Poly(N-tert-butyl acrylamide-b-N-acryloylmorpholine) amphiphilic block copolymers via RAFT polymerization: Synthesis, purification and characterization

Amphiphilic block copolymers consisting of two poly(acrylamide) derivative blocks have been synthesized via the reversible addition fragmentation chain transfer (RAFT) polymerization process with a hydrophobic block, poly(N-tert-butyl acrylamide), poly(TBAm), and a non-ionic hydrophilic one, poly(N-acryloylmorpholine), poly(NAM). Both polymerization orders, poly(TBAm-b-NAM) and poly(NAM-b-TBAm), were compared in terms of conversion and control over molecular weights (MW). Purification of the block copolymers was carried out via several methods in order to optimize their subsequent characterization. ¹H NMR analysis resulted in an accurate determination of the second block MW whereas determination of the CMC by the pendant drop method confirmed the ability of the poly(TBAm-b-NAM) block copolymers to self-assemble into micelles in aqueous phase.     

Synthesis, characterization and self-assembly behavior of six-armed star block copolymers with triphenylene core

Hexa-armed star block copolymers, s-[poly(l-lactide)-b-poly(styrene-co-N-acryloxysuccinimide)]₆ (s-[PLLA-b-poly(St-co-NAS)]₆) with triphenylene core have been successively prepared by the combination of ring-opening polymerization and atom transfer radical copolymerization, and they were used in the self-assembly in tetrahydrofuran, and the micelles with triphenylene core and PLLA as inner layer as well as poly(St-co-NAS) as shell were formed. After shell was cross-linked, PLLA was hydrolyzed in aqueous NaOH solution, the hollow spheres were formed. The structures, molecular weight and polydispersity index of the polymers were characterized by their ¹H NMR and FT-IR spectra, as well as GPC. Their morphologies were studied by TEM. The influence factors on the formation of various morphologies are under investigation.     

Synthesis of comb-shaped copolymers by combination of reversible addition-fragmentation chain transfer polymerization and cationic ring-opening polymerization

Comb-shaped graft copolymers with poly(methyl acrylate) as a handle were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP) techniques in three steps. First, copolymers of poly(styrene-co-chloromethyl styrene), poly(St-co-CMS), were prepared by RAFT copolymerization of St and CMS using 1-(ethoxycarbonyl)prop-1-yl dithiobenzoate (EPDTB) as RAFT agent. Second, the polymerization of MA using poly(St-co-CMS)-SC(S)Ph as macromolecular chain transfer agent produced block copolymer poly(St-co-CMS)-b-PMA. Third, cationic ring-opening polymerization of THF was performed using poly(St-co-CMS)-b-PMA/AgClO₄ as initiating system to produce comb-shaped copolymers. The structures of the poly(St-co-CMS), poly(St-co-CMS)-b-PMA and final comb-shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography (GPC).     

Oligonucleotide synthesis onto poly(N‐acryloylmorpholine‐co‐N‐acryloxysuccinimide): Assessment of the resulting conjugates in a DNA sandwich hybridization test

A water‐soluble statistical poly(N‐acryloylmorpholine‐co‐N‐acryloxysuccinimide) [poly(NAM/NAS)] copolymer was studied for polymer–oligonucleotide (ODN) conjugate elaboration and for further use in diagnostic applications. Three different copolymers were first prepared by free‐radical solution polymerization with different N‐acryloylmorpholine (NAM) and N‐acryloxysuccinimide (NAS) molar ratios (80/20, 70/30, and 60/40). Their number‐average molecular weights ranged from 98,000 to 120,000 g/mol, as determined by aqueous size exclusion chromatography with an online light‐scattering detector. Then, polymer–ODN conjugates were obtained via a strategy consisting of the direct synthesis of ODNs onto polymer chains previously grafted onto a controlled pore glass support. Before the grafting of the polymer onto the solid support, a preliminary step was performed to bind a nucleotide starter along the polymer chain (via the reactive NAS units) to initiate automated DNA synthesis. To multiply the number of ODNs growing from starters, a branched phosphoramidite synthon [bearing two O‐dimethoxytrityl groups] was introduced at the first step of ODN elongation as a short sequence of four branched synthons alternated with three thymidine residues. Conjugates were assessed in a DNA sandwich hybridization test developed for hepatitis B virus detection. Sensitivity limits were evaluated and compared to those obtained with an other polymer, poly(maleic anhydride‐alt‐methyl vinyl ether) [poly(MA/MVE)]. A sensitivity limit of 2.6 × 10⁷ DNA copies/mL was reached with the poly(MA/MVE)–ODN conjugate at the capture phase and with the poly(NAM/NAS)–branched ODN conjugate at the detection phase of the test. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3784–3795, 2004     

