Thermoresponsive polypeptoids are promising candidates for medical applications due to their biomimetic properties. When such polymers are grafted on magnetic nanoparticles, materials can be obtained that combine a temperature‐triggered solubility transition with magnetic extraction. The synthesis of monodisperse, superparamagnetic iron oxide nanoparticles is described with densely surface‐grafted polypeptoid shells that have tunable thermoresponsive colloidal stability. The synthesis combines ligand exchange with controlled surface‐initiated polymerization of N‐substituted N‐carboxyanhydrides for the preparation of well‐defined core–shell nanoparticles.
A series of highly branched star‐comb poly(ε‐caprolactone)‐block‐poly(l ‐lactide) (scPCL‐b‐PLLA) are successfully achieved using star‐shaped hydroxylated polybutadiene as the macroinitiator by a simple “grafting from” strategy. The ration of each segment can be controlled by the feed ratio of comonomers. These star‐comb double crystalline copolymers are well‐defined and expected to illustrate the influences of the polymer chain topology by comparing with their counterparts in linear‐shaped, star‐shaped, and linear‐comb shape. The crystallization behaviors of PCL‐b‐PLLA copolymers with different architectures are investigated systematically by means of wide‐angle X‐ray diffraction, differential scanning calorimetry, and polarized optical microscopy analysis. It is shown that the comb branched architectures promote the crystallization behavior of each constituent significantly. Both crystallinity and melting temperature greatly raise from linear to comb‐shaped copolymers. Compared to linear‐comb topology, the star‐comb shape presents some steric hindrance of the graft points, which decrease the crystallinity of scPCL‐b‐PLLA. Effects of copolymer composition and chain topology on the crystallization are studied and discussed.
A convenient one‐pot method for the controlled synthesis of polystyrene‐block‐polycaprolactone (PS‐b‐PCL) copolymers by simultaneous reversible addition–fragmentation chain transfer (RAFT) and ring‐opening polymerization (ROP) processes is reported. The strategy involves the use of 2‐(benzylsulfanylthiocarbonylsulfanyl)ethanol (1) for the dual roles of chain transfer agent (CTA) in the RAFT polymerization of styrene and co‐initiator in the ROP of ε‐caprolactone. One‐pot polymerizations using the electrochemically stable ROP catalyst diphenyl phosphate (DPP) yield well‐defined PS‐b‐PCL in a relatively short reaction time (≈4 h; = 9600?43 600 g mol?1; / = 1.21?1.57). Because the hydroxyl group is strategically located on the Z substituent of the CTA, segments of these diblock copolymers are connected through a trithiocarbonate group, thus offering an easy way for subsequent growth of a third segment between PS and PCL. In contrast, an oxidatively unstable Sn(Oct)2 ROP catalyst reacts with (1) leading to multimodal distributions of polymer chains with variable composition.
The control of reactivity of several bis(N‐glycidylsulfonamides) by aromatic substituents is presented. Therefore, disulfonamides with electron‐withdrawing or electron‐donating aryl moieties and a linear, branched, or oxygen‐substituted spacer are synthesized and further N‐alkylated with epichlorohydrin. Their curing times with N,N‐dimethyl aminopropyl amine in comparison with standard bisphenol A diglycidyl ether are measured by oscillatory rheology. A dependence of curing time with the Hammett σ‐value is found.
A family of novel (X‐TATAT)n‐type conjugated polymers based on the carbazole (X), thiophene (T), and benzoxadiazole (A) moieties is designed and explored as electron‐donor materials for organic bulk heterojunction solar cells. Incorporation of the branched side chains of different size and shape affects significantly the optoelectronic properties of the materials, particularly frontier energy levels of polymers translated to the open circuit voltages of the photovoltaic cells. The revealed unprecedented correlation between the parameters of the solar cells (V OC, fill factor (FF), J SC) and bulkiness of the alkyl side chains provides useful guidelines for rational design of novel materials for organic photovoltaics.
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.
