Summary: A series of self‐assembled photosensitive ultra‐thin films have been fabricated from poly(4‐diazonium styrene) (PDS) via different driving forces, mainly by electrostatic and H‐bonding interaction. Under exposure of UV light, the weak ionic and H‐bonds between the layers of the film will be converted to covalent bonds through a photoreaction. Thus, the stability of the film towards polar solvents is reinforced greatly.
UV‐vis spectra of the PDS‐MPR film with different bilayers. 相似文献
The development of self‐healing poly(urea‐urethane)s with remarkable mechanical properties as well as self‐healing capability is an important challenge through a low‐cost approach. In this study, cystine dimethyl ester (CDE) is synthesized cost‐effectively using cystine from bio‐based sources as raw material, and a novel self‐healing poly(urea‐urethane) is successfully prepared using synthesized CDE as a disulfide‐containing chain extender through a two‐step approach. The as‐prepared disulfide‐containing poly(urea‐urethane) (SPU) presents an excellent self‐healing capability with self‐healing efficiency of 95.3% at a moderate healing temperature (≈60 °C). Meanwhile, the SPU exhibits robust mechanical properties possessing a maximum tensile strength of 25.80 MPa and a high elongation at break of over 460% simultaneously. The compromise between self‐healing capability and mechanical performance can be responsible for the exchange of dynamic disulfide bonds and the existence of quadruple hydrogen bonding. This strategy provides an available idea to develop robust self‐healing polymer materials cost‐effectively. 相似文献
An amphiphilic graft copolymer using chitosan (CS) as a hydrophilic main chain and poly(lactic‐co‐glycolic acid) (PLGA) as a hydrophobic side chain is prepared through an emulsion self‐assembly synthesis. CS aqueous solution is used as a water phase and PLGA in chloroform is served as an oil phase. A water‐in‐oil (W/O) emulsion is fabricated in the presence of the surfactant span‐80. The self‐assembly reaction is performed between PLGA and CS under the condensation of EDC. Fourier transform IR (FTIR) spectroscopy reveals that PLGA is grafted onto the backbone of CS through the interactions between end carboxyl and amino groups of the two components. 1H NMR spectroscopy directly indicates the grafting content of PLGA in the CS‐graft‐PLGA (CS‐g‐PLGA) copolymer is close to 25%. X‐ray diffraction (XRD) confirms that the copolymer exhibits an amorphous structure. The CS‐g‐PLGA amphiphile can self‐assemble to form micelles with size in the range of ≈100–300 nm, which makes it easy to apply in various targeted‐drug‐release and biomaterial fields. 相似文献
Poly(3‐thiopheneacetate)/dialkyldimethylammonium complexes (PTA‐Cn) were prepared by mixing regiorandom poly(3‐thiopheneacetic acid) with dialkyldimethylammonium bromide to study the effect of their self‐assembled structures on the optical properties. The lengths of the alkyl groups in the ammonium salts were varied from decyl (C10) to octadecyl (C18) groups. These complexes showed fully developed layer structures with ordered mesophases. PTA‐C16 and PTA‐C18 with longer alkyl groups showed side‐chain crystalline phases, and PTA‐C10, PTA‐C12, and PTA‐C14 with shorter alkyl groups showed side‐chain crystalline and liquid crystalline phases at room temperature. When PTA‐C18 was heated, a melting transition from side‐chain crystalline to smectic liquid crystalline phase was observed at 41.5 °C. The maximum absorption and emission wavelengths of these complexes increased with increasing alkyl chain length indicating that the π‐conjugated structure of the regiorandom thiophene backbone changes according to the alkyl groups.
P2VN‐b‐PAA is a novel diblock copolymer which has potential as a self‐assembled nanoscale patterning material. Thin spin cast P2VN‐b‐PAA films rapidly reorganize to vertical lamellar with exposure to acetone vapor. P2VN‐b‐PAA lamellar morphology was aligned by electric field under acetone vapor at a significantly faster rate and at lower electric field strengths than other polymer systems. Observed dry etching selectivity for P2VN to PAA were comparatively high for a variety of etch gases, consistent with estimations from Ohnishi and ring parameters. Block copolymer self assembled patterns were transferred to silicon via two‐step CF4 and SF6 etching.
