Self‐aggregation behavior of amphiphilic polyaspartamide derivatives containing cholesterol moieties

Biodegradable amphiphilic copolymers were successfully synthesized by the conjugation of various densities of hydrophobic biocompatible cholesterol (Chol) moieties onto poly(2‐hydroxyethyl aspartamide) and poly(N‐isopropylaminoethyl‐co‐2‐hydroxyethyl aspartamide). These were obtained from polysuccinimde, the thermal polycondensation product of L‐aspartic acid, via a ring‐opening reaction with multifunctional pendant groups, including ethanolamine and N‐isopropylethylenediamine (NIPEDA). Copolymers containing 5–30 mol % Chol showed self‐aggregation behavior in aqueous solution, as evidenced by the dynamic light scattering measurement of their particle size distribution. The average particle size of these copolymers increased linearly with increasing Chol content. Moreover, the presence of secondary amine groups in the poly(2‐hydroxyethyl aspartamide)–NIPEDA system made the conjugation more efficient; however, these also seemed to accelerate the degradation of the copolymers in an aqueous medium. The degradation behavior and pH dependence of the particle size of these copolymers in aqueous solution were also examined. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel route for synthesis of temperature responsive nanoparticles

We report the preparation of responsive silica nanoparticles by reaction of epoxy modified silica with stimuli responsive poly (acrylic acid‐N‐isopropylacrylamide) (poly (AA‐co‐NIPAAm)). A series of copolymers of poly (AA‐co‐NIPAAm) were synthesized by a novel route, employing solid state condensation of polyacrylic acid and isopropyl amine in different feed ratios (44 mol %–100 mol % AA). The structure of the copolymers was characterized by FT‐IR, ¹H‐NMR. The lower critical solution temperature (LCST) was found to vary with the copolymer composition. The pH dependence of the LCST was also observed, and the copolymers exhibited a higher LCST at neutral pH than at acidic pH (4–5). Selected copolymers were used to prepare responsive core‐shell particles. Silica nanoparticles modified using glycidoxy propyl trimethoxy propyl silane were reacted with the responsive copolymer to form responsive core‐shell particles. The influence of reaction conditions on the modification of silica particles and reaction with responsive copolymers was investigated. The hydrodynamic behavior of the synthesized thermo responsive nanoparticles was also studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of temperature‐responsive poly(vinyl alcohol)‐based copolymers

A poly(vinyl alcohol) (PVA)/sodium acrylate (AANa) copolymer was synthesized to improve the water solubility of PVA at the ambient temperature. Furthermore, a series of temperature‐responsive acetalyzed poly(vinyl alcohol) (APVA)‐co‐AANa samples of various chain lengths, degrees of acetalysis (DAs), and comonomer contents were prepared via an acid‐catalysis process. Fourier transform infrared and ¹H‐NMR techniques were used to analyze the compositions of the copolymers. The measurement of the turbidity change for APVA‐co‐AANa aqueous solutions at different temperatures revealed that the lower critical solution temperature (LCST) of the copolymers could be tailored through the control of the molecular weight of the starting PVA‐co‐AANa, DA, and comonomer ratios. Lower LCSTs were observed for APVA‐co‐AANa with a longer chain length, a higher DA, and fewer acrylic acid segments. In addition, the LCSTs of the APVA‐co‐AANa aqueous solutions appeared to be salt‐sensitive. The LCSTs decreased as the concentration of NaCl increased. Moreover, atomic force microscopy images of APVA‐co‐AANa around the LCST also proved the temperature sensitivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrolysis‐improved thermosensitive polyorganophosphazenes with α‐amino‐ω‐methoxy‐poly(ethylene glycol) and amino acid esters as side groups

