Biocompatible, Thermoresponsive, and Biodegradable:  Simple Preparation of “All-in-One” Biorelevant Polymers

Lutz, Jean‐François; Andrieu, Julien; Üzgün, Senta; Rudolph, Carsten; Agarwal, Seema

doi:10.1021/ma7021474

Cited by 279 publications

(225 citation statements)

References 27 publications

(45 reference statements)

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“…Polymers constructed from oligo(ethylene glycol) methacrylates were reported to be relatively insensitive to hydrolysis in acidic and basic conditions. [30,31] (Figure 3), which is in good agreement with previous reports (high field NMR was necessary to visualize these junction protons as the formed polymers have a relatively high molecular weight). [29,32] However, a weak signal due to methylene protons in a-position of unreacted alkynes could also be observed at 4.73 ppm (Figure 3), indicating that the reaction was not quantitative.…”

Section: Resultssupporting

confidence: 91%

A “Click” Strategy for Tuning in situ the Hydrophilic–Hydrophobic Balance of AB Macrosurfactants

Zarafshani

Akdemir

Lutz

2008

Macromol. Rapid Commun.

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The self‐organization of amphiphilic block copolymers in water strongly depends on their molecular structure, in particular on their hydrophilic–hydrophobic balance. Herein, a simple method for tuning the amphiphilicity of polymeric macrosurfactants in aqueous medium is proposed. This concept relies on the “click” ligation of an amphiphilic block copolymer (AB type) and a hydrophilic homopolymer (B type). In the present communication, the validity of this approach was examined with model polymers based on polystyrene (PS) and poly[oligo (ethylene glycol) acrylate] (POEGA) segments. A well‐defined ω‐azido functional diblock copolymer PS‐b‐POEGA and an α‐alkyne functional homopolymer POEGA were prepared using atom transfer radical polymerization. These two polymers could be efficiently coupled to each other via copper‐catalyzed azide–alkyne click chemistry in aqueous medium. Moreover, in this coupling strategy, an ester group was introduced at the junction between AB and B segments. This labile moiety may be “cut” by hydrolysis.magnified image

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Section: Resultssupporting

confidence: 91%

A “Click” Strategy for Tuning in situ the Hydrophilic–Hydrophobic Balance of AB Macrosurfactants

Zarafshani

Akdemir

Lutz

2008

Macromol. Rapid Commun.

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“…Also, the homopolymerization and copolymerization behaviour of different cyclic ketene acetals with some vinyl monomers like MMA, vinyl anisole, styrene etc. is reported by us [11][12][13][14][15][16][17][18] and others. 10,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] The main problem during the copolymerization is the huge reactivity difference between the CKA and the vinyl monomers leading to either low molecular weight homo vinyl polymers without ester linkages or copolymers incorporating only low amounts of the comonomers with block structure, incomplete ring-opening or no ring-opening at all.…”

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confidence: 74%

Synthesis of Degradable Materials Based on Caprolactone and Vinyl Acetate Units Using Radical Chemistry

