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Click Reaction (click + reaction)
Selected AbstractsChemInform Abstract: Copper(II)/Copper(I)-Catalyzed Aza-Michael Addition/Click Reaction of in situ Generated ,-Azidohydrazones: Synthesis of Novel Pyrazolone,Triazole Framework.CHEMINFORM, Issue 26 2010Orazio A. Attanasi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] An Efficient Synthesis of Poly(ethylene glycol)-Supported Iron(II) Porphyrin using a Click Reaction and its Application for the Catalytic Olefination of AldehydesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Suman Abstract The first successful synthesis of poly(ethylene glycol) (PEG) immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2],cycloaddition is reported. In contrast to the existing methods for the synthesis of PEG-immobilized metalloporphyrins, the click method offers better catalyst loading under comparatively mild reaction conditions. The prepared complex 5 (PEG-C51H39FeN7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration and was recycled for up to ten runs without significant loss of activity. [source] ChemInform Abstract: The Sequential Sonogashira,Click Reaction: A Versatile Route to 4-Aryl-1,2,3-triazoles.CHEMINFORM, Issue 11 2010Krisztian Loerincz Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: A Cu(I)-Promoted One-Pot "SNAr,Click Reaction" of Fluoronitrobenzenes.CHEMINFORM, Issue 37 2009Kulbhushan A. Dururgkar Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: A Fluorogenic "Click" Reaction of Azidoanthracene Derivatives.CHEMINFORM, Issue 38 2008Fang Xie Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] A Facile Strategy to a New Fluorous-Tagged, Immobilized TEMPO Catalyst Using a Click Reaction, and Its Catalytic Activity.CHEMINFORM, Issue 10 2007Alexandru Gheorghe Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Stabilized Copper(I) Oxide Nanoparticles Catalyze Azide-Alkyne Click Reactions in WaterADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Zhenfang Zhang Abstract A novel form of polyvinylpyrrolidone (PVP) coated copper(I) oxide nanoparticle (Cu2O-NP) was prepared and used to catalyze azide-alkyne click reactions in water under aerobic conditions. The nanoparticles were well dispersed in aqueous solutions and have a size of 20±10,nm, as determined by transmission electron microscope (TEM). Inductively coupled plasma (ICP), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses demonstrated that the main content of Cu2O-NP is copper(I). The cytotoxicity of it was evaluated by an in vitro 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and its catalytic efficiency for azide-alkyne click reactions was studied in water and organic solvents at physiological temperatures. Our results indicate that Cu2O-NP is more efficient in catalytic reactions in water for both aliphatic and aromatic azides and alkynes and less toxic than the commonly used CuSO4/reductant catalyst systems. [source] ChemInform Abstract: One-Pot "Click" Reactions: Tandem Enantioselective Biocatalytic Epoxide Ring Opening and [3 + 2] Azide Cycloaddition.CHEMINFORM, Issue 24 2010Lachlan S. Campbell-Verduyn Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2009Changhua Li Abstract Well-defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol), poly(tert -butyl methacrylate), and poly(N -isopropylacrylamide) arms, PEG(- b -PtBMA)- b -PNIPAM, was synthesized via a combination of consecutive click reactions and atom transfer radical polymerization (ATRP). Click reaction of monoalkynyl-terminated PEG with a trifunctional core molecule bis(2-azidoethyl)amine, (N3)2NH, afforded difunctional PEG possessing an azido and a secondary amine moiety at the chain end, PEG- NHN3. Next, the amidation of PEG- NHN3 with 2-chloropropionyl chloride led to PEG-based ATRP macroinitiator, PEG(N3)Cl. The subsequent ATRP of N -isopropylacrylamide (NIPAM) using PEG(N3)Cl as the macroinitiator led to PEG(N3)- b -PNIPAM bearing an azido moiety at the diblock junction point. Finally, well-defined ABC miktoarm star terpolymer, PEG(- b -PtBMA)- b -PNIPAM, was prepared via the click reaction of PEG(N3)- b -PNIPAM with monoalkynyl-terminated PtBMA. In aqueous solution, the obtained ABC miktoarm star terpolymer self-assembles into micelles consisting of PtBMA cores and hybrid PEG/PNIPAM coronas, which are characterized by dynamic and static laser light scattering, and transmission electron microscopy. On heating above the phase transition temperature of PNIPAM in the hybrid corona, micelles initially formed at lower temperatures undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4001,4013, 2009 [source] Synthesis