Biomimetic Construction of the Enamel-like Hierarchical Structure

Enamel, the hardest mineralized tissue of vertebrates, exhibits simultaneously high stiffness, hardness, and viscoelasticity. The excellent mechanical properties of enamel originate from its high inorganic content and intricate hierarchical structure. Biomimetic construction of the enamel-like hierarchical structure has attracted widespread interest during the past decades. This review summarizes recent advances in this area with a special focus on fabrication techniques across different levels of hierarchy. This includes the synthesis of apatite nanorods or nanowires, the basic building block of enamel, the fabrication of oriented apatite nanorod arrays and the construction of the enamel-like multi-level hierarchical structure. Moreover, possible directions of future research and development in this field are proposed.     

A Facile Synthetic Route to L-Phosphinothricin

Phosphinothricin, the active ingredient of the well known broad-spectrum herbicideglufosinate-ammonium, is a naturally occurring amino acid possessing the uniquemethylphosphinate moiety, and its strong herbicidal activity has been attributed to anability to inhibit glutamine synthetase in plants and bacteria1. Further research showedthat L-enantiomer of phosphinothricin was the carrier of the activity, whereas the D formonly had a small action2, therefore the stereoselective synthesis of L-pho…     

Constructing Intrapenetrated Hierarchical Zeolites with Highly Complete Framework via Protozeolite Seeding

Creation of intrapenetrated mesopores with open highway from external surface into the interior of zeolite crystals are highly desirable that can significantly improve the molecular transport and active sites accessibility of microporous zeolites to afford enhanced catalytic properties. Here, different from traditional zeolite-seeded methods that generally produced isolated mesopores in zeolites, nanosized amorphous protozeolites with embryo structure of zeolites were used as seeds for the construction of single-crystalline hierarchical ZSM-5 zeolites with intrapenetrated mesopores (mesopore volume of 0.51 cm³ g⁻¹) and highly complete framework. In this strategy, in contrast to the conventional synthesis, only a small amount of organic structure directing agents and a low crystallization temperature were adopted to promise the protozeolites as the dominant growth directing sites to induce crystallization. The protozeolite nanoseeds provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as-prepared hierarchical ZSM-5 zeolites exhibited ultra-long lifetime of 443.9 hours and a high propylene selectivity of 47.92 % at a WHSV of 2 h⁻¹ in the methanol-to-propylene reaction. This work provides a facile protozeolite-seeded strategy for the synthesis of intrapenetrated hierarchical zeolites that are highly effective for catalytic applications.     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

均相与非均相法合成的纤维素乙酸酯结构与性能的比较研究

研究了离子液体中均相反应制备纤维素乙酸酯(CA_(Homo))与非均相反应制备纤维素乙酸酯(CA_(Hete))的化学结构,进而比较了化学结构差别对纤维素乙酸酯性能的影响.均相与非均相法制备的CA化学结构存在显著差异,CA_(Homo)相比CA_(Hete)具有更好的均匀性,且CA_(Homo)和CA_(Hete)的取代基分布不同,CA_(Homo)的乙酰基取代顺序为C-6C-3C-2,CA_(Hete)的乙酰基取代顺序为C-3C-2C-6.同时对CA_(Homo)和CA_(Hete)的结晶行为、溶解性和热性能进行研究,结果表明,不同化学结构对CA的这些宏观性能影响较小,CA_(Homo)和CA_(Hete)均为无定型结构,可溶解于极性有机溶剂中,玻璃化转变温度和热稳定性相近.因此,通过离子液体均相制备的CA与现有非均相法制备的CA具有相似的物理性能,但均相法制备的CA结构均匀性更好.     

纳米纤维素基多层级孔道结构碳气凝胶的制备及在锂电池中的应用

采用纳米精磨法对商品桉木浆进行纳米纤丝化处理,得到了高长径比、尺寸均一的纳米纤丝化纤维素(NFC),平均直径为230.10 nm,长度达数十微米.将其组装、干燥后制得具有大量介孔的纳米纤丝化纤维素气凝胶(NFCA).将NFCA在氮气氛围下高温碳化制得碳气凝胶(CNFA),或在氢氧化钾条件下辅助碳化制得具有多层级孔道结构的碳气凝胶(CNFA-A),在保留的碳气凝胶骨架结构上进行孔洞构建.通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)表征及Nanomeasure统计分析,发现NFC的平均直径经碳化后减小到53.16 nm.利用X射线衍射(XRD)、BET比表面积测试和拉曼光谱揭示了碳化处理对纳米纤维素结构、比表面积、石墨化程度和缺陷的影响.结果表明,KOH辅助碳化处理后的碳气凝胶不仅保留了纤维素气凝胶前驱体的网络结构,还在其骨架上二次构建了更多的微孔和介孔,其比表面积高达488.92 m2/g,总孔容为0.404 cm3/g,所得的碳骨架被部分石墨化,具有良好的导电性.这类源于生物质的高比表面积碳气凝胶在被用作锂离子电池(LIB)负极材料时表现出优异的电化学性能,在电流密度1 A/g下连续充放电1000次后比容量达到409 m A·h/g,在电流密度高达20 A/g下,比容量还能维持在219 m A·h/g.     

