Temperature- and pH-responsive self-assembly of poly(propylene oxide)-b-poly(lysine) block copolymers in aqueous solution

A series of poly(propylene oxide)-b-poly(L-lysine) (PPO-PK) block copolymers were synthesized using Huisgen's 1,3-dipolar cycloaddition, and the solution self-assembly was studied using transmission electron microscopy, circular dichroism spectroscopy, and dynamic and static light scattering techniques. In contrast to previous studies of poly(lysine)-based block copolymers, PPO-PK exhibits a significant shift in the pH associated with the helix-coil transition of the poly(lysine) block, potentially a result of decreased hydrophobicity in the core PPO block. Given the proximity of the lower critical solution temperature of the PPO block, these materials exhibit both pH and temperature-responsive (i.e., "schizophrenic") self-assembly, the latter of which was interpreted in terms of changes in the second osmotic virial coefficient. Finally, the vesicle morphology obtained from these polymers was studied for the propensity in drug encapsulation and passive release.     

New three-arm amphiphilic and biodegradable block copolymers composed of poly(epsilon-caprolactone) and poly(N-vinyl-2-pyrrolidone). Synthesis, characterization and self-assembly in aqueous solution

The synthesis, characterization and the self-assembly process of a novel biodegradable block copolymer containing a poly(epsilon-caprolactone), PCL, central block and three poly(N-vinyl-2-pyrrolidone), PVP, arms are reported. Three samples with different amounts of PVP were investigated. The copolymers were characterized by FTIR spectroscopy, (1)H NMR and viscosity measurements. The composition and the molecular weights of the block copolymers were established using size exclusion chromatography SEC and (1)H NMR. Micelle formation by these copolymers was monitored by using the vibrational fine structure of pyrene monomer fluorescence and the critical aggregation concentrations, cac, of the copolymers in aqueous solution were determined using sigmoid Boltzmann-type fitting of the fluorescence data. Dynamic light scattering measurements showed a bimodal size distribution for the copolymers in solution, indicating that the micellization is an intermolecular process. Partitioning coefficients of pyrene between copolymer micelles and water were also determined and increase in magnitude with increasing epsilon-caprolactone content of the copolymer.     

Cylindrical micelles from the aqueous self-assembly of an amphiphilic poly(ethylene oxide)-b-poly(ferrocenylsilane) (PEO-b-PFS) block copolymer with a metallo-supramolecular linker at the block junction

A supramolecular AB diblock copolymer has been prepared by the sequential self-assembly of terpyridine end-functionalized polymer blocks by using Ru(III)/Ru(II) chemistry. By this synthetic strategy a hydrophobic poly(ferrocenylsilane) (PFS) was attached to a hydrophilic poly(ethylene oxide) (PEO) block to give an amphiphilic metallo-supramolecular diblock copolymer (PEO/PFS block ratio 6:1). This compound was used to form micelles in water that were characterized by a combination of dynamic and static light scattering, transmission electron microscopy, and atomic force microscopy. These complementary techniques showed that the copolymers investigated form rod-like micelles in water; the micelles have a constant diameter but are rather polydisperse in length, and light scattering measurements indicate that they are flexible. Crystallization of the PFS in these micelles was observed by differential scanning calorimetry, and is thought to be the key behind the formation of rod-like structures. The cylindrical micelles can be cleaved into smaller rods whenever the temperature of the solution is increased or they are exposed to ultrasound.     

Thermal degradation behavior of a carboxylic acid-terminated amphiphilic block copolymer poly(ethylene)-b-poly(ethylene oxide)

The thermal degradation of an amphiphilic block copolymer poly(ethylene)-b-poly(ethylene oxide)-carboxylic acid terminated (PE-b-80%PEO–CH₂COOH) and its salt obtained as intermediary product from chemical oxidation of the end group of poly(ethylene)-b-poly(ethylene oxide) (PE-b-80%PEO) has been studied using a thermogravimetric mass spectrometry (TG/MS) coupled system. The isothermal fragmentation of PE-b-80%PEO–CH₂COOH showed a more complex fragmentation pattern than PE-b-80%PEO owing to the simultaneous occurrence of the polyether block and the carboxylic end group fragmentations. This led to the appearance of four overlapping ion current peaks of fragments with m/z 44 and two peaks relative to m/z 18 at different times by acid-terminated copolymer. For the PE-b-80%PEO copolymer, two ion current peaks associated to m/z 44 and one large peak relative to m/z 18 fragments were detected. The intermediary product (PE-b-80%PEO–CH₂COO⁻ K⁺) showed differences related to the fragmentation behavior. It has more defined ion current signals and presented characteristic peaks attributed to m/z 43 fragment at the very beginning of the thermal degradation process, which it not detected in the acid copolymer.     

