Study on Broadband Emitting Self-Assembled Quantum-Dot Material and Devices

City Univ Hong Kong

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.

Multilayer structured carbon nanotubes/poly-L-lysine/laccase composite cathode for glucose/O-2 biofuel cell

Multilayer film of laccase, poly-L-lysine (PLL) and multi-walled carbon nanotubes (MWNTs) were prepared by a layer-by-layer self-assembly technique. The results of the UV-vis spectroscopy and scanning electron microscopy studies demonstrated a uniform growth of the multilayer. The catalytic behavior of the modified electrode was investigated. The (MWNTs/PLL/laccase)(n) multilayer modified electrode catalyzed four-electron reduction of O-2 to water, without any mediator.

Phase Behavior and self-assembly of poly[N-vinylformamide-co-(acrylic acid)] copolymers under highly acidic conditions

Copolymers of N-vinylformamide and acrylic acid were synthesized by conventional aqueous free-radical polymerization. The phase behavior of the copolymer solutions was investigated through the addition of hydrochloric acid and the variation of the temperature. With a moderate content of N-vinylformamide, the copolymers showed complex phase behaviors. Under low-acidity conditions, a suspending liquid was formed, whereas under high-acidity conditions, the random copolymers could assemble into round nanoparticles with a broad particle size distribution.

[Ru(bpy)(3)](2+)-doped silica nanoparticles within layer-by-layer biomolecular coatings and their application as a biocompatible electrochemiluminescent tag material

[Ru(bpy)(3)](2+)-doped silica (RuSi) nanoparticles were synthesized by using a water/oil microemulsion method. Stable electrochemiluminescence (ECL) was obtained when the RuSi nanoparticles were immobilized on a glassy carbon electrode by using tripropylamine (TPA) as a coreactant. Furthermore, the ECL of the RuSi nanoparticles with layer-by-layer biomolecular coatings was investigated. Squential self-assembly of the polyelectrolytes and biomolecules on the RuSi nanoparticles gave nanocomposite suspensions, the ECL of which decreased on increasing the number of bilayers.

Self-assembly of rod-coil-rod ABA-type triblock copolymers

Self-assembled behavior of symmetric ABA rod-coil-rod triblock copolymer melts is studied by applying self-consistent-field lattice techniques in three-dimensional space. The phase diagram is constructed to understand the effects of the chain architecture on the self-assembled behavior. Four stable structures are observed for the ABA rod-coil-rod triblock, i.e., spherelike, lamellar, gyroidlike, and cylindrical structures. Different from AB rod-coil diblock and BAB coil-rod-coil triblock copolymers, the lamellar structure observed in ABA rod-coil-rod triblock copolymer melts is not stable for high volume fraction of the rod component (f(rod)=0.8), which is attributed to the intramolecular interactions between the two rod blocks of the polymer chain.

Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene

A series of new rare-earth metal bis(alkyl) complexes [L(1-3)Ln(CH2SiMe3)(2)(THF)(n)] (L-1 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H2Me3-2,4,6: Ln = Sc, n = 1 (1a); Ln = Lu, n = 1 (1b); L-2 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H3Et2-2,6: Ln = Sc, n = 1 (2a); Ln = Lu, n = 1 (2b); Ln = Y, n = 1 (2c); L-3 = MeC4H2SCH2NC6H4(Ph)(2)P=(NC6H3Pr2)-Pr-i-2,6: Ln = Sc, n = 0 (3a)) and (LSc)-Sc-4(CH2SiMe3)(2()THF) (4a) (L-4 = C6H5CH2NC6H4(Ph)(2)P=NC6H3Et2-2,6) have been prepared by reaction of rare-earth metal tris(alkyl)s with the corresponding HL1-4 ligands via alkane elimination.

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.

O-2 activation and hydrolysis of Salan rare-earth metal alkyl complexes

Salan ligated yttrium alkyl complex 1, (LY)-Y-1(CH2SiMe3)(THF) (Salan = L-1: [2-O-3,5-tBu(2)-C6H2CH2N(CH3) CH2](2)), was exposed to an oxygen/ nitrogen atmosphere to give a bimetallic alkoxide complex 4, [(LY)-Y-1(mu-OCH2SiMe3)](2). Whilst the lutetium counterparts 2 ((LLu)-Lu-1(CH2SiMe3)(THF)) and 3 ((LLu)-Lu-2(CH2SiMe3)(THF); L-2: [2-O-3-tBu-C6H2CH2N(CH3) CH2](2)) were hydrolysed with moist nitrogen to afford mixed hydroxy/silyloxy complexes 5 and 6 ([(LLu)-Lu-1,2(mu-OSiMe3)(mu-OH) LuL1,2]), respectively.

Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2N=CH)(2)C6H3)LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C2H3-R2N=CH)(2)-C6H3Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry.

Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes

Reaction of 7-{(N-2,6-R)iminomethyl)}lindole (HL1, R = dimethylphenyl; HL2, R = diisopropylphenyl) and rare-earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), generated new rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF) [L = L-1: Ln = Lu. (1a), Sc (1b); L = L-2 : Ln = Lu (3a), Se (3b)] and mono(alkyl) complexes L-2 Lu-2(CH2SiMe3) (4a). Treatment of alkyl complexes 1a and 4a with N,N'-diisopropylcarbodiimide afforded the corresponding amidinates (LLu)-Lu-1{iPr(2)NC(CH2SiMe3) NiPr2}(2) (2a) and L-2 Lu-2{iPr(2)NC(CH2SiMe3)NiPr2} (5a), respectively.

Highly 3,4-selective living polymerization of isoprene with rare earth metal fluorenyl N-heterocyclic carbene precursors

Fluorenyl modified N-heterocyclic carbene ligated rare earth metal bis(alkyl) complexes, (Flu-NHC)Ln(CH2SiMe3)2 (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (1a); Ln = Y (1b); Ln = Ho (1c); Ln = Lit (1d)), were synthesized and fully characterized by NMR and X-ray diffraction analyses. Complexes Ib-d with the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)4] exhibited high activity, medium syndio-but remarkably high 3,4-regio-selectivity, and the unprecedented livingness for the polymerization of isoprene. Such distinguished catalytic performances could be maintained under various monomer-to-initiator ratios (500-5000) and broad polymerization temperatures (25-80 degrees C).

New rare earth metal bis(alkyl)s bearing an iminophosphonamido ligand. Synthesis and catalysis toward highly 3,4-selective polymerization of isoprene

Newrareearth metal bis(alkyl) complexes [(NPNPh)Ln(CH2SiMe3)(2)(THF) (NPNPh:N(Ph)PPh2=NC6H2Me3-2,4,6; Ln = Sc (3a), Ln = Y (3b), Ln = Lu (3c)) and [(NPNPy)Sc(CH2SiMe3)(2)(THF)1 (NPNPY = N(Py)PPh2=NC6H2Me3-2,4,6) (3d)) have been prepared via protonolysis reaction between rare earth metal tris(alkyl)s and the corresponding iminophosphonamines. Complexes 3a-d are analogous monomers of THF solvate. Each metal ion coordinates to a eta(2)-chelated NPN ligand and two cis-located alkyl groups, adopting tetrahedron geometry.

Grown-like macrocycle zinc complex derived from beta-diketone ligand for the polymerization of rac-lactide

Enolic Schiff base zinc (II) complex 1 was synthesized. XRD revealed 1 was a novel crown-like macrocycle structure consisted of hexanuclear units of (LZnEt)(6) via the coordination chelation between the Zn atom and adjacent amine nitrogen atom. Further reaction of 1 with one equivalent 2-propanol at RT produced Zn-alkoxide 2 by in situ alcoholysis. Complex 2 was used as an initiator to polymerize rac-lactide in a controlled manner to give heterotactic enriched polylactide. Factors that influenced the polymerization such as the polymerization time and the temperature as well as the monomer concentration were discussed in detail in this paper.

Micelle-assisted synthesis of polyaniline/magnetite nanorods by in situ self-assembly process

Polyaniline/magnetite nanocomposites consisting of polyaniline (PANI) nanorods surrounded by magnetite nanoparticles were prepared via an in situ self-assembly process in the presence of PANI nanorods. The synthesis is based on the well-known chemical oxidative polymerization of aniline in an acidic environment, with ammonium persulfate (APS) as the oxidant. An organic acid (dodecylbenzenesulfonic acid, DBSA) was used to replace the conventional strong acidic (1 M HCl) environment. Here, dodecylbenzenesulfonic acid is used not only as dopant, but also as surfactant in our reaction system.