点击化学在木质纤维素化学修饰中的研究现状

化学修饰可改善木质纤维素和聚合物基质的相容性且使其具有特定功能。点击化学作为化学修饰的一种重要方法,是由2001年诺贝尔化学奖获得者Sharpless首次提出的,主要包括铜催化叠氮-炔基环加成反应(CuAAC)、环张力催化叠氮-炔基环加成反应(SPAAC)、巯基-烯/炔点击反应(Thiol-Ene/Yne)和狄尔斯-阿尔德尔环加成反应(Diels-Alder)等反应类型。相比传统接枝修饰方法,点击化学具有反应条件温和、环境污染小、副反应少、分离提纯简单、产量和效率高等优点,在木质纤维素的化学修饰方面已有相关应用。在点击反应方法方面,CuAAC反应是一种最普遍的点击反应类型,也是对木质纤维素化学修饰应用最多的一类反应;但CuAAC反应后催化剂很难移除,在一定程度上限定了反应后产品的用途,将Cu(I)通过共价键结合在纳米纤维素气凝胶的表面能使点击反应中的铜有效回收。相比CuAAC反应,Thiol-Ene/Yne反应不需要有毒的铜作为催化剂。点击化学在纤维素的研究方面,将纤维素自身或与聚合物进行点击反应能制备水凝胶和片状纳米纤维素凝胶;此外,荧光标记的纤维素材料能证明点击反应的发生,通过2种点击反应能制备多色荧光标记的纳米纤维素材料。点击化学在半纤维素和木质素的研究方面,木聚糖通过与聚乳酸进行点击反应形成共聚物,能降低玻璃化转变温度,提高热分解温度。通过CuAAC反应能形成苯三唑连接高产率的邻位木糖苷和木二糖苷。木质素和聚苯乙烯通过点击反应能制备一种热塑性聚合物。此外,通过生物正交点击化学能描述活体植物细胞壁的木质化过程。点击化学在木质纤维素上的应用还没有深入研究,扩大点击化学在木质纤维素上的应用范围仍然需要进一步探索。由于点击反应的条件比较温和,很多反应都能在室温下进行,非常有利于在生物医用材料领域的研究,并且纤维素和半纤维素等多糖又具有良好的生物相容性,为纤维素和半纤维素在生物领域的应用创造了有利条件。此外,由于铜催化的毒性作用,无铜催化的点击反应可能会作为一个重要发展方向,像环张力催化叠氮-炔基环加成反应、Diels-Alder反应和Thiol-Ene/Yne反应。     

己唑醇/介孔SiO_2缓释纳米球的制备及其性能

基于St?ber方法,制备出介孔SiO_2纳米球(MSNs)和树枝状介孔SiO_2纳米球(dMSNs),并以己唑醇(He)为模型农药,通过物理吸附方法分别制备了己唑醇/介孔SiO_2复合纳米球(He/MSNs)和己唑醇/树枝状介孔SiO_2复合纳米球(He/dMSNs)。采用透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)对制备的介孔纳米球形貌和结构进行表征;利用Brunauer-Emmett-Teller (BET)气体吸附法对介孔二氧化硅纳米球和树枝状介孔二氧化硅纳米球的孔结构进行表征;通过热重分析(TG)、模拟释放实验和抑菌实验对制备的载药复合纳米球载药量、释药性能及药效进行研究。结果表明,MSNs和d MSNs的平均粒径分别为(210±10)和(235±10) nm,比表面积分别为1 092.867和1 289.110 m^2/g,孔容分别为0.690和0.814 cm^3/g,孔径分别为32.144和32.673?。He/MSNs和He/d MSNs载药率分别达到42%和84%,且缓释作用明显。He/MSNs和He/dMSNs(0.1 mg/m L)对可可毛色二孢菌均表现出良好的抑菌性能。     

