Synthesis of stimuli‐responsive macroazoinitiators and their use as an inistab toward hairy polymer latex particles

Stimuli‐responsive macroazoinitiators with central azo unit have been synthesized by atom transfer radical polymerization (ATRP) of 2‐(dimethylamino)ethyl methacrylate or 2‐(diethylamino)ethyl methacrylate in 2‐propanol at 25 °C. The mean degree of polymerization of the polymer chains besides the azo group was fixed between 25 and 60. ¹H NMR, gel permeation chromatography, UV‐Vis spectrophotometer, and surface tensiometer were used to characterize the stimuli‐responsive macroazoinitiators in terms of their chemical structure, molecular weight, polydispersity, and pH‐responsive behavior, respectively. Eventually, dispersion polymerization of styrene using the poly[2‐(diethylamino)ethyl methacrylate] (PDEA) macroazoinitiator as an inistab (initiator + stabilizer) in 2‐propanol medium was conducted. Near‐monodisperse 98 nm polystyrene (PS) latex particles with pH‐responsive PDEA hair were successfully synthesized. The PS latex particles with the PDEA hair can be dispersed in acidic aqueous media where the PDEA hair was protonated and was solvated, and can be flocculated in basic aqueous media where the PDEA hair was deprotonated and was precipitated. This dispersion‐flocculation cycle was reversible. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3431–3443, 2009     

Synthesis and characterization of thermoresponsive polymers containing reduction‐sensitive disulfide linkage

A novel class of thermoresponsive and reduction‐sensitive polymer, p(PEG‐MEMA‐co‐Boc‐Cyst‐MMAm), containing disulfide linkages and removable hydrophobic tert‐butyloxycarbonyl side chains was synthesized. The cloud points (CP) of p(PEG‐MEMA‐co‐Boc‐Cyst‐MMAm) in water determined by UV/VIS spectrometer were between 20 °C and 57 °C, which shows that the CP can be tuned by adjusting the copolymer composition. Moreover, the thermosensitive polymers p(PEG‐MEMA‐co‐Boc‐Cyst‐MMAm) formed stable nanoparticles in neutral aqueous medium, but rapidly destabilized in an reductive environment mimicking the intracellular space making them suitable for cytoplasmic drug delivery. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5989–5997, 2009     

Polymer hydrogels of 2‐hydroxyethyl acrylate and acrylic acid obtained by frontal polymerization

In this work, we report on the synthesis and characterization of homopolymers and copolymers of acrylic acid and 2‐hydroxyethyl acrylate prepared by the use of the frontal polymerization (FP) technique. Tetraethyleneglycoldiacrylate was used as a crosslinker and benzoyl peroxide as an initiator. The maximum temperatures reached by the front were in the range between 214 °C and 296 °C. Besides, front velocities ranged between 3.9 and 10.8 cm/min, the latter being one of the highest values reported so far in the FP literature. Differential scanning calorimetry was used to estimate the conversion degree, which was always comprised between 90% and 96%, and to determine the glass transition temperatures, which were found to be dependent on the composition, with values ranging from 13 °C to 168 °C. Moreover, the obtained materials were allowed to swell in aqueous solutions at various pH. The samples exhibit a moderate increase of the swelling ratio percentage (SR%) at pH ≈ 5–6, and a sudden and larger SR% increase at pH ≈ 12–13 depending on the composition, thus indicating the obtainment of pH‐responsive polymer hydrogels. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Tuning amphiphilicity/temperature‐induced self‐assembly and in‐situ disulfide crosslinking of reduction‐responsive block copolymers

New poly(ethylene oxide)‐based block copolymers (ssBCs) with a random copolymer block consisting of a reduction‐responsive disulfide‐labeled methacrylate (HMssEt) and a thermoresponsive di(ethylene glycol)‐containing methacrylate (MEO₂MA) units were synthesized. The ratio of HMssEt/MEO₂MA units in the random P(MEO₂MA‐co‐HMssEt) copolymer block enables the characteristics of well‐defined ssBCs to be amphiphilic or thermoresponsive and double hydrophilic. Their amphiphilicity or temperature‐induced self‐assembly results in nanoaggregates with hydrophobic cores having different densities of pendant disulfide linkages. The effect of disulfide crosslinking density on morphological variation of disulfide‐crosslinked nanogels is investigated. In response to reductive reactions, the partial cleavage of pendant disulfide linkages in the hydrophobic cores converts the physically associated aggregates to disulfide‐crosslinked nanogels. The occurrence of in‐situ disulfide crosslinks provides colloidal stability upon dilution. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2057–2067     