of dendritic macromolecules through divergent iterative thio-bromo "Click" chemistry and SET-LRPJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2009Brad M. Rosen Abstract The development of a novel nucleophilic thio-bromo "Click" reaction, specifically base-mediated thioetherification of thioglycerol with ,-bromoesters was reported in an earlier article. The combination of this thio-bromo click reaction with subsequent acylation with 2-bromopropionyl bromide provides an iterative two-step divergent growth approach to the synthesis of a new class of poly(thioglycerol-2- propionate) (PTP) dendrimers. In this article, the addition of a third step, the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), was shown to provides access to a three-step "branch" and "grow" divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self-organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940,3948, 2009 [source] Oligonucleotides Containing 7-Deaza-2,-deoxyinosine as Universal Nucleoside: Synthesis of 7-Halogenated and 7-Alkynylated Derivatives, Ambiguous Base Pairing, and Dye Functionalization by the Alkyne,Azide ,Click' ReactionHELVETICA CHIMICA ACTA, Issue 7 2008Frank Seela Abstract Oligonucleotides containing 7-deaza-2,-deoxyinosine derivatives bearing 7-halogen substituents or 7-alkynyl groups were prepared. For this, the phosphoramidites 2b,2g containing 7-substituted 7-deaza-2,-deoxyinosine analogues 1b,1g were synthesized (Scheme,2). Hybridization experiments with modified oligonucleotides demonstrate that all 2,-deoxyinosine derivatives show ambiguous base pairing, as 2,-deoxyinosine does. The duplex stability decreases in the order Cd>Ad>Td>Gd when 2b,2g pair with these canonical nucleosides (Table,6). The self-complementary duplexes 5,-d(F7c7I-C)6, d(Br7c7I-C)6, and d(I7c7I-C)6 are more stable than the parent duplex d(c7I-C)6 (Table,7). An oligonucleotide containing the octa-1,7-diyn-1-yl derivative 1g, i.e., 27, was functionalized with the nonfluorescent 3-azido-7-hydroxycoumarin (28) by the Huisgen,Sharpless,Meldal cycloaddition ,click' reaction to afford the highly fluorescent oligonucleotide conjugate 29 (Scheme,3). Consequently, oligonucleotides incorporating the derivative 1g bearing a terminal CC bond show a number of favorable properties: i) it is possible to activate them by labeling with reporter molecules employing the ,click' chemistry. ii) Space demanding residues introduced in the 7-position of the 7-deazapurine base does not interfere with duplex structure and stability (Table,8). iii) The ambiguous pairing character of the nucleobase makes them universal probes for numerous applications in oligonucleotide chemistry, molecular biology, and nanobiotechnology. [source] Unsupported Copper Nanoparticles in the 1,3-Dipolar Cycloaddition of Terminal Alkynes and Azides,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2010Francisco Alonso Abstract Readily prepared copper nanoparticles were found to catalyse the 1,3-dipolar cycloaddition of azides and alkynes up to rates comparable to those of microwave chemistry. Both the preparation of the nanoparticles and the click reaction are carried out under mild conditions, in short reaction times and in the absence of any stabilising additive or ligand. A variety of 1,2,3-triazoles were prepared in excellent yields. A reaction mechanism was postulated on the basis of different reactivity studies and deuteration experiments. Copper(I) acetylides were demonstrated to be the real intermediate species. [source] CuI -Catalyzed Azide,Alkyne Intramolecular i -to-(i+4) Side-Chain-to-Side-Chain Cyclization Promotes the Formation of Helix-Like Secondary StructuresEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2010Mario Scrima Abstract A solid-phase assembly of model peptides derived from human parathyroid hormone-related protein (11,19) containing ,-azido- and ,-yl-,-amino acid residues in positions i and i+4 was cyclised in solution by an intramolecular CuI -catalyzed azide,alkyne 1,3-dipolar Huisgen cycloaddition. These series of heterodetic cyclo-nonapeptides varied in the size of the disubstituted 1,2,3-triazolyl-containing bridge, the location and the orientation of the 1,2,3-triazolyl moiety within the bridge. The 1,2,3-triazolyl moiety, presented at either 1,4- or 4,1-orientation, is flanked by side chains containing 1,4 CH2 groups that result in bridges comprised from 4,7 CH2 groups connecting residues 13 and 17. Comprehensive conformational analysis employing CD, NMR and molecular dynamics reveals the conformational propensities of these heterodetic cyclo-nonapeptides. Cyclo-nonapeptides containing either the 