A series of hydrolysis‐improved thermosensitive polyorganophosphazenes with α‐amino‐ω‐methoxy‐poly(ethylene glycol) (AMPEG) and amino acid esters (AAEs) of ‘N,N‐systems’ was synthesized, and their properties were evaluated in comparison with the thermosensitive polyorganophosphazenes with methoxy‐poly(ethylene glycol) (MPEG) and AAEs of ‘O,N‐systems’, by means of ³¹P NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Most of the present polymers showed a lower critical solution temperature (LCST) in the range 32.0–79.0 °C, depending on the kinds of AAE, length of AMPEG and the mol ratio of the two substituents. These polymers exhibited higher LCSTs and faster degradation rates than the MPEG‐based polymers. The aqueous solution of poly(ethyl glycinate phosphazene)‐graft‐poly(ethylene glycol) [NP(GlyEt)_0.94(AMPEG350)_1.06]_n did not show an LCST, which is presumed to be due to its high hydrophilicity, in contrast to [NP(GlyEt)_1.01(MPEG350)_0.99]_n which showing an LCST at 77.5 °C. On the other hand, the polymers with a high content of AAE or with hydrophobic amino acids such as L ‐aspartic acid and L ‐glutamic acid, have shown a similar LCST to those of the MPEG‐based polymers. The half‐lives (t_1/2) for hydrolysis of [NP(AMPEG350)_1.06(GlyEt)_0.94]_n at pH 5, 7.4 and 10 were 9, 16, and 5 days, respectively, which are almost 2.5 to 4 times faster than that of the MPEG‐based polymers. The LCST of the present N,N‐polymers has been shown to be more influenced by salts such as NaCl (‘salting‐out’ effect) and tetrapropylammonium bromide (TPAB) (‘salting‐in’ effect) compared with the ‘O,N‐system’. Such differences of the ‘N,N‐systems’ from the ‘O,N‐systems’ in thermosensitivity, hydrolysis behavior and salt effect seem to be due to the higher hydrophilicity of the amino group in AMPEG. Copyright © 2005 Society of Chemical Industry     

Simultaneous lower and upper critical solution temperature‐type co‐nonsolvency behaviour exhibited in water–dioxane mixtures by linear copolymers and hydrogels containing N‐isopropylacrylamide and N,N‐dimethylacrylamide

The co‐nonsolvency behaviour in water–dioxane mixtures of linear copolymers and hydrogels consisting of N‐isopropylacrylamide (NIPAM) and N,N‐dimethylacrylamide (DMAM) was studied as a function of solvent composition and temperature. The composition of the copolymers, P(NIPAM‐co‐DMAMx), in DMAM units, x, varies from x = 0 up to x = 100%. It is shown that the copolymers combine the lower critical solution temperature (LCST)‐type co‐nonsolvency behaviour of poly‐NIPAM with the upper critical solution temperature (UCST)‐type co‐nonsolvency behaviour of poly‐DMAM. Depending on x, both the LCST‐ and UCST‐type co‐nonsolvency behaviour may be simultaneously observed in water‐rich and dioxane‐rich solvent mixtures, respectively. Due to this complex phase separation behaviour, the variation of the reduced viscosity of the linear copolymers, as well as the swelling–deswelling behaviour of the respective hydrogels, are shown to be temperature‐ and solvent‐sensitive. Copyright © 2006 Society of Chemical Industry     

Carrier‐bound methotrexate. I. Water‐soluble polyaspartamide–methotrexate conjugates with ester links in the polymer–drug spacer

The antifolate‐type anticancer drug methotrexate (MTX) has for many years, in numerous laboratories, been a “workhorse” drug for conjugation with natural and synthetic macromolecular carriers for the purpose of enhancing bioavailability and lowering toxic side effects. In the project here described the polymer–drug conjugation strategy is utilized for the preparation of water‐soluble polyaspartamide–methotrexate conjugates in which the drug is carrier‐anchored through short spacers containing ester groups as biofissionable links. To this end, polyaspartamide carriers 1, poly‐α,β‐D,L ‐N‐(2‐hydroxyethyl)aspartamide, and 2, poly‐α,β‐D,L ‐N‐[2‐(2‐hydroxyethoxy)ethyl]aspartamide, are treated with MTX in DMF solution in the presence of a carbodiimide coupling agent and 4‐(dimethylamino)pyridine catalyst. The molar MTX/OH feed ratios, 0.28 and lower, are chosen in these coupling reactions so as to provide conjugates featuring drug‐loading levels in the approximate range of 3–16 mol % MTX, roughly corresponding to 6–28% by mass. The water‐soluble product polymers are purified by aqueous dialysis, collected in the solid state by freeze‐drying, and structurally characterized by ¹H–NMR spectroscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1844–1849, 2001     