A series of poly(ether ester)s containing different H‐bonding units (amide, carbamate, urea) was prepared by polycondensation in bulk, using Ti(OBu)4 as a catalyst. The copolymers were obtained starting from PEG1000, 1,4‐butanediol, and a symmetrical, bis‐ester terminated monomer carrying H‐bonding units. These materials were designed for biomedical applications, in which ultimate biodegradability of the materials is required. The influence of the nature of the H‐bonding unit and of the length of the methylene spacer between H‐bonding groups on the thermal and solubility properties of copolymers was investigated. Amide containing copolymers were more thermally stable than ones containing carbamate, consistent with the observed behavior of the corresponding monomers. In most cases, differential scanning calorimetry (DSC) traces were quite complex because of phase separation and dependent on the applied cooling rate. Copolymers containing urea bonds were less soluble in most organic solvents, but their thermal properties were not significantly different than their amide containing counterparts.
A series of well‐defined hydroxypropyl methyl cellulose‐block‐poly(l ‐lactide) (HPMC‐b‐PLLA) diblock copolymers are synthesized via UV‐initiated thiol‐ene click reaction of thiol‐terminated HPMC with different block lengths and allyl‐terminated PLLA, using 2,2‐dimethoxy‐2‐phenylacetophenone as photocatalyst. The former is obtained by coupling the reducing aldehyde endgroup of short chain HPMC with the amine group of cysteamine, and the latter by ring‐opening polymerization of l ‐lactide in the presence of allyl alcohol. Fourier transform infrared (FT‐IR), nuclear magnetic resonance (1H NMR), and diffusion ordered spectroscopy NMR confirm the successful coupling of both blocks. The molar mass of the resulting copolymers ranges from 7000 to 12 800 g mol−1 as determined by size exclusion chromatography. The copolymers are able to self‐assemble in aqueous medium, yielding micelles of 50–100 nm with core–shell structure as evidenced by dynamic light scattering, transmission electron microscopy, and 1H NMR. The critical micelle concentration of copolymers ranges from 0.12 to 0.15 mg mL−1. Last but not the least, the copolymers exhibit thermoresponsive behavior with a lower critical solution temperature around 80 °C.
The concept of stereocontrolled entanglements, in which the tunable H‐bonded chiral pairs serve as crosslinks to create topological constraints on the local chain dynamics, is introduced to tailor the crystalline morphology of stereocomplex poly(lactic acid). For the entanglements to be interconnected and activated, poly(d ‐lactic acid) with statistical branched architecture is incorporated, enabling the construction of 3D association with linear poly(l ‐lactic acid) chains. With thermodynamically graded disentanglement relaxation for the blends, the profound influence of entanglements on the crystalline morphology is revealed during isothermal crystallization. Orderly aligned cylindrites some with an exceptional length of over 500 μm, resembling the structural features of the classical shish‐kebab superstructure, are observed in the blends penetrated with dense entanglement constraints. By contrast, only dendritic spherulites are formed in the highly disentangled blends. The selectively suppressed homo‐crystallization by the entanglements offers insights into the contribution of constraints. This bottom‐up strategy opens up pathways to engender oriented crystals of long‐range order under quiescent conditions, which has potential implications for other chiral polymers.
An amphiphilic copolymer brush poly(ethylene oxide‐co‐glycidol)‐graft‐polyacrylonitrile [poly(EO‐co‐Gly)‐g‐PAN], is successfully prepared for the first time by a combination of anionic polymerization and redox free radical polymerization. The final products and intermediates are characterized by NMR and GPC. Aggregates made from the brush copolymers, poly(EO‐co‐Gly)‐g‐PAN, with a long hydrophobic graft length in water are studied by TEM and DLS. The effects of hydrophobic graft length and water content on the morphologies are discussed. Some rare morphologies of aggregates are observed, such as lamellae, bicontinuous networks, bowls or nanosheets, and large compound rods with a brittleness that can be ascribed to the orientation of high content semi‐crystalline PAN segments. 相似文献
An amphiphilic penta‐telechelic polyhedral oligomeric silsesquioxane (POSS)‐containing inorganic/organic hybrid poly(acrylic acid), (Glu‐PAA‐POSS5), is prepared by hydrolysis of penta‐telechelic poly(tert‐butyl acrylate) (Glu‐PtBA‐POSS5), synthesized by the combination of atom transfer radical polymerization (ATRP) and a “click” reaction. The self‐assembly behavior of Glu‐PAA‐POSS5 in aqueous solution at pH 8.5 is investigated by using transmission electron microscopy (TEM), scanning electronic microscopy (SEM), atomic force microscopy (AFM), and dynamic light scattering (DLS). The results show that Glu‐PAA‐POSS5, with a long poly(acrylic acid) (PAA) chain, can self‐assemble in water into giant capsules, which provides an optional approach in the construction of capsules.