核桃壳粉负载纳米Cu催化剂的制备及催化炔酮合成

以核桃壳粉(WSPs)为载体,采用还原沉淀法制备了WSPs负载的铜催化剂(WSPs-Cu),采用红外(FT-IR)、热重分析(TGA)、X射线衍射分析(XRD)、扫描电镜结合X射线能谱(SEM/EDS)等对WSPs-Cu进行表征,结果表明:成功制备出Cu较均匀分布在WSPs表面的WSPs-Cu催化剂,WSPs-Cu的含铜量为3.386%,同时WSPs-Cu在100～200℃范围内具有较好的热稳定性。以WSPs-Cu为异相催化剂,催化苯甲酰氯及其衍生物与苯乙炔之间的偶联反应,制备出炔酮类化合物,结果表明:在无溶剂的条件下,以三乙胺为缚酸剂,微波辐射以及40℃下反应30 min,WSPs-Cu催化合成了5种炔酮化合物(产率61%～90%)。WSPs-Cu循环使用5次后仍保留较高活性,催化合成产物的产率为79%。将模型反应由微量放大到常量,投料量为80 mmol时,WSPs-Cu催化合成炔酮的产率可达到82%。     

基于过氧化氢预处理的巨龙竹木质素提取及结构解析

巨龙竹属禾本科竹亚科牡竹属竹种,是世界上已知最粗大的巨型丛生竹种,具有极高的开发利用价值。本研究采用碱性过氧化氢预处理结合碱抽提的方法提取巨龙竹秆材中的木质素,通过核磁共振、红外光谱以及热稳定性分析等方法,对所得的木质素样品进行了结构表征与解析。结果表明:巨龙竹木质素是典型的禾草类(HGS型)木质素,其大分子结构由对羟基苯丙烷单元、愈创木基单元和紫丁香基单元构成;木质素的结构中的联接结构以β-O-4'联接键居多,β-β'和β-5'联接键较少;巨龙竹木质素有部分在侧链的γ位上与对香豆酸发生酯化反应,形成稳定的对香豆酸酯结构;本研究分离得到的3个巨龙竹木质素样品起始分解温度分别为194.8、195.4、197.9℃,热稳定性良好。     

二乙醇胺基木质素非离子表面活性剂的制备及表征

依据酸沉淀法对碱木质素进行了分级,分级后pH值4 ～ 6的木质素与环氧氯丙烷、二乙醇胺反应,制备了木质素基非离子表面活性剂.通过红外光谱、含氮量的测定对产物的结构进行了表征,通过表面张力测定对产品的表面活性进行了分析.结果表明:木质素基非离子表面活性剂固含量为32.6%,含氮量为1.99%,红外光谱分析可确定在木质素上引入了环氧氯丙烷和二乙醇胺,水溶液表面张力降低到53.27mN/m,表明二乙醇胺基木质素非离子表面活性剂(DLNS)具有良好的表面活性.另外通过与十二烷基磺酸钠(SDS)复配后浊度的测定,表明产品在SDS与DLNS的体积比为20: 3 ～ 20: 20范围与SDS复配,浊度较低,复配效果较好.     

木质素在三氮唑基离子液体中溶解性能的研究

设计合成并表征了3种三氮唑基离子液体:1-丁基-3-甲基咪唑三氮唑盐([Bmim]tr)、N-甲基-N-丁基吗啉三氮唑盐([Bmmo]tr)和N-丁基吡啶三氮唑盐([Bpy]tr),其中木质素在[Bmim]tr中的溶解性能最佳,在55℃的微波加热条件下,木质素溶解度达到58.61 g。采用HSQC、GPC、FT-IR和XRD等技术对[Bmim]tr溶解再生前后的木质素进行了表征,结果表明:在溶解过程中微波加热更有利于破坏木质素的氢键和β-O-4'结构,加速木质素的溶解,并导致木质素非晶态化,而其基本结构单元没有发生改变。分析表明:木质素在离子液体中的溶解机理是氢键的破坏与重组、β-O-4'连接结构的断裂。     

镁离子催化合成木质素-酚醛树脂的结构与固化特性

以纳米氧化镁(MgO)为催化剂,通过在酶解木质素(EHL)、苯酚、甲醛和NaO H反应的初期添加纳米MgO合成MgO催化的木质素-酚醛(MLPF)树脂。采用傅里叶红外光谱(FT-IR)、核磁共振(13C NMR)及差示扫描量热(DSC)技术手段表征MLPF树脂的分子结构与固化反应热行为,并与未添加MgO的对照样木质素-酚醛(LPF)树脂及酚醛(PF)树脂进行对比分析,研究Mg~(2+)对MLPF树脂结构与固化特性的影响,结果表明:Mg~(2+)有效促进了MLPF树脂中羟甲基基团形成,增加了分子结构中亚甲基连接结构数量,抑制了亚甲基醚键生成,使MLPF树脂结构的缩合程度高于LPF树脂;Mg~(2+)可以实现MLPF树脂快速固化,降低树脂的固化反应温度。     

