Synthesis and characterization of dendritic-linear-dendritic triblock copolymers based on poly(amidoamine) and polystyrene

Dendritic-linear-dendritic triblock copolymers composed of linear polystyrene (PSt) and poly(amidoamine) dendrons have been successfully synthesized. Two bromines-terminated PSt with M_n = 13,000 was prepared by atom transfer radical polymerization (ATRP) using α,α′-dibromo-p-xylene as initiator. Then the terminal bromines at both ends of PSt chains were replaced by one imine group of piperazine (PZ), and further Michael addition reaction of terminal PZ with excess 1,3,5-triacryloylhexahydro-1,3,5-triazine (TT) produced the first generation (G₁) of the triblock copolymer. Continuous growth of dendrons from G1.5 to G4 at the both ends of PSt chains was carried out by the iterative Michael addition reactions with excess PZ and following TT. The ABA triblock copolymers composed of the G₁-G₄ dendrons and the linear PSt were obtained. Structures of the triblock polymers were characterized by GPC and ¹H NMR spectra. Thermal phase transitions of the polymers were studied by DSC measurements, and all of the copolymers displayed a glass transition temperature.     

Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG_n)₄, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. ¹H NMR T₁ measurements at 10-70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.     

Rational design,syntheses, characterization and solution behavior of amphiphilic azobenzene-containing linear-dendritic block copolymers

In this paper, based on the synthesis of precursor linear-dendritic block copolymers (LDBCs) with a linear poly(ethylene glycol) (PEG) block of molecular weight around 2000 and dendritic polyamidoamine (PAMAM) segments of generation G0 to G3, a series of azobenzene-containing amphiphilic LDBCs mPEG-dendr[PAMAM-(AZO)_n] (n = 2, 4, 8, 16) have been successfully prepared in moderate yields 45–60%, through complete Michael addition between the peripheral amine groups of dendritic segment and the reactive azobenzene acrylate mesogen units bearing octyloxy tails and flexible decylmethylene spacers. The purified copolymers have been characterized and confirmed by NMR, FT-IR, MALDI-TOF MS, and GPC showing narrow molecular weight distribution in the range 1.09–1.20. A generation-dependent polymeric micellar aggregation behavior of thus obtained amphiphilic LDBCs from nanofibers of uniform diameter around 20 nm to nanospheres/oval sheets, vesicles, and porous large compound micelles (LCMs) of micrometer size has been demonstrated in selective solvent mixture of dioxane/water. Furthermore, photoisomerization transformation of these azobenzene-containing LDBCs and their kinetics of reversible trans-cis-trans photochemical transitions in THF solution have also been investigated, the measured trans-cis photoisomerization rate constant 0.0240 s^?1 for G3 copolymer is twice of the 0.0127 s^?1 determined for the precursor azobenzene compound, manifesting a kind of promising photoresponsive copolymer materials.     

Synthesis and characterization of triazine‐based dendrimers and their application in metal ion adsorption

This article described the synthesis of triazine‐based dendrimers with poly(ethylene glycol) core by convergent method. Compound 1 was prepared by coupling of amino group of diethanolamine with cyanuric chloride in dry THF (tetrahydrofuran). Reaction of compound 1 with p‐aminobenzylamine resulted in compound 2 . Compound 4 was synthesized using coupling reaction of amino group of compound 2 with cyanuric chloride, then coupling of amine groups of p‐aminobenzylamine with compound 3 in the hybrid solvents. The final dendrimer (den‐OH) were synthesized using reaction of dendron 4 with compound 5. Ethylene diaminetetraacetic acid modified final dendrimer were successfully prepared via coupling ethylene diaminetetraacetic acid dianhydride and den‐OH. The growth of dendrons and their structures were investigated by using usual spectroscopy methods and elemental analysis. The chelating behavior and sorption capacities of triazine dendrimers were determined in relation to pH dependency for some metal ions such as Cu⁺², Ni⁺², and Zn⁺² using atomic absorption methods. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of dual stimuli-responsive block copolymers based on poly(N-isopropylacrylamide)-b-poly(pseudoamino acid)