Monolayer-protected gold nanoparticles by the self-assembly of micellar poly(ethylene oxide)-b-poly(epsilon-caprolactone) block copolymer

A study is presented of the preparation of gold nanoparticles incorporated into biodegradable micelles. Poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) copolymer was synthesized by ring-opening polymerization, and the hydroxyl end group of the PCL block was modified with thioctic acid using dicyclohexyl carbodiimide as the coupling reagent. The PEO-b-PCL-thioctate ester (TE) thus obtained was used in a later step to form monolayer protected gold nanoparticles via the thioctate spacer. Gold nanoparticles stabilized with the PEO-b-PCL block (named Au/Block (x/y), where x/y is the mole feed ratio between HAuCl4 and PEO-b-PCL-TE) were prepared and analyzed. Au/Block (1/1), Au/Block (2/1), and Au/Block (3/1) nanoparticles were found to form stable dispersions in the organic solvents commonly used to dissolve the unlabeled block copolymer. The average diameter of the nanoparticles was determined by transmission electron microscopy (TEM) and found to be 6+/-2 nm. Au/Block (4/1) nanoparticle dispersions in organic solvents, on the other hand, were not stable and produced large gold clusters (50-100 nm). Cluster formation was attributed to the low grafting density of the block copolymer, which facilitates agglomeration. For Au/Block (12/1), along the same trend, only an insoluble product was isolated. Micelles in water were prepared by the slow addition of the dilute Au/Block solution in dimethylformamide into a large excess of water with vigorous stirring. Au/Block (1/1) and Au/Block (2/1) formed nanosized structures of 5-7 nm. TEM images of stained Au/Block (1/1) micelles, made in water, clearly showed the formation of core-shell structures. Au/Block (3/1) micelles, on the other hand, were not stable and large agglomerates a few microns in size were observed. The study focuses on the synthesis, characterization, and aggregation behavior of gold-loaded PEO-b-PCL block copolymer micelles, a potential system for drug delivery in conjunction with tissue and subcellular localization studies.     

Mixed self-assembly of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers and sodium dodecyl sulfate in aqueous solution

Interaction of amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers with anionic sodium dodecyl sulfate (SDS) has been investigated in aqueous solution. Formation of mixed micelles has been confirmed by surface tension measurements, whereas the influence of the surfactant on the copolymer self-assembling has been studied by measurement of the 1H NMR self-diffusion coefficients and by small-angle neutron scattering. As a rule, the surfactant decreases the heterogeneity of the micellar structures formed by the copolymer in water. Moreover, increasing the content of SDS results in the increasingly more important extension of the poly(ethylene oxide) (PEO) corona chains and the copolymer micelle deaggregation. The stability of the micelles against SDS increases with the length of the hydrophobic block. Preliminary two-dimensional NMR measurements with nuclear Overhauser enhancement have confirmed the spatial vicinity between SDS and the constitutive blocks of the copolymer.     

Alpha-cyclodextrin-induced self-assembly of a double-hydrophilic block copolymer in aqueous solution

Double-hydrophilic poly(ethylene oxide)-b-poly(acrylic acid) (PEO-b-PAA) self-assembled into nanostructures in basic solution upon the addition of alpha-cyclodextrin (alpha-CD) as a result of the complexation between alpha-CD and PEO. The nanostructures produced were spherical in shape as observed by transmission electron microscopy (TEM) and possessed radii that were much larger than that of a single stretched polymeric chain. The ratio of Rg/Rh (where Rg is the z-average radius of gyration and Rh is the hydrodynamic radius) obtained from laser light scattering (LLS) was approximately approximately 1.0, and the aggregation number was approximately 4100. The zeta-potential of complex particle was -45 mV, suggesting that the particle possessed a stable negatively charged surface, attributed to ionized PAA segments. The above results suggested that the nanostructures formed in the PEO-b-PAA/alpha-CD solution at high pH were likely to be spherical vesicles.     