Unconventional Cellulose Esters: Synthesis, Characterization and Structure–Property Relations

This paper summarizes selected results obtained during a two-year research project in the framework of the focus program Cellulose and cellulose derivatives (SPP 1011), sponsored by the German Science Foundation (DFG). New synthesis paths for the preparation of the most important cellulose ester, cellulose acetate, were investigated. In contrast to conventional methods, cellulose was converted in a homogeneous phase reaction with acetyl chloride in the presence of different bases, including polyvinyl pyridine and cross-linked polyvinyl pyridine. Moreover, results of the conversion in the new solvent dimethyl sulfoxide/tetrabutylammonium fluoride trihydrate are discussed. The structures obtained were analyzed both on the level of the anhydroglucose unit (AGU) and along the polymer chain. It was found that the addition of a base can significantly change the selectivity of the reaction and thereby the properties of the products (e.g., solubility). No signs of a non-statistical distribution of the acetyl groups along the polymer chains were observed. Furthermore, reactivity and selectivity of the acylation reactions, using in situ activation with p-toluenesulfonyl chloride (Tos-Cl), were studied for different long-chain carboxylic acids (capric-, caprylic-, decanoic-, lauric-, palmitic-, stearic acid). The thermogravimetric analysis of these derivatives showed that the decomposition temperature increased with an increasing number of carbon atoms, starting from 292 °C (cellulose caprate) to 318 °C (cellulose stearate). New cellulose derivatives were synthesized, for example, cellulose adamantoyl ester. For this purpose cellulose was converted homogeneously in N,N-dimethylacetamide/LiCl with free acids in the presence of activating reagents, for example, Tos-Cl or 1,1-carbonyldiimidazol.     

A Study on the Preparation,Structure, and Properties of Microcrystalline Cellulose

Abstract

The preparation, structure, and properties of microcrystalline cellulose (MCC) from rice straw were investigated by IR, x-ray, viscometry, polarizing microscope, SEM, etc. The results are as follows:

1. The leveling-off degree of polymerization (LODP) obtained from rice straw is about 80–150. The dimensions of MCC granules are 20–30 μm length, 0.5–0.8 μm thick, and the crystallinity is about 80%.

2. The aqueous suspension of a certain concentration of MCC can form a gel under the effect of shear force. The viscosity of MCC gel increased with an increasing content of MCC in water. A sharper increase of viscosity occurred in the 3–6% range.

3. The addition of one or two valence salts into the MCC gel increased the viscosity.

4. The viscosity of MCC gel has its maximum value at pH 8.

5. The MCC gel as an emulsifying agent can form a stable emulsion in the oil/water system when the ratio of oil/water is below 6/4.     

A Review of Cellulose and Cellulose Blends for Preparation of Bio-derived and Conventional Membranes,Nanostructured Thin Films,and Composites

Cellulose has been used as a raw material for the manufacture of membranes and fibers for many years. This review gives the background of the most recent methods of treating or dissolving cellulose, and its derivatives to form polymer films or membranes for a variety of applications. Indeed, some potential applications of bacterial cellulose, nanofibrillar cellulose (NFC) for films showing enhanced barrier characteristics are reviewed as well as the utilization of cellulose nanonocrystals (CNC) for production of highly oriented super strong films or thin films is discussed. Because of the success of the Lyocell process as well as the amine/metal thiocyanate solvent blends of cellulose and other polysaccharides like starch, chitosan, and other natural polymers. Consequently, the use of cellulose (or its derivatives) and another polysaccharide dissolved as a blend is also elaborated. It is our hope that the reader will want to follow up and investigate these new systems and use them to develop end use materials for all sorts of applications, from medical to water filtration, or electrogels for use in batteries.     