One-pot synthesis of poly(N-vinylcaprolactam)-based biocompatible block copolymers using a dual initiator for ROP and RAFT polymerization

Thermosensitive, biocompatible poly(ε-caprolactone)-b-poly(N-vinylcaprolactam) (PCL-b-PVCL), poly(δ-valerolactone)-b-PVCL, and poly(trimethylene carbonate)-b-PVCL block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate (HECP), as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The hydrophobic blocks were first synthesized by the ROP of cyclic monomers using diphenyl phosphate (DPP) as a catalyst and the RAFT polymerization of the PVCL block was followed by adding N-vinylcaprolactam (VCL) and 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) (V-70) as an initiator to the reaction mixture. This novel one-pot process is convenient and powerful method for the synthesis of the PVCL-based biocompatible block copolymers. The lower critical solution temperature (LCST) of the PVCL-based biocompatible block copolymer can be readily tuned by controlling the hydrophobicity of the block copolymers. By copolymerizing a hydrophilic N-vinylpyrrolidone moiety to the PVCL blocks by RAFT copolymerization, the LCST of the copolymer was matched with the body temperature for its future biomedical applications.     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

Preparation of well‐defined block copolymer having one polystyrene segment and another poly(styrene‐alt‐maleic anhydride) segment with RAFT polymerization

Block copolymers, polystyrene‐b‐poly(styrene‐co‐maleic anhydride), have been prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization technique using three different approaches: 1‐phenylethyl phenyldithioacetate (PEPDTA) directly as RAFT agent, mediated polystyrene (PS) block as the macromolecular PS‐RAFT agent and mediated poly(styrene‐maleic anhydride) (SMA) block with alternating sequence as the macromolecular SMA‐RAFT agent. Copolymers synthesized in the one‐step method using PEPDTA as RAFT agent possess one PS block and one SMA block with gradient structure. When the macromolecular RAFT agents are employed, copolymers with one PS block and one alternating SMA block can be produced. However, block copolymers with narrow molecular weight distribution (MWD) can only be obtained using the PS‐RAFT agent. The MWD deviates considerably from the typical RAFT polymerization system when the SMA is used as the RAFT agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the solution and aqueous emulsion copolymerization of vinylidene chloride with methyl acrylate in the presence a poly(ethylene oxide) macromolecular RAFT agent

The reversible addition-fragmentation chain transfer (RAFT) copolymerization of vinylidene chloride (VDC) with methyl acrylate (MeA) was studied in the presence of poly(ethylene oxide)-based macromolecular RAFT (macroRAFT) agents of the trithiocarbonate type (PEO-TTC) in solution and in aqueous emulsion. Firstly the formation of PEO-b-P(VDC-co-MeA) diblock copolymers was performed in toluene solution at 30 °C and a good control over the polymerization with high chain-end functionality was shown. A first aqueous emulsion copolymerization of VDC with MeA was performed using one of the amphiphilic PEO-b-P(VDC-co-MeA) diblock copolymers as macromolecular stabilizer. Then, in a series of experiments the PEO-TTC macroRAFT agents were directly tested as both chain transfer agents and stabilizing agents in similar conditions (aqueous batch emulsion copolymerization of VDC with MeA at 70 °C). The influence of the nature and concentration of the initiating system and the presence or not of a buffer were studied. We demonstrated that in simple conditions, nanometric latex particles composed of amphiphilic PEO-b-P(VDC-co-MeA) diblock copolymers formed by polymerization-induced self-assembly (PISA). It can thus be concluded that PEO-TTC macroRAFT agents are valuable non-ionic macromolecular stabilizers in the emulsion copolymerization of VDC and MeA and allow the formation of core–shell diblock copolymer particles in the absence of free surfactant. However, when rather high molar masses of the hydrophobic PVDC-based block were targeted, the determined molar masses deviated from the theoretical values.     

