A Biologically Muscle-Inspired Polyurethane with Super-Tough,Thermal Reparable and Self-Healing Capabilities for Stretchable Electronics

Polymeric elastomers play an increasingly important role in the development of stretchable electronics. A highly demanded elastic matrix is preferred to own not only excellent mechanical properties, but also additional features like high toughness and fast self-healing. Here, a polyurethane (DA-PU) is synthesized with donor and acceptor groups alternately distributed along the main chain to achieve both intra-chain and inter-chain donor-acceptor self-assembly, which endow the polyurethane with toughness, self-healing, and, more interestingly, thermal repair, like human muscle. In detail, DA-PU exhibits an amazing mechanical performance with elongation at break of 1900% and toughness of 175.9 MJ m⁻³. Moreover, it shows remarkable anti-fatigue and anti-stress relaxation properties as manifested by cyclic tensile and stress relaxation tests, respectively. Even in case of large strain deformation or long-time stretch, it can almost completely restore to original length by thermal repair at 60 °C in 60 s. The self-healing speed of DA-PU is gradually enhanced with the increasing temperature, and can be 1.0–6.15 µm min⁻¹ from 60 to 80 °C. At last, a stretchable and self-healable capacitive sensor is constructed and evaluated to prove that DA-PU matrix can ensure the stability of electronics even after critical deformation and cut off.     

Facile fabrication of silk fibroin/graphene oxide composite films and real-time morphological observation in stretching

Layer-structured regenerated silk fibroin (SF)/graphene oxide (GO) composite films were fabricated by a facile solution casting method. Fourier transform infrared spectroscopy, X-ray diffraction, and thermal gravity analysis confirmed the successful incorporation and uniform dispersion of graphene oxides in the SF matrix. To visualize GO's effect on the morphological evolution, atomic force microscopic images were recorded in real-time during the composite elongation to establish a correlation between microscopic structural characters and macroscopic mechanical properties. The result showed that the incorporation of graphene oxide into the SF matrix resulted in chain conformational transition, film surface flattening, and mechanical reinforcement. Surface roughness dramatically decreased from 65 to 10 nm, while tensile modulus increased substantially from 8.61 to 22.37 MPa by adding well-dispersed graphene oxide up to 1 wt% into the SF matrix. Through the real-time AFM observation under the horizontal stretching mode, the surface topography of original SF films varied from tori-spherical aggregations to rod-like ones resulting from GO's incorporation. In the meantime, SF's hydrophobicity was also increased, as manifested by contact angle increase from 30.81° to 45.09°.     

弱相互作用调控表面活性剂自组装(Ⅱ)——表面活性剂的结构与设计

介绍了表面活性剂的结构、性质以及分类,综述了阴离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂、非离子表面活性剂的分子间弱相互作用。另外,简述了低聚型表面活性剂和其他新型表面活性剂的结构及应用。     

TiO_2/FeOOH/硅藻土纳米复合材料的制备和光催化性能研究

采用分子组装的方法,以硅藻土为基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料,通过UV-Vis、TEM方法对材料进行表征,以甲基橙溶液为目标降解物探究纳米复合材料的光催化性能,结果表明,基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料对甲基橙均有不错的降解率,其中TiO_2/FeOOH/硅藻土纳米复合材料降解率达到67.16%。     

模板法制备介孔TiO2的研究进展

介绍了采用软模板法和硬模板法制备介孔TiO_2的方法及其优缺点。软模板法和硬模板法制备介孔TiO_2的原理都是先将钛前驱体与模板进行组装,再通过焙烧等方式去除模板得到介孔结构。二者之间的区别在于所使用的模板不同,软模板容易得到,种类较多且方法简单,但不易控制介孔的结构;硬模板虽然种类较少,但胜在可以控制介孔的结构和性能。     

Covalently Assembled Dipeptide Nanoparticles with Adjustable Fluorescence Emission for Multicolor Bioimaging

Peptide self-assembly, inspired by the naturally occurring fabrication principle, remains the most attractive in constructing fluorescent nanoagents towards bioimaging. However, the noncovalent interactions that drive peptide self-assembly are usually susceptible to the complex physiological environment; thus leading to disassembly and dysfunction of fluorescent nanoagents. Herein, a covalently crosslinked assembly strategy for fabrication of stable peptide-based nanoparticles with adjustable emission is introduced. In the process of cationic diphenylalanine peptide (H-Phe-Phe-NH₂ ⋅ HCl) self-assembly, glutaraldehyde is used as a crosslinker and the resulting product of the Schiff base reaction can be fluorescent. More importantly, the emission wavelength can be readily tuned by controlling the covalent reaction time. It has been demonstrated that the nanoparticles are stable, even after intracellular uptake, and can be used for sustainable multicolor fluorescent imaging. The strategy with integrating peptide self-assembly and covalent crosslinking could be promising for the design and engineering of functional fluorescent nanoparticles with robust physiological stability and adjustable emission towards improved bioimaging applications.     