7 methylene bridge (VII and VIII) or the 4 methylene bridge (II) are unstructured in structure-promoting solvent. Cyclo-nonapeptide I in which the 1,4-disubstituted 1,2,3-triazolyl is flanked by 3 and 1 CH2 groups in proximity to the respective residues 13 and 17, is stabilized in a non-canonical structure. All the other heterodetic cyclo-nonapeptides (III,VI) in which the 1,2,3-triazolyl is flanked by a total of 5 or 6 CH2 groups nicely accommodate ,-helical structures and reproduce very closely the helical structure stabilized by the analogous cyclo-nonapeptide in which Lys13 and Asp17 are bridged by the isosteric lactam. These studies suggest that the bioorthogonal i -to-(i+4) side-chain-to-side-chain cyclization via the prototypic "click reaction" offers a new and powerful approach for generating stable helix mimetic structures. [source] Combining Designer Cells and Click Chemistry for a One-Pot Four-Step Preparation of Enantiopure ,-HydroxytriazolesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Wiktor Szymanski Abstract The multistep catalytic process using designer cells, either added as freshly prepared suspensions or as stable lyophilized powder, and click reaction can be performed in one pot. The sequence of four reactions allows the production of both enantiomers of ,-hydroxytriazoles with high enantiomeric excess. [source] Immobilization of Porphyrinatocopper Nanoparticles onto Activated Multi-Walled Carbon Nanotubes and a Study of its Catalytic Activity as an Efficient Heterogeneous Catalyst for a Click Approach to the Three-Component Synthesis of 1,2,3-Triazoles in WaterADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009Hashem Sharghi Abstract An efficient, regioselective, one-pot and two-step synthesis of ,-hydroxy 1,4-disubstituted 1,2,3-triazoles from a wide range of non-activated terminal alkynes and epoxides and sodium azide by way of a three-component click reaction using a catalytic amount of [meso -tetrakis(o -chlorophenyl)porphyrinato]copper(II) (5,mol%) in excellent isolated yields is described. The reactions were performed in water as a green solvent at ambient temperature without any additives. By performing two reaction steps in one pot and purifying only at the final step, this procedure excludes any interim purification of in situ generated organic azide intermediates, which significantly improves the overall yield and reduces the reaction time. To benefit from the recovery and reuse of the catalyst, a new heterogeneous catalyst was prepared by simple and successful impregnation of the catalyst onto activated multi-walled carbon nanotubes (AMWCNT). The heterogeneous catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic forced microscopy (AFM), and thermogravimetric (TG) analysis to estimate the amount of nitrogen adsorption, and Raman and FT-IR spectroscopy. Leaching experiments after ten successive cycles showed that the catalyst is most strongly anchored to the AMWCNT support. Mechanistically, porphyrinatocopper catalyzes each step of the reaction in different ways as a bifunctional catalyst including epoxide ring opening by azide delivery to epoxide, forming in situ generated 2-azido alcohols followed by activation of the CC triple bond of the starting terminal alkynes by forming a porphyrinatocopper-acetylide intermediate and thereby promoting the [3+2]-cycloaddition reaction as the key step to form the triazole framework. [source] Room-temperature RAFT copolymerization of 2-chloroallyl azide with methyl acrylate and versatile applications of the azide copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2010Guang Li Abstract A new vinyl azide monomer, 2-chlorallyl azide (CAA), has been synthesized from commercially available reagent in one step. The reversible addition fragmentation chain transfer (RAFT) copolymerization of CAA with methyl acrylate (MA) was carried out at room temperature using a redox initiator, benzoyl peroxide (BPO)/N,N -dimethylaniline (DMA), in the presence of benzyl 1H -imidazole-1-carbodithioate (BICDT). The polymerization results showed that the process bears the characteristics of controlled/living radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow, and a linear relationship existing between ln([M]0/[M]) and the polymerization time. Chain extension polymerization was performed successfully to prepare block copolymer. Furthermore, the azide copolymers were functionalized by CuI -catalyzed "click" reaction with alkyne-containing poly(ethylene glycol) (PEG) to yield graft copolymers with hydrophilic PEG side chains. Surface modification of the glass sheet was successfully achieved via the crosslinking