Synthesis and characterization of amphiphilic block copolymer of polyphosphoester and poly(L‐lactic acid)

Aliphatic polyesters and polyphosphoesters (PPEs) have received much interest in medical applications due to their favorable biocompatibility and biodegradability. In this work, novel amphiphilic triblock copolymers of PPE and poly(L ‐lactic acid) (PLLA) with various compositions were synthesized and characterized. The blocky structure was confirmed by GPC analyses. These triblock copolymers formed micelles composed of hydrophobic PLLA core and hydrophilic PPE shell in aqueous solution. Critical micellization concentrations of these triblock copolymers were related to the polymer compositions. Incubation of micelles at neutral pH followed by GPC analyses revealed that these polymer micelles were hydrolysized and resulted in decreased molecular weights and small oligomers, whereas its degradation in basic and acid mediums was accelerated. MTT assay also demonstrated the biocompatibility against HEK293 cells. These biodegradable polymers are potential as drug carriers for biomedical application. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6425–6434, 2008     

Synthesis of poly(N-isopropylacrylamide)-b-poly(2-vinylpyridine) block copolymers via RAFT polymerization and micellization behavior in aqueous solution

Poly(N-isopropylacrylamide)-b-poly(2-vinylpyridine) (PNIPAM-b-P2VP) block copolymers were synthesized for the first time via reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of S-1-dodecyl-S(')-(a,a(')-dimethyl-a(')-acetic acid)trithiocarbonate as chain transfer agent (CTA) and 2,2(')-azobis(isobutyronitrile) as initiator. Both pH- and thermo-induced micellization behavior of the PNIPAM(59)-b-P2VP(102) block copolymer in dilute aqueous solution was investigated by pyrene fluorescence, dynamic and static light scattering, transmission electron microscopy and (1)H NMR. The results show that the critical aggregation pH value of the block copolymer is around 5 and the critical aggregation temperature of the block copolymer is around 42 degrees C. A reversible transition between P2VP-core and PNIPAM-core micelles can be observed through an intermediate unimer state in aqueous solution.     

Synthesis and self-assembly behavior of four-arm poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) star block copolymer in salt solutions

A well-defined block copolymer consisting of four-arm poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) (four-arm PEO56-b-PDEAEMA74) was synthesized by atom transfer radical polymerization. The pH-responsive self-assembly behavior was examined by potentiometric titration, surface tensiometry, laser light scattering, and transmission electron microscopy over the course of dissociation by the addition of a base or acid. The apparent hydrodynamic radius (Rh) of the micelle increased from 21 to 56 nm when the degree of protonation of the amine groups was increased from 0 to 0.5 in 0.01 M NaCl solution. In higher concentration NaCl solution, the micelle shrank due to the electrostatic charge screening of the protonated DEAEMA groups. At low pH, the micelles dissociated into unimers.     

聚醚树枝体线性聚(N-异丙基丙烯酰胺)不对称嵌段共聚物的 合成及自组装

采用原子转移聚合方法合成了聚N-异丙基丙烯酰胺和聚醚树技体的不对嵌段共聚物Dendr.PE-PNI-PAM。实验结果表明Dendr.PE-PNIPAM分子在水中能通过疏水缔合作用形成具有双分子膜结构的超分子聚集体。临界缔合浓度(CAC)、聚集体的大小及形貌对树枝体的代数具有明显的依赖关系。该聚集体对温度刺激具有响应性,并在人体体温温度(37.5℃)发生相转变。在高于相转变温度时,Dendr.PE-PNIPAM分子形成管状、带状等多重形态的超级结构的聚集体。     

The radiation-induced peroxidation of poly(N-vinylpyrrolidone) in an aqueous solution

The radiation-induced peroxidation of poly(N-vinylpyrrolidone) (PVP) in its aqueous solution is reported. The amount of peroxides formed in PVP aqueous solution increased with radiation dose. The peroxides decomposed slowly at a low temperature. The molecular weight of PVP decreased with absorbed dose. The peroxidized PVP can function as initiators and crosslinkers for the syntheses of tough hydrogels.     