A study on solution properties of poly(N,N‐diethylacrylamide‐co‐acrylic acid)

Poly(N,N‐diethylacrylamide) (PDEA), poly(acrylic acid) (PAA), and a series of (N,N‐diethylacrylamide‐co‐acrylic acid) (DEA‐AA) random copolymers were synthesized by the method of radical polymerization. The measurement of turbidity showed that the phase behaviors of the brine solutions of the copolymers changed dramatically with the mole fraction of DEA (x) in these copolymers. Copolymers cop6 (x = 0.06) and cop11 (x = 0.11) in which acrylic acid content was higher presented the upper critical solution temperature (UCST) phase behaviors similar to PAA. Copolymer cop27 (x = 0.27) presented the lower critical solution temperature (LCST) behavior similar to PDEA. While copolymer cop18 (x = 0.18) in which acrylic acid content was moderate presented both UCST and LCST behaviors. The solution properties of the polymers were investigated by measurements of viscosity, fluorescence, and pH. It is reasonable to suggest that the sharp change of the phase behavior may be attributed to the interaction between acrylamide group and carboxylic group in the (DEA‐AA) copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Light‐triggered reversible solubility of α‐cyclodextrin and azobenzene moiety complexes in PDMAA‐co‐PAPA via molecular recognition

Photoresponsive polymer with azobenzene pendant group (PDMAA‐co‐PAPA) was synthesized by radical polymerization of N,N‐dimethylacrylamide (DMAA) and N‐4‐phenylazophenyl acrylamide (PAPA), and the characterization of the inclusion complexes of the PDMAA‐co‐PAPA with α‐cyclodextrin (α‐CD) were performed by FTIR, GPC, ¹H NMR, 2D NOESY, and UV–vis spectroscopy. It was found that the solubility of PDMAA‐co‐PAPA and α‐CD inclusion complexes in aqueous solution showed tunable property, which could be triggered by alternating UV–vis light irradiation at a certain temperature due to the effect of molecular recognition of α‐CD with azobenzene moiety in the polymer. After UV irradiation, the lower critical solution temperature (LCST) of the polymer aqueous solution increased slightly without α‐CD while the LCST decreased sharply at presence of α‐CD. Furthermore, UV spectroscopy showed that the photoisomerization of the polymer solution went on rapidly and reversibly, and 2D NOESY data suggested that the inclusion complexation of α‐CD with trans azobenzene moiety and the decomplexation with cis azobenzene resulted in reversible solubility behavior when objected to UV and Vis light irradiation alternately. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Independent control of lower critical solution temperature and swelling behavior with pH for poly(N‐isopropylacrylamide‐co‐maleic acid)

Polymer solutions that gel in response to changes in temperature and pH are of interest for various forms of drug delivery, and it is desirable to increase swelling for diffusion‐controlled release without bringing the lower critical solution temperature (LCST) above 37°C. N‐isopropylacrylamide (NIP) was polymerized with maleic acid (MAc), a diprotic acid, and acrylic acid (AAc), a monoprotic acid, to compare swelling and temperature response with changes in pH. For samples with equal acid contents and almost identical LCST responses to pH, poly(N‐isopropylacrylamide‐co‐maleic acid) (pNIP MAc) demonstrated greater swelling than poly(N‐isopropylacrylamide‐co‐acrylic acid) (pNIP AAc). The LCST increase for MAc occurred at a pH corresponding to the deprotonation of almost all of the first acid groups. Further increases in pH led to the deprotonation of the second ? COOH and only served to increase the charge concentration at a given location. These results provide strong support for the theory that LCST results largely from uninterrupted chain lengths of NIP and that swelling results from the actual charge density of acid groups along the chain. Because the use of a diprotic acid copolymer allows swelling to be decoupled from LCST, pNIP MAc may be an appropriate candidate for pH‐sensitive drug‐delivery applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2110–2116, 2004     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of intermolecular and intramolecular forces on hydrodynamic diameters of poly(N‐isopropylacrylamide) copolymers in aqueous solutions

