摘要：Fostriecin是近年来备受瞩目的新型抗肿瘤天然产物.根据构效关系分析,设计了具有潜在更高活性的含有二氟亚甲基的Fostriecin类似物4,并进行了合成研究.目标分子的骨架结构由片段a,b,c经螯合控制的加成反应和Stille偶联反应汇聚合成.在含氟片段a的合成中应用了以下关键反应:(Z)-烯基碘8与溴二氟乙酸乙酯在铜粉作用下的偶联反应;酶动力学拆分构建C-5位的手性中心.合成甲基酮片段b的关键步骤包括:酶动力学拆分构建C-11位的手性中心和CBS不对称还原α,β-不饱和酮23.从商业可得的原料出发,经最长线性步骤18步以1.28%的总产率成功地得到未脱保护的含有二氟亚甲基的Fostriecin类似物42.但在对42脱除保护基时,没有得到目标分子4.这可能是由于偕二氟亚甲基的强吸电子作用使内酯环极化程度增大,从而导致内酯环易发生水解开环反应.

摘要：“新工科”建设是国家对高等教育的一项重大战略部署,是新形势下人才培养模式的一次新探索,对促进我国高等教育改革和发展具有重要意义。着眼于培养符合国家战略和新产业发展需求的复合材料与工程专业高水平复合型人才,本教学团队于2016年开始筹建“生产实践”课程,作为本专业主要实践课,从“复合材料+X”产教融合交叉人才培养模式、多方协同的实践和创新能力培养平台等多方位入手,并从教学手段、教学方法、教学内容等方面对该课程进行深度优化。本专业于2019年入选复合材料与工程专业全国第一个国家级一流本科专业建设点;2021年顺利通过专业教育工程认证;学生工程实践和创新能力显著提升,2017~2022年连续6年就业率达100%,深造率连年攀升,2022年达到82%。“生产实践”课程在从无到有、从有到精的建设和教学过程中所做的探索与实践为相关新工科专业人才培养体系的构建提供了有益的参考。

摘要：针对生物医学应用,研制了一种新型的具有良好降解性和可3D打印的聚氨酯材料——聚肟氨酯。通过聚己内酯二醇、丁二酮肟和异佛尔酮二异氰酸酯的两步缩聚反应制备得到了可降解的聚己内酯基聚肟氨酯材料(PCL-PU)。利用傅里叶变换红外光谱、核磁共振氢谱、凝胶渗透色谱分析、热重分析、差示扫描量热法、流变学测试、体外酶促降解实验、单轴拉伸试验和压缩试验等分析测试方法对PCL-PU的分子结构和性能进行了表征。研究结果表明,成功合成了聚己内酯基聚肟氨酯材料,该材料具有良好的热稳定性、可降解性和力学性能,体外降解7 d后该材料的降解率可达(44.3±12.9)%。同时,PCL-PU具有良好的加工性能,在99℃时可方便快捷地3D打印。该材料有望应用于组织工程支架等生物医学领域。

摘要：解决“卡脖子”问题,引领新产业发展,是当前中华民族肩负的历史重任,而其中超过50%与材料相关。当前国家推动创新驱动发展,实施“中国制造2025”等重大战略,其中先进制造10大优先领域中8大领域迫切需要轻量化碳纤维复合材料。从区域发展需求看,《上海市制造业转型升级规划》提出加快发展智能制造装备和航空航天等战略性新兴产业,涉及新材料的产值达2 500亿元,复合材料是其中重要组成部分。因此,无论从国家战略、产业发展还是地方经济建设角度。

摘要：采用3D打印的方法制备了由聚癸二酸甘油酯(PGS)和碳纳米管(carbon nanotubes,CNTs)组成的具有多级孔隙结构的柔性纳米摩擦发电机(triboelectric nanogenerator,TENG)。结合TENG对压力变化的响应性以及PGS复合材料良好的弹性,设计了一种能够实现实时监测的可穿戴柔性足弓压力传感器。利用扫描电子显微镜和电子万能试验机分别对3D打印纳米摩擦发电机(3DP-TENGs)的微观结构和力学性能进行表征,并通过高功率数字源表获得3DP-TENGs足弓压力传感器对压力的感应性能和灵敏度参数。结果表明:3DP-TENGs具有多级孔隙结构;在最大压缩应变为30%时,循环压缩50次后3DP-TENGs的弹性滞后可忽略不计,表明其具有良好的弹性与抗疲劳性;设计的足弓压力传感器对压力的感应较为灵敏,能够准确区分出不同条件下的足底压力。