Synthesis and pH-sensitive micellization of doubly hydrophilic poly(acrylic acid)-b-poly(ethylene oxide)-b-poly(acrylic acid) triblock copolymer in aqueous solutions

A doubly hydrophilic triblock copolymer poly(acrylic acid)-b-poly(ethylene glycol)-b-poly(acrylic acid) (PAA-b-PEO-b-PAA) with M _w/M _n = 1.15 was synthesized by atom transfer radical polymerization of t-butyl acrylate (tBA), followed by acidolysis of the PtBA blocks. The pH-sensitive micellization of PAA-b-PEO-b-PAA in acidic solution was investigated by potentiometric titration, fluorescence spectrum, dynamic light scattering and zeta potential. The pK _a was 6.6 and 6.0 in deionized water and in 0.1 mol/L NaCl solution, respectively. The copolymer formed micelles composed of a weakly hydrophobic core of complexed PAA and PEO and a hydrophilic PEO shell in 1 mg/mL solution at pH < 5.5 due to hydrogen bonding. The critical micelle concentration was 0.168 mg/mL at pH 2.0. At pH < 4.5, steady and narrow distributed micelles were formed. Increasing pH to 5.0, unsteady and broad distributed micelles were observed. At pH > 5.5, the micelle was destroyed owing to the ionization of the PAA blocks.     

Organometallic-polypeptide block copolymers: synthesis and self-assembly of poly(ferrocenyldimethylsilane)-b-poly(epsilon-benzyloxycarbonyl-L-lysine)

A new type of metallopolymer-polypeptide block copolymer poly(ferrocenyldimethylsilane)-b-poly (epsilon-benzyloxycarbonyl-L-lysine) was synthesized by ring-opening polymerization of epsilon-benzyloxycarbonyl-L-lysine N-carboxyanhydride initiated by using a primary amino-terminated poly(ferrocenyldimethylsilane). Studies on the self-organization behavior of this polypeptide block copolymer in both the bulk state and in solution were performed. In the bulk state, a cylindrical-in-lamellar structure was observed in a compositionally asymmetric sample. Rod-like micelles with a polyferrocenylsilane core formed in a polypeptide-selective solvent alone or in the presence of a common solvent. Significantly, an additional small quantity of the common solvent assisted the formation of longer micelles and micelles with better shape-regularity. This is attributed to a decrease in the number of nucleation events and PFS core reorganization effects.     

Synthesis and characterization of poly(4-vinyl,2′-carboxybensophenone)

The synthesis and characterization of poly(4-vinyl,2′-carboxybenzophenone) ion exchange resin is described. This resin displays a remarkably high capacity for Cu²⁺. Control of pH permits selective adsorption and estimation of Fe³⁺. This ion-exchanger is quite stable to loading acid washing cycles. © 1995 John Wiley & Sons, Inc.     

Multistimuli responsive amphiphilic graft poly(ether amine): Synthesis,characterization, and self‐assembly in aqueous solution

We reported that multiresponsive amphiphilic graft poly(ether amine)s (agPEAs) comprised of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic octadecyl alkyl chain as side‐chain were prepared through one‐pot synthesis. In aqueous solution, these obtained agPEAs can self‐assemble into stable nanomicelles, whose aggregation can be controlled by temperature, pH, and ionic strength with tunable cloud point (CP). In the presence of these obtained agPEAs, hydrophobic dye Nile red can be dispersed into aqueous solution and hydrophilic dye methyl orange can be dispersed into nonpolar toluene. The agPEAs are expected to be potential in application such as encapsulation and controlled release of drugs, due to their simple synthesis, amphiphilicity, and multistimuli response. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 327–335, 2010     

交联型聚芳醚砜两亲嵌段聚合物的合成与表征

首先分别合成了主链上含有查尔酮结构的疏水段和侧链上含有叔胺的亲水段,然后通过疏水段与亲水段的末端缩合反应合成了一系列光敏性聚芳醚砜两亲嵌段聚合物,其结构和热性能分别通过1 H NMR,FT-IR,UV-Vis光谱,TGA和万能力学试验机等进行表征测试.该两亲性嵌段聚合物具有良好的溶解性、热稳性、力学性能和光敏性,在紫外光谱322nm处有最大吸收峰,在常温下经紫外光照射,分子链之间发生[2+2]环加成反应,聚合物分子之间形成交联结构,最大交联度可达到64%.     

