The state-of-the-art of α-helical polypeptides for biomedical applications, with a special emphasis on the manipulation of helix-to-coil dynamic transition, conformation-associated anti-biofouling surfaces, cellular uptake regulation, and reducing immunogenicity of polypeptide-protein conjugates are reviewed.
Sequenced-defined oligomer has been emerged as one of the hot topics in polymer chemistry due to its capability of precisely controlling both chain length and monomer sequence. Recent efforts have focused on development of synthetic methodologies using state-of-the-art chemistry tools. However, investigating the impact of minor changes in monomer sequence on physical properties of these materials is still underdeveloped. Herein, four sequenced pentamers are synthesized by a reversible addition-fragmentation chain transfer (RAFT) single unit monomer insertion technique, in which a base pentamer possesses a relatively rigid backbone comprising of five cyclic monomer units. One of the cyclic units in this base pentamer is replaced by an acyclic monomer at different locations (the 1st, 3rd and 5th unit) to produce three modified pentamers, which leads to a significant decrease of glass transition temperature (Tg) compared to the base pentamer. Meanwhile, the modified pentamers with identical primary structures but distinct monomer sequences also present different Tg values depending on the position of the acyclic monomer unit. The middle (3rd) position of the acyclic unit causes profound decrease of Tg due to its increased molecular flexibility. These synthetic pentamers have been demonstrated to be excellent oligomeric plasticizers to modulate thermal transitions of bulk polymer materials.
Fully chemical recyclable copolymers, P(GBL-co-((R)-M)), with tunable structures and properties were prepared through ring-opening copolymerization of γ-butyrolactone (GBL) and (R)-3,4-trans six-membered ring-fused GBL ((R)-M) by organomagnesium.
We choose pyromellitic anhydride (PMDA) as branching agent in the terpolymerization of PA, PO and CO2, to synthesize branched PPC-P. As expected, the incorporation of PMDA can effectively increase the MW and dramatically decrease the MFI. What is more, the branched PPC-P exhibits reasonable biodegradability for the family of biodegradable plastics.
The α-imino-ketone nickel catalyst is an emerging versatile platform that is easy to prepare and allows for the production of branched high molecular weight functionalized polyethylenes. However, study on this catalyst system is rare thus far. In this contribution, by introducing different backbones, flexible and rigid axial substituents into the α-imino-ketone framework, a family of cationic nickel catalysts were synthesized and fully characterized. Without the addition of any activator, systematic studies on ethylene polymerization and copolymerization with polar monomers were performed to explore the influence of both backbone and axial substituent on catalytic activity, polymer molecular weight, branching density and incorporation. In particular, owing to the unique semi-opening feature of the α-imino-ketone framework, the preferred nickel catalyst exhibited high activity of 175 kg·mol−1·h−1 to produce functionalized polyethylene with molecular weight of 13.4 kg·mol−1 and co-monomer incorporation of 2.9 mol%.
The solventnatures are crucial to deeply reveal solution behavior of macromolecular chains, physical essence of condensed state structures formation of the film as well as the photoelectronic devices performance. Based on the second virial coefficient (A2), effect of the synergistic action of solvents and external electric field on both solution behavior and the film’s condensed state structure for the semi-rigid conjugated polymer, poly[2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylvinylene] (MEH-PPV) was investigated by dynamic/static light scattering, photoluminescence spectroscopy and transmission electron microscopy, etc. It was found that although the MEH-PPV solutions with different solvents (toluene, chlorobenzene, chloroform and tetrahydrofuran) all could generate a response to the external electric field, the degree of response varied significantly with the change of solvent nature. Furthermore, ordered degree of the film from the solutions was also obviously different. The essential reason for this responsive difference was firstly revealed in the research, which actually depended on the degree of interaction between the solute and solvent, and this degree of interaction could be quantitatively described by the second virial coefficient (A2). The bigger the A2, the stronger the interaction between solvent and solute in the solution, and the stronger the response to the external electric field. Further, under the induction of external electric field, chains aggregations with different sizes were formed accompanied by large-scale chains ordered structure in the solution. This ordered structure not only can effectively transfer to film prepared by the precursor solution but also is beneficial to enhance the carrier mobility and device efficiency of the photoelectronic film.
Improvement of the treatment for Glioblastoma multiforme (GBM) especially the development of in situ controllable drug release is still a major concern. In this study, we developed waterborne biodegradable polyurethane (WBPU) scaffolds incorporated with redox-sensitive and RGD-decorated paclitaxel (PTX) polymer-drug conjugates (PDCs) for targeted GBM therapy in situ. The drug scaffolds could be implanted at residual GBM site post-operation. Dual-targeting PTX-PDCs were obtained through step-by-step conjugation of disulfide linked PTX, poly(ethylene glycol) (PEG), and arginine-glycine-aspartic acid (RGD). The RGD-modified PTX-PDCs were spherical nanoparticles (NPs) that would be released from scaffolds and identified GBM cells actively. Internalized redox-sensitive PTX-PDCs would be decomposed and release PTX inside GBM cells under the circumstances of glutathione (GSH). The release profiles of PTX from the scaffolds with/without GSH were investigated. In vitro cytotoxicity assay revealed that the dual-targeting PTX-PDCs from scaffolds could specifically kill GBM cells and protect normal cells, suggesting that dual-targeting PTX-PDC-loaded scaffolds may have the potential to repair tumor-induced brain injury. In vivo anti-recurrence assay indicated that the PTX-PDC-scaffolds could deliver PTX-PDCs to the GBM cells followed by inhibiting tumor growth and inducing apoptosis. In general, the PTX prodrug-loaded devices exhibited significant anti-GBM effects and normal tissue protection simultaneously, indicating that the WBPU scaffolds incorporated with dual-targeting PTX-PDCs may be a promising strategy for local therapy of GBM.
Two competitive processes including post-curing and network destruction occur simultaneously. FTIR and XPS further reveal that the network destruction happens preferentially on the crosslink points of TAIC structure and a schematic degradation process of TAIC structure is proposed according to the results of microscopic experiments.
Novel hybrid fillers were fabricated byin situ synthesizing one-dimensional PPynws on the two-dimensional MoS2, which integrated the good ion polarization ability of PPynws and the high insulation and adjustable band gap of MoS2. An optimal ternary composite with 1 wt% MoS2-PPynws showed a high dielectric constant (15@1 kHz), suppressed dielectric loss (0.027@1 kHz), and high breakdown strength (422.1 mV/m).
Based on the conformation distribution and bending energy theory of worm-like chain, a new method for characterizing plant fiber bending flexibility was developed.
The effect of viscosity of non-translocated (cis) side, ηcis, on the driven translocation of charged polymers through nanopores is investigated using Langevin dynamics simulation. Results show that the translocation of polymer chains can be regulated by changing ηcis. As ηcis decreases, the translocation time τ decreases, and the exponent δ in the scaling relation with driving force f, τ~f−δ, increases whereas α in the scaling relation with chain length N, τ~Nα, decreases. Simultaneously, the conformation of the polymer chain at the cis side gravitates towards an equilibrium state. The results imply a relationship between the translocation and the conformation of polymer chains. To verify this hypothesis, we change the conformation of polymer by artificially relaxing the translocating polymer via adding an additional relaxation time in the simulation. A sufficient large additional relaxation time for the translocating polymer chain at the cis side only or at both cis and trans sides results in exponents α and δ both close to 1, in contrast to α=1.36 and δ=0.8 for the translocation without the additional relaxation. The additional relaxation for the polymer chain at the cis side accelerates the translocation and plays a more important role than that for polymer chain at the trans side.