reaction of the azide copolymer under UV irradiation at ambient temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1348,1356, 2010 [source] Synthesis and hierarchical superstructures of side-chain liquid crystal polyacetylenes containing galactopyranoside end-groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2009Ming-Shou Ho Abstract Three kinds of chiral saccharide-containing liquid crystalline (LC) acetylenic monomers were prepared by click reaction between 2-azidoethyl-2,3,4,6-tetraacetyl-,- D -galactopyranoside and 1-biphenylacetylene 4-alkynyloxybenzoate. The obtained monomers were polymerized by WCl6 -Ph4Sn to form three side-chain LC polyacetylenes containing 1-[2-(2,3,4,6-tetraacetyl-,- D -galactopyranos-1-yl)-ethyl]-1H -[1,2,3]-triazol-4,-biphenyl 4-alkynyloxybenzoate side groups. All monomers and polymers show a chiral smectic A phase. Self-assembled hiearchical superstructures of the chiral saccharide-containing LCs and LCPs in solution state were studied by field-emission scanning electron microscopy. Because of the LC behavior, the LC molecules exhibit a high segregation strength for phase separation in dilute solution (THF/H2O = 1:9 v/v). The self-assembled morphology of LC monomers was dependent upon the alkynyloxy chain length. Increasing the alkynyloxy chain length caused the self-assembled morphology to change from a platelet-like texture (LC-6) to helical twists morphology (LC-11 and LC-12). Furthermore, the helical twist morphological structure can be aligned on the polyimide rubbed glass substrate to form two-dimensional ordered helical patterns. In contrast to LC monomers, the LCP-11 self-assembled into much more complicate morphologies, including nanospheres and helical nanofibers. These nanofibers are evolved from the helical cables ornamented with entwining nanofibers upon natural evaporation of the solution in a mixture with a THF/methanol ratio of 3:7. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6596,6611, 2009 [source] Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2009Changhua Li Abstract Well-defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol), poly(tert -butyl methacrylate), and poly(N -isopropylacrylamide) arms, PEG(- b -PtBMA)- b -PNIPAM, was synthesized via a combination of consecutive click reactions and atom transfer radical polymerization (ATRP). Click reaction of monoalkynyl-terminated PEG with a trifunctional core molecule bis(2-azidoethyl)amine, (N3)2NH, afforded difunctional PEG possessing an azido and a secondary amine moiety at the chain end, PEG- NHN3. Next, the amidation of PEG- NHN3 with 2-chloropropionyl chloride led to PEG-based ATRP macroinitiator, PEG(N3)Cl. The subsequent ATRP of N -isopropylacrylamide (NIPAM) using PEG(N3)Cl as the macroinitiator led to PEG(N3)- b -PNIPAM bearing an azido moiety at the diblock junction point. Finally, well-defined ABC miktoarm star terpolymer, PEG(- b -PtBMA)- b -PNIPAM, was prepared via the click reaction of PEG(N3)- b -PNIPAM with monoalkynyl-terminated PtBMA. In aqueous solution, the obtained ABC miktoarm star terpolymer self-assembles into micelles consisting of PtBMA cores and hybrid PEG/PNIPAM coronas, which are characterized by dynamic and static laser light scattering, and transmission electron microscopy. On heating above the phase transition temperature of PNIPAM in the hybrid corona, micelles initially formed at lower temperatures undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4001,4013, 2009 [source] Synthesis of dendritic macromolecules through divergent iterative thio-bromo "Click" chemistry and SET-LRPJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2009Brad M. Rosen Abstract The development of a novel nucleophilic thio-bromo "Click" reaction, specifically base-mediated thioetherification of thioglycerol with ,-bromoesters was reported in an earlier article. The combination of this thio-bromo click reaction with subsequent acylation with 2-bromopropionyl bromide provides an iterative two-step divergent growth approach to the synthesis of a new class of poly(thioglycerol-2- propionate) (PTP) dendrimers. In this article, the addition of a third step, the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), was shown to provides access to a three-step "branch" and "grow" divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self-organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940,3948, 2009 [source] One-pot synthesis of ABC miktoarm star terpolymers by coupling ATRP, ROP, and click chemistry techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2009Yanfeng Zhang Abstract We report on the one-pot synthesis of well-defined ABC