A novel copolymer, poly(N‐isopropylacrylamide‐co‐hydroxypropyl methacrylate‐co‐3‐trimethoxysilypropyl methacrylate) has been synthesized and the hydrodynamic diameters in various aqueous solutions under different temperatures are determined by dynamic light scattering. The results show that the hydrodynamic diameters of copolymers have no obvious change in each working solution below lower critical solution temperature (LCST); across LCST, the diameters increased suddenly at different initial temperature in various aqueous solutions; above LCST, they decreased slightly as the temperature increased in UHQ water, and increased continuously with increasing temperature or salt concentration in saline solutions, and reduced with the rising of pH value in pH buffer. These are attributed to different intermolecular and intramolecular forces leading to disparity in dimension, conformation, and LCST of copolymers. The hydrogen bonding between water molecules and copolymer chains could maintain size and conformation of copolymer single chain; the hydrogen bonding between amide linkages and hydrophobic interactions between isopropyl groups result in intramolecular collapse and intermolecular aggregation; the electrostatic repulsion weakens aggregation extent of copolymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Stereoselective partitioning of organic substrates by thermoresponsive polymers in aqueous phases

Partitioning of organic substrates by thermoresponsive polymer having N‐acryloylaminoalcohol moieties in aqueous phase has been studied. Thermoresponsive polymers, such as poly(N‐isopropylacrylamide) (PNIPAAm) and poly(NIPAAm‐co‐N‐acryloyl‐(±)‐alaninol) (poly(NIPAAm‐co‐HIPAAm)), were found to concentrate several organic substrates into the hydrophobic field generated during their phase transition. The amount of the substrates recoverd from the polymer phase mainly depended on the hydrophobicity of the substrates. Aqueous solutions of PNIPAAm (lower critical solution temperature, LCST = 33°C) and poly(NIPAAm‐co‐HIPAAm) (LSCT = 41°C) containing 1‐phenylethanol showed LCSTs at 22°C and 33°C, respectively. The changes of LCSTs indicate that specific interactions such as hydrogen bonding between the side chain functionalities of the polymers and the substrates influence the phase transition behavior. Moreover, new optically active polymers having chiral aminoalcohol moieties have been synthesized by copolymerizations of NIPAAm with N‐acryloylaminoalcohols such as N‐acryloyl‐(S)‐alaninol and N‐acryloyl‐(S)‐prolinol. The (R)/(S) ratio of 1‐phenylethanol recovered from poly(NIPAAm‐co‐N‐acryloyl‐(S)‐alaninol) and poly(NIPAAm‐co‐N‐acryloyl‐(S)‐prolinol) were determined to be 75/25 and 68/32, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3458–3464, 2013     

Cephazoline sodium release from poly(N‐isopropyl acrylamide‐co‐N,N‐dimethylacrylamide) hydrogels

Hydrogels are hydrophilic polymers that swell to an equilibrium volume in the presence of water, preserving their shape. The dynamic swelling behavior of poly(N‐isopropylacrylamide‐co‐N,N‐dimethylacrylamide) [poly(NIPA‐co‐DMA)] copolymers at 37°C was investigated. It was observed that the swelling degree in the copolymers decreases with the N‐isopropylacrylamide content. In addition, the liberation mechanism was found to be Fickian. Diffusion coefficients according to Fick′s law as a function of the N‐isopropylacrylamide concentration and results of the release process are reported. The kinetics of cephazoline sodium release from poly(NIPA‐co‐DMA) hydrogels with different compositions was studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3433–3437, 2004     

Characterization of photo‐ and thermoresponsible amphiphilic copolymers having azobenzene moieties as side groups

