Search results for "cationic polymerization"

The first structurally characterized cationic lanthanide–alkyl complexesElectronic supplementary information (ESI) available: experimental and spectr…

2002

Reaction of rare earth metal–alkyl complexes [Ln(CH2SiMe3)3(THF)2] (Ln = Y, Lu) with B(C6X5)3 (X = H, F) in the presence of crown ethers gives crystallographically characterized ion pairs [Ln(CH2SiMe3)2(CE)(THF)n]+[B(CH2SiMe3)(C6X5)3]– (CE = [12]-crown-4, n = 1; CE = [15]-crown-5 and [18]-crown-6, n = 0).

NHC-Stabilized Gold(I) Complexes: Suitable Catalysts for 6-exo-dig Heterocyclization of 1-(o-Ethynylaryl)ureas

2010

3-Substituted 1-(o-ethynylaryl)ureas 1 selectively undergo either 6-exo-dig or 5-endo-dig cyclization (to give 4-methylene-3,4-quinazolin-2-ones 2 or indoles 3, respectively) depending on the choice of the metal, ligand, and reaction conditions. The best results (up to 96% yield) in the preparation of the hydroamination products 2 are achieved with the highly bulky NHC-stabilized cationic gold(I) complex [Au(IPr)](+). Conversely, ureas bearing an internal alkyne lead to the 5-endo-dig cyclization mode regardless of the gold(I) complex employed. Whereas the nature of the substituent at N-3 does not have any influence on the regiochemistry observed, it does, in some cases, affect the efficien…

Degradable cationic nanohydrogel particles for stimuli-responsive release of siRNA.

2014

Well-defined nanogels have become quite attractive as safe and stable carriers for siRNA delivery. However, to avoid nanoparticle accumulation, they need to provide a stimuli-responsive degradation mechanism that can be activated at the payload's site of action. In this work, the synthetic concept for generating well-defined nanohydrogel particles is extended to incorporate disulfide cross-linkers into a cationic nanonetwork for redox-triggered release of oligonucleotide payload as well as nanoparticle degradation under reductive conditions of the cytoplasm. Therefore, a novel disulfide-modified spermine cross-linker is designed that both allows disassembly of the nanogel as well as removal…

Cover Picture: Pleiotropic Role of Recombinant Silaffin-Like Cationic Polypeptide P5S3: Peptide-Induced Silicic Acid Stabilization, Silica Formation …

2016

Cyclodextrins in polymer synthesis: free radical polymerization of cyclodextrin complexes with oxazoline-functionalized vinyl monomers as guest molec…

2000

The synthesis of five new oxazoline functionalized vinyl monomers N-[4-(4′,5′-dihydrooxazol-2-yl)phenyl]acrylamide (3 a), N-[4-(4′,5′-dihydrooxazol-2-yl)phenyl]-2-methylacrylamide (3 b), N-{10-[4-(4′,5′-dihydrooxazol-2-yl)phenylcarbamoyl]decyl}-2-acrylamide (5 a), N-{10-[4-(4′,5′-dihydrooxazol-2-yl)phenylcarbamoyl]decyl}-2-methylacrylamide (5 b) and N-[4-(4′,5′-dihydrooxazol-2-yl)-phenyl]-4-vinylbenzamide (7) is described. With an equimolar amount of 2,6-dimethyl-β-cyclodextrin (DMCD) these monomers formed hydrophilic inclusion complexes 3 a,b-DMCD, 5 a,b-DMCD and 7-DMCD. These complexes were polymerized radically in an aqueous medium. Resulting polymers P-(3 a, b), P-(5 a, b) and P-(7) pre…

Block and graft copolymers of 2-oxazolines

1994

The cationic ring-opening polymerization of 2-oxazolines is known to be initiated by alkyl halides, Lewis acids and esters of strong acids. The polymerization proceeds by a living mechanism. Numerous block and graft copolymers have already been described. Recently it was found that chloroformates (R-O-CO-CI) are also useful initiators. The mechanism of the initiation and propagation is discussed. This type of initiators allows the synthesis of different novel two-block and three-block copolymers, star-shape polymers, and a graft copolymer with a polyvinylacetate backbone.

Nonlinear Macromolecules by Ring-Opening Polymerization

2012

Ring-opening polymerization (ROP) is a well-established method for the controlled synthesis of linear polymers, which can be found in various everyday applications. However, during the past decades, there has been an increasing interest in the generation of nonlinear highly branched polymers, profiting from the fascination created by the structurally perfect dendrimers. The applicability of various heterocyclic monomers renders the ring-opening multibranching polymerization (ROMBP), a versatile tool for the generation of multifunctional hyperbranched polymers. First, the historical key steps leading to the development of ROMBP are described, which is the basis for the controlled synthesis o…

(Co-)solvent selection for single-wall carbon nanotubes: best solvents, acids, superacids and guest-host inclusion complexes.

2011

Analysis of 1-octanol-water, cyclohexane-water and chloroform (CHCl(3))-water partition coefficients P(o-ch-cf) allows calculation of molecular lipophilicity patterns, which show that for a given atom log P(o-ch-cf) is sensitive to the presence of functional groups. Program CDHI does not properly differentiate between non-equivalent atoms. The most abundant single-wall carbon nanotube (SWNT), (10,10), presents a relatively small aqueous solubility and large elementary polarizability, P(o-ch-cf) and kinetic stability. The SWNT solubility is studied in various solvents, finding a class of non-hydrogen-bonding Lewis bases with good solubility. Solvents group into three classes. The SWNTs in so…

Star poly(2-ethyl-2-oxazoline)s-synthesis and thermosensitivity

2011

A series of star-shaped poly(2-ethyl-2-oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4-nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. …

Hyperbranched aliphatic polyether polyols

2012

Hyperbranched polymers, dendritic macromolecules with branch-on-branch structures, have become an important polymer class since the early 1990s. They combine several advantages of the perfectly branched dendrimers with easy accessibility, typically in a one-step synthesis. Hyperbranched polyethers are a particularly interesting class of chemically stable and often biocompatible materials. Multifunctional hyperbranched polyethers with controllable molar mass and comparably low polydispersities can been prepared using hydroxyl-functional epoxides or oxetanes for polymerization via anionic and cationic polymerization mechanisms. Here, we review the progress in the preparation, characterization…