Thermoresponsive super water absorbent hydrogels prepared by frontal polymerization

Frontal polymerization was used as an alternative technique for the preparation of super water absorbent hydrogels obtained from acrylamide and 3‐sulfopropyl acrylate, potassium salt (SPAK) in the presence of N,N′‐methylene‐bisacrylamide as a crosslinker. All samples were synthesized in dimethyl sulfoxide, and their swelling behavior in water was investigated. It was found that their features are dependent on the monomer ratio used, which influenced the porous morphology, and consequently, the swelling capability. The swelling ratio ranges from about 1000% for the acrylamide homopolymer up to 14,000% for the sample containing 87.5 mol % of SPAK, thus indicating that this parameter can be easily tuned by using the appropriate monomer ratio. The affinity towards water was eventually confirmed by contact angle analysis. Polymer hydrogels made from at least 62.5 mol % SPAK exhibit a thermoresponsive behavior, with a lower critical solution temperature of ～30 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2486–2490, 2010     

Mesoglobules of random copolyethers as templates for nanoparticles

An approach to nanoparticles based upon the thermosensitivity of a copolyether is described. Two thermosensitive copolymers of glycidol with molar masses of 800,000 g/mol randomly substituted with ethyl isocyanate (28 and 35% substitution) were used to obtain mesoglobules. The effects of copolymer concentration and of the presence of surfactants (sodium dodecyl sulfate and hexadecyltrimethylammonium bromide) on the size of the mesoglobules formed were investigated. The obtained mesoglobules were monomodal and of narrowly distributed diameters, as shown by dynamic light scattering and atomic force microscopy measurements. The radical nucleated copolymerization of N‐isopropylacrylamide with N,N′‐methylenebisacrylamide as a crosslinker was performed in the presence of the mesoglobules. Nanoparticles of monomodal size distribution and low dispersity were obtained. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4074–4083, 2010     

Synthesis and characterization of stimuli‐sensitive micro‐ and nanohydrogels based on photocrosslinkable poly(dimethylaminoethyl methacrylate)

The aim of this work was the development of a versatile route for the preparation of temperature‐ and pH‐responsive hydrogels with small dimensions. The copolymerization of N,N‐dimethylaminoethyl methacrylate with various amounts (5 and 10 mol %) of dimethylmaleimidoethyl methacrylate in solution with 2,2′‐azobisisobutyronitrile as an initiator is described. The structural and molecular characterization of the copolymers was performed with proton nuclear magnetic resonance, Fourier transform infrared, and ultraviolet spectroscopy, as well as size exclusion chromatography. Differential scanning calorimetry and thermogravimetry were used for the thermal characterization of the copolymers. Micro‐ and nanohydrogels of the copolymers were prepared by photocrosslinking. The gels obtained by photocrosslinking were characterized with a combination of surface plasmon resonance and optical waveguide spectroscopy, dynamic light scattering, and scanning electron microscopy. The hydrogels showed temperature‐ and pH‐responsive behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 669–679, 2007     

Self‐immolative nanoparticles triggered by hydrogen peroxide and pH

The azomethine‐based oligomers bearing boronate groups and imine moieties in the main chain were synthesized from a dialdehyde monomer and an aromatic (oligomer 4 ) diamine or an aliphatic diamine (oligomer 5 ). Based on the oligomers, the nanoparticles with hydrogen peroxide (H₂O₂) and pH dual‐responsive properties were constructed and encapsulated nile red inside. The nanoparticles disassembled either by the trigger of H₂O₂ or by the attack of H⁺, thus leading to the release of loaded species. Compared to oligomer 4 , oligomer 5 showed a faster degradation rate in the presence of H₂O₂, especially in a weak acidic environment. No significant cytotoxicity was observed as HeLa cells incubated in the nanoparticles with the concentration up to 200 μg/mL evidenced by cytotoxicity assay in vitro. Such a system capable of dual response of H₂O₂ and H⁺ may have potential application as a carrier for drug delivery. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1962–1969     

