Janus nanosheets were prepared from K4Nb6O17·3H2O by modifying surfaces of their two distinct interlayers in a regioselective and sequential manner and subsequent exfoliation. The surface properties of nanosheets were investigated by phase atomic force microscopy imaging and two types of surfaces were discriminated, indicating that Janus nanosheets were successfully prepared.
Inorganic Janus nanosheets were successfully prepared using the difference in reactivity between interlayers I and II of layered hexaniobate K 4 Nb6O 17 ·3H 2 O. Janus nanosheets exhibit the highest anisotropy among Janus compounds due to their morphology. It is therefore important to prepare Janus nanosheets with stable shapes in various solvents, robust chemical bonds between nanosheets and fuctional groups and high versatility due to surface functional groups. K 4 Nb 6 O 17 ·3H 2 O, which possesses two types of interlayers and two types of organophosphonic acids that react with metal oxides to form robust covalent bonds, was employed to prepare Janus nanosheets for this study. Interlayer I was modified by octadecylphosphonic acid, followed by modification by carboxypropylphosphonic acid mainly at interlayer II. Preparation of Janus nanosheets with two organophosphonate moieties was confirmed by 31 P MAS NMR. After these regioselective and sequential modifications, the products were exfoliated into single-layered nanosheets in THF. Two types of derivatives with different repeating distances were recovered from a dispersion containing nanosheets exfoliated by different processes, centrifugation, and solvent evaporation. AFM analysis of the exfoliated nanosheets revealed that the products were Janus compounds. There are high expectations for application of these types of Janus nanosheets in various fields and for design of various Janus nanosheets using this preparation method.There are various methods of preparing Janus nanoparticles. Regioselective surface modification of nanoparticles can produce Janus nanoparticles [11]. By forming nanoparticles with two raw materials, Janus nanoparticles with different compositions can be prepared [2]. Self-assembly and subsequent cross-linking of polymer chains can also produce Janus nanoparticles [12]. Janus rods can be prepared by forming silica using TEOS by the sol-gel method on Fe 3 O 4 regioselectively [13]. Janus cylinders can be prepared by masking one side of a cylinder and conducting subsequent modification of the other side [14].Janus nanosheets exhibit the highest anisotropy among Janus compounds due to their unique morphology. They are also useful as emulsifiers, because Janus nanosheets cannot rotate at the interfaces of micelles [15]. Most Janus nanosheets reported so far have consisted of polymers. Stupp et al. reported the preparation of Janus nanosheets by polymerization of oligomers with polymerizable groups [16]. Polymerization of oligomers led to the formation of sheet morphology, because the polymerizable groups were located at the center of an oligomer. Walther et al. used triblock copolymers, polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate), for preparing Janus nanosheets [17]. Janus nanosheets were prepared by cross-linking polybutadiene domains of the triblock copolymers, and the resulting Janus nanosheets had two types of surfaces, polystyrene, and poly(tertbutyl methacrylate) moieties. These methods are based on selective polym...
Natural polysaccharides represent a renewable resource whose effective utilization is of increasing importance. Chemical modification is a powerful tool to transform them into processable materials but usually sacrifices the original structures and properties of value. Here we introduce a chemical modification of Curdlan, a β-1,3-glucan, via 4,6-acetalization. This modification has successfully combined a helix-forming ability of Curdlan with new solubility in organic media. Furthermore, it has operationalized efficient cohelical crossovers (CCs) among the helices to demonstrate the formation of an extensive supramolecular network that goes well beyond the nanoscopic regime, allowing for preparation of flexible self-supporting films with macroscopic dimensions. This protocol, which is now viewed as supramolecular polymerization of a helical polysaccharide macromer, can add a new dimension to "polysaccharide nanotechnology", opening a door for the creation of unconventional polymer materials based on the cohelical crossover network (CCN).
Molecular nonwoven fabrics in the form of ultrathin layer-by-layer (LbL) helical polymer films with covalent cross-linking were assembled on substrates by an alternate ester-amide exchange reaction between poly(γ-methyl L-glutamate) (PMLG) and cross-linking agent ethylene diamine or 4,4'-diamino azobenzene. The regular growth of helical monolayers without excessive adsorption and the formation of amide bonds were confirmed by ultraviolet-visible (UV-vis) spectrophotometry, quartz crystal microbalance (QCM), ellipsometry, and infrared reflection-absorption spectroscopy (IR-RAS) measurements. Nanostructures with high uniformity and ultrathin films with few defects formed by helical rod segments of PMLG were characterized by atomic force microscopy (AFM) and Kelvin probe force microscopy (KFM).
This work describes synthesis of graphene sheets with modified surface by sodium lauryl sulfate (SLS) surfactant using one-pot solvothermal reaction method. Effect of sodium lauryl sulfate surfactant amount on surface modification level of graphene sheets was investigated. Ether (-S-OR-at 762 cm −1-863 cm −1), thiocarbonyl (=C=S at 1050 cm −1-1176 cm −1) and sulfoxide (S-O, V s and V as at 1030 cm −1-1450 cm −1) functional groups released from sodium lauryl sulfate (SLS) surfactant during solvothermal reaction and attached on the surface of graphene sheets were detected by (attenuated total reflectance-fast Fourier infrared) ATR-FTIR spectroscopy. (Atomic force microscope) AFM observations revealed apparent surface of graphene sheets modified by surfactant molecules with an average multiple profile of graphene nanosheets ≈ 4.8 nm high. This synthesis way of surface modified graphene sheets can be considered as easy, one-step and cheap method for manufacturing of novel biosurface with graphene, as reinforcement for biopolymer coatings such as ultra-high molecular weight polypropylene (UHMWPE), metallic biomaterials (Ti and Ti alloys) and bioceramics as hydroxyapatite (HA).
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