Summary: 5‐Fluorouracil‐poly(L ‐lactide) (5‐Fu‐PLLA) microparticles have been prepared by an SEDS process. First, the 5‐Fu is successfully micronized and is then used to produce the 5‐Fu‐PLLA microparticles. The 5‐Fu‐PLLA microparticles synthesized by the SEDS process exhibit a rather spherical shape and a narrow particle size distribution, where it ranges from 615 to 1 990 nm, with a mean particle size of 980 nm. The dichloromethane residue in the 5‐Fu‐PLLA microparticles without any further treatment is 46 ppm. The average drug load and encapsulation efficiency of the 5‐Fu‐PLLA microparticles are 3.05 and 17.8%, respectively. The rate of drug release from the 5‐Fu‐PLLA microparticles shows mainly first‐order kinetics.
Scanning electron spectroscopy image of 5‐Fu‐PLLA microparticles. 相似文献
Novel π‐conjugated coil–rod–coil triblock oligomers containing optoelectronic active oligoaniline segments were synthesized. The block oligomer can self‐assemble into diverse aggregating morphologies including spherical micelles and thin‐layer vesicles in THF, which is found associated with the removing of the protecting groups of oligoaniline segments. A possible mechanism was proposed to explain the self‐assembly behavior changes in which chain conformation variation of the aniline segments initiated from deprotection of the nitrogen atoms is pointed to be the key factor that dominates the transition process.
In this work, the formation of two‐compartment micelles from symmetric pentablock copolymers in selective solvents was studied using the dissipative particle dynamics simulation technique, and the effects of block lengths and solvent quality were investigated. The simulations revealed several new morphologies and their formation mechanisms were elucidated at the molecular level, providing useful information that may contribute to the future rational design and synthesis of novel multicompartment micelles with tailored structures.
Summary: Amphiphilic triblock copolymers (PEOx‐b‐PDMSy‐b‐PEOx) with different block lengths were synthesized and multi‐morphological complex crew‐cut, star‐like, and short‐chain aggregates were prepared by self‐assembly of the given copolymers. The morphologies and dimensions of the aggregates can be well controlled by variation of the preparation conditions. TEM, SEM, FFR‐TEM, and LLS studies show the resulting morphologies range from LCMs, unilamellar or multilayer vesicles, LCVs, porous spheres to nanorods.
TEM images of the vesicles formed from PEO‐b‐PDMS‐b‐PEO. 相似文献
Amphiphilic H‐shaped block copolymers (PTMSPMA)2PEG(PTMSPMA)2 with 91 ethylene glycol (EG) units and four PTMSPMA chains have been synthesized by atom transfer radical polymerization of trimethoxylsilylpropyl methacrylate (TMSPMA) at room temperature in methanol. The structure, molecular weight, and molecular weight distribution have been characterized by 1H NMR spectroscopy and GPC traces. These H‐shaped block copolymers can self‐assemble in DMF/water, and multiple vesicle aggregates from large‐compound vesicles, to multilayer vesicles and unilamillar vesicles are formed. These morphologies can be simply controlled by variation of the chain length ratios.
A series of well‐defined rod‐coil PAA‐b‐DPS block copolymers, containing Fréchet‐type dendronized polystyrene (DPS) with different generation as a rod‐like hydrophobic block and poly(acrylic acid) (PAA) as a hydrophilic coil were synthesized. The procedure included the following steps: the precursor PMA‐b‐DPS copolymer was prepared through ATRP of Fréchet‐type dendritic styrene macromonomer bearing the first to the third generation (G1–G3), respectively, initiated by poly(methyl acrylate) (PMA‐Br). Then, by converting PMA into PAA by subsequent hydrolysis, the targeted amphiphilic copolymers were obtained. Moreover, by using the rod‐coil amphiphiles as building blocks, large compound micelles and vesicles were formed in a binary solvent mixture of DMF/H2O. Morphological changes in self‐assembly showed dependence on the length of the dendronized block.
