3D打印用高分子材料及其复合材料的研究进展北大核心CSCD

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。作为第三次工业革命的代表性技术之一,3D打印材料是影响3D打印技术发展与应用的关健因素。而高分子聚合物在打印材料中占据主要地位,其中高分子复合材料具有明显优势。本文综述了近年来3D打印用高分子材料及其复合材料的研究现状,包括高分子丝材、光敏树脂、高分子粉末、高分子凝胶及其它高分子材料,并对高分子材料在3D打印领域的发展进行了展望。     

3D打印用高分子材料及其复合材料的研究进展

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。作为第三次工业革命的代表性技术之一,3D打印材料是影响3D打印技术发展与应用的关健因素。而高分子聚合物在打印材料中占据主要地位,其中高分子复合材料具有明显优势。本文综述了近年来3D打印用高分子材料及其复合材料的研究现状,包括高分子丝材、光敏树脂、高分子粉末、高分子凝胶及其它高分子材料,并对高分子材料在3D打印领域的发展进行了展望。     

植物纤维及其提取物增强聚合物的3D打印成型研究

3D打印技术作为新型成型技术,近年来受到了巨大的关注,但常见的PLA、ABS等单体打印耗材由于其自身的不同缺点,限制了其进一步的应用。本文综述了植物纤维及其提取物增强聚合物复合材料在3D打印领域的应用研究进展,重点阐述了木纤维、竹纤维,秸秆纤维等常见植物纤维用于3D打印的研究现状,还介绍了纤维素、木质素、半纤维素等植物纤维提取物增强聚合物用于3D打印的研究情况。同时对植物纤维/聚合物材料存在的一些问题及改性方法进行了分析与展望。     

光固化3D打印及其在齿科行业中的应用

光固化3D打印是最早出现的3D打印技术,经过30多年的发展,先后发展出液态树脂固化或光固化（stereolithography,SLA）、数字光处理（digital light processing,DLP）、液晶显示（liquid crystal display,LCD）、连续无分层液体界面提取技术（layerless continuous liquid interface production,CLIP）、双光子3D打印（two-photon polymerization,TPP）、全息3D打印技术等多种打印技术。光固化3D打印技术具有精度高、成型速度快等特点,因此在许多领域都有良好的应用,且前景广阔。在众多领域中,齿科领域个性化特征明显,对打印材料精度要求高,是目前光固化3D打印最有应用潜力和高附加值的领域。本文综述了光固化3D打印技术的种类、原理和技术的优缺点,并简述了光固化3D打印在齿科领域的应用。     

3D打印用光敏树脂的高性能化及功能化研究进展

3D打印,又称增材制造,是一项新兴的智能制造技术。光固化3D打印技术是增材制造的主要方向之一,具有成型精度高、打印速度快及工艺成熟等优点。处在高速发展之中的光固化3D打印技术对光敏树脂提出了越来越高的要求,3D打印用光敏树脂的高性能及功能化研究受到极大关注。本文综述了高性能光敏树脂的最新研究进展,重点讨论了其用于构筑复杂结构导电导热聚合物、形状记忆聚合物、特殊浸润性聚合物、生物医用聚合物及凝胶材料的设计思路及相应构件所展示的优异功能性,同时对光敏树脂基3D打印材料的发展趋势及应用前景进行了分析和展望。     

光固化3D打印聚酰亚胺研究进展

近年来,光固化3D打印技术因高精度、定制化、整体免装配以及快速制造等成形优点,用于解决聚酰亚胺(polyimide, PI)的微型精密、异形复杂及其功能结构一体化制造技术难题,受到了研究者的广泛研究和关注。基于光固化3D打印成形原理与PI的物理化学特性,发展了一系列光固化3D打印PI材料及其成形技术。本文归纳总结了光固化3D打印PI材料设计制备准则,重点介绍了立体光刻技术(SLA)、数字光处理技术(DLP)和紫外辅助直书写技术(UV-DIW)等光固化3D打印PI研究进展,最后通过光固化3D打印PI的应用和产业化现状提出研究发展对策。     