Amine‐derivatized poly(diallyldimethylammonium chloride) from N‐vinylformamide copolymerization

The reactivity ratios for the aqueous free‐radical copolymerization of diallyldimethylammonium chloride and N‐vinylformamide were found to be 0.13 and 1.92, respectively, from a Fineman–Ross analysis of a series of batch polymerizations. Because batch polymerization could not give a uniform product in a high yield with two monomers of such different reactivities, a semibatch procedure was developed in which the more reactive N‐vinylformamide was added in 10 steps over the course of the copolymerization. The poly(diallyldimethyl‐ ammonium chloride‐co‐N‐vinylformamide) copolymers were hydrolyzed to give poly(diallyldimethylammonium chloride‐co‐vinylamine). The utility of the vinylamine/diallyldimethylammonium chloride copolymers was demonstrated by the preparation and characterization of three derivatives: (1) a copolymer with coupled dansyl groups for fluorescence detection; (2) a copolymer with coupled dabsyl groups for ultraviolet–visible detection; and (3) an ultra‐high‐molecular‐weight (1.6 × 10⁶ Da) poly(diallyldimethylammonium chloride) by chain extension (coupling) with glycerol diglycidyl ether. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1068–1075, 2007     

Synthesis of rapid responsive gels comprising hydrophilic backbone and poly(N-isopropylacrylamide) graft chains by RAFT polymerization and end-linking processes

A thermosensitive poly(N-isopropylacrylamide) (PNIPAM) grafted gel, which comprises hydrophilic backbone and freely mobile PNIPAM graft chains, was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and end-linking processes. Functional PNIPAM bearing dithiobenzoate end group (-C(S)S-R) was prepared first, and then it was reacted with divinyl compounds to obtain gel. In order to adjust the composition of the gels, two divinyl compounds, N,N-methylenebisacrylamide (BIS) and poly(ethylene glycol) diacrylate (PEGDAC), were used. The cross-linking polymerization mechanism was proposed. The swelling and deswelling kinetics of the hydrogels were measured. The gels exhibit rapid deswelling kinetics. At the same time, they show rapid swelling kinetics within 30 min, whereas a conventional PNIPAM-co-PEG-co-BIS gel with the same feed composition requires more than 10 h to reach swelling equilibrium.     

High molecular weight hydrophilic functional copolymers by free‐radical copolymerization of acrylamide and of N‐acryloylmorpholine with N‐acryloxysuccinimide: Application to the synthesis of a graft copolymer

Free‐radical solution copolymerization of acrylamide (AAm) and of a disubstituted acrylamide derivative, N‐acryloylmorpholine (NAM), with N‐acryloxysuccinimide (NAS) was investigated with the aim to obtain a copolymer of at least 100,000 g mol^?1. Different polymerization conditions likely to increase the molecular weight were studied such as monomer and initiator concentrations, temperature, and nature of the solvent. The molecular weights were determined by SEC using a light‐scattering detector. The grafting of end‐functionalized polysaccharide chains onto such high molecular weight poly(NAM‐co‐NAS) was performed and a graft copolymer bearing a high number of saccharidic branches was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1808–1816, 2003     

Honeycomb structured porous films from amphiphilic block copolymers prepared via RAFT polymerization

