聚砜/环氧树脂体系的双连续相结构及其应变激励下的修复性能

研究了聚砜含量为10%的E-51/PSF/MTHPA/2,4-EMI共混体系在等温固化时双连续相相结构的演变过程及在不同应变下的自修复性能。扫描电子显微镜(SEM)和倒置相差显微镜照片验证了双连续相相结构的演变过程。倒置相差显微镜测试的结果表明,90℃固化3 h后聚砜/环氧固化体系伸长率较高,回弹及应力松弛性能较好,后固化样品的自修复性能较理想。     

Plasticized polylactic acid nanocomposite films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: Effects on mechanical,thermal and optical properties

Triacetate citrate plasticized poly lactic acid and its nanocomposites based on cellulose nanocrystals (CNC) and chitin nanocrystals (ChNC) were prepared using a twin-screw extruder. The materials were compression molded to films using two different cooling rates. The cooling rates and the addition of nanocrystals (1 wt%) had an impact on the crystallinity as well as the optical, thermal and mechanical properties of the films. The fast cooling resulted in more amorphous materials, increased transparency and elongation to break, (approx. 300%) when compared with slow cooling. Chitin nanocomposites were more transparent than cellulose nanocomposites; however, microscopy study showed presence of agglomerations in both materials. The mechanical properties of the plasticized PLA were improved with the addition of a small amount of nanocrystals resulting in PLA nanocomposites, which will be further evaluated for film blowing and thus packaging applications.     

核壳型PBA/P(St-co-MMA)乳胶粒子热力学平衡形态分布

采用饥饿态加料的半连续乳液聚合法,制备了系列PBA/P（St-co-MMA）复合乳液,通过改变St/MMA配比调节第Ⅱ阶段无规共聚物极性,利用透射电子显微镜观测到从反向核壳向正向核壳形态变化的复合乳胶体系,发现同一乳液样品在相同处理条件下存在着粒子形态的多样性,提出采用数学统计的方法来描述这种形态分布,对粒子形态分布的量化,可使核壳型乳胶粒子形态的表述更为直观、准确.根据不同温度处理方式下所得粒子形态分布结果的对比,判定了核壳型乳胶粒子热力学平衡形态的趋向。     

Evaluation of starch based cryogels as potential biomaterials for controlled release of antibiotic drugs

In the present study starch has been blended with poly(vinyl alcohol) to design macroporous architectures following a repeated freeze-thaw method. These macroporous cryogels were loaded with an antibiotic drug, ciprofloxacin hydrochloride (Cfx), and evaluated for its in vitro delivery in a completely controlled manner thus exploring possibilities to use it as a biomaterial in burn or wound healing applications. The key advantage of the present system is that cryogels formed do not contain any chemical crosslinking agent which is often harmful to organic compounds. These Cfx loaded cryogels were characterized by infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The controlled release of Cfx drug from cryogels was investigated under varying experimental conditions such as percent loading of the antibiotic drug, chemical architecture of the cryogels and pH, temperature, and nature of the release media. The prepared cryogels show promise to provide a possible pathway for controlling delivery of antibiotic drug thus minimizing the known side effects and improving efficacy also.     

A triple-network tricontinuous cubic liquid crystal

Soft matter such as surfactant-water systems, block copolymers or liquid crystals can form periodic structures on nanometre to micrometre scales. This property can be used for templating nanoporous ceramics, surface patterning for electronic devices, or generation of photonic materials. Much attention has been paid to structures appearing between the layer and cylinder phases, the three so-called bicontinuous cubic phases. These are formed by two continuous interpenetrating networks of channels. In this article we describe a related phase, which has the first reported structure consisting of three interpenetrating infinite networks. It is a thermotropic (solvent-free) liquid crystal of cubic symmetry Im3m. The structure is one of the most complex in liquid crystals, and is determined by direct Fourier reconstruction of electron density. We discuss the possible rationale for the existence of such a phase, its structural relationship with the bicontinuous phases, and its position in the phase diagram.     

Perforated Bicontinuous Cubic Phases with pH‐Responsive Topological Channel Interconnectivity

