A strategy for synthesis of ion-bonded supramolecular star polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization

We have developed a novel strategy for the preparation of ion-bonded supramolecular star polymers by RAFT polymerization. An ion-bonded star supramolecule with six functional groups was prepared from a triphenylene derivative containing tertiary amino groups and trithiocarbonate carboxylic acid, and used as the RAFT agent in polymerizations of tert-butyl acrylate (tBA) and styrene (St). Molecular weights and structures of the polymers were characterized by H-1 NMR and GPC. The results show that the polymerization possesses the character of living free-radical polymerization and the ion-bonded supramolecular star polymers PSt, PtBA, and PSt-b-PtBA, with six well-defined arms, were successfully synthesized.

Surface-enhanced Raman scattering from surfactant-free 3D gold nanowire networks substrates

A useful method for the fabrication of three-dimensional gold nanowire networks based on the chemical reduction of HAuCl4 with trisodium citrate was presented. The coverage of the 3D gold nanowire networks was tunable by altering precursor concentration. The as-prepared 3D gold nanowire networks could be used as surface-enhanced Raman scattering (SERS) substrates and examined by 4-aminothiophenol (4-ATP) as a probe molecules.

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Self-assembled 3D Architectures of LuBO3 : Eu3+: Phase-selective synthesis, growth mechanism, and tunable luminescent properties

Rhombohedral-calcite and hexagonal-vaterite types of LuBO:Eu3+ microparticles with various complex self-assembled 3D architectures have been prepared selectively by an efficient surfactant- and template-free hydrothermal process for the first time. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, photoluminescence, and cathodoluminescence spectra as well as kinetic decays were used to characterize the samples.

One-step aqueous solvothermal synthesis of In2O3 nanocrystals

Highly crystalline and nearly monodisperse In2O3 nanocrystals with both cube and flower shapes were successfully synthesized in one step through a facile aqueous solvothermal method for the first time, free of any surfactant or template. X-ray diffraction (XRD), transmission electron microscopy (TEM), selective area electron diffraction (SAED), and high-resolution transmission electron microscopy (HRTEM) were used to characterize the samples. In our work, the use of diethylene glycol (DEG) is a crucial factor for the formation of the In2O3 phase.

Hydrothermal synthesis and luminescent properties of LuBO3: Tb3+ microflowers

Hexagonal vaterite-type LuBO3:Tb3+ microflower-like phosphors have been successfully prepared by an efficient surfactant- and template-free hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectrometry transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence(PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples.

Rare-Earth Metal Bis(alkyl)s Supported by a Quinolinyl Anilido-Imine Ligand: Synthesis and Catalysis on Living Polymerization of epsilon-Caprolactone

The tridentate ligand N-(2-((2,6-diisopropylphenylimino)methyl)phenyl)quinolin-8-amine (HL) was prepared. Treatment of HL with 1 equiv of Ln(CH2SiMe3)(3)(THF)(2) afforded the corresponding rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF)(n) (Ln = Sc, n = 0 (1); Y, n = 1 (2); Lu, n = 0 (3)) in high yields. Variable-temperature H-1 NMR spectral analysis showed that these complexes were fluxional at room temperature. Complexes 1 and 3 were THF-free, where the metal center adopted a square-pyramidal geometry, while in 2 the metal center generated a distorted octahedral geometry owing to the coordination of a THF molecule.

Template-free, surfactantless route to fabricate In(OH)(3) monocrystalline nanoarchitectures and their conversion to In2O3

In this work, a one-dimensional microrod-based three-dimensional flowerlike indium hydroxide (In(OH)(3)) structure was fabricated, without any templates or surfactants, using a well-known hydrothermal approach at a non-high temperature. In2O3 with similar morphology was formed by annealing In(OH)3 precursors and was characterized by Raman spectrum and photoluminescence (PL) spectrum in detail.

Sonochemical synthesis of monodispersed KY3F10 : Eu3+ nanospheres with bimodal size distribution

Monodispersed KY3F10:Eu3+ nanospheres with bimodal size distribution have been successfully synthesized via a facile and efficient sonochemical method in a surfactant-free system. Rare-earth nitrate (Y, Eu)(NO3)(3) and potassium fluoborate (KBF4) were used as precursors. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectra were used to characterize the samples.

One-Step Synthesis of Folic Acid Protected Gold Nanoparticles and Their Receptor-Mediated Intracellular Uptake

We report here a facile method to obtain folic acid (FA)-protected gold nanoparticles (Au NPs) by heating an aqueous solution of HAuCl4/FA in which FA acts as both the reducing and stabilizing agent. The successful formation of FA-protected Au NPs is demonstrated by UV/Vis spectroscopy, transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). ne intracellular uptake of these nanoparticles is facilitated by HeLa cells overexpressing the folate reporter, which itself is significantly inhibited by free FA in a competitive assay as quantified by inductively coupled plasma mass spectroscopy (ICP-MS). This simple one-step approach affords a new perspective for creating functional nanomaterials, and the resulting biocompatible, functional Au NPs may find some prospective applications in various biomedical fields.

Synthesis of Hyperbranched Polymers with Pendent Norbornene Functionalities via RAFT Polymerization of a Novel Asymmetrical Divinyl Monomer

Hyperbranched polymers with numerous pendent norbornene functionalities have been synthesized via the radical polymerization of a novel asymmetrical divinyl monomer hearing a higher reactivity methacrylate group and it lower reactivity norbornene group. Mediated by a rapid reversible addition-fragmentation chain transfer (RAFT) equilibrium, the concentration of polymeric chain radicals is decreased, and thus the gelation did not occur until higher monomer conversions (ca. 90%). An increase in reaction temperature call also significantly promote the formation of the hyperbranched structure owing to the decreased stability of the intermediate radicals derived from the norbornene group, which was confirmed by a model copolymerization system of two single vinyl monomers with similar structures to the vinyl groups in the asymmetrical divinyl monomer. Furthermore, Tri-SEC and conventional Sin-SEC as well as H-1 NMR.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.

One-step synthesis of Ru(2,2 '-bipyridine)(3)Cl-2-immobilized silica nanoparticles for use in electrogenerated chemiluminescence detection

One-step synthesis of Ru (bpy)(3) Cl-2-immobilized (bpy = 2,2'-bipyridine) silica nanoparticles (Ru-silica nanoparticles) for use in electrogenerated-chemiluminescence (ECL) detection is reported. Ru-silica nanoparticles are prepared by using the Stober method. Compared with free Ru(bpy)(3)Cl-2, Ru-silica nanoparticles are seen to exhibit a red-shift of the UV-vis absorbance peak and a longer fluorescence lifetime, which are attributed to the electrostatic interaction of Ru(bpy)(3)(2+) and silica. Because silica nanoparticles are used as immobilization matrices, the surfaces of Ru-silica nanoparticles are easily modified or functionalized via the assembly of other nanoparticles, such as Au. For ECL detection, Au-colloid-modified Ru-silica nanoparticles are immobilized on a 3-mercaptopropyl-trimethoxysilane-modified indium tin oxide electrode surface by Au-S interaction; the surface concentration of electroactive Ru(bpy)(3)Cl-2 is obviously higher than that in silica films.

Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.