Self-assembly of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers in aqueous solution

The associative behavior of monodisperse diblock copolymers consisting of a hydrophilic poly(ethylene oxide) block and a hydrophobic poly(epsilon-caprolactone) or poly(gamma-methyl-epsilon-caprolactone) block has been studied in aqueous solution. Copolymers have been directly dissolved in water. The solution properties have been studied by surface tension, in relation to mesoscopic analyses by NMR (self-diffusion coefficients), transmission electron microscopy, and small-angle neutron and X-ray scattering. The experimental results suggest that micellization occurs at low concentration (approximately 0.002 wt %) and results in a mixture of unimers and spherical micelles that exchange slowly. The radius of the micelles has been measured (ca. 11 nm), and the micellar substructure has been extracted from the fitting of the SANS data with two analytical models. The core radius and the aggregation number change with the hydrophobic block length according to scaling laws as reported in the scientific literature. The poly(ethylene oxide) blocks are in a moderately extended conformation in the corona, which corresponds to about 25% of the completely extended chain. No significant modification is observed when poly(gamma-methyl-epsilon-caprolactone) replaces poly(epsilon-caprolactone) in the diblocks.     

Synthesis and self-assembly of an amphiphilic poly(phenylene ethynylene) ionomer

We have synthesized a conjugated amphiphilic polyelectrolyte, a poly(phenylene ethynylene) (PPE), and the structurally analogous neutral polymer. The solution-phase aggregation of the uncharged PPE can be reversibly controlled by varying the solvent polarity and concentration, while the charged polymer appears to self-assemble at any concentration in compatible solvents. These conclusions are based on a combination of absorption and photoluminescence spectroscopy and dynamic light scattering. Photoinduced absorption spectroscopy was also employed to investigate interchain electronic communication and the photoinduced production of free charge carriers. The uncharged PPE had a relatively high polaron yield, indicating pi-stacking of adjacent PPE chains and efficient exciton splitting, while the charged polymer did not produce polarons, indicating that the polymers are not pi-stacked despite their tendency to form aggregates. This is most likely due to the presence of the cationic trimethylammonium side chains which force neighboring polymer chains too far apart to achieve effective pi-orbital overlap. Polarons were observed in both polymers after chemical doping with iodine. The ability to control aggregation and interchain electronic communication could be a useful tool in designing nanostructured electronic materials.     

Synthesis and characterization of ABA-type block copolymer of poly(trimethylene carbonate) with poly(ethylene glycol): Bioerodible copolymer

ABA-type block copolymers of poly(trimethylene carbonate) with poly(ethylene glycol) (M_n 6820), PTMC-b-PEG-b-PTMC, were synthesized by the ring-opening polymerization of 1,3-dioxan-2-one (trimethylene carbonate) in the presence of poly-(ethylene glycol) with stannous octoate catalyst, and the copolymers with various compositions were obtained. The PTMC-b-PEG-b-PTMC copolymers were characterized with Fourier transform infrared and nuclear magnetic resonance spectroscopies. The intrinsic viscosities of resulting copolymers increased with the increase of 1,3-dioxan-2-one content in feed while the molar ratio of monomer over catalyst kept constant. It has been observed that the glass transition temperature (T_g) of the PTMC segments in copolymers, recorded from differential scanning calorimetry, was dependent on the composition of copolymers. The melting temperature (T_m) of PEG blocks in copolymer was lower than that of PEG polymer, and then disappeared as the length of PTMC blocks increased. The results of dynamic contact angle measurement clearly revealed that the hydrophilicity of resulting copolymers increased greatly with the increase of PEG content in copolymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 695–702, 1998