Lipidic lyotropic liquid crystals are at the frontline of current research for release of target therapeutic molecules due to their unique structural complexity and the possibility of engineering stimuli‐triggered release of both hydrophilic and hydrophobic molecules. One of the most suitable lipidic mesophases for the encapsulation and delivery of drugs is the reversed double diamond bicontinuous cubic phase, in which two distinct and parallel networks of ～4 nm water channels percolate independently through the lipid bilayers, following a Pn3m space group symmetry. In the unperturbed Pn3m structure, the two sets of channels act as autonomous and non‐communicating 3D transport pathways. Here, a novel type of bicontinuous cubic phase is introduced, where the presence of OmpF membrane proteins at the bilayers provides unique topological interconnectivities among the two distinct sets of water channels, enabling molecular active gating among them. By a combination of small‐angle X‐ray scattering, release and ion conductivity experiments, it is shown that, without altering the Pn3m space group symmetry or the water channel diameter, the newly designed perforated bicontinuous cubic phase attains transport properties well beyond those of the standard mesophase, allowing faster, sustained release of bioactive target molecules. By further exploiting the pH‐mediated pore‐closing response mechanism of the double amino acid half‐ring architecture in the membrane protein, the pores of the perforated mesophase can be opened and closed with a pH trigger, enabling a fine modulation of the transport properties by only moderate changes in pH, which could open unexplored opportunities in the targeted delivery of bioactive compounds.     

In situ electrochemical monitoring of selective etching in ordered mesoporous block-copolymer templates

We present a simple in situ electrochemical probe for the selective etching of the PLA component of thin film poly(4-fluorostyrene)-b-poly(D,L-lactide) (PFS-b-PLA) mesoporous block copolymer templates with a range of highly ordered microphase morphologies. Etching rates between 0.6 and 0.9 nm s?1 were measured in electric-field aligned standing PLA cylinders 12 nm wide and up to 800 nm long. The etching rate within a bicontinuous gyroid network morphology is comparable to that of the hexagonally ordered cylindrical array. A microphase-separated, nonaligned but film-spanning PLA pore structure is found in cylinder forming PFS-b-PLA films immediately after spin coating that could have applications in patterning of functional nanostructured arrays. Cross-film percolation of the PLA phase is confirmed electrochemically, with an etching rate approximately half that of the highly ordered morphologies. The etching rate is independent of template thickness in all three morphologies.     

In-situ preparation of polymer scaffolds in retarded cement slurries: An emulsion templating approach for rapid, on-demand strength development

We demonstrate in this communication that stable high internal phase emulsions consisting of a majority dispersed cement slurry as aqueous phase and a continuous but minority monomer oil phase can be produced. Polymerisation of the monomer phase using both a conventional thermal method as well as by fast setting using carbon fibres as resistance heaters results in bicontinuous polymer cement hybrid materials. We found that a reduction of the polymerisation time from 24 h to 90 min did not affect the physical characteristics, such as density and porosity, of the polymer-cement hybrids but results in a decrease of the crush strength and a significantly reduced elastic modulus.     

Dynamically Reconfigurable,Multifunctional Emulsions with Controllable Structure and Movement

Dynamically reconfigurable oil‐in‐water (o/w) Pickering emulsions are developed, wherein the assembly of particles (i.e., platinum‐on‐carbon and iron‐on‐carbon particles) can be actively controlled by adjusting interfacial tensions. A balanced adsorption of particles and surfactants at the o/w interface allows for the creation of inhomogeneity of the particle distribution on the emulsion surface. Complex Pickering emulsions with highly controllable and reconfigurable morphologies are produced in a single step by exploiting the temperature‐sensitive miscibility of hydrocarbon and fluorocarbon liquids. Dynamic adsorption/desorption of (polymer) surfactants afford both shape and configuration transitions of multiple Pickering emulsions and encapsulated core/shell structured can be transformed into a Janus configuration. Finally, to demonstrate the intrinsic catalytic or magnetic properties of the particles provided by carbon bound Pt and Fe nanoparticles, two different systems are investigated. Specifically, the creation of a bimetallic microcapsule with controlled payload release and precise modulation of translational and rotational motions of magnetic emulsions are demonstrated, suggesting potential applications for sensing and smart payload delivery.     

聚合物模板法制备介孔材料

聚合物模板剂因其能够自组装成形态不同、尺寸可调的纳米单元,且在反应后易于除去等特点而在介孔材料的合成过程中起着重要的作用。本文中对近几年聚合物模板制备介孔材料的研究做了简要的回顾与总结,介绍了交联及嵌段共聚物、乳液及微乳液以及生物大分子作为模板制备介孔材料的研究进展,对现代物理测试技术如TEM、SEM、XRD和N2吸附-脱附曲线等在介孔材料的制备表征中的应用做了较详细的分析与探讨。     

Hierarchical self-assembly of a collagen mimetic peptide (PKG)n(POG)2n(DOG)n via electrostatic interactions

A new type of collagen mimetic peptide, (PKG)_n(POG)_2n(DOG)_n, with charged-domain ends had been designed and successfully prepared in this work, which self-assembled into collagen-like triple helices homotrimers. The collagen-like homotrimers underwent higher level of self-assembly via static electrical interaction between positive and negative domains. Transmission electron microscope (TEM) examinations showed three typical morphologies of homotrimer assembly, which were defined as film, bicontinuous and fibril morphology in this paper. The film was formed in the initial stage and gradually transformed to bicontinuous or fibril morphology to improve stability of the assemblies or decrease surface energy. Furthermore, mechanism of assembly process was proposed based on TEM observations and theoretical analyses of packing equation.     