Two series of amphiphilic copolymers, poly(HPMA‐co‐MPAP) I–V with n = 0.05–0.29 of the molar ratio of MPAP and poly(HPMA‐co‐MPAH)‐I–V with n = 0.05–0.23 of the molar ratio of MPAH, were prepared by radical copolymerization of N‐(2‐hydroxypropyl) methacrylamide (HPMA) with azo‐monomers such as 4‐(4‐methoxyphenylazo) phenyl methacrylate (MPAP) and 6‐[4‐(4‐methoxyphenylazo) phenoxy] hexyl methacrylate (MPAH) using 2,2′‐azobisisobutyronitrile as an initiator. Self‐organization of these copolymers in water was confirmed by disappearance of the proton signal of the methoxyazobenzene in ¹H‐NMR spectra measured in the solvent system of D₂O and CD₃OD. It was also found from the λ_max, located near 344 nm, that azobenzene groups self‐organized to form the dimeric chromophore type of aggregate. The aqueous solutions of poly(HPMA‐co‐MPAP) and poly(HPMA‐co‐MPAH) exhibited the lower critical solution temperature (LCST) from at 68 to 40°C and from at 70 to 52°C in the dark state, respectively, with increasing the molar ratios of azo‐monomers. On the other hand, the LCST measured in the photostationary state showed the higher temperature by 2–4°C compared with that in the dark state. It was found that the adsorption of poly(HPMA‐co‐MPAP)‐V (n = 0.29) on polystyrene microspheres was photoregulated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3056–3063, 2001     

Biodegradations of statistical copolymers composed of D,L‐lactide and cyclic carbonates

Syntheses and biodegradation of statistical copolymers of D ,L ‐lactide (D ,L ‐LA) with trimethylene carbonate (TMC), rac‐1‐methyltrimethylene carbonate (1‐MTMC) and 2,2‐dimethyltrimethylene carbonate (2,2‐DTMC) were investigated at various monomer ratios using SmMe(C₅Me₅)₂THF as an initiator at 80 °C for 24 h in toluene. Biodegradations of poly(D ,L ‐LA‐co‐racemo‐1‐MTMC) (95/5) and poly(D ,L ‐LA‐co‐2,2‐DTMC) (98/2) with a compost at 60 °C proceed rapidly. Enzymatic degradations of these polymers were also performed using cholesterol esterase, lipoprotein lipase and proteinase K. Only poly(D ,L ‐LA‐co‐TMC) was biodegraded with cholesterol esterase, while poly(TMC), poly(1‐MTMC), poly(2,2‐DTMC) and poly(D ,L ‐LA) were barely degraded with these enzymes. Biodegradations of poly(D ,L ‐LA‐co‐TMC) (87/13) and poly(D ,L ‐LA‐co‐racemo‐1‐MTMC) (95/5) are rapid using proteinase K. Physical properties of these copolymers were also described. © 2003 Society of Chemical Industry     

Synthesis and characterization of degradable copoly(trans‐4‐hydroxy‐L‐proline/ϵ‐caprolactone)

The melt polycondensation reaction of N‐protected trans‐4‐hydroxy‐L ‐proline (N‐Z‐Hpr) and ?‐caprolactone (?‐CL) over a wide range of molar fractions in the feed produced new and degradable poly(N‐Z‐Hpr‐co‐?‐CL)s with stannous octoate as a catalyst. The optimal reaction conditions for the synthesis of the copolymers were obtained with 1.5 wt % stannous octoate at 140°C for 24 h. The synthesized copolymers were characterized by IR spectrophotometry, ¹H NMR, differential scanning calorimetry, and Ubbelohde viscometry. The values of the inherent viscosity (η_inh) and glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of N‐Z‐Hpr. With an increase in the trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) feed from 10 to 90 mol %, a decrease in η_inh from 2.47 to 1.05 dL/g, and an increase in T_g from ?48 to 49°C were observed. The in vitro degradation of these poly(N‐CBz‐Hpr‐co‐?‐CL)s was evaluated from weight‐loss measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3176–3182, 2003     

