Effect of dopant structure on refractive index and glass transition temperature of polymeric fiber‐optic materials

Graded‐index plastic optical fibers, composed of doped polymers, have advantages over conventional glass optical fibers, but need to be developed further for practical application. Here, a variety of aromatic sulfide dopants were synthesized, and their effects on the refractive indexes and glass transition temperatures (T_g) of poly(methyl methacrylate) and methyl 2‐chloroacrylate/2,2,2‐trichloroethyl methacrylate copolymers were studied. While polymers containing large dopants exhibited relatively high refractive indices, their T_g values were low, making these materials unsuitable for graded‐index plastic optical fiber applications. Six dopants yielded polymers that exhibited higher T_g values than the conventionally used (diphenyl sulfide)‐doped polymer. The dopant dibenzothiophene, in particular, yielded polymers with the highest refractive indexes and T_g values, and polymers containing (phenylthio)benzene dopants also performed well. Copyright © 2013 John Wiley & Sons, Ltd.     

Multi‐Colored Fibers by Self‐Assembly of DNA,Histone Proteins,and Cationic Conjugated Polymers

The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color‐encoded IPC fibers were also obtained based on the co‐assembly of DNA, histone proteins, and blue‐, green‐, or red‐ (RGB‐) emissive CCPs by tuning the fluorescence resonance energy‐transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP‐coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi‐colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering.     

Cooperative,Reversible Self‐Assembly of Covalently Pre‐Linked Proteins into Giant Fibrous Structures

We demonstrate a simple bioconjugate polymer system that undergoes reversible self‐assembling into extended fibrous structures, reminiscent of those observed in living systems. It is comprised of green fluorescent protein (GFP) molecules linked into linear oligomeric strands through click step growth polymerization with dialkyne poly(ethylene oxide) (PEO). Confocal microscopy, atomic force microscopy, and dynamic light scattering revealed that such strands form high persistence length fibers, with lengths reaching tens of micrometers, and uniform, sub‐100 nm widths. We ascribe this remarkable and robust form of self‐assembly to the cooperativity arising from the known tendency of GFP molecules to dimerize through localized hydrophobic patches and from their covalent pre‐linking with flexible PEO. Dissipative particle dynamics simulations of a coarse‐grained model of the system revealed its tendency to form elongated fibrous aggregates, suggesting the general nature of this mode of self‐assembly.     

N‐Alkylacylamides in Thin Films Display Infrared Spectra of 310‐, α‐, and π‐Helices with Visible Static and Dynamic Growth Phases

A peptide model is a physical system containing a CONH group, the simplest being HCONHCH₃, N‐methylformamide (NMF). We have discovered that NMF and N‐methylacetamide (NMA), which form hydrogen‐bonded oligomers in thin films on a planar AgX fiber, display infrared (IR) spectra with peaks like those of polypeptide helices. Structures can be assigned by their amide I maxima near 1672 (3₁₀), 1655 (3₁₀), 1653 (α), 1655 (π), and 1635 cm^?1 (π), which are the first IR data for the π‐helix. Sharp peaks are an outcome of immobilization of polar species on the polar surface of silver halides. We report the first use of expanded thin‐film IR spectroscopy, in which plots of every spectrum over the amide I–II range show pauses or slow stages in the increase or decrease of absorption. These are identified as static phases followed by dynamic phases, with the incremental gain or loss of a helix turn. A general theory can be stated for such processes. Density functional calculations show that the NMA α‐helix pentamer (crystal structure geometry) is transformed into a π‐helix‐like form. For the first time, an entire sequence (3₁₀‐helix, α‐helix, π‐helix, quasiplanar species) of spectra has been recorded for NMA.     

Anisotropic Protein Organofibers Encoded With Extraordinary Mechanical Behavior for Cellular Mechanobiology Applications

Hydrogels enable a variety of applications due to their dynamic networks, structural flexibility, and tailorable functionality. However, their mechanical performances are limited, specifically in the context of cellular mechanobiology. It is also difficult to fabricate robust gel networks with a long-term durability. Thus, a new generation of soft materials showing outstanding mechanical behavior for mechanobiology applications is highly desirable. We combined synthetic biology and supramolecular assembly to prepare elastin-like protein (ELP) organogel fibers with extraordinary mechanical properties. The mechanical performance and stability of the assembled anisotropic proteins are superior to other organo-/hydrogel systems. Bone-derived mesenchymal cells were introduced into the organofiber system for stem-cell lineage differentiation. This approach demonstrates the feasibility of mechanically strong and anisotropic organonetworks for mechanobiology applications and holds great potential for tissue-regeneration translations.     