Self-organization in phase separation of a lyotropic liquid crystal into cellular, network and droplet morphologies

Phase separation is one of the most fundamental physical phenomena that controls the morphology of heterogeneous structures. Phase separation of a binary mixture of simple liquids produces only two morphologies: a bicontinuous or a droplet structure in the case of a symmetric or an asymmetric composition, respectively. For complex fluids, there is a possibility to produce other interesting morphologies. We found that a network structure of the minority phase can also be induced transiently on phase separation if the dynamics of the minority phase are much slower than those of the majority phase. Here we induce a cellular structure of the minority phase intentionally with the help of its smectic ordering, using phase separation of a lyotropic liquid crystal into the isotropic and smectic phase. We can control the three morphologies, cellular, network and droplet structures, solely by changing the heating rate. We demonstrate that the kinetic interplay between phase separation and smectic ordering is a key to the morphological selection. This may provide a new route to the formation of network and cellular morphologies in soft materials.     

Effect of chitosan-gluconic acid conjugate/poly(vinyl alcohol) cryogels as wound dressing on partial-thickness wounds in diabetic rats

We previously developed chitosan cryogels from chitosan-gluconic acid conjugate without using toxic additives for wound care. In this study, we improved physiological characteristics of the previous cryogels by incorporating poly(vinyl alcohol) that also form cryogels. Mechanical strength of the cryogels was more than two times higher than that of the previous cryogels. Furthermore, the incorporation of poly(vinyl alcohol) enhanced water retention and resistance to degradation of the gels by lysozyme. The cryogels retained the favorable biological properties of the previous cryogels that they accelerate infiltration of inflammatory cells into wound sites. Time period for repairing 50 % of initial area of partial-thickness skin wound treated with the cryogels (4.0 ± 1.1 days) was shorter than those with gauze (6.5 ± 0.3 days) or a commercial hydrogel dressing (5.7 ± 0.3 days). Finally, we confirmed that incorporation of basic fibroblast growth factor into the cryogels was effective to further accelerate wound healing (2.7 ± 1.0 days). These results demonstrate that the cryogels in this study are promising for wound care.     

新型多级形貌的硅酸盐空心球的合成

由化学方法制备的氧化硅通常是在较苛刻的条件下制备的,如升高的温度、较高压力和/或强酸性、强碱性媒介,相比之下,在自然界里具有精致形貌的硅藻氧化硅构架在温和周围环境下的水相中就可以形成.本文中我们系统研究了具有相似于硅藻多级形貌的氧化硅空心球的合成,该合成经过一步步骤,采用嵌段高分子EO76PO29EO76基的乳液和廉价硅酸钠溶液为硅源.     

The fabrication of cryogel scaffolds incorporated with poloxamer 407 for potential use in the regeneration of the nucleus pulposus

Degeneration of the nucleus pulposus (NP) is the primary cause of back pain in almost 80% of the world population. The current gold standard treatment for a degenerated NP is a spinal fusion surgery which is costly, temporary, and extremely invasive. Research has been moving towards minimally invasive methods to lessen the collateral damage created during surgery. The use of a tissue-engineered scaffold has the potential to promote a healthy and hydrated environment to regenerate the NP. Cryogels are unique polymeric scaffolds composed of a highly connected, macroporous structure, and are capable of maintaining stability under high deformations. For this study, cryogels have been developed using gelatin and poloxamer 407 (P407) at varying ratios to determine the ideal combination of stability, water retention, and pore size. For the application of NP regeneration, a gelatin-P407 cryogel should be both stable and a well hydrated carrier. The cryogels created varied from a 1:1 gelatin to P407 ratio to a 10:1 ratio. The inclusion of P407 in the cryogels resulted in a significant increase in hydrophilicity, ideal pore size for cell infiltration, mechanical stability over 28 days, and cell infiltration after just 21 days. This novel gelatin-P407 composite cryogel has the potential to be a practical alternative to the spinal fusion procedure, saving patients hundreds of thousands of dollars and, ideally, leading to improved patient outcome.     

