Covalent organic frameworks (COFs) are an emerging class of photoactive materials, solely composed of light elements. Their ordered structure, crystallinity, and high porosity led to enormous worldwide attention in many research fields. The extensive π-electron conjugation, light-harvesting and charge transport characteristics make them a fascinating polymer for photocatalytic systems. Versatile selection of building blocks and innumerable synthetic methodologies enable them to be a robust platform for solar energy production. In this mini-review, we summarized recent progress and challenges of the design, construction, and applications of COFs-based photocatalysts, and also presented some perspectives on challenges.

A series of novel cis poly(phenylacetylene)s (PPAs) substituted at meta-position(s) by two alkoxycarbonyl pendants, i.e., sP-Me-C8/rP-Me-C8, P-Me-C12, sP-Et-C4, sP-2C4 and sP-Oct-C4, were synthesized under the catalysis of [Rh(nbd)Cl]₂ (nbd = norbornadiene). The dependence of elongation, screw sense, and stimuli response of helical polyene backbone on the structure of pendant, solvent, and temperature was systematically investigated in both solution and solid states. Because of n→π* interaction between vicinal carbonyl groups, sP-Me-C8/rP-Me-C8 could adopt contracted cis-cisoid helix in THF, toluene, CH₂Cl₂, and CHCl₃. Such an intramolecular interaction was sensitive to the hydrogen bond donating ability of solvent and temperature, but insensitive to the dielectric constant and polarity of solvent. In poly(3-methoxycarbonyl-5-alkoxycarbonylphenylacetylene), the longer the chiral alkyl chain was, the easier the stable cis-cisoid helix could be achieved. However, when the methoxycarbonyl was changed to ethoxycarbonyl, sec-butyloxycarbonyl, and octyloxycarbonyl pendant groups, only cis-transoid helix was obtained at room temperature due to the increased steric hindrance. Moreover, lowering temperature was found to facilitate the stabilization of n→π* interactions, and reversible temperature-dependent stereomutations were achieved in sP-Me-C8 and sP-Et-C4 depending on the solvent where they were dissolved. These results suggested that the long alkyl chain, small pendant size, and lower temperature favored the stabilization of intramolecular n→π* interactions and the formation of contracted, cis-cisoid helices for poly(3,5-diester substituted phenylacetylene)s.

Cell behaviors are regulated by a dynamic and complex environment characterized by biophysical, mechanical and biochemical properties. However, most works regulate cell behaviors under static conditions or by external factors. To control cell adhesion and proliferation with a dynamic and mechanical environment, we pattern the surface on self-healing copolymer P(MMA/nBA). The copolymer P(MMA/nBA) with the composition of 48/52 (MMA/nBA) recovers nearly 100% of its original tensile strains after 86 h of recovery from deformation. The physical patterns on P(MMA/nBA) film are obtained over large areas and the size of the hole and the width of connecting bar are in line with the copper grid specifications. The patterned surface tends to be flat after 12 h with almost 75%−80% recovery. Compared with cell incubation on polystyrene flat and patterned surface of P(MMA/nBA) film without self-healing capability, the number and morphology of cells are well manipulated on the patterned surface of self-healing P(MMA/nBA) film. This approach provides a convenient method for dynamically regulating the cell behaviors on the surface of self-healing materials without chemical or biological modifications.

The novel quaternized hydroxypropyl cellulose-g-poly(THF-co-epichlorohydrin) graft copolymers, HPC-g-QCP(THF-co-ECH), have been successfully synthesized to combine the properties from hydrophilic hard HPC biomacromolecular backbone and hydrophobic flexible polyether branches. Firstly, the P(THF-co-ECH) living chains were synthesized by cationic ring-opening copolymerization of THF with ECH. Secondly, P(THF-co-ECH) living chains were grafted onto HPC backbone by reaction with ―OH groups along HPC to produce HPC-g-P(THF-co-ECH) graft copolymers. Thirdly, the mentioned graft copolymers were quaternized by reaction with ternary amine to generate functionalized HPC-g-QCP(THF-co-ECH). The HPC-g-QCP(THF-co-ECH) graft copolymers exhibited good antibacterial ability against S. aureus or E. coli bacteria. The ibuprofen (IBU)-loaded microparticles of HPC-g-(QC)P(THF-co-ECH) graft copolymers were prepared by electrospraying. The in vitro pH-responsive drug-release behavior of IBU reached up to 75% of drug-loaded at pH = 7.4. This quaternized graft copolymer was beneficial to solving the problems of a burst effect and fast release of HPC as drug carriers.

