Controlled Synthesis of Polyaniline-Based Nanomaterials with Self-Assembly and Interface Manipulation.

Versatile nanostructures of conducting polymers are highly relevant based on unique properties, including electrical, optical, and thermal, with changes in morphology. This contribution reports a facile and reproducible synthesis approach for the design of conducting polymer nanostructures from zero- to three-dimensional composites. Two polymerization steps, namely, self-assembly-directed and interface thin layer-templated polymerizations in this synthesis, were kinetically controlled to fabricate such nanostructures directly. The uniquely designed bicontinuous nanoreactor offers an easy synthesis technique for fabricating 3D multifunctional conducting polymer composites. Self-assembly-directed polymerization could be controlled to form nanorods and further directed to form nanobowl/hollow spherical structures. The interface thin layer template process was tuned to produce hollow spherical and 2D film nanostructures. Kinetic control of polymerization was able to provide access to unprecedented nanostructures of the conducting polymers ranging from DNA origami to gecko-inspired nanostructures, with potential applications in drug delivery, energy storage, and adhesive materials. For example, this is the first conducting polymer material that can demonstrate similar adhesiveness (around 8 N/cm2) to gecko finger hairs.

Mechanically-robust electrospun nanocomposite fiber membranes for oil and water separation.

Mechanically-robust nanocomposite membranes have been developed via crosslinking chemistry and electrospinning technique based on the rational selection of dispersed phase materials with high Young's modulus (i.e., graphene and multiwalled carbon nanotubes) and Cassie-Baxter design and used for oil and water separation. Proper selection of dispersed phase materials can enhance the stiffness of nanocomposite fiber membranes while their length has to be larger than their critical length. Chemical modification of the dispersed phase materials with fluorochemcials and their induced roughness were critical to achieve superhydrophobocity. Surface analytic tools including goniometer, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, atomic force microscopy (AFM) and scanning electron microscope (SEM) were applied to characterize the superhydrophobic nanocomposite membranes. An AFM-based nanoindentation technique was used to measure quantitativly the stiffness of the nanocomposite membranes for local region and whole composites, compared with the results by a tensile test technique. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to confirm composition and formation of nanocomposite membranes. These membranes demonstrated excellent oil/water separation. This work has potential application in the field of water purification and remediation.

Efficient One-Step Synthesis of a Pt-Free Zn0.76Co0.24S Counter Electrode for Dye-Sensitized Solar Cells and Its Versatile Application in Photoelectrochromic Devices.

In this study, we synthesized a ternary transition metal sulfide, Zn0.76Co0.24S (ZCS-CE), using a one-step solvothermal method and explored its potential as a Pt-free counter electrode for dye-sensitized solar cells (DSSCs). Comprehensive investigations were conducted to characterize the structural, morphological, compositional, and electronic properties of the ZCS-CE electrode. These analyses utilized a range of techniques, including X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The electrocatalytic performance of ZCS-CE for the reduction of I3- species in a symmetrical cell configuration was evaluated through electrochemical impedance spectroscopy and cyclic voltammetry. Our findings reveal that ZCS-CE displayed superior electrocatalytic activity and stability when compared to platinum in I-/I3- electrolyte systems. Furthermore, ZCS-CE-based DSSCs achieved power conversion efficiencies on par with their Pt-based counterparts. Additionally, we expanded the applicability of this material by successfully powering an electrochromic cell with ZCS-CE-based DSSCs. This work underscores the versatility of ZCS-CE and establishes it as an economically viable and environmentally friendly alternative to Pt-based counter electrodes in DSSCs and other applications requiring outstanding electrocatalytic performance.

Strategic Synthesis of 2D and 3D Conducting Polymers and Derived Nanocomposites.

In recent decades, there has been a great deal of interest in conducting polymers due to their broad applications. At the same time, various synthetic techniques have been developed to produce various nanostructures of the conducting polymers with their fascinating properties. However, the techniques for the manufacture of 2D nanosheets are either complex or expensive. No comprehensive approach for constructing 2D and 3D materials or their composites has been documented. Herein, a simple and scalable synthetic protocol is reported for the design of 2D, 3D, and related conducting polymer nanocomposites by interface manipulation in a bicontinuous microemulsion system. In this method, diverse bicontinuous thin layers of oil and water are employed to produce 2D nanosheets of conducting polymers. For the fabrication of 3D polypyrrole (PPY) and their composites, specially designed linkers of the monomers are applied to lock the 3D networks of the conducting polymers and their composites. The technique can be extended to the fabrication of most conducting polymer composites, being cost-effective and easily scalable. The optimum electrical conductivity obtained for 2D PPY nanosheets is 219 S cm-1 , the highest literature value reported to date to the best of knowledge.

Crystal structure of 5,15-bis-(4-methyl-phen-yl)-10,20-bis-(4-nitro-phen-yl)porphyrin nitro-benzene disolvate.

The whole mol-ecule of the title porphyrin, C46H32N6O4·2C6H5NO2, which crystallized as a nitro-benzene disolvate, is generated by inversion symmetry. The porphyrin macrocycle is almost planar, the maximum deviation from the mean plane of the non-hydrogen atoms is 0.097 (2) Å. The aryl rings at the meso positions are inclined to this mean plane by 74.84 (6)° for the nitro-phenyl rings and 73.37 (7)° for the tolyl rings. In the crystal, the porphyrin mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains along [100]. The solvent mol-ecules are also linked by C-H⋯O hydrogen bonds, forming chains along [100]. Inter-digitation of the p-tolyl groups along the c axis creates rectangular channels in which the solvent mol-ecules are located.

Biocompatible scaffolds based on natural polymers for regenerative medicine.

The chitosan and gelatine are commonly used biopolymers for the tissue engineering applications. In the previous methods for the cryogels synthesis, multistep preparation methods using toxic cross-linking agents such as glutaraldehyde are reported. Here, we present a two-step preparation method of gelatin macroporous cryogels and one-step preparation method of chitosan or gelatin cryogels. The physico-chemical properties of obtained scaffolds were characterized using FTIR, zeta potential, SEM and laser confocal microscopy. Non-toxic and biodegradable cross-linking agents such as oxidized dextran and 1,1,3,3-tetramethoxypropane are utilized. The one-step chitosan cryogels had degradation degree ~2 times higher compared to the cryogels prepared with a two-step method i.e. reduced by borohydride. Scaffolds cross-linked by glutaraldehyde had about 40% viability, whereas nine various compositions of cryogels showed significantly higher viability (~80%) of fibroblast cells in vitro. The cryogels were obtained without using the harmful compounds and therefore can be used straightforward as biocompatible and biodegradable scaffolds for the cell culturing purposes and other biomedical applications.