具有包络辨识特性的功能高分子进展

具有包络辩识特性的功能高分子是仿生化学领域的重要研究课题之一.本文对包络辨识现象以及具有包络辨识功能的高分子结构、性能及其发展作了介绍和评述.     

液相合成彩色氮化碳及其光电化学特性研究

减小带隙值和获得有序二维微结构是提高氮化碳光电化学性能的关键. 通过调控尿素和柠檬酸的比例, 采用室温熟化工艺, 合成出不同颜色的氮化碳材料, 成功地将其带隙减小至1.74 eV, 并获得了由有序二维网络构建的多孔微结构. 所得氮化碳获得了一定光电转换性能, 并随着带隙值的减小和二维网络结构的构建, 表现出少见的光诱导电荷存储行为.     

仿生高分子的研究进展

本文介绍了近年来结构仿生高分子材料和功能仿生高分子材料方面的研究进展,介绍了生物材料的多级有序结构、智能水凝胶、仿荷叶表面、高分子在细胞培养和生物矿化等方面的研究结果,探讨了这一领域的可能发展方向.     

仿生多尺度功能水凝胶的设计与制备:从二维界面到三维网络

水凝胶是以大量水为分散介质的三维高分子网络.高分子网络和水分子之间的氢键将水束缚在网络内部,从而使体系丧失流动性并转变成一种准固态物质.水凝胶能够在多种外界刺激下改变形状和体积,因此在软体机器人、柔性电子器件和传感器等领域具有广泛的应用前景,也引起了科研人员的关注.在生物软组织中,多尺度结构(如表面微/纳米结构,有序三维网状结构)的存在对于生物材料的自清洁、耐冻、环境适应性和优异的机械性能等功能至关重要.受生物水凝胶结构与功能特性的启发,研究人员开发了一系列对各种机械和环境条件具有高度适应性的仿生多尺度水凝胶.本文将从水凝胶的二维界面和三维网络的设计2个方面总结和讨论近年来仿生多尺度水凝胶的研究成果.二维界面设计包括表面化学/物理修饰、表面微/纳米结构构筑,能够调节水凝胶的表面浸润性和黏附性,拓展水凝胶在生物医学、海洋防污等领域的应用;三维网络设计,如引入非共价交联作用、设计有序网络结构、复合异质网络等,能够赋予水凝胶自修复性能、各向异性、高强度、形状记忆性能及抗冻性等优异的特性,拓展了水凝胶在可穿戴设备、软体机器人等领域以及复杂环境中的应用.最后我们对仿生水凝胶网络的设计、异质网络的分散以及无损表征等方面未来的发展以及该领域所存在的挑战作出展望.     

羟基磷灰石/明胶复合纤维的制备及其蛋白吸附研究

自然界中的一些物质(如骨)具有多重复杂分级结构,这种高度有序的微结构赋予了这些物质独特的近乎完美的综合性能。受此启发,制备具有仿生天然硬组织微结构的生物材料具有重要的意义。本文采用静电纺丝法成功制备出具有微结构的羟基磷灰石/明胶纳米复合纤维。探讨了明胶浓度、羟基磷灰石颗粒浓度和粒径对复合纤维形貌的影响,并对其牛血清白蛋白的吸附性能进行了讨论。研究结果表明,明胶浓度增大,纤维直径增大,其浓度过大会出现粘连现象,明胶浓度为15%纺丝较好;羟基磷灰石粒径为12μm,浓度为3%时的复合纤维为纳米级,纤维均匀。复合纤维的微结构是通过导电模板的拓扑结构来实现,研究发现纤维主要集中分布在图案化导电模板的棱上,实现了对复合纤维的有序调控即材料的结构设计。羟基磷灰石/明胶纳米复合纤维对牛血清白蛋白的吸附浓度主要取决于复合纤维的有效吸附面积,且牛血清白蛋白主要吸附在复合纤维的棱上。     

高分子Langmuir-Blodgett膜的研究进展

利用Langmuir-Blodgett(LB)膜技术能够使薄膜中聚合物分子链获得高度有序的排列与组装,并使沉积后的膜具备可控的特殊结构以及不同寻常的物理化学性质.高分子LB膜可用于制造非线性光学材料、光电子器件、传感器单元、电极修饰膜,也可作为研究催化反应、电子转移、仿生模拟的理想模型.本文评述了芳杂环类合成高分子(聚酰亚胺、聚噻吩、聚乙烯基咔唑和聚苯胺)与几种天然高分子(木质素、纤维素、壳聚糖和蛋白质)的LB膜最近的研究进展,并详细讨论了高分子LB膜的制备、结构与表征,指出了这两类高分子LB膜的研究重点,并对该两类高分子LB膜潜在的应用进行了展望.     