The current study synthesized amphiphilic thermal/pH-sensitive block copolymers PNiPAAm-b-PHpr by condensation polymerization of trans-4-hydroxy-l-proline (Hpr) initiated from hydroxy-terminated poly(N-isopropylacrylamide) (PNiPAAm) as the macroinitiator in the presence of the catalyst, SnOct₂. ¹H NMR, FTIR, and gel permeation chromatography (GPC) characterized these copolymers. Their solutions showed reversible changes in optical properties: transparent below a lower critical solution temperature (LCST) and opaque above the LCST. The LCST values depended on the polymer composition and the media. With critical micelle concentrations (CMCs) in the range of 1.23-3.73 mg L⁻¹, the block copolymers formed micelles in the aqueous phase owing to their amphiphilic characteristics. Increased hydrophobic segment length or decreased hydrophilic segment length in an amphiphilic diblock copolymer produced lower CMC values. The current work proved the core-shell structure of micelles by ¹H NMR analyses of the micelles in D₂O. Transmission electron microscopy analyzed micelle morphology, showing a spherical core-shell structure. The micelles had an average size in the range of 170˜210 nm (blank), and 195˜280 nm (with drug). Observations showed high drug entrapment efficiency and drug-loading content for the drug micelles.     

Synthesis of Miktoarm Dumbbell-Like Amphiphilic Triblock Copolymer by Combination of Consecutive RAFT Polymerizations and ATRP

Summary  A novel synthetic route, combining three reversible addition-fragmentation chain transfer (RAFT) and one atom transfer radical polymerization (ATRP) processes, for the preparation of a miktoarm dumbbell-like amphiphilic triblock copolymer, poly(poly(ethylene glycol) methyl ether methacrylate)-b-polystyrene-b-(poly(4-vinylbenzyl chloride)-g-polystyrene) (PPEGMA-b-PS-b-(PVBC-g-PS)), was developed using 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as a RAFT agent, and the benzyl chloride group of the VBC units in the PVBC block as active ATRP macroinitiators, respectively. The structures of the obtained (co)polymers were characterized by ¹H NMR spectroscopy. The obtained PPEGMA-b-PS-b-(PVBC-g-PS) amphiphilic triblock graft copolymer could self-assemble into spherical micelles with 100-300 nm diameters in a selective solvent.     

Novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers produced through a unique and highly efficient synthesis

Polyamidoamine (PAMAM) dendrimers have unique attributes that have led to their use in a wide variety of biomedical applications. However, the complex synthesis of this polymer leads to variations in the structure and consistency of the final product, and makes scale-up of manufacturing difficult. This has limited the clinical translation of PAMAM-based materials. Here we describe a rapid and highly efficient two-step method for the synthesis of novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers that have many of the favorable characteristics of PAMAM dendrimers. Generation 0 (G0) to 5 (G5) PETAA dendrimers were synthesized using a 3-(bis(2-(2,2,2,-trifluoroacetamido)ethyl)amino)propanoic acid AB₂ (compound 1) building block via a divergent approach. An ethylenediamine core was coupled with the AB₂ building block via O-(7-Azabenzotriazol-1-yl)N,N,N’,N’-tetramethyluronium hexafluorophosphate (HATU) in the presence of diisopropylethyl amine to give a G0 trifluoroacetamide surface dendrimer. The G0 amine surface dendrimer was then obtained by treating the G0 trifluoroacetamide surface dendrimer with potassium carbonate. Repetitions of these two coupling/deprotection reactions were then used to build the dendrimer by coupling the surface amino groups to the carboxyl moiety of the AB₂ building block, followed by the deprotection step with potassium carbonate. The resulting PETAA dendrimers have the same number of surface primary amino groups, the same number of chemical bonds between the dendrimer core and the surface, and the same number of tertiary amino groups throughout the structures as similar generations of PAMAM dendrimers. In contrast, the structure of the PETAA dendrimers is more complete and more uniform than PAMAM dendrimers, especially at higher generations. This unique synthetic process for PETAA dendrimers also offers the potential for large-scale production, therefore providing inherently more uniform and complete structures for exacting biomedical applications.     

Synthesis of novel pseudo‐Fréchet‐type dendrons and their fluorescent enhancement to Eu3+ ion

Novel pseudo‐Fréchet‐type dendrons with 1,3,5‐triazine structure G1.0(NOT) and G2.0(NOT) were synthesized under mild conditions by cyanuric chloride, β‐naphthol, and 3,5‐dihydroxybenzyl alcohol with the yields of 96.3 and 85.6%. The structure of the dendrons was characterized by elementary analysis, IR spectrum, ¹H‐NMR, and FAB‐MS. The dendrons had good thermo stability and solubility. They could partially transfer their absorbed energy to Eu³⁺ ion in tetrahydrofuran/acetone solutions. When the concentration of G1.0(NOT), G2.0(NOT), and Eu³⁺ ion was 5 × 10^?4 mol/L, G1.0(NOT) could enhance the fluorescent intensity of Eu³⁺ ion at 613 nm by 4.2‐fold, whereas G2.0(NOT) could enhance the fluorescent intensity of Eu³⁺ ion at 465 and 613 nm by 18.6‐ and 11.7‐fold, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of amphiphilic temperature‐sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers and micellar characterization