以碱木质素胺盐为模板制备纳米二氧化钛及其光催化性能研究

为提高制浆造纸工业废水中的木质素的利用率,以减少对环境的污染,利用碱木质素改性制备了两种木质素胺盐,并以这两种木质素胺盐为模板剂,通过水热合成法制备了二氧化钛纳米粒子。通过X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和BET比表面积分析等手段对制得的二氧化钛纳米粒子进行表征测试。结果表明:以木质素的乙二胺盐和三甲胺盐所制得的二氧化钛纳米粒子的粒径分别为15~25 nm和20~35 nm,粒子分散均匀,两种样品的比表面积分别为104.2 m2/g和71.7 m2/g。通过在紫外光下催化降解罗丹明B考察了所制备的二氧化钛的光催化活性,实验结果表明所制备的二氧化钛具有与P25相当的光催化活性。     

超声-弱碱协同作用下巨龙竹木质素的分离及表征

巨龙竹是一种具有极高研究和开发价值的大型经济用材竹种,其基础理化性质有待进一步解析研究。为表征巨龙竹木质素的化学结构,在超声-弱碱协同作用下处理竹材原料,脱蜡竹粉在2%NaOH溶液中分别经超声处理5,20,40,60和90 min,并设置仅在2%NaOH溶液中抽提90 min的对照组,最后得到6个木质素样品L_1~L_6。采用红外光谱(FTIR)、核磁共振碳谱(~(13)C NMR)和二维核磁共振(2D HSQC)分别对分离得到的巨龙竹木质素进行结构分析。结果表明:超声-弱碱协同处理对竹材木质素具有良好的促溶效果,随着超声作用时间的增加,木质素得率从6.6%提高到22.9%;巨龙竹木质素大分子主要由愈创木基(G)、紫丁香基(S)和对羟基苯基(H)结构单元构成,属于禾草类木质素(GSH型);巨龙竹木质素大分子的主要联接键为β-O-4'醚键,其次是β-β'和β-5'结构;但随着超声处理时间的增加,巨龙竹木质素中一定量的β-O-4'联接键会被打断。     

季铵化纳米SiO_2抑菌性能和改性竹材疏水性的研究

利用纳米SiO_2表面羟基,与不同的硅烷偶联剂以及叔胺反应制得了2种季铵化纳米Si0_2,对产物进行了表征、抑菌性评价,并对产物浸渍改性处理后竹材的疏水性进行研究。结果表明:1)2种合成方法均制得了季铵化纳米Si0_2,Zeta电位为正值,平均粒径QASN-1纳米SiO_2QASN-2。2)抑菌圈试验表明,季铵化纳米SiO2_对竹材8种主要侵害菌有不同程度的抑制作用。3)经过改性的竹块表面由亲水性变为疏水性,且水接触角减小的速度要小于改性前的。由此可见,季铵化纳米Si0_2可用于竹材的侵害菌防护和防水。     

Investigation on hydrophobic modification of bamboo flour surface by means of atom transfer radical polymerization method

To convert the hydrophilic surface of bamboo flour into a hydrophobic surface, methyl methacrylate (MMA) was grafted onto bamboo flour surface by means of atom transfer radical polymerization (ATRP) method. The grafted bamboo flour was characterized by using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), water contact angle and thermogravimetric analysis. The results from FTIR and SEM have confirmed that MMA groups have been successfully grafted onto bamboo surface by means of the ATRP method, which caused the water contact angle increase to be 128.7°, i.e., hydrophilic bamboo flour turned into hydrophobicity. However, the thermal stability of grafted bamboo flour decreased compared with pure bamboo flour.     