Sequence-Dependent Nanofiber Structures of Phenylalanine and Isoleucine Tripeptides

The molecular design of short peptides to achieve a tailor-made functional architecture has attracted attention during the past decade but remains challenging as a result of insufficient understanding of the relationship between peptide sequence and assembled supramolecular structures. We report a hybrid-resolution model to computationally explore the sequence–structure relationship of self-assembly for tripeptides containing only phenylalanine and isoleucine. We found that all these tripeptides have a tendency to assemble into nanofibers composed of laterally associated filaments. Molecular arrangements within the assemblies are diverse and vary depending on the sequences. This structural diversity originates from (1) distinct conformations of peptide building blocks that lead to different surface geometries of the filaments and (2) unique sidechain arrangements at the filament interfaces for each sequence. Many conformations are available for tripeptides in solution, but only an extended β-strand and another resembling a right-handed turn are observed in assemblies. It was found that the sequence dependence of these conformations and the packing of resulting filaments are determined by multiple competing noncovalent forces, with hydrophobic interactions involving Phe being particularly important. The sequence pattern for each type of assembly conformation and packing has been identified. These results highlight the importance of the interplay between conformation, molecular packing, and sequences for determining detailed nanostructures of peptides and provide a detailed insight to support a more precise design of peptide-based nanomaterials.     

Self-Assembly of Proteinaceous Shells around Positively Charged Gold Nanomaterials Enhances Colloidal Stability in High-Ionic-Strength Buffers

The enzyme lumazine synthase (LS) has been engineered to self-assemble into hollow-shell structures that encapsulate unnatural cargo proteins through complementary electrostatic interactions. Herein, we show that a negatively supercharged LS variant can also form organic–inorganic hybrids with gold nanomaterials. Simple mixing of LS pentamers with positively charged gold nanocrystals in aqueous buffer spontaneously affords protein-shelled gold cores. The procedure works well with differently sized and shaped gold nanocrystals, and the resulting shelled complexes exhibit dramatically enhanced colloidal stability over a wide range of pH (4.0–10.0) and at high ionic strength (up to 1 m NaCl). They are even stable over days upon dilution in buffer. Self-assembly of engineered LS shells in this way offers an easy and attractive alternative to commonly used ligand-exchange methods for stabilizing inorganic nanomaterials.     

Controllable layer-by-layer assembly based on brucite and alginates with the assistance of spray drying and flame retardancy influenced by gradients of alginates

With the aim of tailoring and controlling surface assembly, multifunctional flame retardants (FRs) were obtained based on depositing alginates and silane coupling agents on brucite via the spray-drying-assisted layer-by-layer assembly technique. The assembly was controllable in both structure and gradient mass. Two series of FRs were named CuFR1-3 and NiFR1-3 based on the assembly content of metal alginates. With the assistance of spray drying, good compatibility between FRs and ethylene-vinyl acetate (EVA) was obtained, resulting in better mechanical properties. Meanwhile, the FRs improved flame retardancy and smoke suppression when used in EVA composites. With 55 wt % loading, composites with CuFR3 and NiFR1 passed UL 94 V-0 rating, while those with brucite were not rated. The peak of heat release rate decreased by 51.7 and 49.3% while the residue increased by 9.8 and 11.9%, respectively. The FRs also reduced the smoke and CO production rates. For the two series of FRs, the relationship between FR efficiency and alginate contents is different. The CuFRs assembled more copper alginates and exerted better flame retardancy caused by lower catalytic graphitization. NiFRs exerted a higher catalyzing efficiency at low assembly content. However, at high assembly content, the catalytic graphitization effect would decrease by thermally oxidized degradation leading to excess nickel alginates. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47570.     

Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

Herein, phloroglucinol tristearate (PhgTS) was used to study the crystallization process due to its unique symmetric structure containing a benzene ring and three aliphatic chains. Spherulites of crystallized PhgTS from four solvents under diverse conditions were analyzed in detail and their formation process was studied. Maltese cross is shown by PhgTS spherulites obtained from aprotic solvents via polarized optical microscopy. In comparison, no Maltese cross can be observed from branch-like crystals formed from protic solvents. Independent on the microscaled morphology, lamellae were found to be the basic blocks constructing both PhgTS spherulites and branch-like crystals, which were formed predominantly by stacked PhgTS molecules. Although differential characters of the solvents did not affect the formation of lamellas, the solvents played a crucial role in the formation of self-assembled microscaled morphologies. In particular, the morphologies of spherulites were strongly affected by the concentration of PhgTS solutions, surrounding temperature and evaporation rate of solvents. Generally, a higher concentration of PhgTS led to more homogeneous spherulites, a lower evaporation rate resulted in more compact spherulites, and a higher surrounding temperature generated preferentially more ring-banded spherulites of PhgTS.