Transparent film materials with excellent mechanical and thermal properties were elaborated by drying a latex suspension of armored polymer/Laponite composite particles. Low‐temperature TEM observation of ultrathin cross‐sections of the films indicated a unique network morphology characterized by a “honeycomb” distribution of the Laponite platelets remindful of the original particles morphology.
Summary: A new calix[4]arene‐based periodic mesoporous organosilica has been synthesized using tetraethoxysilane (TEOS) and a calix[4]arene‐based silane monomer as the precursors and cetyltrimethylammonium bromide (CTAB) surfactant as the structure‐directing template, and is shown to be capable of visual detection and entrapment of NO2.
Synthesis of the novel mesoporous organosilica material containing covalently bound tetra‐O‐alkylated calix[4]arene hosts. 相似文献
Random copolymers of poly(9,9‐di‐n‐octylfluorene) (PF8) incorporating 0, 8, 12, 15, and 20% dibenzothiophene (DBT), and copolymers with 2, 5, 8, 12, and 15% dibenzothiophene‐S,S‐dioxide (S‐unit) were synthesised. Absorption and emission spectra of thin films indicate that the DBT system shows a linear decrease of toluene vapour induced β phase with increasing DBT content to a 20% cutoff, whilst in the S‐unit copolymers the β phase is present up to 12% co‐monomer content, and at 15% the characteristic absorption peak is absent or masked. These results demonstrate the limits, in thin films, at which the β phase can be formed in widely used PF8 copolymer systems for device applications and clearly show that it is practical to use copolymers having electron or hole transport units in the polyfluorene backbone and still be able to form efficient β phase emission sites.
Novel linear poly(NIPA‐co‐CL) copolymers have been synthesized by radical copolymerization of N‐isopropylacrylamide (NIPA) and 2‐methylene‐1,3‐dioxepane (MDO). The structure of copolymers was confirmed by 1H NMR and IR spectroscopy. Cross‐linked poly(NIPA‐co‐CL) hydrogels have also been prepared in toluene using N,N′‐methylenebisacrylamide as cross‐linking agent. The hydrogels thus obtained exhibit good temperature response and are biodegradable in the presence of proteinase K.
Temperature influence on the enzymatic degradation by proteinase K of poly(NIPA‐co‐CL) hydrogel (G‐60). 相似文献
Summary: Heparin, a potent anticoagulant, has been used for the first time for the synthesis of PPy nanowires serving not only as an anion dopant but also as an effective morphology‐directing agent. The obtained PPy nanowires exhibit long and fine structures with smooth surface and the average diameter of the nanowires is about 90–100 nm and lengths are several hundred nanometers to micrometers. The possible formation mechanism of PPy nanowires may be related to the chain structure of heparin with functional groups ( SO and COO−) on the surface. The effect of concentrations of pyrrole monomers and heparin on the morphology and size of PPy nanowires has been investigated.
SEM image of PPy nanowires synthesized in the presence of heparin. 相似文献
Thiol‐responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono‐cleavable block copolymers, ss‐ABP2) were synthesized by atom transfer radical polymerization in the presence of a disulfide‐labeled difunctional Br‐initiator. These brush‐like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and 1H NMR results confirmed the synthesis of well‐defined mono‐cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self‐assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL−1. In response to reductive reactions, disulfides in thiol‐responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller‐sized assembled structures in water. Moreover, in a biomedical perspective, the mono‐cleavable block copolymer micelles are not cytotoxic and thus biocompatible.
A novel amphiphilic diblock copolymer composed of a hydrophilic poly(ethylene oxide) block and a hydrophobic block copolymerized by azobenzene‐containing methacrylate and N‐isopropylacrylamide was synthesized using ATRP. The polymer micelles showed dual responsiveness to heat and light. The size of the micelles was dependent on temperature and the encapsulated substance in the hydrophobic cores was released during heating and cooling processes. The hydrophobicity of the micellar cores appeared as a reversible change in response to light with neither disruption of the micelles nor leakage of the encapsulated substance while H‐aggregation of the azobenzene moieties was detected.
α‐Methoxy‐ω‐alkyne poly(ethylene glycol) (PEG) was tagged with pendent N‐hydroxy‐succinimidyl activated esters by photografting of a molecular clip. This easily synthesized heterofunctional PEG was found to be a versatile building block for (i) conjugation with an amino derivative and (ii) grafting to azido functional aliphatic polyesters backbone by Huisgen's 1,3‐dipolar cycloaddition. This original combination of “clip” and “click” reactions provides a versatile and straightforward pathway for the synthesis of functional amphiphilic and degradable copolymers valuable for biomedical applications such as in drug‐delivery.
A new copolymer bearing a cysteine moiety, designed for molecular interaction, metal‐ion detection, and chiral recognition, was synthesised starting from the dibromo derivative of methyl N‐(tert‐butoxycarbonyl)‐S‐thien‐3‐ylcysteinate and distannylthiophene through a Stille coupling reaction. UV‐vis spectroscopy, circular dichroism, NMR spectroscopy, and gel permeation chromatography analyses evidenced that this polymer is able to form self‐assembling structures, through the formation of a hydrogen‐bond network, not only in the solid state but also in solution.
Summary: Amphiphilic graft polyphosphazenes (EtTrp/PNIPAm‐PPP) with different mole ratios of hydrophobic groups to hydrophilic segments were synthesized by ring‐opening polymerization and subsequent substitution reactions. The self‐assembly behavior of these graft copolymers was studied in detail by TEM, SEM, CLSM, and AFM. Depending on the copolymer composition and common organic solvent employed in dialysis process, supramolecular aggregates ranging from network, nanospheres, high‐genus particles to macrophage‐like aggregates were produced with graft copolymers.