A series of poly(methyl methacrylate‐co‐methacrylic acid) (PMMA‐co‐MAA) random copolymers ranging in MAA content from 0–15 mol% is synthesized and blended with poly(vinylidene fluoride) (PVDF). Using infrared spectroscopy, it is observed that the absorption bands attributed to hydrogen‐bonded carbonyl groups increase in intensity as the amount of MAA in the copolymer increases. In DSC analysis, the crystallization temperature of the PVDF in the blend initially decreases by ca. 12 °C with MAA contents ranging from 0 to 5.5 mol%; however, a PVDF blend with a 15 mol% MAA copolymer has a crystallization temperature that is only ca. 3 °C below that of pure PVDF. Similarly, spherulitic growth rate analysis initially shows a decrease in radial growth rate for PVDF in blends with PMMA‐co‐MAA copolymers containing less than 5.5 mol% MAA. At higher MAA copolymer contents, the spherulitic growth rate approaches that of pure PVDF. It is concluded that the presence of the MAA comonomer in the PMMA‐co‐MAA copolymer initially (<5.5 mol% MAA) increases the intermolecular interactions between the copolymer and the PVDF. However, as the MAA content of the copolymer rises above 5.5 mol%, intramolecular hydrogen bonding interactions within the PMMA‐co‐MAA copolymer cause the copolymer to be less compatible with PVDF.
The layer‐by‐layer (LbL) assembly technique was applied for the surface modification of biodegradable poly(lactide‐co‐glycolide) nanoparticles (NPs), employing poly(acrylic acid) (PAA), and polyethylenimine (PEI) as building blocks. Amino terminated poly(ethylene glycol) (PEG) and folate decorated PEG (PEG‐FA) were grafted onto the multilayers via condensation between carboxylic groups and amine groups from PEG or PEG‐FA. The LbL assembly and the covalent functionalization were monitored by means of ζ‐potential measurements and the quartz crystal microbalance with dissipation technique (QCM‐D). Protein adsorption after incubation of the NPs in culture medium containing optionally the serum proteins was investigated and related to cellular uptake. Experiments on cellular uptake showed that after PEGylation the uptake ratio of the NPs decreased significantly, but became three times larger when PEG‐FA was grafted on the NPs instead of the PEG.
Herein, a novel coil‐rod‐coil triblock copolymer with the coil blocks composed of poly(ethylene glycol) methyl ether and the rigid midterm block alternatively connected with isophorone diisocyanate and isophorone diamine is developed. The triblock copolymer can self‐assemble into ellipsoidal micelles in 1‐methyl‐2‐pyrrolidinone. After the addition of a second coil‐selective solvent (water) to the micellar solutions, these ellipsoidal micelles can further transform into chain‐like nanostructures. The self‐assembly behavior is highly influenced by the additional order of the solvents, which is considerably due to the impacts of the hydrogen‐bonding urea groups and rigid motifs. The transition of the ellipsoidal micelles to chain‐like nanostructures is governed by the water molar fractions. The sizes of the chain‐like nanostructures increase first and then decrease with the growth of the water molar fractions in the mixed solutions.
Summary: A series of poly(ether ester)s containing amide and carbamate groups as H‐bonding units and 13–50 mol‐% of poly(ethylene glycol) (PEG) segments were prepared by polycondensation in bulk using Ti(OBu)4 as a catalyst. The copolymers were obtained starting from PEG/1,4‐butanediol mixtures and a synthetic monomer carrying H‐bonding groups. These polymers were designed for biomedical applications, where material biodegradability is required. The influence of the nature of the H‐bonding units, the length of the polymethylene spacer between the H‐bonding groups and the PEG content on the thermal and solubility properties of the copolymers was investigated. Amide‐containing copolymers were more thermally stable than those containing carbamate groups. The PEG content also slightly affected the polymer thermal stability. The DSC traces of all samples presented multiple transitions, whose shape and peak temperature were strongly dependent on the PEG content. Polymer hydrophilicity, surface free energy and equilibrium swelling in phosphate buffer solution (PBS) at 37 °C were mainly influenced by the PEG content, whereas the nature of the H‐bonding groups had little effect.
An H‐bonded main‐chain liquid‐crystalline (LC) polymer was obtained by in situ photochemical conversion from an H‐bonded LC dimer. A bifunctional compound, 1 , having a cinnamoyl group at one end and a carboxylic acid group at the other, was synthesized as the H‐bonded LC dimer. UV irradiation of 1 in the LC phase in the presence of a sensitizer resulted in its conversion to a photodimer, with a carboxylic acid at both ends, through photocycloaddition of the cinnamoyl moiety. The LC phase was maintained during irradiation, because that of the photodimer was more thermally stable than that of 1 . FT‐IR analysis revealed that the carboxylic acids of the photodimer dominantly formed hydrogen bonds in the LC phase, which suggests that the photodimers assembled into an H‐bonded main‐chain LC polymer.