Amphiphilic thermally sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers were synthesized by ring‐opening polymerization of tetramethylene carbonate with hydroxyl‐terminated poly(N‐isopropylacrylamide) (PNiPAAm) as macro‐initiator in the presence of stannous octoate as catalyst. The synthesis involved PNiPAAm bearing a single terminal hydroxyl group prepared by telomerization using 2‐hydroxyethanethiol as a chain‐transfer agent. The copolymers were characterized using ¹H NMR and Fourier transform infrared spectroscopy and gel permeation chromatography. Their solutions show reversible changes in optical properties: transparent below the lower critical solution temperature (LCST) and opaque above the LCST. The LCST depends on the polymer composition and the media. Owing to their amphiphilic characteristics, the block copolymers form micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range 1.11–22.9 mg L^?1. Increasing the hydrophobic segment length or decreasing the hydrophilic segment length in the amphiphilic diblock copolymers produces lower CMCs. A core‐shell structure of the micelles is evident from ¹H NMR analyses of the micelles in D₂O. Transmission electron microscopic analyses of micelle morphology show a spherical structure of both blank and drug‐loaded micelles. The blank and drug‐loaded micelles have an average size of less than 130 nm. Observations show high drug‐entrapment efficiency and drug‐loading content for the drug‐loaded micelles. Copyright © 2010 Society of Chemical Industry     

Studies on the complexation between generation‐4.5 methyl ester‐terminated poly(amidoamine) dendrimer and Pd2+ ions in methanol

Poly(amidoamine) (PAMAM) dendrimers have attracted attention because of their well‐defined molecule structures and chemical versatility, which also complicate the mechanism of interactions between metal ions and PAMAM dendrimers. To further understand the complexation of dendrimers with metal ions, the interactions between Pd²⁺ ions and G4.5‐COOCH₃ PAMAM dendrimers were investigated by UV‐vis and FTIR spectrophotometric method. The results show that the addition of K₂PdCl₄ results in covalent attachment of the PdCl alcoholysis product of this complex to tertiary amines within the dendrimers under the appropriate conditions. This process was also supported by X‐ray photoelectron spectroscopy data of the new complex which indicated a 1 : 3 Pd/Cl ratio. The maximum loading of 80 Pd²⁺ ions within the G4.5‐COOCH₃ dendrimers and the best pH value of 8.3 for complexation system are also obtained. Details regarding the Pd species present in solution of different chemical environments are reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thiophene-based dendronized macromonomers and polymers

The synthesis of thiophene-containing second (G2) and third generation (G3) dendronized macromonomers with methacrylate polymerizable units as well as their corresponding dendronized polymers is reported. The dendrons are prepared from branched thiophene oligomers and are decorated with straight alkyl chains for solubility reasons. The polymerization reactions were done with AIBN as initiator and the polymers were characterized by NMR spectroscopy, elemental analysis and GPC. Molar masses are in the range of 2.2-5.4 × 10⁵ g mol⁻¹ (G2) and 1.3-3.0 × 10⁴ g mol⁻¹ (G3) for different runs. These polymers are investigated by cyclic voltammetry and optical spectroscopy.     

A study of antimicrobial property of textile fabric treated with modified dendrimers

Dendrimers have been used as a vehicle to develop the antimicrobial properties of textile fabrics. We have taken advantage of the large number of functional groups present in the regular and highly branched three‐dimensional architecture of dendrimers. In this study, the poly(amidoamine) (PAMAM) G‐3 dendrimer was modified to provide antimicrobial properties. Following a procedure similar to what is suggested in the literature, PAMAM (G3) with primary amine end groups was converted into ammonium functionalities. The modification was then confirmed by FTIR and ¹³C‐NMR analysis. Dendrimers have unique properties owing to their globular shape and tunable cavities, this allows them to form complexes with a variety of ions and compounds; and also act as a template to fabricate metal nanoparticles. AgNO₃–PAMAM (G3) complex as well as a MesoSilver–PAMAM (G3) complex were formed and these modified dendrimers were characterized by a UV–Visible spectrophotometer to study the complex formation. Modified dendrimers were applied to the Cotton/Nylon blend fabric. SEM and EDX analysis were performed to study the dispersion of silver nanoparticles onto the fabric. An antimicrobial test of the treated‐fabric against Staphylococcus aureus exhibited significant biocidal activities for each type of modified‐dendrimer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ratiometric fluorescent chemosensor based on the block copolymer of poly(N-isopropylacrylamide)-b-poly(N-vinylcarbazole) containing rhodamine 6G and 1,8-naphthalimide moieties