The micellization of a polysiloxane‐ketimine has been studied in solvents of different polarity, i.e., dimethylformamide (DMF) and toluene. The critical micelle concentration was determined from surface tension measurements ‐in DMF‐, and from viscosity variation with concentration. Metal complex nanoparticles have been synthesized from this macromolecular ligand in DMF and in toluene, using the formed micelles as templates. Spectroscopic data (IR and UV‐vis) confirmed the metal complexation. TEM observations revealed the formation of nanoparticles with different morphologies, which were consistent with the assumed conformation of the ligand in solutions of the two selective solvents.
Some new water‐soluble bis‐porphyrins, constituted of two porphyrin units spaced by means of aliphatic bridges of different lengths, were synthesized and characterized by MALDI‐TOF mass spectrometry, 1H NMR and UV‐vis spectroscopy. The hydrosolubility of these uncharged compounds was guaranteed from the presence of six long PEG chains bound on the peripheral positions of the two porphyrins. Cobalt and zinc derivatives were also prepared. In the case of Co‐bis‐porphyrin, the appearance of induced circular dichroism (ICD) signals in water solution confirmed the formation of stable complexes with some amino acids, in which the bis‐porphyrin behaves like molecular tweezers.
A novel top‐surface imaging process was successfully established using selective chemisorption of amine‐functionalized poly(dimethyl siloxane) onto the carboxylic groups formed on the surface of diazoketo‐functionalized polymer film by UV light irradiation. The chemisorbed poly(dimethyl siloxane) worked as an efficient etch mask for the subsequent oxygen plasma etching process for pattern generation. High‐resolution patterns were resolved with the new imaging process.
Summary: A series of helix‐coil diblock copolymers based on poly(ethylene oxide) and optically active helical poly{(+)‐2,5‐bis[4′‐((S)‐2‐methylbutoxy)phenyl]styrene} (PMBPS) were synthesized via atom transfer radical polymerization (ATRP). The synthetic methodology permitted straightforward preparation of the diblock copolymers with relatively low polydispersities and a broad range of compositions and molecular weights. Depending on the composing block length and the initial concentration, the copolymers self‐assembled into different supramolecular structures in aqueous solution, including spherical micelles, vesicles, multilamellar vesicles, large compound vesicles, and tubules.
Schematic representation of the synthesis of PEO‐b‐PMBPS block copolymers and their aggregation in aqueous solution. 相似文献
The helical mechanoclinic deformation of a main‐chain chiral smectic elastomer, which is prepared by a crosslinking reaction under twist deformation, is investigated. The twist deformation induces a layer tilt angle that depends on the handedness of twist. The layer tilt angle in the right‐handedly twisted elastomer, of which the handedness is consistent with that of the helix in the SmC* phase of the non‐crosslinked backbone polymer, is estimated to be up to 16° at room temperature, although that in the left‐handedly twisted elastomer is less than several degrees. The experiments provide evidence of chiral coupling between tilt and twist for helical mechanoclinic deformation in the chiral smectic system.
A new polyhedral oligomeric silsesquioxane macromer, octakis[N‐(6‐aminopyridin‐2‐yl)undecanamide‐10‐dimethyl‐siloxy]silsesquioxane (POSS‐C11‐Py), containing eight diaminopyridine arms, is able to self‐assemble to form a physically crosslinked polymer‐like structure with good mechanical properties (tensile strength = 46.1 MPa, tensile modulus = 0.58 GPa, elongation = 49.3%) through quadruple hydrogen bonding interactions between these arms. POSS‐C11‐Py is the first organic/inorganic supermolecule possessing polymer‐like mechanical properties as a result of self‐complementary interactions, providing a potential route toward the design and fabrication of polymer‐like supramolecular materials.
Summary: Nylon 6/clay nanocomposites (N6CN) with different cooling histories were investigated by differential scanning calorimetry (DSC) and variable‐temperature X‐ray diffraction (XRD). Above the melting temperature, new endothermic peaks appeared in the DSC trace for N6CN. All the neat nylon 6 samples presented amorphous XRD patterns when heated up to the melting range. However, for N6CN samples, undefined crystalline structures remained in the substantially molten polymer matrix up to 300 °C.