miktoarm star terpolymers consisting of poly(2-(dimethylamino)ethyl methacrylate), poly(,-caprolactone), and polystyrene or poly(ethylene oxide) arms, PS(- b -PCL)- b -PDMA and PEO (- b -PCL)- b -PDMA, taking advantage of the compatibility and mutual tolerability of reaction conditions (catalysts and monomers) employed for atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP), and click reactions. At first, a novel trifunctional core molecule bearing alkynyl, hydroxyl group, and bromine moieties, alkynyl(OH)Br, was synthesized via the esterification reaction of 5-ethyl-5-hydroxymethyl-2,2-dimethyl-1,3-dioxane with 4-oxo-4-(prop-2-ynyloxy)butanoic acid, followed by deprotection and monoesterification of alkynyl(OH)2 with 2-bromoisobutyryl bromide. In the presence of trifunctional core molecule, alkynyl(OH)Br, and CuBr/PMDETA/Sn(Oct)2 catalytic mixtures, target ABC miktoarm star terpolymers, PS(- b -PCL)- b -PDMA and PEO(- b -PCL)- b -PDMA, were successfully synthesized in a one-pot manner by simultaneously conducting the ATRP of 2-(dimethylamino)ethyl methacrylate (DMA), ROP of ,-caprolactone (,-CL), and the click reaction with azido-terminated PS (PS- N3) or azido-terminated PEO (PEO- N3). Considering the excellent tolerability of ATRP to a variety of monomers and the fast expansion of click chemistry in the design and synthesis of polymeric and biorelated materials, it is quite anticipated that the one-pot concept can be applied to the preparation of well-defined polymeric materials with more complex chain architectures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3066,3077, 2009 [source] Gold nanoparticle-incorporated core and shell crosslinked micelles fabricated from thermoresponsive block copolymer of N -isopropylacrylamide and a novel primary-amine containing monomerJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2008Yueming Zhou Abstract A novel primary amine-containing monomer, 1-(3,-aminopropyl)-4-acrylamido-1,2,3-triazole hydrochloride (APAT), was prepared from N -propargylacrylamide and 3-azidopropylamine hydrochloride via copper-catalyzed Huisgen 1,3-dipolar cycloaddition (click reaction). Poly(N -isopropylacrylamide)- b -poly(1-(3,-aminopropyl)-4-acrylamido-1,2,3-triazole hydrochloride), PNIPAM- b- PAPAT, was then synthesized via consecutive reversible addition-fragmentation chain transfer polymerizations of N -isopropylacrylamide and APAT. In aqueous solution, the obtained thermoresponsive double hydrophilic block copolymer dissolves molecularly at room temperature and self-assembles into micelles with PNIPAM cores and PAPAT shells at elevated temperature. Because of the presence of highly reactive primary amine moieties in PAPAT block, two types of covalently stabilized nanoparticles namely core crosslinked and shell crosslinked micelles with ,inverted' core-shell nanostructures were facilely prepared upon the addition of glutaric dialdehyde at 25 and 50 °C, respectively. In addition, the obtained structure-fixed micelles were incorporated with gold nanoparticles via in situ reduction of preferentially loaded HAuCl4. High resolution transmission electron microscopy revealed that gold nanoparticles can be selectively loaded into the crosslinked cores or shells, depending on the micelle templates employed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6518,6531, 2008 [source] Dendrimer-like miktoarm star terpolymers: A3 -(B-C)3 via click reaction strategyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2008Ozcan Altintas Abstract Two samples of dendrimer-like miktoarm star terpolymers: (poly(tert -butyl acrylate))3 -(polystyrene-poly(,-caprolactone))3 (PtBA)3 -(PS-PCL)3, and (PS)3 -(PtBA-poly(ethylene glycol)3 were prepared using efficient Cu catalyzed Huisgen cycloaddition (click reaction). As a first step, azido-terminated 3-arm star polymers PtBA and PS as core (A) were synthesized by atom transfer radical polymerization (ATRP) of tBA and St, respectively, followed by the conversion of bromide end group to azide. Secondly, PS-PCL and PtBA-PEG block copolymers with alkyne group at the junction as peripheral arms (B-C) were obtained via multiple living polymerization mechanisms such as nitroxide mediated radical polymerization (NMP) of St, ring opening polymerization (ROP) of ,-CL, ATRP of tBA. Thus obtained core and peripheral arms were linked via click reaction to give target (A)3 -(B-C)3 dendrimer-like miktoarm star terpolymers. (PtBA)3 -(PS-PCL)3 and (PS)3 -(PEG-PtBA)3 have been characterized by GPC, DSC, AFM, and SAXS measurements. (PtBA)3 -(PS-PCL)3 did not show any self-organization with annealing due to the miscibility of the peripheral arm