丝素蛋白3D打印在生物医学领域中的应用

增材制造,也称为三维(3D)打印,正推动制造、工程、医学等领域的全面创新升级。3D打印技术由于能够个性化定制生物的复杂3D微结构,构建仿生的功能化活组织或人工器官,近十年来在生物医学领域中取得了长足的发展。丝素蛋白(SF)是一种来源丰富、生物可降解、力学性能优良、细胞相容性极佳的天然有机高分子,为3D打印墨水的设计提供了一种有前景的选择。然而,作为结构蛋白,单一组分的SF具有的生理功能有限,且其经过打印后的稳定性较差,限制了SF在3D打印以及生物医药领域中的进一步发展。为此,研究人员通过化学改性技术和先进3D打印技术相结合,使得改性后的SF能够更适用于3D打印,并发展成为一种具有应用价值的生物材料。本文综述了SF的结构特征、SF的化学修饰策略、打印墨水的制备策略以及3D打印SF材料在生物医学领域的最新应用进展,并展望了3D打印SF生物材料的未来发展趋势,为其在更广阔领域的应用提供一定的借鉴。     

3D打印微流控芯片技术研究进展

近年来,微流控技术在生命科学和医学诊断等领域得到广泛的应用,显示出了其在检测速度、精度以及试剂损耗等方面相比传统方法的显著优势.然而,使用从半导体加工技术继承而来的微加工技术制作微流控芯片具有比较高的资金和技术门槛,在一定程度上阻碍了微流控技术的推广和应用.近年来随着3D打印技术的兴起,越来越多的研究者尝试使用3D打印技术加工微流控芯片.相比于传统的微加工技术,3D打印微流控芯片技术显示出了其设计加工快速、材料适应性广、成本低廉等优势.本文针对近年来国内外在3D打印微流控芯片领域的最新进展进行了综述,着重介绍了采用微立体光刻、熔融沉积成型以及喷墨打印等3D打印技术加工制作微流控芯片的方法,以及这些微流控芯片在分析化学、生命科学、医学诊断等领域的应用,并对3D打印微流控芯片技术未来的发展进行了展望.     

基于纳米碳填料可拉伸导电聚合物复合材料的制备

碳系材料具有导电性强、稳定性好、价格低廉等优点,被广泛用于制备可拉伸导电复合材料,并且在可拉伸、可穿戴电子设备等领域有巨大的应用潜力,引起了研究者的密切关注。本文介绍了碳系材料的种类,主要有炭黑、碳纳米管和石墨烯等;总结了3种纳米复合材料的主要制备工艺:原位聚合法、熔融共混法和溶液混合法,并介绍了传统印刷技术和新型打印技术。分析了复合材料的导电机理,介绍了渗流阈值理论;并重点探讨了其在可拉伸传感器和可拉伸能量储存设备领域的应用。针对基于纳米碳填料制备的可拉伸导电聚合物复合材料指出目前研究的不足之处:导电填料分散性差、导电网络不稳定和无法大规模生产等,并提出了多种解决方案。对基于纳米碳填料制备的可拉伸导电聚合物复合材料在微型化、可拉伸、可穿戴电子设备领域的应用前景作出了展望。     

3D打印生物医用材料研究进展

3D打印(亦称增材制造)技术因其独特的材料成型优势,在组织工程、航空航天、汽车制造、以及电子工业等众多领域显示出巨大的应用潜力。然而,在实际生物医学应用中,3D打印生物器件和组织器官除了要求具有复杂的结构和优异的生物学性能外,其打印结构的表面性质也需满足某些特定的要求,如3D打印组织骨架和器官必须具有生物相容性、抗菌性及细胞粘附性等。因此,将3D打印与传统表面修饰技术相结合,在不改变材料三维结构的基础上调控其表面生物化学性质,从而赋予3D打印生物骨架器官多功能化,可实现更为广泛的应用。本文以3D打印生物骨架及器官的表面修饰为主要内容对就近年来3D打印生物医用材料的最新研究进展进行了综述。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.