含肽侧链仿生高分子吸附剂的合成与性能

模拟β-内酰胺酶结合部位的结构,设计了一系列含肽的仿生高分子吸附剂,用对称酸酐法以固相合成技术将肽段分步接枝在功能基化的交联聚(N,N-二甲基丙烯酰胺)载体上,然后研究了仿生吸附剂对β-内酰胺抗生素氨苄青霉素和头孢噻肟的吸附性能.结果说明,当肽段富含赖氨酸时,相应的吸附剂具有良好的吸附性能,而且证明静电作用和氢键作用在吸附过程中发挥着重要作用.     

有机基质在仿生材料合成中的应用

利用有机基质的模板作用通过仿生合成可以制备出性能优异的无机材料。文章综述了两亲有机分子、有机高分子、生物大分子三种有机基质在仿生材料合成中的应用 ,并对仿生材料合成这一新兴研究领域的发展趋势及广阔前景作了进一步的展望。     

聚合物限域和预有序熔体的结晶行为及结构调控

高分子物理领域的挑战性难题之一是调控高分子的结晶行为.高分子结构具有多尺度的特点,且易受到各种本征因素以及加工过程中引入的外场与受限作用的影响.高分子的结晶过程复杂多变,为避免最终产品性能的良莠不齐,促进高分子材料的实际生产和应用,需要建立高分子结构与性能的直接关系并实现对高分子结晶结构的精细化调控.本文以几种典型高分子为例,重点阐述了我们课题组在有关薄膜和纳米孔道构筑的限域空间与分子链预有序熔体对高分子结晶行为的影响、相关结晶结构调控机制以及结构-性能关系等方面的研究工作,阐明了聚合物多层次结构调控领域存在的科学问题,并展望了其未来发展方向.     

以液晶高分子为结构导向设计与合成新型分子筛

利用液晶的有序结构为模板可以制备出性能优异的新型分子筛。综述了双亲分子液晶模板合成分子筛的优缺点,展望了以高分子液晶为模板在分子筛合成与修饰方面的潜力,并预见了以高分子液晶为模板仿生合成具有新型结构分子筛的广阔前景。     

磷脂聚合物的研究进展

磷脂聚合物是一类生物相容性很好的生物材料。本文从其化学组成和微观结构出发 ,综述了磷脂聚合物的发展及应用现状。     

Preparation and potential application of functional ordered microstructures

With the development of science and technology,ordered microstructures with special functions have aroused intense research interest.These functional microstructures have been widely used in fields of microelectronic devices,micro-reactors,biochemical sensors and optical devices,etc.This paper summaries our work on preparation and application of microscopic patterned surfaces with ordered microstructures,and looks into the future development of this field.     

功能性有序微结构的制备及潜在应用

随着科技的发展进步,具有特殊功能的有序微结构日渐引起人们浓厚的研究兴趣,并被广泛应用于微电子器件、微反应器、生物化学传感器以及光学器件等领域.本文总结了我们课题组在微观表面图案化和有序微结构制备及应用方面的研究工作,重点介绍我们在该方向工作的最新进展,并对该领域的发展前景进行了展望.     

Protein directed assembly of lipids

Highly ordered ring-like structures are formed via the directed assembly of lipid domains in supported bilayers, using the extracellular matrix protein fibronectin. The ability of biological molecules to guide nanoscale assembly suggests potential biomimetic approaches to nanoscale structures.     

Biomimetic Fabrication of Polymer Film with High Adhesive Superhydrophobicity by Duplicating Locust Wing Surface

Locust is a common flying insect. Locust wings were used as biomimetic templates to fabricate multi-functional polymer(polydimethylsiloxane, PDMS) films by soft lithography. The microstructure and wettability of the natural and artificial locust wing surfaces were investigated by means of a scanning electron microscope(SEM) and a video-based contact angle meter. The natural locust wing surface exhibits complicated hierarchical structures and high adhesive superhydrophobicity(contact angle 152°). The prepared polymer film faithfully reproduces the surface microstructures of the bio-template, and displays a good hydrophobicity and high adhesion(contact angle 144°). The complex wettability of the natural and artificial locust wing surfaces ascribes to the cooperative effect of hydrophobic composition and multi-dimensional rough microstructures. This work not only promotes our understanding of the wetting mechanism on bio-surfaces, but offers an inexpensive and effective approach for biomimetic fabrication of multi-functional interfacial materials.     