Copolymerization of carbon dioxide (CO2) and propylene oxide (PO) is employed to generate amphiphilic polycarbonate block copolymers with a hydrophilic poly(ethylene glycol) (PEG) block and a nonpolar poly(propylene carbonate) (PPC) block. A series of poly(propylene carbonate) (PPC) di‐ and triblock copolymers, PPC‐b‐PEG and PPC‐b‐PEG‐b‐PPC, respectively, with narrow molecular weight distributions (PDIs in the range of 1.05–1.12) and tailored molecular weights (1500–4500 g mol?1) is synthesized via an alternating CO2/propylene oxide copolymerization, using PEG or mPEG as an initiator. Critical micelle concentrations (CMCs) are determined, ranging from 3 to 30 mg L?1. Non‐ionic poly(propylene carbonate)‐based surfactants represent an alternative to established surfactants based on polyether structures.
Dendrigraft poly(l ‐lysine) (DGL) polyelectrolytes, obtained by iterative polycondensation of N‐trifluoroacetyl‐l ‐lysine‐N‐carboxyanhydride, constitute very promising candidates in many biomedical applications. In order to get a better understanding of their structure–property relationships in these applications, their absolute average molecular weights have to be accurately measured. Size‐exclusion chromatography coupled to a multi‐angle laser‐light‐scattering detector (SEC‐MALLS) is known to be the most appropriate analytical tool. These measurements require the determination of the refractive index increment, dn/dc, of these highly branched polycationic macromolecules in aqueous solution. This optical property has to be measured in the same aqueous conditions as SEC‐MALLS eluents. Consequently, data are determined and discussed as a function of different aqueous SEC‐MALLS eluents, as well as different counter‐ions of the many ammonium groups of DGL (generation 3, DGL‐3, used as a model herein). The resulting number‐average molecular weights, , are found to be very dissimilar when the measured dn/dc values are directly considered. In contrast, very close values are obtained (average = 18 700, standard error of 1110 g mol?1) with a low coefficient of variation for such data (ca. 6% for six analyses), when the dn/dc are corrected by the exact lysine amount (measured by the total Kjeldahl nitrogen method).
Random copolymer gels of N‐isopropylacrylamide (NIPAM) and N‐ethylacrylamide (NEAM) are synthesized using different monomer compositions in 1:1 methanol–water mixtures. The samples are characterized by scanning electron microscopy, atomic force microscopy (AFM), and rheological studies. It is observed that with the variation of the monomer compositions in the reaction mixture, the thermoresponsive, morphological, AFM, and rheological properties varied significantly. Porosity and roughness of the gels gradually increase with the gradual increase in NIPAM loading in the gels, lower critical solution temperature, mechanical strength (Young's modulus, storage modulus) significantly decreases with the increase in poly(N‐isopropylacrylamide) loading in the gels. All results can be explained on the basis of the differences in thermoresponsive character of homo‐ and copolymer gels of NIPAM and NEAM in water, their composition in the reaction mixtures, and their different kind of interactions with solvents.
A new synthetic strategy is developed for the synthesis of polyphosphazene bearing stable nitroxide radicals as a pendant group. The resulting material is investigated as a cathode‐active material for rechargeable lithium–ion batteries that performs 80 mAh g−1 capacities at a C/2 current density over 50 cycles. Thus, the inorganic–organic hybrid system can be proposed as an alternative cathode‐active material with improved performance.
The incorporation of Au nanoparticles to polystyrene‐b‐quaternized poly(2‐vinylpyridine) (SQVP) micelles and their interaction with DNA in aqueous solutions is investigated. Micelles of a well‐defined single population in solution keep their size while AuNPs appear to bind near their core, as observed by static and dynamic light scattering. The apparent molecular weight increases as a function of Au concentration, which proves controllable NP loading. Au‐loaded SQVP micelles create complexes with DNA where the micelles still preserve their morphology and size. The fluorescence intensity from SQVP‐Au aggregates drops as Au accumulates on the micelles. The fluorescence spectrum remains practically unaffected by the addition of DNA. SQVP micelles offer a stable and well‐defined template for the formulation of drug and DNA nanocarriers as hierarchically self‐assembled hybrid nanostructured functional materials.