Sol-Gel Route to Direct Formation of Silica Aerogel Microparticles Using Supercritical Solvents

A simple and versatile method to obtain silica aerogel particles based on the hydrolysis and subsequent condensation of silicon alkoxides in supercritical fluids is proposed. This microparticle production route reduces the number of steps of traditional microparticle sol-gel processing.A case example is explained in more detail. Spherical and fiber silica morphologies were obtained by a one step method using a sol-gel process with supercritical acetone as a solvent. Particle size was controlled by varying the relative amounts of alkoxysilane, water and acetone. The resulting materials are influenced by a large number of experimental parameters; it has been observed that a quite relevant one is the supercritical fluid venting rate. The morphology of the particles was characterized by electron microscopy (SEM and TEM) and Atomic Force Microscopy (AFM). Alternatively, a low temperature synthesis can be performed by using supercritical carbon dioxide as solvent and formic acid as condensation agent.     

A New Method for the Synthesis of Ketone Diperoxide

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以新型模板方法合成中孔SiO2分子筛

以廉价、生物可降解的两性表面活性剂十四烷基甜菜碱作为模板剂,以正硅酸乙酯为 硅源,在酸性条件下成功地合成了具有螺旋状孔道结构的SiO2中孔分子筛.热重表征结果说 明,采用溶剂萃取（乙醇的水溶液为萃取剂）的方法,近乎100％的模板剂可以脱除回收.     

A Comparative Simulation: Difference between Chemical Grafting and Physical Doping of Cellulose by Using Polysilsesquioxane

In order to study the effect of different modification methods on polysilsesquioxane (POSS) modified cellulose, a molecular dynamics method was used to establish a pure cellulose model and a series of modified models modified by polysilsesquioxane in different ways. And their thermodynamic properties were calculated. The results showed that the performance of cellulose models was better than that of unmodified model, and the modified effect was the best when two cellulose chains were grafted onto polysilsesquioxane by chemical bond (M2 model). Compared with pure cellulose model, the cohesive energy density and solubility parameters of M2 model are increased by 9%, and the values of tensile modulus, bulk modulus, shear modulus and Cauchy pressure increased by 38.6%, 29.5%, 41.1% and 29.5%, respectively. In addition, the free volume fraction and mean square displacement of each model were calculated and analyzed in this work. Compared with the pure cellulose model, the molecular chain entanglement of cellulose was increased due to the existence of the chemical bonds in the M2 model, which made the cellulose molecular chains occupy more free volume, so that the system had a smaller free volume fraction, inhibited the chain movement of cellulose chains, and thus improved the thermal stability of cellulose.     

A Novel of PTA/ZIF-8@Cellulose Aerogel Composite Materials for Efficient Photocatalytic Degradation of Organic Dyes in Water

A novel PTA/ZIF-8@CA composite material (PTA = phosphotungstic acid; CA = cellulose aerogel) with multilayer three-dimensional network structure was synthesized with cellulose aerogel as the framework and MOFs as the filler. The results showed that the degradation rates of methylene blue at δ = 10 ppm reached 99.8 % respectively in 30 min under the conditions of PTA/ZIF-8@CA input amount of 0.6 g · L^–1 and pH = 5. The degradation rate of rhodamine B at δ = 10 ppm reached 99.7 % in 60 min. This shows that PTA/ZIF-8@CA has excellent degradation efficiency and short-term performance. In addition, after 5 photocatalytic cycles, the degradation rates of methylene blue and rhodamine B by PTA/ZIF-8@CA were still 83.0 % and 82.5 %, respectively, reflecting that PTA/ZIF-8@CA has terrific photocatalysis stability.     

A Facile Route to Rapid Synthesis of Soluble Monodisperse Oligo(1,4-phenyleneethynylene)s

Introduction Recently, much attention has been paid to monodisperse, well-defined conjugated oligomers as candidates for molecular wires and molecular scale electronic devices[1-7]. Shape persistent oligo(1,4-phenyleneethynylene)s are especially attractive for their excellent main-chain rigidity and interesting electronic characteristics[3-7]. Different iterative divergent/convergent routes have been reported by several groups for the rapid synthesis of oligo(1,4-phenyleneethynylene)s. Godt et al.[5]     