segments. In contrast, the micro-phase separation of the peripheral arm segments in (PS)3 -(PtBA-PEG)3 resulted in self-organized phase-separated morphology with a long period of , 13 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5916,5928, 2008 [source] One-pot preparation of 3-miktoarm star terpolymers via click [3 + 2] reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2007Ozcan Altintas Abstract The preparation of 3-miktoarm star terpolymers using nitroxide mediated radical polymerization (NMP), ring opening polymerization (ROP), and click reaction [3 + 2] are carried out by applying two types of one-pot technique. In the first one-pot technique, NMP of styrene (St), ROP of ,-caprolactone (,-CL), and [3 + 2] click reaction (between azide end-functionalized poly(ethylene glycol) (PEG-N3)/or azide end-functionalized poly(methyl methacrylate) (PMMA-N3) and alkyne) are carried out in the presence of 2-(hydroxymethyl)-2-methyl-3-oxo-3-(2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethoxy) propyl pent-4-ynoate, 2, as an initiator for 48 h at 125 °C (one-pot/one-step). As a second technique, NMP of St and ROP of ,-CL were conducted using 2 as an initiator for 20 h at 125 °C, and subsequently PEG-N3 or azide end-functionalized poly(tert -butyl acrylate (PtBA-N3) was added to the polymerization mixture, followed by a click reaction [3 + 2] for 24 h at room temperature (one-pot/two-step). The 3-miktoarm star terpolymers, PEG-poly(,-caprolactone)(PCL)-PS, PtBA-PCL-PS and PMMA-PCL-PS, were recovered by a simple precipitation in methanol without further purification. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3588,3598, 2007 [source] Sugars-grafted aliphatic biodegradable poly(L -lactide- co -carbonate)s by click reaction and their specific interaction with lectin moleculesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2007Changhai Lu Abstract A novel biodegradable aliphatic poly(L -lactide- co -carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L -lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 °C and subsequently used for grafting 2-azidoethyl ,- D -glucopyranoside and 2-azidoethyl ,-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3204 ,3217, 2007 [source] Divergent synthesis of dendrimer-like macromolecules through a combination of atom transfer radical polymerization and click reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2007Qingchun Liu Abstract This article describes a divergent strategy to prepare dendrimer-like macromolecules from vinyl monomers through a combination of atom transfer radical polymerization (ATRP) and click reaction. Firstly, star-shaped polystyrene (PS) with three arms was prepared through ATRP of styrene starting from a three-arm initiator. Next, the terminal bromides of the star-shaped PS were substituted with azido groups. Afterwards, the azido-terminated star-shaped PS was reacted with propargyl 2,2-bis((2,-bromo-2,-methylpropanoyloxy)methyl)propionate (PBMP) via click reaction. Star-shaped PS with six terminal bromide groups was afforded and served as the initiator for the polymerization of styrene to afford the second-generation dendrimer-like PS. Iterative process of the aforementioned sequence of reactions could allow the preparation of the third-generation dendrimer-like PS. When the second-generation dendrimer-like PS with 12 bromide groups used as an initiator for the polymerization of tert -butyl acrylate, the third-generation dendrimer-like block copolymer with a PS core and a poly (tert -butyl acrylate) (PtBA) corona was afforded. Subsequently PtBA segments were selectively hydrolyzed with hydrochloric acid, resulting an amphiphilic branched copolymer with inner dendritic PS and outer linear poly(acrylic acid) (PAA). Following the same polymerization procedures, the dendrimer-like PS and PS- block -PtBA copolymers of second generation originating from six-arm initiator were also synthesized. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3330,3341, 2007 [source] A Polycation Scaffold Presenting Tunable "Click" Sites: Conjugation to Carbohydrate Ligands and Examination of Hepatocyte-Targeted pDNA DeliveryMACROMOLECULAR BIOSCIENCE, Issue 6 2010Chen-Chang Lee Abstract A versatile polycation scaffold that can easily be modified with targeting ligands has been designed, synthesized, and characterized. A series of galactose-containing polymers has been produced to demonstrate the ease of modification of this polynucleotide delivery vehicle motif via the click reaction and to study how various structural modifications affect recognition by ASGPr on hepatocytes. A small library of structures was