XRD patterns of a quenched nylon 6 sample annealed at 210 °C and N6CN samples annealed at 210, 230, and 300 °C, respectively. 相似文献
This work focused on the synthesis and aqueous self‐assembly of a series of novel hyperbranched star copolymers with a hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] (HBPO) core and many linear poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) arms. The copolymers can synchronously form unimolecular micelles (around 10 nm) and large multimolecular micelles (around 100 nm) in water at room temperature. TEM measurements have provided direct evidence that the large micelles are a kind of multimicelle aggregates (MMAs) with the basic building units of unimolecular micelles. It is the first demonstration of the self‐assembly mechanism for the large multimolecular micelles generated from the solution self‐assembly of hyperbranched copolymers.
Layer‐by‐layer (LbL) assembly was conducted on CaCO3 microparticles pre‐doped with polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles, and resulted in micelles encapsulation in the microcapsules after core removal. Distribution of the micelles in the templates and capsules was characterized by transmission electron microscopy and confocal laser scanning microscopy. The micelles inside the capsules connected with each other to form a chain and network‐like structure with a higher density near the capsule walls. The hydrophobic PS cores were then able to load small uncharged hydrophobic drugs while the negatively charged PAA corona could induce spontaneous deposition of water‐soluble positively charged drugs such as doxorubicin.
Polyaniline‐polypyrrole (PANI‐PPy) nanofibers with high aspect ratios have been synthesized by a one‐step, surfactant‐assisted chemical oxidative polymerization from mixtures of aniline (An) and pyrrole (Py) monomers. PANI‐PPy nanofibers synthesized with an excess of either PANI or PPy show similar spectral (UV‐vis and FT‐IR) characteristics as the individual homopolymers, whereas nanofibers from an equimolar mixture of An and Py display unique spectral characteristics. PANI‐PPy nanofibers undergo a spontaneous redox reaction with metal ions to produce metal nanoparticles with various morphologies and/or sizes. These findings may open new opportunities for synthesizing functional polymer nanofibers and metal nanoparticles with controllable sizes and/or morphologies.
Summary: Raspberry‐like aggregates containing secondary nanospheres were studied. The formation of raspberry‐like aggregates was due to complexation between core‐shell microspheres and core‐corona micelles. The core‐shell microspheres were synthesized with soap‐free polymerization of styrene and methyl acrylic acid, which included carboxyl groups in the periphery. The micelles were self‐assembled by polystyrene‐block‐poly(4‐vinylpyridine), which contained pyridine groups in the corona. The driven force to form raspberry‐like aggregates was due to the affinity between the carboxyl and pyridine groups. The morphology of the raspberry‐like aggregates could be tuned by changing the ratio of the microspheres to micelles. IR measurements suggested that the raspberry‐like aggregates were like zwitterions.
TEM image of the raspberry‐like aggregates formed at a molar ratio of MAA to 4VP at 1:4. 相似文献
A novel well‐defined amphiphilic block copolymer, with the polyhedral oligomeric silsesquioxane (POSS) moiety at the junction of the two blocks of polystyrene and poly(ethylene oxide) (PEO), was designed and synthesized. First, a macroinitiator containing a POSS moiety and a PEO chain was prepared and then atom transfer radical polymerization of styrene was carried out in the presence of the macroinitiator in bulk. The polymerization results show that the process bears the characteristics of controlled/living free radical polymerizations. The structure and molecular weight of the polymers were characterized by GPC, 1H NMR, and FT‐IR spectroscopy. The self‐assembly behaviors of the polymers was investigated by TEM and SEM. It was observed that the polymers can self‐assemble into vesicles in aqueous solution.
A direct access to photochromic polymeric vesicles was demonstrated via polymerization‐induced self‐assembly and reorganization (PISR). The resulting vesicles displayed interesting photochromic behaviors different from that of their free polymer chains in DMF, and the vesicles exhibited stronger fluorescence and excellent photostability due to confinement of conformational flexibility of the polymer chains in aggregates.