Thermo characteristics of steam-exploded bamboo (Phyllostachys pubescens) lignin

Bamboo (Phyllostachys pubescens) internode was subjected to steam explosion treatment to produce an excellent fiber for binderless boards. Lignin was isolated from extract-free bamboo meal with Björkman’s procedure and steam-exploded pulp. The self binding-mechanism was discussed by scanning electron microscopy (SEM), thermo-gravimetry (TG), differential scanning calorimetry (DSC) and analytical ozonation. It is well-known that steam explosion treatment liberates lignin from the cell wall to the fiber surface, which is the most important component relevant to binderless board production. Results of TG and DSC analyses showed that steam-exploded bamboo pulp started mass loss at lower temperature compared to bamboo internode meal. The thermal softening temperature of lignin prepared from steam-exploded pulp was much lower than that of lignin prepared from extract-free bamboo meal. This suggests that intermonomer linkages of lignin, especially β-aryl-ether linkage which is the major intermonomer linkage of lignin, were cleaved during steam explosion treatment resulting in low molecular weight phenolic compounds. The cleavage of β-aryl-ether intermonomer linkage of lignin was also confirmed by ozonation analysis.     

Ag_2O/再生纤维素球形气凝胶的性能表征

为了探讨再生纤维素气凝胶对碘蒸气的吸附去除能力,用天然竹纤维制备再生纤维素球形气凝胶(RCSA),然后通过银氨络离子在纤维素表面的吸附和反应,得到Ag2O/再生纤维素球形复合气凝胶(Ag2O/RCSA),以127I作为放射性131I的同位素研究了复合气凝胶对碘的吸附。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)和BET比表面积等检测手段对制备的Ag2O/RCSA样品的形貌、晶型、孔隙结构和碘吸附性能进行了表征。研究结果表明:纳米Ag2O粒子的引入使RCSA颜色由白色变为棕色,RCSA原始的三维网结构没有发生变化;纳米Ag2O粒子均匀分布在纤维素骨架中,并与纤维素紧密结合;Ag2O/RCSA与RCSA一样都表现为Ⅳ型吸附/脱附等温线,BET比表面积、BJH孔体积比RCSA明显减小,平均孔径大小变化不大;Ag2O/RCSA对碘蒸气的吸附是气凝胶孔隙的物理吸附和Ag2O转变为Ag I的化学吸附共同作用,总吸附量为87.8 mg/g。     

Surface deterioration of moso bamboo (<Emphasis Type="Italic">Phyllostachys pubescens</Emphasis>) induced by exposure to artificial sunlight

The effect of ultraviolet-visible light irradiation on changes in surface chemistry and morphology of moso bamboo (Phyllostachys pubescens Mazel) was investigated. Fourier transform infrared (FT-IR) and FT-Raman spectroscopy were used in combination to study chemical changes induced by exposure to artificial sunlight (xenon lamp) for up to 160 h, and the resulting physical changes of cell walls of bamboo surfaces were examined by scanning electron microscopy (SEM). FT-IR results showed that significant changes occurred in the lignin component as indicated by considerable decreases in the intensities of the characteristic aromatic lignin peak at 1512 cm⁻¹ and other associated bands. This was accompanied by formation of new carbonyl groups at 1735 cm⁻¹, resulting in photooxidation of bamboo surfaces. The photosensitive nature of bamboo lignin was also demonstrated by FT-Raman analysis, in which obvious decreases in intensities of Raman bands at 1604 and 1630 cm⁻¹ mainly derived from lignin and free and esterified p-coumaric and ferulic acids were observed. SEM micrographs of the irradiated cross sections of bamboo revealed that significant damage occurred to the fiber walls, whereas the parenchyma cells exhibited slight distortion and some cracks occurred in the cell walls. The structures of cell corners and middle lamellae were nearly intact after irradiation.     

竹原纤维和竹粉纤维形态和化学成分分析

以3年生毛竹材为原料,研究了毛竹竹粉和竹原纤维的纤维形态和化学成分。纤维形态分析结果表明:竹原纤维的宽度(143μm)与竹粉(136μm)相当,长度(22.63 mm)远高于竹粉(0.61 mm),使其长宽比(158.25)远高于竹粉(4.49)。化学成分分析表明:竹原纤维的纤维素含量(65.6%)比竹粉(37.3%)高得多,聚戊糖含量(17.1%)略低于竹粉(20.1%)。竹粉中的木质素含量为24.5%,是竹原纤维中木质素含量(11.5%)的2倍多。竹原纤维的高纤维素含量和低木质素含量是其广泛应用于制浆造纸行业的重要原因。     

毛竹水解渣木质素氢解制备芳香化学品

以毛竹水解渣为原料,分别采用过氧化氢法和甲醇法提取木质素,在相同的反应条件下对比了两种木质素转化及产物分布的结果,并进一步优化了过氧化氢法提取的木质素的氢解转化最优条件.研究结果表明:温度为220℃,反应时间60 min时,过氧化氢木质素可以全部转化为可溶物,单体收率为14.85％;甲醇法提取的甲醇木质素,转化产物中可...     