created where DCS and alkyl spacer length between the targeting group and the polymer backbone was varied. The novel polymer scaffold described proves to be a valuable tool for understanding structure/activity relationships of complexes made with receptor-targeted polymers. [source] Synthesis of Well-Defined Figure-of-Eight-Shaped Polymers by a Combination of ATRP and Click ChemistryMACROMOLECULAR RAPID COMMUNICATIONS, Issue 20 2008Gang-Yin Shi Abstract Well-defined figure-of-eight-shaped (8-shaped) polystyrene (PS) with controlled molecular weight and narrow polydispersities has been prepared by the combination of atom transfer radical polymerization (ATRP) and click chemistry. The synthesis involves two steps: 1) Preparation of a linear tetrafunctional PS with two azido groups, one at each end of the polymer chain, and two acetylene groups at the middle of the chain. 2) Intramolecular cyclization of the linear tetrafunctional PS at a very low concentration by a click reaction to produce the 8-shaped polystyrenes. The resulting intermediates and the target polymers were characterized by 1H NMR and FT-IR spectroscopy, and gel permeation chromatography. The glass transition temperatures (Tgs) were determined by differential scanning calorimetry and it was found that the decrease in chain mobility by cyclization resulted in higher Tgs for 8-shaped polystyrenes as compared to their corresponding precursors. [source] Intramolecular Click Cycloaddition: An Efficient Room-Temperature Route towards Bioconjugable Polymeric NanoparticlesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 12-13 2008Alaitz Ruiz de Luzuriaga Abstract A highly efficient room-temperature synthetic route to bioconjugable polymeric nanoparticles in the 5,20 nm size range based on single-chain intramolecular click cycloaddition is described. It is illustrated by preparing single-chain cross-linked polymeric NPs from poly[MMA- co -(3-azidopropyl methacrylate)- co -(3-trimethylsilyl-propyn-1-yl methacrylate)] terpolymers using a one-pot procedure and a continuous addition technique. For polymeric NPs with an excess of azide groups, aminoacid/PMMA NPs were easily obtained by performing a second click reaction with propargyl glycine. This versatile and general method opens the way to the synthesis of other kinds of polymeric and bioconjugated NPs beyond those reported in this communication. [source] Application of the 1,3-Dipolar Cycloaddition Reaction in Chemical Biology: Approaches Toward Multivalent Carbohydrates and Peptides and Peptide-Based PolymersMOLECULAR INFORMATICS, Issue 11-12 2007Roland Abstract In this mini review we highlight our recent results and the related literature regarding the application of the Cu(I)-catalyzed 1,3-dipolar cycloaddition "click" reaction. The synthetic applications of the click reaction focus on multivalent carbohydrates and peptides and peptide-based polymers. Furthermore, a related reaction is described involving the coupling of thio acids and sulfonyl azides leading to the chemoselective formation of amides. [source] Synthesis and characterization of hyperbranched polytriazole via an ,A2 + B3' approach based on click chemistryPOLYMER INTERNATIONAL, Issue 8 2008Jianda Xie Abstract BACKGROUND: The ,A2 + B3' type of polymerization has been demonstrated to be an alternative route towards hyperbranched polymers. Some highly crosslinked hyperbranched polymers have been prepared via copper(I)-catalyzed click reactions of multivalent azides and alkynes. To obtain hyperbranched polymers without gelation and develop the A2 + B3 type of polymerization based on click reactions, the specific reaction conditions need to be investigated. RESULTS: In this work, a hyperbranched polytriazole (hb -PTA) was synthesized through the A2 + B3 approach using a click reaction. 4- N,N,-bis(2-azidoethyl)amino-4,-nitroazobenzene and 1,3,5-tris(alynyloxy)benzene were synthesized for use as the A2 and B3 monomers, respectively. This was a ,one-pot' polymerization carried out using a slow-addition method. The obtained hb -PTA was soluble in common organic solvents. The molecular structure was characterized using 1H NMR, Fourier transform infrared and gel permeation chromatography analyses. The degree of branching of hb -PTA was determined to be around 0.50. CONCLUSION: The hb -PTA was successfully synthesized via the A2 + B3 approach based on a click reaction. The polymerization conducted in dilute solution adopting slow addition of A2 to B3 resulted in hb -PTA in the absence of gelation. The obtained hb -PTA exhibited high thermal stability. Copyright © 2008 Society of Chemical Industry [source] | |||||||||||||