Thermosensitive graphene‐polymer composites have been prepared by attaching poly(N‐isopropylacrylamide) (PNIPAAm) onto the basal plane of graphene sheets via π‐π stacking. Pyrene‐terminated PNIPAAm was synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene‐functional RAFT agent. Aqueous solutions of the graphene‐polymer composites were stable and thermosensitive. The lower critical solution temperature (LCST) of pyrene‐terminated PNIPAAm was measured to be 33 °C. When the pyrene‐functional polymer was attached to graphene the resultant composites were also thermosensitive in aqueous solutions exhibiting a reversible suspension behavior at 24 °C. Atomic force microscopy (AFM) analysis revealed that the thickness of a graphene‐PNIPAAm (Mn: 10,000 and PDI: 1.1) sheet was ∼5.0 nm. The surface coverage of polymer chains on the graphene basal plane was calculated to be 7.2 × 10−11 mol cm−2. The graphene‐PNIPAAm composite material was successfully characterized using X‐ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR‐IR) spectroscopy, and thermogravimetric analysis (TGA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 425–433, 2010

The spectroscopic and photophysical properties of three gold( 1)-acetylide complexes [N (PPh,),] -[Au(CzCPh),], [Au(PPh,)(C-CPh)] and [{Au(C-CPh)},(p-dppe)] [dppe = 1,2-bis(diphenyIphosphino)ethane] are described. X-Ray crystal analysis of the latter showed a weak metal-metal interaction in the solid state with the shortest Au -Au separation being 3.1 53(2) A. The gold(1)acetylide complexes have long-lived and emissive ,(n,n*) excited states in solutions at room temperature. The photoreaction of [Au( PPh,) (C-CPh)] with methyl viologen has been investigated by Stern-Volmer quenching and flash-photolysis experiments.

Well-controlled poly(N-vinylpyrrolidone) (PVP)-grafted silicon surfaces were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) with 1,4-dioxane/water mixtures as solvents and CuCl/5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (Me6TATD) as a catalyst. The thickness of the PVP layer on the surface increased with reaction time, suggesting that the ATRP grafting of N-vinylpyrrolidone (NVP) from the silicon surfaces was a well-controlled process. The water contact angle and X-ray photoelectron spectroscopy (XPS) were used to characterize the modified surfaces. The protein adsorption property of the PVP-grafted surfaces was evaluated using a radiolabeling method. Compared with unmodified silicon surfaces, a Si-PVP60 surface with a PVP thickness of 15.06 nm reduced the level of adsorption of fibrinogen, human serum albumin (HSA), and lysozyme by 75, 93, and 81%, respectively. Moreover, the level of fibrinogen adsorption decreases gradually with an increase in PVP thickness. However, no significant difference in fibrinogen adsorption was found when the PVP layer was thicker than the critical thickness of 13.45 nm.

Polymer self-assembly has been one of the most important strategies for preparation of multicompartment micelles (MCMs). However, the traditional self-assembly techniques are constrained by limited common solvent, complex kinetic factors, low solids content, etc. Polymerization-induced self-assembly (PISA) is a novel technique for preparation of polymer assemblies at high solids content and has been exploited to produce MCMs. Nevertheless, the morphology evolution of the MCMs obtained through PISA has not yet been well understood. Herein, we study the compartmentalization behaviors of a series of MCMs constituted by poly­(N,N-dimethyl­aminoethyl methacrylate)-b-poly­(benzyl methacrylate)-b-poly­(2-perfluorohexylethyl methacrylate) (PDMA-b-PBzMA-b-PFHEMA) triblock terpolymers, which were synthesized by seeded reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of FHEMA using PDMA-b-PBzMA micelles, wormlike micelles, or vesicles as the seeds. Because of the strong incompatibility between PBzMA and PFHEMA, MCMs with abundant compartmentalized nanostructures were produced. Phosphotungstic acid- and RuO4-stained TEM images of these MCMs indicate that their morphologies are controlled by both the DPs of PBzMA and PFHEMA. Our results suggest that PISA could serve as a reliable platform for revealing the compartmentalization behaviors of polymeric assemblies.

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Design of functional carbon-based nanomaterials from metal-organic frameworks (MOFs) has attracted soaring interests in recent years. However, a MOF-derived strategy toward two-dimensional (2D) nanomaterials remains a great challenge. In this work, we develop a layered Ni-hexamine framework as efficient precursor to prepare a 2D NiSe/N-rich carbon nanocomposite by a simple pyrolysis and subsequent selenization process. In the 2D NiSe/N-rich carbon nanocomposite, NiSe nanoparticles with diameters of ca. 75 nm are homogeneously distributed in the N-rich carbon nanosheets. When serving as anode materials for sodium-ion batteries, the 2D nanocomposites exhibit a high reversible capacity of 410 mAh g at 1 A g and maintain a value of 255 mAh g even at 10 A g. The excellent electrochemical performance can be attributed to the synergistic effects between the N-rich carbon nanosheets and NiSe nanoparticles. More importantly, the hexamine-based MOFs can be regarded as new and powerful platforms for the fabrication of 2D N-rich carbon-based nanomaterials, which is of great importance for various potential applications.

Accurate monitoring of physiological temperatures is important for the diagnosis and tracking of various medical conditions. This work presents the design, fabrication, and characterization of temperature sensors using conductive polymer composites (CPCs) patterned on both flexible and stretchable substrates through both drop coating and direct ink writing (DIW). These composites were formed using a high melting point biopolymer polyhydroxybutyrate (PHB) as the matrix and the graphenic nanomaterial reduced graphene oxide (rGO) as the nanofiller (from 3 to 12 wt%), resulting in a material that exhibits a temperature-dependent resistivity. At room temperature the composites exhibited electrical percolation behavior. Around the percolation threshold, both the carrier concentration and mobility were found to increase sharply. Sensors were fabricated by drop-coating PHB-rGO composites onto ink-jet printed silver electrodes. The temperature coefficient of resistance was determined to be 0.018 /°C for pressed rGO powders and 0.008 /°C for the 3 wt% samples (the highest responsivity of all composites). Composites were found to have good selectivity to temperature with respect to pressure and moisture. Thermal mapping was demonstrated using 6 × 7 arrays of sensing elements. Stretchable devices with a meandering pattern were fabricated using DIW, demonstrating the potential for these materials in healthcare monitoring devices.

A series of polymerization-induced self-assembly (PISA) formulations are developed based on reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization of semi-fluorinated methacrylates. Alcoholic RAFT dispersion polymerization of 2-(perfluorobutyl)ethyl methacrylate (FBEMA), 2-(perfluorohexyl)ethyl methacrylate (FHEMA), and 2-(perfluorooctyl)ethyl methacrylate (FOEMA) is systematically evaluated to extend the general usability of semi-fluorinated methacrylates to PISA. The nanostructure of the assemblies is correlated to the side-chain length of the monomer: RAFT dispersion polymerization of FBEMA produces spherical micelles, wormlike micelles, and vesicles depending on its degree of polymerization (DP), while only spheres are generated for the PISA of FHEMA. PISA of FOEMA generates liquid crystalline cylindrical micelles, whose diameter increases with the DP of FOEMA. These results demonstrate the general feasibility of semi-fluorinated methacrylates to PISA. Besides, PISA of FHEMA is also realized in a variety of solvents, including iso-propanol, toluene, dioxane, and dimethyl formamide, exhibiting the superior solvent serviceability of the PISA formulations based on semi-fluorinated methacrylates.