纤维素及其衍生物催化脱氧转化制化学品

Biomass, as a renewable carbon resource in nature, has been considered as an ideal starting feedstock to produce various valuable chemicals, fuels, and materials, and thus, can help build a sustainable chemical industry. Because cellulose is one of the richest components in lignocellulosic biomass, the efficient transformation of cellulose plays a crucial role in biomass utilization. However, there are many oxygen-containing groups in cellulose, and therefore, the selective removal of particular functional groups from cellulose becomes an essential step in the synthesis of the chemicals or fuels that can meet the requirements set by current chemical industries. In the past decades, several efficient catalytic systems have been developed to selectively split the C―O bonds inside cellulose and its derivatives, thereby producing various valuable chemicals. In this review article, we highlight recent progress made in the selective deoxygenation of cellulose and its derived key platforms such as glucose and 5-hydroxymethyl furfural (HMF) into ethanol, dimethyl furfural (DMF), 1, 6-hexanediol (1, 6-HD), and adipic acid. The selection of these reactions is primarily because these chemicals are of great significance in chemical industries. More importantly, the formation of these chemicals represents the cleavage of different C―O bonds in biomass molecules. For instance, the synthesis of ethanol requires cleaving of only one C―O bond and two C―C bonds of the glucose unit inside cellulose. If two or more C―O bonds in the sugar or sugar acids are cleaved, olefins, oxygen-reduced sugars, and adipic acid will be attained. HMF has a furan ring linked by hydroxyl/carbonyl groups, and hence, either a furanic compound (e.g., DMF) or linear products (e.g., 1, 6-HD and adipic acid) can be synthesized by selective removal of hydroxyl/carbonyl oxygen or ring oxygen atoms. This article focuses on the selective cleavage of particular C―O bonds via heterogeneous catalysis. Efficient catalytic systems using hydrogenolysis and/or deoxydehydration strategies for these transformations are discussed. Moreover, the functions of typical catalysts and reaction mechanisms are presented to obtain insight into the C―O bond cleavage in these biomass molecules. Additionally, other factors such as reaction conditions that also influence the deoxygenation performance are analyzed. We hope that these knowledge gained on the catalytic deoxygenation of cellulose and its derived platforms will promote the rational design of effective strategies or catalysts in the future utilization of lignocellulosic biomass.     

纤维素及其衍生物催化脱氧转化制化学品

纤维素是木质纤维素生物质中最为丰富的组分,将其催化转化制备高附加值化学品在生物质资源化利用中占据极为重要的一席之地。由于纤维素中氧含量过高,需选择性地脱除部分氧原子才可获得满足当前化学工业对各类高值化学品的要求。近年来,针对纤维素以及由其衍生的关键平台分子葡萄糖和5-羟甲基糠醛(HMF)等催化脱氧的研究已引起广泛关注,并取得诸多重要进展。在此,我们总结了具有代表性的多相催化剂体系,讨论了利用氢解或脱水脱氧策略分别将纤维素和葡萄糖等分子中一个或多个C―O键裁剪制备乙醇、烯烃或己二酸等的研究。我们还着重介绍了HMF和其衍生的呋喃化合物选择性剪切C―OH/C＝O键或呋喃环中的C―O―C键分别制备二甲基呋喃和1, 6-己二醇等催化体系。此外,对各多相催化剂的作用机制和特定C―O断键机理也分别进行了探讨,以期深入理解纤维素及其衍生物的催化脱氧反应。     

Lewis酸催化纤维素制乳酸机理研究

乳酸是制备可降解聚合物聚乳酸的主要单体。利用秸秆等原生生物质为原料经过化学催化转化制备乳酸对于碳减排具有重要意义。本工作利用同位素核磁和质谱详细探究了不同Lewis酸(Y³⁺,Sc³⁺,Al³⁺)催化纤维素制乳酸的反应选择性和机理。发现葡萄糖异构化为果糖的过程是决定纤维素制乳酸多步串联反应最终选择性的关键步骤,并明确了1, 3-二羟基丙酮生成乳酸经历了烯醇互变异构过程而非经典的1, 2-shift机理。     

A Facile Route to Rapid Synthesis of Soluble Monodisperse Oligo （1,4-phenyleneethynylene） s

Recently, much attention has been paid to monodisperse, well-defined conjugated oligomers as candidates for molecular wires and molecular scale electronic devices. Shape persistent oligo ( 1,4-phenylene-ethynylene) s are especially attractive for their excellent main-chain rigidity and interesting electronic characteristics.     

Lewis酸催化纤维素制乳酸机理研究

Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y³⁺, Sc³⁺, and Al³⁺) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y³⁺ > Al³⁺ > Sc³⁺. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y³⁺ > Al³⁺, Y³⁺ > Sc³⁺), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc³⁺ > Y³⁺ > Al³⁺), and the conversion of DHA or GLY to the final product lactic acid (Al³⁺ > Y³⁺ > Sc³⁺). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.