Amphiphilic hybrid π‐conjugated polymers that have polyhedral oligomeric silsesquioxanes on their side chains have been successfully synthesized by the Sonogashira–Hagihara polycondensation reaction. The obtained polymers were studied with ultraviolet‐visible absorption and photoluminescence spectra. In these polymers, the π‐conjugation length was extended along the poly(p‐phenylene‐ethynylene) backbone. Furthermore, the content of the POSS substituents can influence the aggregation behavior of the polymers and subsequent luminescent properties.
The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.
A polymeric aminoglycoside was prepared by a facile chemoenzymatic reaction. Boc‐protected aminoglycoside, amikacin, was chemoselectively esterified with divinyl sebacate at a hydroxyl group in the C6″ position by protease from Bacillus subtilis. The resulting 3,6′,3″,4?‐tetra‐N‐Boc‐6″‐O‐vinyl sebacate was copolymerized with maltitol 6‐vinyl sebacate to yield a polymeric amikacin. The polymeric amikacin showed a modest inhibitory effect on in vitro protein synthesis, and a little antibiotic activity in minimum inhibitory concentration (MIC) assay in the presence of protease.
The synthesis of Boc‐protected amikacin ester by an enzyme‐catalyzed (protease) esterification. 相似文献
Summary: Poly(vinyl alcohol) (PVA) was derivatized by polymer analogous reaction with thienyl acryloyl chloride and processed to submicrometer fibers by electrospinning from aqueous solution. Water solubility of otherwise water‐soluble PVA fibers was reduced considerably by UV crosslinking of thienyl acrylate modified PVA fibers in the solid state. Water stability of these crosslinked fibers was proven by water steam test at 95 °C.
UV/Vis spectrum of PVA‐Thio fibers irradiated for different periods at 300 nm. 相似文献
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 synthesis of poly(β‐alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring‐opening of 2‐azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(β‐alanine) is obtained. The formation of the polymer is confirmed with 1H NMR spectroscopy and MALDI‐TOF mass spectrometry. The average degree of polymerization of the obtained polymer is limited to = 8 by its solubility in the reaction medium. Control experiments with β‐alanine as a substrate confirmed that the ring structure of the 2‐azetidinone is necessary to obtain the polymer.
Based on the Hammett equation, a general method is established to relate the polycondensation monomer reactivity with both the monomer structural parameters and the properties of the solvent used for the non‐equilibrium ternary copolycondensation to give copolyamides. Linear plots of the logarithm of the monomer reactivity ratio, log r, versus structure parameter ΔpK could be represented by the equation log r = ρΔpK.
Relationship between log r and ΔpK using THF as the solvent. 相似文献
A fluorene diol derivative, 9,9‐bis[4‐(2‐hydroxyethoxy)phenyl]fluorene ( 1 ), reacted with diisocyanates such as 1,3‐bis(isocyanatomethyl)cyclohexane ( 2a ), 1,6‐diisocyanatohexane ( 2b ), and 1,3‐bis(isocyanatomethyl)benzene ( 2c ) under temperature‐controlled microwave irradiation to form the corresponding polyurethanes with being 30 000 to 60 000, measured by GPC with reference to polystyrene standards within 5 to 10 min at 160 to 200 °C. In the reactions of 2a and b , the molecular weights were 15 to 20 times higher than those obtained by conventional oil bath heating. For a solvent of the microwave‐promoted reaction, a hydrocarbon compound, decalin, is preferably used to undergo the polymerization cleanly without unfavorable coloration and/or gelation.
The dual self‐assembling polycondensation of p‐acetoxybenzoic acid (ABA) and p‐acetamidobenzoic acid in Therm S 800 was examined at 300 °C. Needle‐like crystals and lath‐like crystals were formed simultaneously through reaction‐induced crystallization of oligomers at a molar ratio of 30–50 mol‐% ABA in the feed. The needle‐like crystals comprised more p‐oxybenzoyl units, whereas the lath‐like ones contained higher amounts of p‐benzamide moieties.