Dynamic adsorption of α-pinene and linalool on silica nanoparticles for enhanced antifeedant activity against agricultural pests

The terpene compounds, α-pinene and linalool were formulated with silica nanoparticles (SNPs) by a simple immersion method and the antifeedant activity of these formulations was evaluated against two major agricultural pests, the tobacco cutworm (Spodoptera litura F.) and the castor semilooper (Achaea janata L.) in laboratory bioassays. The interaction between terpenes and SNPs, shelf-life, suspension stability as well as the bioactivity of the nanoformulations were also studied. Both these terpenes in their pure form are known to deter feeding in several lepidopterous insects. However, formulating these pure terpene compounds with nano silica enhanced their biological activity up to 25 times to S. litura. Fourier transform infrared spectroscopy analysis of these nano botanical formulations indicated the presence of hydrogen bonding between terpenes and the surface of SNPs. Transmission electron microscopy images confirmed the higher aggregation property of the SNPs. Suspension studies validated the improved shelf-life of the nano-biocomposites, while X-ray diffraction (XRD) revealed the amorphous nature of formulations and no crystalline impurities. Adsorption of α-pinene and linalool onto SNPs resulted in an effective formulation that enhanced the antifeedant potential of the individual terpenes against insects while producing longer shelf-life for the terpenes.     

竹材木质素降解菌的筛选与鉴定*

竹材木质素的降解一直是制约竹材资源利用的重要影响因素。文章通过对49 份腐烂的竹材样品进行平板划线分离纯化得到74 株真菌,利用PDA- 愈创木酚变色及PDA- 苯胺蓝退色反应,初步筛选出具有木质素降解酶能力的4 株木质素降解菌,通过酶活力测定对初筛得到的4 株木质素降解菌进行复筛,发现FG-22 菌株具有较好木质素降解能力,对FG-22 降解菌株进行形态学和分子生物学鉴定,确定FG-22 为杂色云芝（Trametes versicolor）。     

竹炭陶土复合材料的制备和结构性能表征

以竹炭粉、陶土为主要原料,经混合、成型、干燥和煅烧等工艺制得竹炭陶土复合材料(以下称竹炭陶),采用扫描电子显微镜(SEM)、X射线衍射(XRD)仪、拉曼光谱测试仪(Raman)、傅里叶变换红外光谱(FTIR)和比表面积测试仪等仪器,对竹炭陶的微晶构造、孔隙结构、吸附和红外辐射性能等进行表征。结果表明:竹炭微粒镶嵌在陶土基体中,保留原有以中孔为主的孔隙结构和类石墨化晶体结构,获得的竹炭陶具有较大的比表面积和中孔为主的孔隙结构,能有效地吸附甲醛、苯等有害气体。加入一定量的竹炭能提高竹炭陶的远红外发射率,其红外发射率均高于陶土和竹炭,结合红外吸收光谱谱图分析,竹炭陶具有高红外发射率的本质在于具有倍频吸收、分子基团振动、转动及晶格振动。     

Ultraviolet resistance and other physical properties of softwood polymer nanocomposites reinforced with ZnO nanoparticles and nanoclay

Wood polymer nanocomposites (WPNCs) based on nano-ZnO and nanoclay were prepared by impregnation of melamine formaldehyde–furfuryl alcohol copolymer, 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU), a cross-linking agent and a renewable polymer obtained as a gum from the plant Moringa oleifera under vacuum condition. Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometry (XRD) studies were employed for the characterization of modified ZnO and WPNCs. The change in crystallinity index (CrI) value of the cellulose in wood and the distribution of ZnO nanoparticles in composites were determined using FTIR and XRD. Scanning electron microscopy and Transmission electron microscopy showed the presence of nanoparticles and nanoclay in the cell lumen or cell wall of wood. An enhanced UV resistance property was shown by the treated wood samples as judged by lower weight loss, carbonyl index, lignin index, cellulose CrI values, and mechanical property loss compared to the untreated wood samples. Wood polymer composites treated with 3 phr each of nanoclay, ZnO, and the plant gum showed an improvement in mechanical properties, flame-retarding properties, thermal stability, and lower water uptake capacity.