Porous protein-based scaffolds prepared through freezing as potential scaffolds for tissue engineering

Successful tissue engineering with the aid of a polymer scaffold offers the possibility to produce a larger construct and to mould the shape after the defect. We investigated the use of cryogelation to form protein-based scaffolds through different types of formation mechanisms; enzymatic crosslinking, chemical crosslinking, and non-covalent interactions. Casein was found to best suited for enzymatic crosslinking, gelatin for chemical crosslinking, and ovalbumin for non-covalent interactions. Fibroblasts and myoblasts were used to evaluate the cryogels for tissue engineering purposes. The stability of the cryogels over time in culture differed depending on formation mechanism. Casein cryogels showed best potential to be used in skeletal tissue engineering, whereas gelatin cryogels would be more suitable for compliable soft tissues even though it also seemed to support a myogenic phenotype. Ovalbumin cryogels would be better suited for elastic tissues with faster regeneration properties due to its faster degradation time. Overall, the cryogelation technique offers a fast, cheap and reproducible way of creating porous scaffolds from proteins without the use of toxic compounds.     

Microfluidic Generation of All‐Aqueous Double and Triple Emulsions

Higher order emulsions are used in a variety of different applications in biomedicine, biological studies, cosmetics, and the food industry. Conventional droplet generation platforms for making higher order emulsions use organic solvents as the continuous phase, which is not biocompatible and as a result, further washing steps are required to remove the toxic continuous phase. Recently, droplet generation based on aqueous two‐phase systems (ATPS) has emerged in the field of droplet microfluidics due to their intrinsic biocompatibility. Here, a platform to generate all‐aqueous double and triple emulsions by introducing pressure‐driven flows inside a microfluidic hybrid device is presented. This system uses a conventional microfluidic flow‐focusing geometry coupled with a coaxial microneedle and a glass capillary embedded in flow‐focusing junctions. The configuration of the hybrid device enables the focusing of two coaxial two‐phase streams, which helps to avoid commonly observed channel‐wetting problems. It is shown that this approach achieves the fabrication of higher‐order emulsions in a poly(dimethylsiloxane)‐based microfluidic device, and controls the structure of the all‐aqueous emulsions. This hybrid microfluidic approach allows for facile higher‐order biocompatible emulsion formation, and it is anticipated that this platform will find utility for generating biocompatible materials for various biotechnological applications.     

3D Printable Gelatin Methacryloyl (GelMA)-Dextran Aqueous Two-Phase System with Tunable Pores Structure and Size Enables Physiological Behavior of Embedded Cells In Vitro

The restricted porosity of most hydrogels established for in vitro 3D tissue engineering applications limits embedded cells with regard to their physiological spreading, proliferation, and migration behavior. To overcome these confines, porous hydrogels derived from aqueous two-phase systems (ATPS) are an interesting alternative. However, while developing hydrogels with trapped pores is widespread, the design of bicontinuous hydrogels is still challenging. Herein, an ATPS consisting of photo-crosslinkable gelatin methacryloyl (GelMA) and dextran is presented. The phase behavior, monophasic or biphasic, is tuned via the pH and dextran concentration. This, in turn, allows the formation of hydrogels with three distinct microstructures: homogenous nonporous, regular disconnected-pores, and bicontinuous with interconnected-pores. The pore size of the latter two hydrogels can be tuned from ≈4 to 100 µm. Cytocompatibility of the generated ATPS hydrogels is confirmed by testing the viability of stromal and tumor cells. Their distribution and growth pattern are cell-type specific but are also strongly defined by the microstructure of the hydrogel. Finally, it is demonstrated that the unique porous structure is sustained when processing the bicontinuous system by inkjet and microextrusion techniques. The proposed ATPS hydrogels hold great potential for 3D tissue engineering applications due to their unique tunable interconnected porosity.     

Periodic bicontinuous composites for high specific energy absorption

We report on the mechanical behavior of an interpenetrating carbon/epoxy periodic submicrometer-scale bicontinuous composite material fabricated following the design principles deduced from biological composites. Using microscopic uniaxial compressive tests, the specific energy absorption is quantitatively evaluated and compared with the epoxy/air and carbon/air precursors. The carbon/epoxy material demonstrates extremely high specific energy absorption up to 720 kJ/kg and shear-dominant interphase interactions from the interlocked hard (carbon) and soft (epoxy) phases. Such bicontinuous nanocomposites are a new type of structural metamaterial with designed cell topology and mechanical anisotropy. Their inherent small length scale can play a critical role in prohibiting segregated mechanical responses leading to flaw tolerance.     

Morphology and pore characteristics of bacterial cellulose/multiwalled carbon nanotube composite cryogels

Bacterial cellulose/multiwalled carbon nanotube (MWCNT) composite cryogels were prepared via sol-gel chemistry using epichlorohydrin as a crosslinker. Their morphology and pore characteristics were examined under various conditions. The bacterial cellulose/MWCNT composite cryogels had a macroporous structure that contained mesopores and micropores due to the MWCNTs that were homogeneously incorporated in the macroporous network structure.