The controlled synthesis of poly(oligo(2‐ethyl‐2‐oxazoline)methacrylate) (P(OEtOxMA)) polymers by Cu(0)‐mediated polymerization in water/methanol mixtures is reported. Utilizing an acetal protected aldehyde initiator for the polymerization, well‐defined polymers are synthesized (>99% conversion, Ð < 1.25) with subsequent postpolymerization deprotection resulting in α‐aldehyde end group containing comb polymers. These P(OEtOxMA) are subsequently site‐specifically conjugated, via reductive amination, to a dipeptide (NH2‐Gly‐Tyr‐COOH) as a model peptide, prior to conjugation to the functional peptide oxytocin. The resulting oxytocin conjugates are evaluated in comparison to poly(oligo(ethylene glycol) methyl ether methacrylate) combs synthesized in the same manner for potential effects on thermal stability in comparison to the native peptide.
Since nanostructured amphiphilic macromolecules capable of affording high ion and water transport are becoming increasingly important in a wide range of contemporary energy and environmental technologies, the swelling kinetics and temperature dependence of water uptake are investigated in a series of midblock‐sulfonated thermoplastic elastomers. Upon self‐assembly, these materials maintain a stable hydrogel network in the presence of a polar liquid. In this study, real‐time water‐sorption kinetics in copolymer films prepared by different casting solvents are elucidated by synchrotron small‐angle X‐ray scattering and gravimetric measurements, which directly correlate nanostructural changes with macroscopic swelling to establish fundamental structure–property behavior. By monitoring the equilibrium swelling capacity of these materials over a range of temperatures, an unexpected transition in the vicinity of 50 °C has been discovered. Depending on copolymer morphology and degree of sulfonation, hydrothermal conditioning of specimens to temperatures above this transition permits retention of superabsorbent swelling at ambient temperature.
Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas‐liquid microfluidic reactor with top‐down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates.
In this work, the synthesis of various halogenated thiophenol derivatives is presented. These thiophenols are used as monomers in light‐initiated SRN1‐type radical polymerization reactions. The method provides easy access to industrially relevant poly(paraphenylene sulfide) and poly(metaphenylene sulfide). The influence of the halide leaving group and of other substituents in the thiophenol monomer on the polymerization process is investigated.
A series of high‐efficiency, full‐color fluorescent elastomers based on polysiloxane matrix prepared by an easy thiol‐ene “click” reaction is reported here. It is found for the first time that the same elastomer can emit transformable colors by conveniently altering the excitation wavelength because of the effect of energy transfer and the “fluorescence switch” of lanthanide ions. A fluent change in emission colors can also be feasible and conveniently reproducible by varying the stoichiometric ratio of lanthanide ions and rhodamine‐B in solution and in polymer elastomers. The obtained elastomers are further coated onto commercially available UV‐LED cells from the solution medium followed by an in situ cross‐linking step.
Carbazole‐based liquid single‐crystal elastomers (LSCEs) are valuable fluorescent flexible materials to perform optical mechanotransduction under ambient conditions. Indeed, the covalent incorporation of carbazole derivatives into nematic LSCEs allows to tune their luminescence on demand under mechanical control in a quick and reversible fashion. Specifically, the fluorescence intensity for these materials can be switched back and forth in less than a second. Moreover, such a process can be performed several times without detecting any sign of fatigue in the system. In addition, these materials show excellent resistance to aging; 2 years after their preparation they exhibit the very same mechanofluorescent behavior as when freshly prepared. In fact, the here reported fluorescent systems are highly sensitive; the application of a force of 70 mN decreases the fluorescence in the elastomeric material by 7%. Thus, mechanical forces are attractive external stimuli to modulate the fluorescence of nematic elastomers rapidly and reversibly enabling thereby mechanotransduction.
The surface of polyacrylonitrile (PAN) film is treated with ethyleneamines (EDA) in a simple chemical vapor phase reaction. Successful introduction of amine functional groups on the cyano group of PAN backbone is verified by FT‐IR and NMR measurements. Further UV‐vis and photoluminescence analyses show a red shift of the emission peak after repeated EDA treatment, which might be attributed to the formation of imine conjugation from newly formed carbon‐nitrogen bonds on the PAN backbone. Further confocal laser scanning microscopy reveals that selective patterning of EDA on PAN films is possible via local polydimethylsiloxane masking. The results indicate that both chemical and optical patterning on PAN film can be realized via a single reaction and show the potential of this novel methodology in selective patterning.
A unique fabrication process of low molar mass, crystalline polypeptoid fibers is described. Thermoresponsive fiber mats are prepared by electrospinning a homogeneous blend of semicrystalline poly(N‐(n‐propyl) glycine) (PPGly; 4.1 kDa) with high molar mass poly(ethylene oxide) (PEO). Annealing of these fibers at ≈100 °C selectively removes the PEO and produces stable crystalline fiber mats of pure PPGly, which are insoluble in aqueous solution but can be redissolved in methanol or ethanol. The formation of water‐stable polypeptoid fiber mats is an important step toward their utilization in biomedical applications such as tissue engineering or wound dressing.
Rewritable optical storage has been obtained in a spiropyran doped liquid crystal polymer films. Pictures can be recorded on films upon irradiation with UV light passing through a grayscale mask and they can be rapidly erased using visible light. Films present improved photosensitivity and optical contrast, good resistance to photofatigue, and high spatial resolution. These photochromic films work as a multifunctional, dynamic photosensitive material with a real‐time image recording feature.
The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.