We utilized two structurally different long chains (linear and branched ultra-high molecular weight polyethylene) to reveal the dependence of flow-induced crystallization on long chain architecture, and prepared two bi-disperse systems of 98 wt% short chain and 2 wt% long chain. A flow field was applied to the bi-disperse polyethylene melt by a modified injection-molding machine, known as oscillation shear injection molding (OSIM). For the first time, the structural influence of long chains on flow-induced shish-kebab formation was systematically investigated. For the intermediate layer of OSIM samples, the branched long chains were better than the linear long chains at inducing shish-kebab formation, agreeing with the reported literatures, because the branches can maintain their oriented conformations longer. But unexpectedly, the reverse is the case for the core layer of OSIM samples, where the shear flow was much weaker than the intermediate layer. To understand the unexpected phenomenon, the lifetime of shishes induced by different long chains was compared. Result demonstrated that the linear-induced shishes possessed higher thermal stability than the branched-induced ones so that the linear-induced shishes could survive in the core layer of OSIM samples. Additionally, unlike other methods for flow-induced crystallization, OSIM could create samples for measuring mechanical properties, and thus offer the chance to reveal the relationship between structure and performance. The mechanical results demonstrated that both long chains remarkably enhanced the mechanical properties because of the significant promoting effect of long chains and intense flow fields on shish-kebab formation. However, the linear long chains induced more stable and flawless shishes with higher tensile strength and modulus (80.4 and 1613.5 MPa, respectively) than the branched ones (74.4 and 1489.3 MPa). Our research not only helps elucidate the mechanism of shish-kebab formation but also provides a better choice to reinforce polymers by adding long chains with suitable structure.

Glass fibers (GFs)/epoxy laminated composites always present weak interlaminar shear strength (ILSS) and low cross-plane thermal conductivity coefficient (λ_┴). In this work, silica-sol, synthesized from tetraethyl orthosilicate (TEOS) and KH-560 via sol-gel method, was employed to functionalize the surface of GFs (Si-GFs). Together with a spherical boron nitride (BNN-30), the thermally conductive BNN-30/Si-GFs/epoxy laminated composites were then fabricated. Results demonstrate that Si-sol is beneficial to the improvement of mechanical properties for epoxy laminated composites (especially for ILSS). The BNN-30/Si-GFs/epoxy laminated composites with 15 wt% BNN-30 fillers display the optimal comprehensive properties. In-plane λ (λ_//) and λ_┴ reach the maximum of 2.37 and 1.07 W·m⁻¹·K⁻¹, 146.9% and 132.6% higher than those of Si-GFs/epoxy laminated composites (λ_// = 0.96 W·m⁻¹·K⁻¹ and λ_┴ = 0.46 W·m⁻¹·K⁻¹), respectively, and also about 10.8 and 4.9 times those of pure epoxy resin (λ_// = λ_┴, 0.22 W·m⁻¹·K⁻¹). And the heat-resistance index (T_HRI), dielectric constant (ε), dielectric loss (tanδ), breakdown strength (E₀), surface resistivity (ρ_s) as well as volume resistivity (ρ_v) are 197.3 °C, 4.95, 0.0046, 22.3 kV·mm⁻¹, 1.8 × 10¹⁴ Ω, and 2.1 × 10¹⁴ Ω·cm, respectively.

The microstructural development of bimodal high density polyethylene subjected to tensile deformation was investigated as a function of strain after annealing at different temperatures by means of a scanning synchrotron small angle X-ray scattering (SAXS) technique. Two different deformation mechanisms were activated in sequence upon tensile deformation: intralamellar slipping of crystalline blocks dominates the deformation behavior at small deformations whereas a stress-induced crystalline block fragmentation and recrystallization process occurs at a critical strain yielding new crystallites with the molecular chains preferentially oriented along the drawing direction. The critical strain associated with the lamellar-to-fibrillar transition was found to be ca. 0.9 in bimodal sample, which is significantly larger than that observed for unimodal high-density polyethylene (0.4). This observation is primarily due to the fact that the bimodal sample possesses a greater mobility of the amorphous phase and thereby a reduced modulus of the entangled amorphous network. The conclusion of the mobility of the amorphous phase as a determining factor for the critical strain was further proven by the ¹H-NMR T₂ relaxation time. All these findings contribute to our understanding of the excellent slow crack growth resistance of bimodal polyethylene for pipe application.

A series of novel poly(amide-imide) (PAI) films with different amide contents were prepared from pyromellitic dianhydride and four amide-containing diamines. These PAI films exhibited excellent mechanical and thermal properties with tensile strength of 203.7−297.4 MPa and T_g above 407 °C. The rigid backbone structures combined with strong intermolecular interactions provided PAI films with ultralow in-plane CTE values from −4.17 ppm/°C to −0.39 ppm/°C in the temperature range of 30−300 °C. The correlation between thermal expansion behavior and aggregation structures of PAI film was investigated. The results suggested that hydrogen bonding interactions could be maintained even at high temperature, thus resulting in good dimension reversibility of films in multiple heating-cooling cycles. It is demonstrated that dimensional stabilities of PAI films are determined by the rigidity, orientation, and packing of molecular chains. Heat-resistant PAI films with ultralow CTE can be developed as flexible substrates by regulating backbones and aggregation structures for optoelectronic application.