Cationic polyelectrolytes find potential applications in electronic device fabrication, biosensing as well as in biological fields. Herein, a series of cationic main‐chain polyelectrolytes with pyridinium‐based p ‐phenylenevinylene units that are connected via alkylene spacers of varying lengths are synthesized by a base‐catalyzed aldol‐type coupling reaction. Their mean average molecular weights range from 15 000 to 32 000 g mol‐1, corresponding to about 16–33 repeat units. Due to the presence of alkyl side‐chains and alkylene spacers as well as cationic hard‐charges the polymers are endowed with amphiphilic character and hence, aggregation of these polyelectrolytes at high concentration leads to thermoreversible physical gel formation in dimethyl sulfoxide accompanied by interchain interactions. Morphological analysis shows spherical aggregates in case of C16‐Poly‐S12 in dimethyl sulfoxide. Dependence of gelation behavior on the length of alkyl side‐chains and alkylene spacers of the polyelectrolytes are addressed.
Three perylene‐containing conjugated microporous polymers (PrCMPs) are synthesized via Suzuki–Miyaura cross‐coupling reaction from perylene with four polymerizable functional groups and a range of different substituted benzene derivatives. The pore property and bandgap of the resulting PrCMPs can be tuned by changing the comonomer of benzene with different substituted groups and positions. The photocatalytic performances of the polymers are highly dependent on the surface area, geometry, and bandgap of the PrCMPs. It was found that the 1,2,4,5‐linked polymer of PrCMP‐3 shows the highest hydrogen evolution rate (HER) of 12.1 µmol h−1 under UV–vis light irradiation among the three polymers because of its high surface area, broad light absorption, and suitable bandgap. PrCMP‐3 also exhibits good photocatalytic stability for prolonged hydrogen production reaction. This result demonstrates that the crucial role of the linkage geometry offers a general principle for the rational design of conjugated microporous polymer photocatalysts.
Synthesis and investigation of the phase behavior and photo‐optical properties of two chiral liquid‐crystalline polymers with azobenzene‐containing side groups having different spacer lengths, 6 and 10 methylene groups ( PMAzo‐6 and PMAzo‐10 , respectively) are described. Formation of different smectic phases and high‐temperature cholesteric phase is studied by polarizing optical microscope, differential scanning calorimetry, and X‐ray investigations. It is shown that UV‐irradiation induces effective reversible E –Z photoisomerization in polymer solutions and films. Atomic force microscopy (AFM) study reveals substantial changes in the surface topography of the polymer PMAzo‐6 film after UV‐irradiation, whereas PMAzo‐10 surface remains the same. Irradiation by polarized light (457 nm) results in photo‐orientation process in polymer films consequential in significant alignment of the chromophores in direction perpendicular to the polarization plane of the incident light. A significant difference is found in thermal stability of the photoinduced alignment; an annealing of PMAzo‐10 irradiated samples results in a slight decrease of dichroism values (down to 0.57); whereas the dichroism increases up to very high values (0.91) for PMAzo‐6 .
Melting and reorganization of conformationally disordered crystals (α′‐phase) of poly(l ‐lactic acid) (PLLA) are analyzed as a function of the rate of heating in a wide range between about 10?1 and 103 K s?1. It is found for the first time that the reorganization of conformationally disordered α′‐crystals into stable α‐crystals can be suppressed by fast heating. Heating of α′‐crystals of PLLA at a constant rate, faster than 30 K s?1, leads to its complete melting between 150 and 160 °C and suppression of formation of α‐crystals on continuation of heating. Non‐isothermal reorganization of α′‐crystals into α‐crystals only occurs when heating at a rate slower than 30 K s?1. It is evidenced that isothermal reorganization of α′‐crystals into α‐crystals at 150–160 °C proceeds via melting followed by recrystallization rather than a solid–solid phase transition.
