶胀平衡时, 共混片基的溶胀率越高, 越容易降解. 磷酸酯的引入使聚合物的熔点(T_m)和热稳定性(T_d)降低.     

Thermoluminescence detection of Korean traditional foods exposed to gamma and electron-beam irradiation

Thermoluminescence(TL) analysis was applied to detect irradiated Korean traditional condiments and soup mixes containing salt(NaCl). These food items, which are commercially irradiated in Korea, showed a consistently high correlation(R²) between the absorbed doses and the corresponding TL responses. It was proved that table salt played a role as an in-built indicator in TL measurements and its concentration in test samples was proposed as a correction factor for varying conditions of TL measurements. Pre-established threshold values were successfully adopted to identify 167 coded samples of Ramen soup mixes, both non-irradiated and irradiated with gamma and electron-beam energy. The TL intensity of irradiated soup mixes decreased with the lapse of time, but was still distinguishable from that of the non-irradiated samples at the fourth month of ambient storage. Expected estimates of absorbed doses, 2.85 and 4.75 kGv were obtained using a quadratic equation with average values of 1.57 and 4.90 kGy, respectively.     

侧链含有蓝相液晶基元的聚硅氧烷液晶的合成及表征

采用蓝相小板块液晶单体反式-4-乙烯基-反式-4′-丙基双环己烷（3HHV）和反式-4-丙烯基-反式-4′-丙基双环己烷（4HHV）同时接枝到聚甲基含氢硅氧烷上,制备了聚硅氧烷侧链液晶聚合物。采用红外光谱和核磁共振氢谱对液晶单体及相应的聚合物进行结构表征,采用热台偏光显微镜,X-射线衍射和热分析对单体和聚合物的液晶行为及热性能进行研究。结果表明：液晶单体3HHV显示蓝相镶嵌织构,液晶单体4HHV显示胆甾相油纹状织构,它们的介晶区间温度分别为30.6°C和49.7°C,且均在低于室温就显示出液晶性。相应的液晶聚合物显示向列相纹影织构,介晶区间温度为192.6°C,在低于室温时也显示出液晶性,且热分解温度达到310°C以上,比其他环芳烃类介晶基元接枝聚硅氧烷主链的液晶聚合物具有更优越的热稳定性。