The synthesis of polystyrene-block-poly(N,N-dimethylacrylamide) (PS-b-PDMA) via RAFT polymerization was investigated in detail. Two different RAFT agents - benzyl dithiobenzoate and 3-(benzylsulfanylthiocarbonylsufanyl) propionic acid, were employed to prepare polystyrene macroRAFT agents with molecular weights varying between 3000 g mol⁻¹ and 62,000 g mol⁻¹ and polydispersities between 1.1 and 1.4. Chain extensions with N,N-dimethylacrylamide (DMA) were carried out using a constant monomer to RAFT agent concentration ([DMA]/[RAFT] = 500), to compare the rate of polymerization in dependency of the polystyrene chain length. A decreasing rate of polymerization with increasing block length was observed. Depending on the sizes of the first block and type of RAFT agents used, chain extension polymerization with DMA was found to be incomplete, leading to significant low molecular weight tailing in the GPC analyses. Block copolymers prepared using 3-(benzylsulfanylthiocarbonylsufanyl) propionic acid, followed the expected molecular weight evolutions with polydispersity indices of 1.2-1.4. In contrast, block copolymers using benzyl dithiobenzoate clearly showed bimodal molecular weight distributions, especially when the longest PS macroRAFT agent with a molecular weight of 38,000 g mol⁻¹ was employed. These amphiphilic block copolymers were used to fabricate honeycomb structured porous films using the breath figure technique. The regularity of the film was considerably influenced by the humidity of the environment, which could be controlled by the rate of the airflow or the humidity in the casting chamber. The interaction between the hydrophilic block copolymer and the humidity was found responsible for the delicate equilibrium during the casting process, which prevented high pores regularity at very low (below 50%) and at elevated (above 80%) humidity. The interactions of the hydrophilic block with the humidity were observed to superimpose an additional nano-scaled order onto the hexagonal micron-sized porous array. Pores, which are created by encapsulation of water droplets, were found to be more hydrophilic than the surface. Confocal microscopy studies were employed to locate hydrophilic blocks within the film using a fluorescence labeled PDMA polymer.     

Synthesis and properties of thermosensitive, crown ether incorporated poly(N-isopropylacrylamide) hydrogel

A crown ether derivative (4′-allyldibenzo-18-crown-6, CE) was covalently incorporated into the network of temperature sensitive poly(N-isopropylacrylamide) (PNIPA) hydrogels by copolymerization in a mixed solvent of water and tetrahydrofuran (H₂O/THF). The poly(N-isopropylacrylamide-co-4′-allyldibenzo-18-crown-6) (poly(NIPA-co-CE)) hydrogels exhibited dramatically faster deswelling rates than normal PNIPA hydrogels at a temperature (50 °C) above their lower critical solution temperatures. The effect of the solvent component ratio in the mixed solvent during the copolymerization on the swelling properties of the poly(NIPA-co-CE) hydrogel was investigated. The thermosensitive poly(NIPA-co-CE) hydrogels have potential applications in the extraction of cations and separation of chiral drugs.     

Functional bioengineering copolymers. II. Synthesis and characterization of amphiphilic poly(N-isopropyl acrylamide-co-maleic anhydride) and its macrobranched derivatives

Radical-initiated copolymerization of N-isopropyl acrylamide (NIPA) with maleic anhydride (MA) and macromolecular reactions of synthesized poly(NIPA-co-MA) with polyethyleneglycol (PEG with a methoxy chain end and molecular weight of 2000 g mol⁻¹) and polyethyleneimine (PEI with molecular weight of 2000 g mol⁻¹) have been studied as a way to obtain new reactive amphiphilic water-soluble polymers potentially useful as carriers for gene delivery. Structure, composition and thermal behaviour of synthesized copolymers and their macrobranched architectures are determined by FTIR, ¹H and ¹³C NMR spectroscopy, elemental (N content) and chemical (acid number) analysis and differential scanning calorimetry, differential thermal and thermal gravimetric methods. It is shown that synthesized copolymers with given composition have low critical solution temperature (LCST) in the range of 30.2-46.4 °C at pH values of 4.0-7.4, which suggest the possibility of their biomedical applications.     