Molecular‐recognition‐responsive characteristics of a novel poly(N‐isopropylacrylamide‐co‐benzo‐12‐crown‐4‐acrylamide) (PNB12C4) hydrogel have been investigated. In the prepared PNB12C4 hydrogel, benzo‐12‐crown‐4 (B12C4) groups act as guest molecules and γ‐cyclodextrin (γ‐CD)‐receptors, and poly(N‐isopropylacrylamide) (PNIPAM) networks act as phase‐transition actuators. The formation of stable γ‐CD/B12C4 complexes enhances the hydrophilicity of the PNB12C4 hydrogel networks, and induces positive shift of the volume phase transition temperature (VPTT) of PNB12C4 hydrogel. Moreover, the PNB12C4 hydrogel also shows thermoresponsive adsorption property selectively towards γ‐CD. The γ‐CD‐recognition sensitivity of PNB12C4 hydrogel can be dramatically improved by increasing γ‐CD concentration in solution or B12C4 content in PNB12C4 copolymer networks. The results in this study provide valuable information for developing crown ether‐based smart materials in various applications.
The controlled radical polymerization of 2‐vinylpyridine is reported using commercial blue light‐emitting diodes as visible light source in the presence of S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐aceticacid) trithiocarbonate without exogenous initiators or photocatalysts. With this system, poly(2‐vinylpyridine) with well‐regulated molecular weight and narrow dispersity (?) (? = 1.13) and a conversion efficiency of 84.9% is obtained after 9 h irradiation. The polymerization can be instantly switch “on” or “off” in response to visible light while maintaining a linear increase in molecular weight with conversion and first order kinetics. These results demonstrate the simplicity and efficiency of the photocatalysts‐free, visible light mediated reversible addition fragmentation chain transfer polymerization as a platform to achieve well‐defined poly(2‐vinylpyridine) under mild conditions.
Semi‐interpenetrating polymer network (semi‐IPN) strategy is employed to fabricate uniform microspheres with temperature and pH dual‐responsive behavior, which is composed of poly(N‐isopropylacrylamide) and poly(acrylic acid) in the presence of N ,N ′‐methylenebisacrylamide (MBA) as the cross‐linker. The influences of MBA amount (M m) on the structures and properties of the microspheres are investigated in terms of particle size, surface morphology, pH sensitivity, and thermo‐sensitivity with low critical solution temperature in the range M m = 2.5–15%. Additionally, functional group distributions in the microspheres are probed by titration and employing the Henderson–Hasselbalch equation. The results show that all the properties strongly change depending on M m. Based on transmission electron microscopy and confocal laser scanning microscopy measurements, and these properties, the Mm‐induced changes in the structures of the semi‐IPN microspheres are discussed.
The application of selenol‐X chemistry in nucleophilic substitution and Se‐Michael addition reactions for polymer chain end modification is presented. Selenol‐labeled polystyrene can easily react with alkyl halides, methyl methacrylate, methyl acrylate, pentafluorostyrene, etc. The mild conditions make it attractive for the synthesis of macromonomers. The resulting polymers are analyzed and characterized by UV, size‐exclusion chromatography (SEC), NMR, and matrix assisted laser desorption/ionization time of flight mass spectroscopy.
A low molecular weight hydrazide compound, tetramethylenedicarboxylic di (2‐hydroxybenzohydrazide) (TMBH), greatly improves the crystallization rate and crystallinity of poly(l ‐lactide) (PLLA). The nucleating efficiency of TMBH on the crystallization of PLLA exhibits obvious concentration dependence, which increases first and then decreases slightly with the increase of TMBH loading, reaching a maximum at 0.3 wt%. Time‐resolved Fourier transform infrared spectroscopy spectra indicate that the formation of skeletal conformational ordering structure of PLLA has been accelerated in the presence of TMBH, which can act as efficient precursors speeding up both the nucleation of PLLA on TMBH surface and the formation of intrachain 103 helix structure. The possible hydrogen bonding interaction between the ? OH or ? NH groups in TMBH and the ? C?O groups in PLLA backbones is supposed to be an important factor, which promotes the migration of PLLA chains to TMBH crystallites and the emergence of interchain interactions as well as the conformational ordering.
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