et al. 2009

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Present studies are carried out with an aim to make degradable materials based on caprolactone and vinyl acetate units using radical chemistry. Radical ring-opening copolymerization of 2-methylene-1,3-dioxepane (MDO) with vinyl acetate in presence of AIBN initiator at 70 C was carried out to achieve the aim. The copolymerization introduced degradable PCL repeat units onto the C-C backbone of poly(vinyl acetate). Microstructure analysis of the copolymers is done using different 1D and 2D NMR techniques. Complete ring-opening polymerization of MDO to give ester units was observed during copolymerizations. Reactivity ratios were found out by Kelen Tüdos method and were r VAc ¼ 1:53 and r MDO ¼ 0:47 leading to statistical introduction of ester linkages onto the polymer backbone. The materials showed varied glass transition temperatures (from 37 to À44 C) depending upon the amount of ester linkages and very high elongations. The hydrolysis products were also tested for cytotoxicity studies in L929 cells and compared with that of known and accepted standard materials like poly(ethyleneimine). The hydrolysed products were non toxic and showed a cell viability > 95%. Keeping in view the combined properties like degradability, non-toxicity and low glass transition temperatures, the resulting materials could therefore be proposed for different applications like degradable gums, coatings etc.KEY WORDS: Radical Ring-Opening Polymerization / Polymer Synthesis / Degradable Polymers / Characterization / Ring-opening polymerization of "-caprolactone using anionic or metal catalysts is conventionally used for the synthesis of polycaprolactone (PCL), a well studied and in-demand degradable aliphatic polyester.1-7 A less known route to the formation of poly(caprolactone), first shown by Bailey et al. and later followed by some others, 9,10 is by radical ringopening polymerization of 2-methylene-1,3-dioxepane (MDO). 2-methylene-1,3-dioxepane is an interesting cyclic ketene acetal monomer giving poly("-caprolactone) (PCL), on the radical-ring-opening homopolymerization (RROP) and can introduce ester groups onto the vinyl polymer backbones during copolymerizations with vinyl monomers. The careful examination of 13C and 1 H NMR spectra by us 11 showed the occurrence of 100% ring-opening polymerization but the presence of about 9% branched structures in the resulting homopolymer obtained by RROP of MDO. This method of making ester linkages could be very well utilized for introducing degradability onto the nondegradable vinyl polymer backbones by copolymerizations. Also, the homopolymerization and copolymerization behaviour of different cyclic ketene acetals with some vinyl monomers like MMA, vinyl anisole, styrene etc. is reported by us 11-18 and others. 10,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] The main problem during the copolymerization is the huge reactivity difference between the CKA and the vinyl monomers leading to either low molecular weight homo vinyl polymers without ester linkages or copolymers incorpor...

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“…This particular category of oligo(ethylene glycol)-based macromolecules has been exponentially studied in recent years [23][24][25][26][29][30][31][32][33][34][35]. Indeed, these polymers may be synthesized using straightforward controlled radical polymerization techniques such as atom transfer radical polymerization (ATRP) [36,37] or reversible addition-fragmentation transfer polymerization (RAFT) [38][39][40], but also functionalized using versatile ligation tools such as click chemistry [41][42][43][44].…”

Section: Introductionmentioning

confidence: 99%

Design of Oligo(ethylene glycol)-Based Thermoresponsive Polymers: an Optimization Study

Lutz

Hoth

Schade

2009

Designed Monomers and Polymers

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Co-polymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA 300 , M n = 300 g/mol) of various composition were synthesized at 60 • C in ethanol solution either by conventional radical polymerization (RP) or atom transfer radical polymerization (ATRP). Both techniques led to co-polymers P(MEO 2 MA-co-OEGMA 300 ) in high yields. However, ATRP provided better defined co-polymers with controlled molecular weight, composition and molecular weight distribution. Nevertheless, all the samples exhibited a lower critical solution temperature (LCST) in aqueous medium (i.e., pure deionized water or physiological buffer). Sharp and reversible phase transitions were observed in all cases by turbidimetry and dynamic light scattering. This thermoresponsive behavior was demonstrated to be directly linked to the MEO 2 MA/OEGMA 300 composition of the formed co-polymers. Thus, the LCST of the co-polymers could be precisely adjusted in the temperature range 28-65 • C. © Koninklijke Brill NV, Leiden, 2009

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Biocompatible, Thermoresponsive, and Biodegradable: Simple Preparation of “All-in-One” Biorelevant Polymers

Cited by 279 publications

References 27 publications

A “Click” Strategy for Tuning in situ the Hydrophilic–Hydrophobic Balance of AB Macrosurfactants

A “Click” Strategy for Tuning in situ the Hydrophilic–Hydrophobic Balance of AB Macrosurfactants

Synthesis of Degradable Materials Based on Caprolactone and Vinyl Acetate Units Using Radical Chemistry

Design of Oligo(ethylene glycol)-Based Thermoresponsive Polymers: an Optimization Study

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