Single-Carbon-Fiber-Powered Microsensor for In Vivo Neurochemical Sensing with High Neuronal Compatibility

The development of new principles and techniques with high neuronal compatibility for quantitatively monitoring the dynamics of neurochemicals is essential for deciphering brain chemistry and function but remains a great challenge. We herein report a neuron-compatible method for in vivo neurochemical sensing by powering a single carbon fiber through spontaneous bipolar electrochemistry as a new sensing platform. By using ascorbic acid as a model target to prove the concept, we found that the single-carbon-fiber-powered microsensor exhibited a good response, high stability and, more importantly, excellent neuronal compatibility. The microsensor was also highly compatible with electrophysiological recording, thus enabling the synchronous recording of both chemical and electrical signals. The sensing principle could be developed for in vivo monitoring of various neurochemicals in the future by rationally designing and tuning the electrochemical reactions at the two poles of the carbon fiber.     

The effect of short glass fibers on the process behavior of polyamide 12 during selective laser beam melting

In additive manufacturing, polymer composites are used for setting tailored properties. Short glass fibers can be used as fillers for polyamide 12 for enhancing stiffness or tensile strength as well as for reducing shrinkage. In this paper, the effects of short glass fibers on polyamide 12 concerning powder properties, process behavior and part properties in laser beam melting of polymers (SLS) are investigated. It could be shown that by increasing the short glass fiber content powder properties as well as part properties are immensely affected. By adding glass fibers, powder properties, like flowability and diffuse reflection decrease. The isothermal crystallization changes resulting in a narrower processing window. Concerning mechanical properties, short glass fibers allow for a higher stiffness until a critical limit of filler concentration within this study is reached, after which the tensile strength decreases. The elongation of break decreases by rising the filler content.     

三元Ho3+-TiO2/Bi等离子体复合纤维制备及其可见光催化产氢性能

以电纺Ho³⁺-TiO₂纳米纤维为基质,葡萄糖酸钠为还原剂,采用水热法制备Ho³⁺-TiO₂/Bi等离子体复合纤维光催化剂。 利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)和瞬时光电流(IP)等分析测试手段对样品的物相、形貌和光电性能等进行表征。 以三乙醇胺为电子给体,研究了Ho³⁺-TiO₂/Bi光催化分解水产氢的反应过程。 结果表明:在水热过程中,Bi³⁺被葡萄糖酸钠还原成单质Bi纳米颗粒,复合在Ho³⁺-TiO₂纳米纤维表面形成肖特基结。 金属Bi通过局域表面等离子体共振效应结合稀土元素丰富的能级结构和4f电子跃迁特性,对TiO₂进行双重修饰改性,有效提高了TiO₂的光催化活性和稳定性,可见光下产氢速率最大为43.6 μmol/(g·h)。     

超疏水超亲油玉米秸秆粉油污吸附剂的制备及其在油水分离中的应用

超疏水超亲油材料因其在油水分离等领域有广泛的应用前景而引起人们极大关注。 目前,有很多方法可以用来制备超疏水超亲油材料,但因其过程复杂、成本高、环境适应性差限制了其在实际生产、生活中应用。 本文以玉米秸秆为原料,经TiO₂ 溶胶浸涂并经辛基三甲氧基硅烷修饰后显示出超疏水和超亲油,水滴、油滴在其表面的接触角分别为160°和0°。 研究结果显示,玉米秸秆粉表面的超疏水性源于其表面微纳米复合阶层结构及低表面能化学组成的协同作用。 利用玉米秸秆粉表面的憎水性和亲油性,能将其用于水面油污的吸附和分离,具有分离效率高、稳定性好、可循环利用的优点。 相比于其它材料,以玉米秸秆为原料制备超疏水超亲油的油污吸附剂,原料丰富、成本低、过程简单、易降解、可循环利用,有望在生产、生活中得到应用。     

Preparation of Ag/C fiber with nanostructure through in situ thermally induced redox reaction between PVA and AgNO3 and its catalysis for 4‐nitrophenol reduction

A novel synthesized Ag/C fibrous catalyst based on in situ thermally induced redox reaction of PVA/AgNO₃ composite fibers was proposed. Utilizing the plasticization and complexation of AgNO₃ solution, the melt spinning of PVA/AgNO₃ composites was accomplished. Through the in situ thermally induced redox reaction on PVA/AgNO₃ composite fibers combined with carbonization of PVA and reduction of Ag+, the synthesized Ag/C fibrous catalyst was prepared with nanosilver particles with average diameter of 130 nm immobilized on the loose microstructural carbon layers. The synthesized Ag/C fibrous catalyst exhibited excellent catalytic activity and reused for at least five cycles for the reduction of 4‐nitrophenol, which may hold great promise in effective and eco‐friendly waste water treatment.