Atom transfer radical polymerization synthesis and photoresponsive solution behavior of spiropyran end‐functionalized polymers as simplistic molecular probes

Poly(methyl methacrylate)s (PMMAs) of two different molecular weights having a single photochromic benzospiropyran (BSP) end‐group were synthesized by atom transfer radical polymerization (ATRP). Polymer characterization by ¹H NMR and matrix‐assisted laser desorption/ionitiation time of flight‐mass spectroscopy confirms that using an ATRP initiator equipped with BSP, a near quantitative functionalization of the PMMA with the BSP was achieved. Both polymers exhibit photochroism characterized by the UV‐induced transition from BSP to benzomerocyanine (BMC) in acetonitrile. However, a strong molecular weight dependence of the thermal relaxation kinetic of the BMC was found with a significantly faster temperature‐dependent transition for the higher molecular weight polymer. Thermodynamic analysis of the process revealed a higher gain in the entropy of activation ΔS^± for the transition process in the higher molecular weight polymer. This suggests an energetically unfavorable nonpolar environment of the BMC group in the higher molecular weight polymers, although a higher solvation of the BMC in the lower molecular weight polymer contributes to its stabilization. The ability of the BMC polymer end‐groups to organize was shown in metal ion‐binding experiments forming bivalently linked complexes with Co ions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of well‐defined 7‐arm and 21‐arm poly(N‐isopropylacrylamide) star polymers with β‐cyclodextrin cores via click chemistry and their thermal phase transition behavior in aqueous solution

The syntheses of well‐defined 7‐arm and 21‐arm poly(N‐isopropylacrylamide) (PNIPAM) star polymers possessing β‐cyclodextrin (β‐CD) cores were achieved via the combination of atom transfer radical polymerization (ATRP) and click reactions. Heptakis(6‐deoxy‐6‐azido)‐β‐cyclodextrin and heptakis[2,3,6‐tri‐O‐(2‐azidopropionyl)]‐β‐cyclodextrin, β‐CD‐(N₃)₇ and β‐CD‐(N₃)₂₁, precursors were prepared and thoroughly characterized by nuclear magnetic resonance and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. A series of alkynyl terminally functionalized PNIPAM (alkyne‐PNIPAM) linear precursors with varying degrees of polymerization (DP) were synthesized via atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide using propargyl 2‐chloropropionate as the initiator. The subsequent click reactions of alkyne‐PNIPAM with β‐CD‐(N₃)₇ and β‐CD‐(N₃)₂₁ led to the facile preparation of well‐defined 7‐arm and 21‐arm star polymers, namely β‐CD‐(PNIPAM)₇ and β‐CD‐(PNIPAM)₂₁. The thermal phase transition behavior of 7‐arm and 21‐arm star polymers with varying molecular weights were examined by temperature‐dependent turbidity and micro‐differential scanning calorimetry, and the results were compared to those of linear PNIPAM precursors. The anchoring of PNIPAM chain terminal to β‐CD cores and high local chain density for star polymers contributed to their considerably lower critical phase separation temperatures (T_c) and enthalpy changes during phase transition as compared with that of linear precursors. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 404–419, 2009     

Stimulus‐responsive polymers based on 2‐hydroxypropyl acrylate prepared by RAFT polymerization

Homopolymerization and diblock copolymerization of 2‐hydroxypropyl acrylate (HPA) has been conducted using reversible addition fragmentation chain transfer (RAFT) chemistry in tert‐butanol at 80 °C. PHPA homopolymers were obtained with high conversions and narrow molecular weight distributions over a wide range of target degrees of polymerization. Like its poly(2‐hydroxyethyl methacrylate) isomer, PHPA homopolymer exhibits inverse temperature solubility in dilute aqueous solution, with cloud points increasing systematically on lowering the mean chain length. The nature of the end groups is shown to significantly affect the cloud point, whereas no effect of concentration was observed over the PHPA concentration range investigated. Various thermoresponsive PHPA‐based diblock copolymers were prepared via one‐pot syntheses in which the second block was either permanently hydrophilic or pH‐responsive. Preliminary studies confirmed that poly(ethylene oxide)‐poly(2‐hydroxypropyl acrylate) (PEO₄₅‐PHPA₄₈) and poly(2‐hydroxypropyl acrylate)‐ poly(2‐hydroxyethyl acrylate) (PHPA₄₉‐PHEA₆₈)diblock copolymers formed well‐defined PHPA‐core micelles in 10 mM sodium nitrate solution at 40 °C and 70 °C with mean hydrodynamic diameters of 20 nm and 35 nm, respectively. In contrast, most other PHPA‐based diblock copolymers investigated formed larger colloidal aggregates in 10 mM NaNO₃ solution at elevated temperatures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2032–2043, 2010     