摘要：Polyurethane elastomers with covalent adaptable networks(PU-CANs)based on the dynamic urethane bond have attracted remarkable attention owing to their reprocessability,adaptability,and ***,it is still a formidable challenge to achieve excellent dynamics at low temperatures since the urethane bond energy is usually ***,a fluorinated phenolic polyurethane(FPPU)elastomer with CANs based on phenol±carbamate bonds was successfully designed and ***,the effects of fluorine atoms on the mechanical properties,thermal stability,reprocessability,and self-healability,surface free energy,and hydrophobicity of the prepared elastomers were systematically *** FPPU elastomer showed notch-insensitivity,remarkable self-healable efficiency(98%),low dynamic dissociation temperature(60℃),excellent reprocessability,and low surface energy(62 MJ m^(-2))compared with non-fluorinated counterpart phenolic polyurethane elastomer(APPU).Based on the above-mentioned features,FPPU was selected as an elastic substrate to assemble into a triboelectric nanogenerator(TENG)to harvest energy from natural *** TENG exhibited an excellent electrical output performance with a peak open-circuit voltage of 103 V,a peak short-circuit current of 4.7μA and a peak short-circuit charge of 43 *** addition,the TENG possessed high selfcleaning and reprocessing ***,a stretchable and self-healing composite conductor based on FPPU was fabricated for flexible electronic devices.

摘要：Three-dimensional(3 D)printing has had a large impact on various fields,with fused deposition modeling(FDM)being the most versatile and cost-effective 3 D printing ***,FDM often requires sacrificial support structures,which significantly complicates the processing and increases the ***,poor layer-to-layer adhesion greatly affects the mechanical stability of 3D-printed ***,we present a new Print-Healing strategy to address the aforementioned challenges.A polymer ink(Cu-DOU-CPU)with synergetic triple dynamic bonds was developed to have excellent printability and room-temperature self-healing *** with various shapes were printed using a simple compact 3D printer,and readily assembled into large sophisticated architectures via *** dynamic bonds induce strong binding between ***,damaged printed objects can spontaneously heal,which significantly elongates their service *** work paves a simple and powerful way to solve the key bottlenecks in FDM 3D printing,and will have diverse applications.

摘要：液晶聚芳酯(LCPs)具有优异的热稳定性和力学性能,被广泛应用于航空航天、电子工业等前沿领域,但LCPs面临高熔点(t_(m)>350℃)所带来的加工难题。利用活性端基苯炔基封端LCPs主链,在不破坏液晶性的基础上有效调控分子量并降低聚合物熔点,获得综合性能优异的液晶聚芳酯固化物(LCTs);调控的主链结构可进一步调控LCTs的热学性能。通过一步熔融缩聚法合成由对羟基苯甲酸(HBA)、对苯二甲酸(TA)、对苯二酚(HQ)、4,4'-二羟基二苯甲酮(DHBP)和2,6-萘二甲酸(NDA)构成主链并由苯炔基封端的LCTs。为进一步研究酮羰基与LCTs热学性能的关系,调节HQ与DHBP的比例合成一系列LCTs。结果表明:制得的LCTs均具有高热稳定性(t_(d,5%)>470℃)、典型向列相液晶纹影织构与取向微纤形貌;酮羰基的引入影响分子链的规整度及软硬段比例,随着酮羰基含量增多,LCTs的玻璃化转变温度降低。

摘要：Long-segment defects remain a major problem in clinical treatment of tubular tissue *** design of tubular scaffold with desired structure and functional properties suitable for tubular tissue regeneration remains a great challenge in regenerative ***,we present a reliable method to rapidly fabricate tissueengineered tubular scaffold with hierarchical structure via 4-axis printing *** fabrication process can be adapted to various biomaterials including hydrogels,thermoplastic materials and thermosetting *** polycaprolactone(PCL)as an example,we successfully fabricated the scaffolds with tunable tubular architecture,controllable mesh structure,radial elasticity,good flexibility,and luminal *** a preliminary demonstration of the applications of this technology,we prepared a hybrid tubular scaffold via the combination of the 4-axis printed elastic poly(glycerol sebacate)(PGS)bio-spring and electrospun gelatin *** scaffolds seeded with chondrocytes formed tubular mature cartilage-like tissue both via in vitro culture and subcutaneous implantation in the nude mouse,which showed great potential for tracheal cartilage reconstruction.

摘要：随着全球环保意识的增强,无溶剂型的绿色环保胶粘剂引起了人们的广泛关注。聚氨酯热熔胶作为环保型胶粘剂的一种,体量庞大且发展迅猛,其结构可设计性强,性能可调节范围宽,得到了广泛的研究与应用。本文重点阐述了聚氨酯热熔胶的分类及其分子结构、粘接机理和性能特点,综述了其近年来的研究进展,最后对其未来的发展方向作出了展望。