Synthesis of α,ω‐isocyanate telechelic polymethacrylate soft segments with activated ester side functionalities and their use for polyurethane synthesis

The synthetic route for the preparation of α,ω‐isocyanate‐telechelic poly(methyl methacrylate‐co‐acryloxysuccinimide) and α,ω‐ isocyanate‐telechelic poly(methyl methacrylate‐co‐acrylamidohexanoic succinimide) soft segments is presented. The strategy includes reversible addition fragmentation chain transfer (RAFT) copolymerization and two post polymerization modification steps. The RAFT polymerizations result in copolymers with an activated ester proportion within the polymer chains of 8% N‐acryloxysuccinimide and 5% 6‐acrylamidohexanoic succinimide. The reactivity ratios of the monomer pairs were determined. In a first post polymerization reaction carboxylic acid homo telechelic polymers were prepared by reacting the ω‐dithiobenzoate end‐group with an excess of azobis(cyanovaleric acid). In a second modification step the α‐ and ω‐carboxylic acid end‐groups were reacted with hexamethylene diisocyanate and 100% isocyanate telechelic copolymers were obtained. Finally segmented polyurethanes were prepared by coupling hexamethylene diisocyanate (HDI) end capped soft segments with hard segments composed of 1,4‐butanediol and HDI. © 2013 Society of Chemical Industry     

One-step synthesis of poly(2-oxazoline)-based amphiphilic block copolymers using a dual initiator for RAFT polymerization and CROP

A range of poly(2-oxazoline) (POx)-based amphiphilic block copolymers were synthesized using 4-cyano-4-(dodecylthiocarbonothioylthio)pentyl-4-methylbenzenesulfonate (CDPS) as a dual initiator for reversible addition-fragmentation chain transfer (RAFT) polymerization and cationic ring-opening polymerization (CROP) in a one-step procedure. Methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, and N-isopropylacrylamide were polymerized for the hydrophobic block, and 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline were used as the hydrophilic block. RAFT polymerization and CROP proceeded independently in a controlled manner and resulted in amphiphilic block copolymers with a narrow molecular weight distribution. CDPS was found to be a useful dual initiator for the one-step synthesis of POx-based amphiphilic block copolymers via a combination of RAFT polymerization and CROP.     

Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers

N,N-dimethylacrylamide (DMA) and N-acryloxysuccinimide (NAS) were copolymerized by the reversible addition–fragmentation chain transfer (RAFT) polymerization technique, to obtain random and block copolymer precursors onto which different side-groups may be statistically grafted via the reactive NAS units. These reactive copolymers have interesting applications in various fields such as coatings and paints, water purification and biology. Random poly(DMA-co-NAS) copolymer chains were synthesized with a 75/25 molar ratio, high conversion, an excellent molecular weight (MW) control from 5000 to 130 000 g mol⁻¹, and low polydispersity index (M_w/M_n<1.1). Poly(DMA-b-NAS) block copolymers were synthesized by a two step method, in which a poly(DMA) homopolymer was prepared first and then used as macro-chain transfer agent to polymerize NAS. For example, a poly(DMA-b-NAS) sample was obtained with an average molecular weight of 44 300/7400 g mol⁻¹ corresponding to 447 DMA and 44 NAS units. Such block copolymers had not yet been synthesized by any controlled polymerization technique. They can be used to prepare polymers with exactly the same backbone and an increasing number of different side groups (e.g. hydrophobic, ionic or fluorescent).     

RAFT polymerization and self-assembly of thermoresponsive poly(N-decylacrylamide-b-N,N-diethylacrylamide) block copolymers bearing a phenanthrene fluorescent α-end group