A rigid aromatic diamine monomer containing di-tert-butylbenzene and dimethyl groups, 3,3′-dimethyl-4,4′-diaminophenyl- 3″,5″-di-tert-butyltoluene, was successfully synthesized by a simple coupling reaction using 3,5-di-tert-butylbenzaldehyde and o-toluidine as starting materials. A series of novel polyimides (PI 3a−3c) with large pendant groups were prepared with the obtained diamine monomer and three different commercial aromatic dianhydrides (3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride) by one-step high temperature polycondensation. The prepared polyimides exhibited high solubility and good membrane forming ability: they could be dissolved not only in some high boiling solvents such as DMF, NMP, DMAc, and m-Cresol at room temperature, but also in some low boiling solvents such as CHCl₃, CH₂Cl₂, and THF. Their solubility in most solvents could exceed 10 wt%, and the flexible membranes could be obtained by casting their solutions. The prepared membranes exhibited good gas separation properties. The permeability coefficients of PI 3c for CO₂ and O₂ were up to 124.6 and 42.8 barrer, respectively, and the selectivity coefficients for CO₂/CH₄ and O₂/N₂ were 14.7 and 3.3, respectively. The membranes had light color and good optical transmission. Their optical transmittance at 450 nm wavelength was in the range of 67%−79%, and the cutoff wavelength was in the range of 310−348 nm. They also had good thermal properties with glass transition temperature (T_g) values in the range of 264−302 °C. In addition, these membranes possessed good mechanical properties with tensile strength ranging between 77.8−87.4 MPa, initial modulus ranging between 1.69−1.82 GPa, and elongation at break ranging between 4.8%−6.1%.

Management of discarded tires is a compelling environmental issue worldwide. Although there are several approaches developed to recycle waste tire rubbers, their application in solid-state cooling is still unexplored. Considering the high barocaloric potential verified for elastomers, the use of waste tire rubber (WTR) as a refrigerant in solid-state cooling devices is very promising. Herein, we investigated the barocaloric effects in WTR and polymer blends made of vulcanized natural rubber (VNR) and WTR, to evaluate its feasibility for solid-state cooling technologies. The adiabatic temperature changes and the isothermal entropy changes reach giant values, as well as the performance parameters, being comparable or even better than most barocaloric materials in literature. Moreover, pure WTR and WTR-based samples also present a faster thermal exchange than VNR, consisting of an additional advantage of using these discarded materials. Thus, the present findings evidence the encouraging perspectives of employing waste rubbers in solid-state cooling based on barocaloric effects, contributing to both the recycling of polymers and the sustainable energy technology field.

We employ finite element method to investigate the kinematics of non-axially positioned vesicles through a pore. To complete the coupling between fluid flow and the vesicle membranes, we use the fluid structure interactions with the arbitrary Lagrangian Eulerian method. Our results demonstrate that the vesicles show different deformations in migration process, in turn an oblique ellipse-shape, slipper-shape, oval-shape. We find that the rotation angle of non-axially positioned vesicles mainly shows the trend of increase, besides the small fluctuation induced by deformation relaxation. Moreover, when the vesicles move towards the axis of the channel, the rotation angle exhibits a decrease because of the decrease of the shear force. However, rotation of axially positioned vesicles hardly occur due to symmetrical shear force. Our results further indicate that the rotation is faster nearby the pore for non-axially positioned vesicles. Our work answers the mapping between the positions of vesicles and deformed states, as well as the change of rotation angle and rotation velocity, which can provide helpful information on the utilization of vesicles in pharmaceutical, chemical, and physiological processes.

A polymer chain usually contains two or more types of monomeric species from the perspective of polymer chemistry, which poses a challenge to the understanding of structure-property relationships. It is of course true in the field of polymer translocation. In the present work, I investigate the translocation dynamics of heterogeneous flexible polymers composed of two types of monomers labeled A and B through a nanopore assisted by binding particles (BPs) by using the coarse-grained Langevin dynamics simulations in two-dimensional domains. Specifically, multiblock copolymers with different block lengths and monomeric components are considered. I critically examine how the translocation dynamics responds to the variations in the block length and the monomeric content. Interestingly, it is found that the periodic structure of a multiblock copolymer causes an obvious fingerprint feature in the residence time of individual monomers in which the number of peaks is exactly equal to the number of blocks. These findings provide a basic understanding about the sequence-dynamics relationship for the BPs-assisted translocation of heterogeneous flexible polymers.