A new strategy for the synthesis of polyamides from polyesters of hydroxyl‐containing amino acids using a multi O N acyl transfer reaction was developed. This original approach allowed the synthesis of three generations of polymers from the same starting monomer. The polymerization of N‐benzyloxycarbonyl‐serine and its γ‐homologated derivative provided the Z‐protected polyesters; then the water‐soluble polycationic polyesters were obtained by removal of the Z‐protecting group; and finally the polyamides were obtained by a base‐induced multi O N acyl transfer, both in aqueous or organic medium. The key step transfer reaction was monitored by the disappearance and appearance of characteristic NMR proton signals and IR bands of polyesters and polyamides.
The synthesis of P(VA‐co‐VAc)‐graft‐PDMS copolymers has been achieved in microsuspension by direct reaction between an epoxy‐terminated PDMS and some pendant alcohol groups in P(VA‐co‐VAc). In this synthesis, the copolymer is used both as dispersant and reactant. The hydrophilic/hydrophobic character of the final material can be varied at will by incorporating various contents of epoxy‐functionalized PDMS through optimized reaction conditions. The final composition was determined by TGA and 1H NMR. Products prepared from monofunctional PDMS were easily redispersed in water whereas a film of crosslinked materials, arising from difunctional PDMS, showed the best waterproofing as shown by contact angle analysis.
Several poly(ionic liquids) have been synthesized based on poly(1‐vinyl‐3‐tert‐butoxycarbonylmethylene imidazolium) salts with different counterions to investigate the tert‐butyl ester pyrolysis of these compounds. It is found that the counterions strongly influence the temperature of the pyrolysis. The pyrolysis temperature shifts to higher or lower temperatures depending on the nature of the counterions. The use of microwave irradiation was employed to accelerate the gas release because of the high dipolar interaction of amorphous salts with microwaves. The result of these reactions is the formation of organic foams that could be of industrial interest.
Photoinduced microphase separation in block copolymers (BCP) was achieved for the first time, using a rationally designed diblock copolymer composed of two side‐chain liquid crystalline polymers (SCLCP). The miscibility of the two blocks was promoted by the miscibility between the two types of mesognic side groups, while upon UV exposure inducing the trans–cis isomerization of azobenzene mesogens on one SCLCP, the shape incompatibility of bent cis isomers with an ordered liquid crystalline phase drove the separation of the two blocks resulting in a microphase separated morphology. This result shows the perspective of using light to process and organize BCP morphology and related nanostructures in a lithography‐free manner.
Summary: A water‐soluble gold nanoparticle aggregate 2 was prepared by chloroauric acid and a polypseudorotaxane 1 of mono‐6‐thio‐β‐cyclodextrin with poly(propylene glycol) bis(2‐aminopropyl ether) ( ≈ 2 000) in the presence of sodium borohydride in N,N‐dimethylformamide (DMF) solution. The investigative results indicated that the gold nanoparticle aggregate 2 might act as an efficient DNA‐cleavage reagent.
A typical TEM image of gold nanoparticle aggregate 2 . 相似文献
A series of thermo‐responsive PNIPAM copolymers containing different amounts of fulgimide moieties has been synthesized via a polymer analogous reaction of poly(pentafluorophenyl acrylate). All copolymers were designed to exhibit a lower critical solution temperature (LCST) in water, which was only weakly dependent on the amount of incorporated chromophoric fulgimide groups. The copolymers showed a photocyclization of the fulgimide side groups upon irradiation with UV‐light accompanied with a color change. The closed form of the chromophore had a halftime of 136 min for the visible reisomerization and did not affect the LCST of the polymer. This led to the realization of a logic “NOT A” for the fulgimide containing PNIPAM, while a corresponding azobenzene containing PNIPAM resulted in a different logic “A implies B”.