Phenanthrene α-end-labeled poly(N-decylacrylamide-b-N,N-diethylacrylamide) (PDcA_n-b-PDEA_m) block copolymers consisting in a highly hydrophobic block (n = 11) and a thermoresponsive block with variable length (79 ≤ m ≤ 468) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. A new phenanthrene-labeled chain transfer agent (CTA) was synthesized and used to control the RAFT polymerization of a hydrophobic acrylamide derivative, N-decylacrylamide (DcA). This first block was further used as macroCTA to polymerize N,N-diethylacrylamide (DEA) in order to prepare diblock copolymers with the same hydrophobic block of PDcA (number average molecular weight: M_n = 2720 g mol⁻¹, polydispersity index: M_w/M_n = 1.13) and various PDEA blocks of several lengths (M_n = 10,000-60,000 g mol⁻¹) with a very high blocking efficiency. The resulting copolymers self-assemble in water forming thermoresponsive micelles. The critical micelle concentration (CMC) was determined using Förster resonance energy transfer (FRET) between phenanthrene linked at the end of the PDcA block and anthracene added to the solution at a low concentration (10⁻⁵ M), based on the fact that energy transfer only occurs when phenanthrene and anthracene are located in the core of the micelle. The CMC (∼2 μM) was obtained at the polymer concentration where the anthracene fluorescence intensity starts to increase. The size of the polymer micelles decreases with temperature increase around the lower critical solution temperature of PDEA in water (LCST ∼ 32 °C) owing to the thermoresponsiveness of the PDEA shell.     

Synthesis of PAA-g-PNIPAM well-defined graft polymer by sequential RAFT and SET-LRP and its application in preparing size-controlled super-paramagnetic Fe3O4 nanoparticles as a stabilizer

A series of well-defined double hydrophilic graft copolymers, poly(acrylic acid)-g-poly(N-isopropylacrylamide) (PAA-g-PNIPAM), was employed as a novel water-soluble coating for constructing superparamagnetic iron oxide nanoparticles. The copolymer was synthesized via a three-step procedure: firstly, a well-defined hydrophobic PtBA-based backbone, poly(tert-butyl 2-((2-chloropropanoyloxy)-methyl)acrylate)-co-poly(tert-butyl acrylate), (PtBCPMA₁₉-co-PtBA₁₈), was prepared through RAFT copolymerization of a new trifunctional acrylic monomer, tert-butyl 2-((2-chloropropanoyloxy)methyl)acrylate and tert-butyl acrylate; secondly, taking this backbone as a macroinitiator to initiate SET-LRP of N-isopropylacrylamide resulted in well-defined (poly(tert-butyl 2-((2-chloropropanoyloxy)methyl)-acrylate)-co-poly(tert-butyl acrylate))-g-poly(N-isopropylacrylamide) ((PtBCPMA-co-PtBA)-g-PNIPAM) amphiphilic graft copolymers with relatively narrow polydispersities (M_w/M_n ≤ 1.31); thirdly, handling (PtBCPMA-co-PtBA)-g-PNIPAM in acidic conditions afforded PAA-g-PNIPAM graft copolymers. The resulting PAA-g-PNIPAM copolymers were directly utilized as a polymeric stabilizer in the preparation of superparamagnetic Fe₃O₄ nanoparticles. The particle size can be readily tuned in the range of 12.1–23.2 nm by varying the amount of PAA-g-PNIPAM copolymer or the length of PNIPAM side chain. Besides, the structure and properties of prepared Fe₃O₄/polymer nanocomposites were characterized by XRD, FT-IR, TGA, TEM, and magnetic measurement in detail.     

pH- and thermo-multi-responsive fluorescent micelles from block copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization

Well-defined pH- and thermo- multi-responsive fluorescent micelles based on the self-assembly of diblock copolymers poly[(N-isopropyl-acrylamide-co-N-vinylcarbazole)-b-2-(dimethylamino)ethyl acrylate], (PNIPAAM-co-PNVC)-b-PDMAEA, are described. The diblock copolymers are prepared via the reversible addition fragmentation chain transfer (RAFT) copolymerization of N-isopropyl-acrylamide (NIPAAM) and N-vinylcarbazole (NVC) followed by chain extension in presence of 2-(dimethylamino)ethyl acrylate) (DMAEA). The micelles are formed in aqueous solutions in a wide range of temperature (25-60 °C), and their sizes increase from 40 to 65 nm when varying pH from basic to acidic. The cross-linking of the PDMAEA-containing shell with 1,2-bis(2-iodoethoxy)ethane (BIEE) results in spherical soft nanoparticles which size is increased by 20-25% when compared to the micelles. The presence of NVC in concentrations as low as 4% in the core of the micelles allow the nanoparticles to be tagged by fluorescence, making them well suited for therapeutic applications.