In situ encapsulation of hydrogel in ultrafine fibers by suspension electrospinning

Composite ultrafine fibers of hydrogel/polylactide copolymer were successfully electrospun from water‐in‐oil suspensions. Effects of the suspension composition on the morphology and microstructure of the obtained fibers were investigated, including both aqueous phase and oily phase, that is, hydrogel (chitosan or gelatin), polylactide copolymers [poly(ethylene glycol)‐b‐poly (L ‐lactide‐co‐caprolactone) (PELCL) or poly(L ‐lactide‐co‐glycolide) (PLGA)], organic solvents and surfactants. Scanning electron micrographs showed that mixed solvents of chloroform and N,N‐dimethyl formamide or 2,2,2‐trifluoroethanol were preferred to form beads‐free ultrafine fibers with diameter in the range of 230–470 nm. With ethyl acetate as organic solvent, compared with chitosan hydrogel/PELCL composite fibers, chitosan hydrogel/PLGA fibers showed narrower distribution of diameter in 230–590 nm. Different hydrogel and surfactants used in this experiment had slight effects on the morphology of the obtained fibers, whereas transmission electron micrographs exhibited chitosan and gelatin hydrogel could be in situ encapsulated in the fibers discontinuously. This method may promise a new aqueous reservoir for encapsulation and controlled release of bioactive agents. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Use of a CO2‐switchable hydrophobic associating polymer to enhance viscosity–response

A series of copolymers, poly(acrylamide)‐co‐poly(N,N‐dimethylaminoethyl methacrylate)‐co‐poly(N‐cetyl DMAEMA) (abbreviation PDAMCn), was synthesized with different monomer ratios. The resulting copolymer solution shows pronounced viscosity–response property which is CO₂‐triggered and N₂‐enabled. Electrical conductivity experiment shows that tertiary amine group on DMAEMA experiences a protonate and deprotonate transition upon CO₂ addition and its removal. In addition, different incorporation rates of DMAEMA leads to two kinds of morphological change in the presence of CO₂ and thus induces different rheological behaviors. PDAMCn incorporating longer hydrophobic monomer (C₁₈DM) show more pronounced initial viscosity and higher critical stress required to cause network deformation, which consequently enhances the viscosity–response property of the solution. The addition of NaCl could also tune the viscosity of PDAMCn solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41468.     

Synthesis and characterization of amphiphilic block polymers with amino groups and their conjugates with folic acid and fluorescent probes

Amphiphilic amino‐bearing biodegradable copolymers, [methoxy‐poly(ethylene glycol)]‐block‐poly[(L ‐lactide)‐co‐(serinol carbonate)] (mPEG‐block‐P(LA‐co‐CA)), are prepared by synthesizing amino‐bearing cyclic carbonate monomer N‐benzoxycarbonylserinol carbonate (CAB) starting from serinol, by ring‐opening polymerization of L ‐lactide and CAB using diethylzinc as catalyst and mPEG as macroinitiator, and by subsequent removal of the protective benzyloxycarbonyl groups by HBr treatment. After deprotection, the pendant amino groups on the carbonate units are reacted with N‐hydroxylsuccinimide‐activated folic acid (FA) to achieve mPEG‐block‐P(LA‐co‐CA/FA) conjugate and with fluorescein isothiocyanate (FITC) to achieve mPEG‐block‐P(LA‐co‐CA/FITC) conjugate. The structures of mPEG‐block‐P(LA‐co‐CAB), mPEG‐block‐P(LA‐co‐CA), mPEG‐block‐P(LA‐co‐CA/FA) and mPEG‐block‐P(LA‐co‐CA/FITC) are confirmed using ¹H NMR and Fourier transform infrared spectroscopy. The block copolymers can self‐assemble into micelles in aqueous solution. Because of the functionality of FA and FITC, these copolymers can find important applications in drug delivery systems to serve as targeting moieties and fluorescent probes. Copyright © 2011 Society of Chemical Industry