In this work, the synthesis of 3‐methacryloxypropylheptaphenyl POSS, a new POSS macromer (denoted MA‐POSS) is reported. The POSS macromer is used to synthesize PEO‐b‐P(MA‐POSS)‐b‐PNIPAAm triblock copolymers via sequential atom transfer radical polymerization (ATRP). The organic‐inorganic, amphiphilic and thermoresponsive ABC triblock copolymers are characterized by means of nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and atomic force microscopy (AFM) show that the hybrid ABC triblock copolymers are microphase‐separated in bulk. Cloud point measurements show that the effect of the hydrophiphilic block (i.e. PEO) on the LCSTs is more pronounced than the hydrophobic block (i.e. P(MA‐POSS)). Both transmission electron microscopy (TEM) and dynamic light scattering (DLS) show that all the triblock copolymers can be self‐organized into micellar aggregates in aqueous solutions. The sizes of the micellar aggregates can be modulated by changing the temperature. The temperature‐tunable self‐assembly behavior is interpreted using a combination of the highly hydrophobicity of P(MA‐POSS), the water‐solubility of PEO and the thermoresponsive property of PNIPAAm in the triblock copolymers. 相似文献
In this paper, we report a simple and effective method for the preparation of stable core‐crosslinked micelles after the self‐assembly of thymine‐functionalized polystyrene (PVBT) and adenine‐terminated poly(ethylene oxide) (PEO‐A) homopolymers, and subsequent bioinspired photo‐crosslinking of the thymine units in PVBT. We obtained “graft‐like” copolymers from the interactions of PEO‐A with the PVBT chains through complementary multiple hydrogen bonding in a common solvent (dimethylformamide) after the addition of selective solvents (H2O and MeCN for PVBT and PEO‐A, respectively). Stable micelles featuring PVBT as the core and PEO‐A as the shell were formed via selective solvent pairs; they were clearly visualized using transmission electronic microscopy and staining techniques. The shapes and sizes of the core/shell micelle structures did not change after exposure to UV light, revealing the enhanced dimensional stability of these photo‐core‐crosslinked micelles. 相似文献
The preparation and structural organization of a new bioinspired nanomaterial are investigated. A hybrid conjugate is obtained by end‐linking a linear octapeptide with regular alternating enantiomeric sequence to poly(ethylene glycol). This conjugate is able to self‐assemble, forming well‐defined nanorods having core/shell morphology with an internal peptide single channel that has, for the first time, been clearly visualized by transmission electron microscopy (TEM) images. It is remarkable that well‐defined cylindrical nanoparticles can be formed starting from a linear oligopeptide, the synthesis of which is significantly easier than that of the homologous cycles. In addition, the synthetic strategy and the structure of the conjugate ensure a controlled and regular pegylation of the aggregates and high density PEG blocks in the corona, making the nanoparticles more resistant to phagocytosis and able to prevent biofouling. Such features, along with biocompatibility and stability, make these nanoparticles promising candidates for drug delivery.
The amphiphilic triblock copolymer PLA‐b‐PLL‐b‐MPEG is prepared in three steps through acylation coupling between the terminal amino groups of PLA‐b‐PZLL‐NH2 and carboxyl‐terminal MPEG, followed by the deprotection of amines. The block copolymers are characterized via FT‐IR, 1H NMR, DSC, GPC, and TEM. TEM analysis shows that the triblock polymers can form polymeric micelles in aqueous solution with a homogeneous spherical morphology. The cytotoxicity assay indicates that the final triblock polymer micelles after deprotection show low cytotoxicity against Bel7402 human hepatoma cells. MPEG and PLL were introduced into the main chain of PLA affording a kind of ideal bioabsorbable polymer materials, which is expected to be useful in drug and gene delivery.
Injectable polymeric hydrogels with self‐healing property are extremely appealing in biomedical applications for the reason that they could be transplanted via direct injection, which causes minimal invasion to human body. This work presents a novel injectable hydrogel based on strong interaction of quadruple hydrogen bonding from ureido pyrimidinone (UPy) moieties. A new monomer ureido pyrimidinone‐diisocyanate‐2‐hydroxyethyl‐methylene acrylic ester (named UPy‐NMA) carrying UPy moiety is synthesized for the first time and copolymerized with acrylamide to prepare hydrogel copolymer (PAU). The hydrogel is prepared by dissolving corresponding copolymer into deionized water under certain conditions. Mechanical property of prepared hydrogel is measured by rheometer and the results show that the developed hydrogel display excellent self‐healing ability as well as outstanding injectable property. In addition, adequate pore size of hydrogels from scanning electron microscopy also hints that the fabricated hydrogel can provide an intriguing glimpse for potential applications of tissue engineering.
下载免费PDF全文