Two novel monovinyl β‐cyclodextrin (β‐CD) monomers are synthesized. Their chemical compositions are characterized by means of element analysis, NMR and FT‐IR spectroscopy. The results show that the synthesis techniques used are convenient and efficient. Using N‐isopropylacrylamide as a comonomer, two novel linear copolymers can also be synthesized.
Summary: Copolymers of poly(ethylene oxide) (PEO) and 5,5′‐azodisalicylic acid (Olsalazine, OLZ) were synthesized and evaluated by hydrolysis and in‐vitro biodegradation with azoreductase. It was found that changing the molecular weight of the PEO blocks affected the loading ratio of OLZ, and resulted in significant differences in the hydration and degradability of the copolymers. These novel azo‐containing copolymers can be used in colon‐specific drug delivery.
Release of 5‐ASA from OLZ and PEO‐OLZ copolymers incubated with rat cecum content in the presence of benzyl viologen and α‐D ‐glucose. 相似文献
Summary: The cationic ring‐opening copolymerization behavior of SOC1 with BOXT and the properties of the obtained cross‐linked copolymers are described. SOC1 and BOXT are cationically copolymerized under various feed ratios to obtain the corresponding cross‐linked copolymers in 73–96% yields. The volume change during copolymerization could be controlled by the addition of SOC1 to obtain non‐shrinking or volume‐expanding copolymers. The glass transition temperatures (Tg) of the copolymers also decrease linearly with the feed ratio of SOC1, which suggests that the introduction of the flexible poly(SOC1) segment into the rigid BOXT cross‐linked segment relieves the internal stress in the resins that severely degrade their mechanical properties.
Summary: A chitin‐xylan hybrid polysaccharide having β(1 → 4)‐linked alternating structure of N‐acetyl‐D ‐glucosamine and D ‐xylose was synthesized via chitinase‐catalyzed polymerization. An oxazoline derivative of D ‐xylosyl‐β(1 → 4)‐N‐acetyl‐D ‐glucosamine ( 1 ) was effectively polymerized by the catalysis of chitinase from Bacillus sp., giving rise to a water‐soluble chitin‐xylan hybrid polysaccharide ( 2 ) in good yields. Molecular weights ( ) of 2 reached 1 500, which corresponds to 8–10 saccharide units.
A chitin‐xylan hybrid polysaccharide ( 2 ) synthesized via chitinase‐catalyzed polymerization. 相似文献
The layer‐by‐layer (LBL) assembly of poly(diallyldimethylammonium chloride) and poly(sodium styrene sulfonate) on poly(sulfo propyl methacrylate) brushes resulted in films with nanometer‐ and micrometer‐sized holes and ledges, observed by atomic force microscopy and scanning electron microscopy. Polyelectrolyte assembly was followed by the quartz microbalance technique. The formation of ledges and holes is explained by the interaction of the brush polymers with the incoming polyelectrolytes during the LBL assembly, inducing a spatially localized and self‐organized accumulation of the assembled polymers.
Supramolecular poly(vinyl acetate) PVAc 3‐arms stars were successfully generated by Reversible Addition–Fragmentation chain Transfer (RAFT)‐polymerized chains bearing hydrogen‐bonding heterocomplementary associating units. Chain Transfer Agents (CTA) bearing thymine‐ and diaminopyridine‐based units were first synthesized and proved to mediate efficiently the polymerization of VAc. The binding ability of the chains in solution was then demonstrated by 1H NMR and GPC measurements, proving the formation of the supramolecular stars.
The self‐assembly of two types of linear ABA triblock copolymers confined in cylindrical nanopores is studied using simulated annealing. The effects of pore size and block copolymer chain architecture on morphology, chain conformations and bridging fraction are investigated. For the bulk cylinder‐forming copolymers, novel structures such as helices and stacked toroids form, which depend sensitively on the pore size. Several significant differences between the two types of copolymers are predicted and explained based on the differences in their chain conformations and chain architectures. A simple model is proposed to explain the mean square radius of gyration for the bridge and loop chains.
While miniemulsion polymerization has proven to be well‐suited for conducting living/controlled radical polymerizations, emulsion polymerizations have proven to be far more challenging. Ab initio emulsion polymerizations, in which monomer droplets are present during polymerization, have thus far not been successful with TEMPO‐mediated polymerizations, as a result of colloidal instability and coagulum formation. By selectively inhibiting polymerization in the monomer droplets, it is demonstrated that droplet polymerization is responsible for the formation of large (>1 µm) particles that can lead to coagulum formation. Furthermore, we show that coagulum‐free latexes can be produced using a TEMPO‐mediated ab initio emulsion polymerization by suppressing droplet polymerization.
A series of new copolymers with high molecular weight and low polydispersity, prepared from tetrahydroxydinaphthyl, tetrahydroxyspirobisindane, and tetrafluoroterephthalonitrile monomers, prevent efficient space packing of the stiff polymer chains and consequently show intrinsic microporosity. One copolymer, DNPIM‐33, has an excellent combination of properties with good film‐forming characteristics and gas transport performance, and exhibits higher selectivity than the corresponding spirobisindane‐based homopolymer PIM‐1 for gas pairs, such as O2/N2, with a corresponding small decrease in permeability. This work demonstrates that significant improvements in properties may be obtained through development of copolymers with intrinsic microporosity (CoPIMs) that extends the spectrum of high‐molecular‐weight ladder structures of poly(dibenzodioxane)s.