Double responsive copolymer hydrogels prepared by frontal polymerization

Frontal polymerization was successfully used to synthesize copolymer hydrogels of poly(N‐vinylcaprolactam‐co‐itaconic acid). All materials were characterized by response to stimuli (pH and/or temperature), depending on the itaconic acid content. Namely, relatively low amounts of this latter were found to be crucial for determining the degree of swelling. In particular, hydrogels behave differently if swollen at pH values that are higher or lower of 7–8, and exhibit temperature response as well (lower critical solution temperature at ca. 30 °C), which makes these materials potentially interesting for biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2166–2170     

High molecular weight polyacrylamides by atom transfer radical polymerization: Enabling advancements in water‐based applications

Through the use of copper (I) chloride (CuCl) and tris(2‐dimethylaminoethyl)amine (Me₆‐TREN) as a metal/ligand pair, conditions for the robust, fast, and controlled radical polymerization of high molecular weight N‐hydroxyethylacrylamide (HEAm),N‐isopropylacrylamide (NIPAm), N,N′‐dimethylacrylamide (DMAm), and acrylamide (Am) at ambient temperature are reported. Linear evolution of molecular weight and narrow molecular weight distribution was observed for all monomers with degrees of polymerization ranging from 50 to 5000. Random copolymers of several acrylamide‐based monomers are also reported with excellent control over molecular weight and polydispersity. Characterization of high molecular weight poly (NIPAm) demonstrated large changes in the lower critical solution temperature observed on heating and cooling, and this hysteresis was exploited for the controlled release of doxorubicin from poly(NIPAm) spheres. This study represents the first example of preparation of high molecular weight acrylamide polymers by a metal‐mediated controlled radical polymerization technique. Access to these materials, as well as to NIPAm polymers in particular, opens new doors for interesting applications in a variety of fields including tissue engineering, drug delivery, and controlled solution viscosity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Aqueous micro and nanoreactors based on alternating copolymers of phenylmaleimide and vinylpyrrolidone bearing pendant l‐proline stabilized with PEG grafted chains

Proline may work efficiently in water as catalyst of aldol reactions if it is hydrophobically activated. In this work, we have maximized this hydrophobic activation by the preparation of linear alternating copolymers of hydrophobic phenylmaleimide and a vinylpyrrolidone derivative bearing proline. These copolymers were water soluble above pH 5.0 and, unlike the free proline, exhibited efficient catalysis at pH 7.0. Moreover, they catalyzed and presented enantioselectivity in an aggregated form at pH 4.0 (close to the isoelectric point, IEP, of the polymer). This enantioselectivity has been related to the exclusion of water at this IEP. To control the size and stabilize the aggregates, PEG grafted copolymers were prepared by the incorporation of a PEG‐macromer (2–10 mol%), which rendered stable nano‐aggregates in water at the IEP. At this pH they catalyzed the aldol reaction in a higher rate than the non‐grafted polymer, but the enantioselectivity was decreased. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 55, 1228–1236     

Synthesis of low‐polydispersity poly(N‐ethylmethylacrylamide) by controlled radical polymerizations and their thermal phase transition behavior

Controlled radical polymerizations of N‐ethylmethylacrylamide (EMA) by atom transfer radical polymerization and reversible addition‐fragmentation chain transfer processes were investigated in detail for the first time, employing complementary characterization techniques including gel permeation chromatography, ¹H NMR spectroscopy, and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry. In both cases, relatively good control of the polymerization of EMA was achieved, as revealed by the linear evolution of molecular weights with monomer conversions and the low polydispersity of poly(N‐ethylmethylacrylamide) (PEMA). The thermal phase transitions of well‐defined PEMA homopolymers with polydispersities less than 1.2 and degrees of polymerization up to 320 in aqueous solution were determined by temperature‐dependent turbidity measurements. The obtained cloud points (CPs) vary in the range of 58–68 °C, exhibiting inverse molecular weight and polymer concentration dependences. Moreover, the presence of a carboxyl group instead of an alkyl one at the PEMA chain end can elevate its CP by ～3–4 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 60–69, 2008     