We have synthesized an amphiphilic block copolymer poly(N-isopropylacrylamide)-b-poly(N-vinylcarbazole) containing 1,8-naphthalimide and spirolactam rhodamine 6G moieties via reversible addition-fragmentation chain transfer radical polymerization. The photoluminescence (PL) spectrum of the poly(N-vinylcarbazole) block well matches the absorption spectrum of the 1,8-naphthalimide moiety and the enhanced emission with a peak at 510 nm from the 1,8-naphthalimide moiety is found in the block copolymer film for excitation at 330 nm. The 560-nm emission from the rhodamine 6G moiety is observed as the block copolymer film sprayed by Britton-Robinson (B-R) buffers or Fe³⁺ aqueous solutions for excitation at 330 and 400 nm. The PL intensity at 560 nm is markedly increased for the pH value of the B-R buffer lower than 3.0 or the Fe³⁺ concentration in water higher than 5 × 10⁻⁴ M. The 560-nm PL intensity is much higher for the block copolymer film photoexcited at 330 nm than that photoexcited at 400 nm due to double-step resonance energy transfer. The PL intensity ratio of 560 to 510 nm (I₅₆₀/I₅₁₀) is dependent on the resonance energy transfer from 1,8-naphthalimide to rhodamine 6G, which is sensitive to the concentrations of H⁺ and Fe³⁺ ions in water.     

Preparation and characterization of silver nanoparticles with dendrimers as templates

In this study, crystal silver nanoparticle clusters, prepared by the reduction of AgNO₃ in the presence of third-to-sixth-generation dendrimers with a trimesyl core, were characterized with ultraviolet–visible spectroscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The results showed that the particle size of the silver nanoparticles was considerably affected by the generation of the dendrimers as well as the dendrimer concentration. When the concentration ratios of Ag⁺ to the third-to-sixth-generation dendrimers were all 4 : 1, the average diameters of the obtained particles were 6.7, 6.0, 5.2, and 4.3 nm, respectively. The data from high-resolution transmission electron microscopy and electron diffraction indicated that the particles belonged to a simple cubic crystal structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of quaternary ammonium PEGDA dendritic copolymer networks for water disinfection

Quaternary ammonium compounds are some of the most widely used antimicrobial agents for various medical applications due to their low toxicity and broad spectrum antimicrobial activity. Various generations of poly(ethyleneglycol)diacrylate (PEGDA) based dendrimers were synthesized by Michael addition reaction of PEGDA with ethylene diamine and diethyl amine. The percentage yield of different generation of dendrimers were 70%, 66%, 60%, and 85% for G1.0 (=), G1.5 (NH₂), G2.0 (=), and G2.5 (=, NEt₂), respectively. Synthesized dendrimers were also copolymerized with ethyleneglycol dimethacrylate by free radical bulk polymerization at room temperature using ammonium persulphate/N,N,N′,N′‐tetramethyl ethylenediamine as a redox initiator system to form dendritic copolymer networks. These networks were quaternized with hydrochloric acid by continuously refluxing at 40°C for 6 h. Dendrimers and quaternized dendritic copolymer networks were characterized by ¹HNMR, FTIR, Differential scanning calorimetry, Thermogravimetric analysis, Scanning electron microscope, swelling, and leaching studies. Synthesized quaternary ammonium dendritic copolymer networks were found to be biostable and insoluble in water and capable of killing both Gram‐positive and Gram‐negative bacteria when contaminated water was treated with them. It was also observed that antimicrobial efficiency of dendritic copolymer networks increases with the increase in nitrogen atoms in the copolymer. The dendritic copolymer network with 16 quaternary ammonium groups (G2.5 (=, NEt₂): EGDMA QHCl) were highly efficient to disinfect 10 mL bacterial solution of 2000 cfu/mL within 2 min even at a very low concentration of 0.005 g/mL. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A novel thermosensitive triblock copolymer from 100% renewably sourced poly(trimethylene ether) glycol