A new method for fabricating hydrogels with intricate control over hierarchical 3D porosity using microfiber porogens is presented. Melt electrospinning writing of poly(ε‐caprolactone) is used to create the sacrificial template leading to hierarchical structuring consisting of pores inside the denser poly(2‐oxazoline) hydrogel mesh. This versatile approach provides new opportunities to create well‐defined multilevel control over interconnected pores with diameters in the lower micrometer range inside hydrogels with potential applications as cell scaffolds with tunable diffusion and transport of, e.g., nutrients, growth factors or therapeutics.
Five different poly(arylene‐diarylvinylene)s have been synthesized by reductive polyolefination starting from the corresponding bis(α,α‐dichlorobenzyl)‐substituted monomers and dicobaltoctacarbonyl as reducing agent. The resulting polymers all contain main chain tetraphenylethylene units. Thanks to the aggregation‐induced emission effect, the corresponding polymer films show remarkably high photoluminescence quantum yields (PLQYs) of 32%–73%. The polymer with the highest PLQY is tested as solid state sensing material for the PL‐quenching‐based detection of nitroaromatic analytes (1,3,5‐trinitrobenzene as prototypical analyte).
Epoxy polymers (EPs) derived from soybean oil with varied chemical structures are synthesized. These polymers are then cured with anhydrides to yield soybean‐oil‐derived epoxy thermosets. The curing kinetic, thermal, and mechanical properties are well characterized. Due to the high epoxide functionality per epoxy polymer chain, these thermosets exhibit tensile strength over an order of magnitude higher than a control formulation with epoxidized soybean oil. More importantly, thermosetting materials ranging from soft elastomers to tough thermosets can be obtained simply by using different EPs and/or by controlling feed ratios of EPs to anhydrides.
A novel and non‐cytotoxic self‐healing supramolecular elastomer (SE) is synthesized with small‐molecular biological acids by hydrogen‐bonding interactions. The synthesized SEs behave as rubber at room temperature without additional plasticizers or crosslinkers, which is attributed to the phase‐separated structure. The SE material exhibits outstanding self‐healing capability at room temperature and essential non‐cytotoxicity, which makes it a potential candidate for biomedical applications.
Inspired by the multifunctionality of vitamin D‐binding protein and the multiple transient‐binding behavior of some intrinsically disordered proteins (IDPs), a polymeric platform is designed, prepared, and characterized for combined delivery of dermal protective and anticancer bioactive cargos on the basis of artificial single‐chain nano‐objects mimicking IDPs. For the first time ever, simultaneous delivery of folic acid or vitamin B9, and hinokitiol, a relevant natural bioactive compound that exhibits anticancer activity against human malignant melanoma cells, from these multidirectionally self‐assembled unimolecular nanocarriers is illustrated.
The ruthenium benzimidazolylidene‐based N‐heterocyclic carbene (NHC) complex 4 catalyzes the direct dehydrogenative condensation of primary alcohols into esters and primary alcohols in the presence of amines to the corresponding amides in high yields. This efficient new catalytic system shows a high selectivity towards the conversion of diols to polyesters and of a mixture of diols and diamines to polyamides. The only side product formed in this reaction is molecular hydrogen. Remarkable is the conversion of hydroxytelechelic polytetrahydrofuran ( = 1000 g mol−1)—a polydispers starting material—into a hydrolytically degradable polyether with ester linkages ( = 32 600 g mol−1) and, in the presence of aliphatic diamines, into a polyether with amide linkages in the back bone ( = 16 000 g mol−1).
Ethylene–propylene–methyl methacrylate (MMA) and ethylene–hexene–MMA A‐B‐C block copolymers with high molecular weight (>100 000) are synthesized using fluorenylamide‐ligated titanium complex activated by modified methylaluminoxane and 2,6‐di‐tert‐butyl‐4‐methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks.
A special artificial spider silk is presented which is fabricated by using both an elastic polymer and a fiber, and the water collection behavior is investigated. Through exerting tension in varying degree, the length of the three‐phase contact line (TCL) and the area of spindle knot can be regulated readily, which makes a great contribution to the improvement of collecting efficiency and water‐hanging ability. The water‐hanging ability can be predicted at a given stretching ratio according to the given expression of the TCL. As a result, liquid capture or release of distinct measure can be achieved via exerting tension. This research is helpful to design smart materials for developing applications in fogwater collection, dehumidification, high‐efficiency humidity control, and controllable adhesion.
A simplified one‐pot and less harmful method has been introduced for the synthesis of borinic acid monomer. The corresponding borinic acid polymer (PBA) has been prepared by reversible addition‐fragmentation chain transfer polymerization. Property investigations confirm the characteristics of PBA as a new type of “smart material” in the field of thermo‐responsive polymer. The potential application of PBA in the field of enzymatic biofuel cell has been illustrated with a wide open circuit potential of 0.92 V.
By simply blending two diblock copolymers with the same chemistry but with different compositions one is able to create well‐defined larger soft nanoparticles as well as bimodal soft nanoparticles. Specifically, blending two diblock copolymers in a solvent good for both blocks followed by a gradual introduction of a non‐solvent results in a mixed micelle, larger than their pure block‐copolymer‐forming micelles. The formation of well‐defined larger micelle is due to the balance between the ability of the mixed micelles to assemble or merge in comparison to their pure diblock copolymer micelles. Evidently, the blending ratio, the mixing protocol, and non‐solvent addition rate are crucial to achieving well‐defined larger or bimodal micelles.