A facile pathway for the fast synthesis of colloidal crystal‐loaded hydrogels via frontal polymerization

In this work, a dually sensitive colloidal crystal (CC)‐loaded hydrogel has been synthesized via frontal polymerization (FP) in a facile and rapid way. First, a polystyrene CC film was fabricated by vertical deposition on the inner wall of a test tube. Then, a mixture of acrylic acid (AAc), 2‐hydroxyethyl methacrylate (HEMA), and glycerol along with the initiator and crosslinker was added to this test tube to carry out FP, resulting in the formation of CC‐loaded hydrogel. The influence of the mass ratios of HEMA/AAc on front velocity and temperatures were studied. The swelling behavior, the morphology, and the stimuli‐responsive behavior of the CC‐loaded hydrogels prepared via FP were thoroughly investigated on the basis of swelling measurement, scanning electron microscopy, and reflection spectra. Results show that the as‐prepared CC‐loaded hydrogels exhibit excellent dual sensitivity to both methanol concentrations and pH values with very short response time, which can be observed visually without the aid of instruments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Stimuli‐responsive polymer hydrogels containing partially exfoliated graphite

In this work, a new stimuli‐responsive composite polymer hydrogel containing partially exfoliated graphite was prepared by frontal polymerization. The materials obtained were characterized by differential scanning calorimetry, RAMAN, scan electron microscopy, transmission electron microscopy, atomic force microscopy, and in terms of swelling behavior. It was found that the maximum temperature reached by the polymerization front and the lower critical solution temperature are affected by the graphite content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Thermo-responsive polymer brushes as intelligent biointerfaces: preparation via ATRP and characterization

PIPAAm-brush grafted glass substrates with various graft densities and chain lengths were prepared via surface-initiated ATRP. Temperature-dependent physicochemical properties of the surfaces were characterized by means of ATR/FT-IR spectroscopy, XPS, AFM, and contact angle measurements. ATRP conditions influence the amount of grafted PIPAAm and the surface wettability and roughness of the substrate. Fibronectin adsorption and EC adhesion increased with decreasing density of PIPAAm brushes. EC adhesion was diminished with increasing PIPAAm graft length. Thus, the preparation of PIPAAm brush surface with various graft densities and chain lengths using the surface-initiated ATRP is an effective method for modulating thermo-responsive properties of surfaces.     

Photoresponsive oil sorbers

A photoresponsive oil sorber (POS) with a hydrophobic, photoresponsive core and shell has been synthesized via suspension polymerization. Lauryl acrylate, isodecyl acrylate, and tert‐butylstyrene were used as monomers, 4‐(methacrylamino)azobenzene (Azo‐M) used as photoresponsive monomer, and bis(methacryloylamino)azobenzene (Azo‐CL‐M) used as photoresponsive surface crosslinker. The POS prefers nonpolar solvents. It absorbed 15 times its dry weight in toluene, 19 times its dry weight in chloroform, and 16 times its dry weight in dichloromethane. Rapid and photoresponsive desorption of solvent (86% of solvent expulsed in 30 min) was characteristic. POS is an excellent gasoline absorber rapidly increasing its body weight in its presence. The new POS is less dense than water, and can potentially be used for cleaning oil spills on water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 55–62, 2010     

Photocrosslinkable smart terpolymers responding to pH,temperature, and ionic strength

A series of copolymers of acrylic acid, N‐isopropylacrylamide (NIPAM), and cinnamoyloxyethyl acrylate were synthesized and studied. The polymers were responsive to four stimuli: UV light, temperature, pH, and ionic strength. The polymeric cinnamoyl chromophores underwent efficient photodimerization with concomitant photocrosslinking of the polymeric micelles. Because of the content of NIPAM, the terpolymers displayed a lower critical solution temperature, which could be controlled by the polymer composition, pH, and ionic strength. The ability to respond to the pH resulted from the content of acrylic carboxyl groups, which became protonated at low pHs. The changes in the polymer properties due to the application of the aforementioned stimuli were studied with pyrene and perylene as fluorescent probes. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3879–3886, 2004