Bio‐based amphiphilic triblock copolymers with 100% renewably sourced poly(trimethylene ether) glycol (PO3G) as the hydrophobic blocks and statistical copolymer of 2‐(2‐methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligo(ethylene glycol)methacrylate (OEGMA) [P(MEO₂MA‐stat‐OEGMA)] as the hydrophilic blocks are synthesized and characterized. It is found that the molar ratio of MEO₂MA/OEGMA among the resulting copolymers is approximately 70/30. The degree of polymerization (DP) of P(MEO₂MA‐stat‐OEGMA) block ranges from 16 to 90, and the DP of PO3G block is fixed at 35. The amphiphilic copolymers could form core‐shell micelles self‐assembly in aqueous solution at low concentrations, and the micelles are in spherical shape with sizes varying from 121 to 188 nm. With the increasing length of hydrophilic blocks, the critical micelle concentration increases from 2.15 to 13.8 mg L^?1, and the lower critical solution temperature improves from 32.5 to 38.4 °C. The in vitro doxorubicin (DOX) release study shows that all DOX‐loaded micelles have a higher release rate at 37 °C than that at 25 °C. Cytotoxicity test reveals that the blank micelles are nearly nontoxic. These results indicate that the block copolymer micelles containing 100% renewably sourced PO3G can serve as a potential drug delivery carrier. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46112.     

Preparation and study of cellulose acetate membranes modified with linear polymers covalently bonded to Starburst polyamidoamine dendrimers

Novel ion‐selective membranes were prepared by means of the noncovalent modification of a cellulose acetate (CA) polymer with either poly(ethylene‐alt‐maleic anhydride) or poly(allylamine hydrochloride) chains covalently linked to Starburst amine‐terminated polyamidoamine (PAMAM) dendrimers generations 4 and 3.5, respectively. Linear polymer incorporation within the porous CA membrane was performed with mechanical forces, which resulted in modified substrates susceptible to covalent adsorption of the relevant dendritic materials via the formation of amide bonds with a carbodiimide activation agent. The membranes thus prepared were characterized by chemical, physical, and spectroscopic measurements, and the results indicate that the dendrimer peripheral functional groups were the species that participated in the ion‐exchange events. The prepared materials were also evaluated for their ion‐exchange permeability with sampled current voltammetry experiments involving cationic and anionic species {[Ru(NH₃)₆]³⁺ and [Fe(CN₆)]^3?, respectively} as redox probe molecules under different pH conditions. As expected, although permeability was favored by opposite charges between the dendrimer and the electroactive probe, a clear blocking effect took place when the charge in the dendritic polymer and the electroactive complex was the same. Electrochemical impedance spectroscopy measurements, on the other hand, showed that the PAMAM‐modified membranes were characterized by good selectivity and low resistance values for multivalent ions compared to a couple of commercial ion‐exchange membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New self-assembling biocompatible-biodegradable amphiphilic block copolymers

New biodegradable-biocompatible amphiphilic block copolymers were prepared in good yields by SnOct₂ catalyzed ring opening polymerization of ε-caprolactone initiated by monomethoxy-terminated poly(ethylene glycol) (MPEG). Coupling of the AB copolymers with hexamethylene diisocyanate afforded ABA (formally ABBA) block copolymers. Both AB and ABA copolymers were thoroughly characterized by IR and NMR spectroscopy, size exclusion chromatography, TGA and DSC thermal analysis. In particular, DSC measurements evidenced that the copolymer hydrophilic-lipophilic balance appreciably affected the state of adsorbed water. Polarized optical microscopy of bulk materials and pyrene fluorescence emission of polymer water solutions highlighted the copolymer tendency to phase separation and self-organization, respectively. Most of the prepared materials formed micelles in water and the copolymer structure appreciably affected their critical micellar concentration. In vitro cytocompatibility tests confirmed the low toxicity of the prepared polymeric materials which enhances their potential for biomedical applications.     

Synthesis and Characterization of GAP-PEG Copolymers

ABSTRACT

A series of glycidylazide–poly(ethylene glycol) (GAP-PEG) copolymers were synthesized by cationic ring-opening polymerization of epichlorohydrin (ECH) in the presence of poly(ethylene glycol) (PEG) using borontrifluoride etherate (BF₃-etherate) as catalyst, followed by the conversion of the CH₂Cl groups of poly(epichlorohydrin) (PECH) to CH₂N₃ groups. The formation of PECH-b-PEG-b-PECH triblock copolymers was confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy. The corresponding GAP-b-PEG-b-GAP triblock copolymers were characterized by UV, IR, ¹H NMR, and ¹³C NMR spectroscopy. The copolymers have shown an increment in their molecular weights as the higher analogue molecular weight PEGs were used in the polymerizations. The thermogravimetry-differential thermogravimetry (TG-DTG) and differential scanning calorimetry (DSC) studies of the GAP triblock copolymers indicate an increase in the decomposition temperature of the azide groups of GAP block in the copolymers caused by the introduction of higher molecular weight PEG blocks. GAP-PEG copolymers have shown lower glass transition temperatures than the homo glycidylazide polymer. The nitrogen content of the GAP-PEG copolymers was estimated by various methods and the value was in good agreement with the estimated values.