The strong MRI relaxivity of paramagnetic nanoparticles

We developed a method to synthesize paramagnetic nanoparticles of Gd@C82(OH)22+/-2. Such nanoparticles are with ordered microstructures and have strong MRI proton relaxation in vitro/vivo. Compared with commercial Gd-DTPA, a 12x MRI relaxivity of Gd@C82(OH)22+/-2 nanoparticles with ordered microstructures was achieved in vitro. The small Gd@C82(OH)22+/-2 nanoparticles, approximately 65nm, could easily escape the RES uptake in vivo; this opens the door for their clinical applications.     

1,4-二氰基萘一维亚微米结构材料的制备及光学性能

用再沉淀法制备了1,4-二氰基萘（DCN）一维亚微米结构。通过改变制备条件分别得到了DCN的线状及管状一维结构。所制备的有机亚微米材料具有良好的结晶性,不同结构的生长取向存在一定的差别。由于DCN分子的有序堆积,亚微米结构的的发光比溶液的发光有一定的红移。通过对单根材料的表征发现,DCN亚微米结构具有良好的光波导性能。空心结构的光波导性能要明显优于实心结构,主要原因在于空气介质减小了光学损耗。     

3D Bioprinting of Artificial Tissues: Construction of Biomimetic Microstructures

It is promising that artificial tissues/organs for clinical application can be produced via 3D bioprinting of living cells and biomaterials. The construction of microstructures biomimicking native tissues is crucially important to create artificial tissues with biological functions. For instance, the fabrication of vessel‐like networks to supply cells with initial nutrient and oxygen, and the arrangement of multiple types of cells for creating lamellar/complex tissues through 3D bioprinting are widely reported. The current advances in 3D bioprinting of artificial tissues from the view of construction of biomimetic microstructures, especially the fabrication of lamellar, vascular, and complex structures are summarized. In the end, the conclusion and perspective of 3D bioprinting for clinical applications are elaborated.     

A Dipeptide-Based Hierarchical Nanoarchitecture with Enhanced Catalytic Activity

Achieving synthetic architectures with simple structures and robust biomimetic catalytic activities remains a great challenge. Herein, we explore a facile supramolecular assembly approach to construct a dipeptide-based hierarchical nanoarchitecture with enhanced enzyme-like catalytic activity. In this nanoarchitecture, nanospheres are put in a chain-like arrangement through coordination-driven directional self-assembly. The reversible transformation of anisotropic nanochains to isotropic nanospheres switches biomimetic activity. Notably, the assembled nanoarchitecture exhibits a high enzyme-like activity and remarkable long-term stability to promote hydroquinone oxidation, superior to the natural counterpart. This work will pave the way to develop reversible and reusable supramolecular biocatalysts with ordered hierarchical structures for accelerating chemical transformations.     

Microphase separation in polyelectrolytic diblock copolymer melt: weak segregation limit

The authors present a generalized theory of microphase separation for charged-neutral diblock copolymer melt. The stability limit of the disordered phase for salt-free melt has been calculated using random phase approximation (RPA) and self-consistent-field theory (SCFT). Explicit analytical free energy expressions for different classical ordered microstructures (lamellar, cylinder, and sphere) are presented. The authors demonstrate that the chemical mismatch required for the onset of microphase separation (chi*N) in charged-neutral diblock melt is higher and the period of ordered microstructures is lower than those for the corresponding neutral-neutral diblock system. Theoretical predictions on the period of ordered structures in terms of Coulomb electrostatic interaction strength, chain length, block length, and chemical mismatch between blocks are presented. SCFT has been used to go beyond the stability limit, where electrostatic potential and charge distribution are calculated self-consistently. Stability limits calculated using RPA are in perfect agreement with the corresponding SCFT calculations. Limiting laws for the stability limit and the period of ordered structures are presented and comparisons are made with an earlier theory. Also, transition boundaries between different morphologies have been investigated.