In this work, we designed and synthesized a novel naphthalenediimide-based n-type conjugated polymer PNDICl, which bears asymmetric backbone containing a 3-chlorothiophene unit. The asymmetric structure associated with steric effects of the chlorine atom imparts remarkable solubility to PNDICl in various organic solvents, enabling the fabrication of all-polymer solar cells (all-PSCs) by using an environmentally friendly solvent of d-limonene. Combined with a novel pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione based p-type conjugated polymer P2F-Si with deep highest occupied molecular orbital energy level, the resulting d-limonene-processed all-PSCs presents an impressively high open-circuit voltage of approaching 1.0 V, corresponding to a very small energy loss of 0.49 eV. Through further morphology optimization by using γ-valerolactone, we demonstrated an impressive device efficiency of 4.2%, which is among the best photovoltaic performance of devices processed using d-limonene and comparable to that processed by conventional solvent, suggesting the great promise of using greener solvent for fabricating high-performance all-PSCs.

In this study, wide bandgap (WBG) two-dimensional (2D) copolymer donors (DZ1, DZ2, and DZ3) based on benzodithiophene (BDT) on alkoxyphenyl conjugated side chains without and with different amounts of chlorine atoms and difluorobenzotriazole (FBTZ) are designed and synthesized successfully for efficient non-fullerene polymer solar cells (PSCs). Three polymer donors DZ1, DZ2, and DZ3 display similar absorption spectra at 300−700 nm range with optional band-gap (E_g^opt) of 1.84, 1.92, and 1.97 eV, respectively. Compared with reported DZ1 without chlorine substitution, it is found that introducing chlorine atoms into the meta-position of the alkoxyphenyl group affords polymer possessing a deeper the highest occupied molecular orbital (HOMO) energy level, which can increase open circuit voltage (V_OC) of PSCs, as well as improve hole mobility. Non-fullerene bulk heterojunction PSCs based on DZ2:MeIC demonstrate a relatively high power conversion efficiency (PCE) of 10.22% with a V_OC of 0.88 V, a short-circuit current density (J_SC) of 17.62 mA/cm², and a fill factor (FF) of 68%, compared with PSCs based on DZ1:MeIC (a PCE of 8.26%) and DZ3:MeIC (a PCE of 6.28%). The results imply that adjusting chlorine atom amount on alkoxyphenyl side chains based on BDT polymer donors is a promising approach of synthesizing electron-rich building block for high performance of PSCs.

Photoresponsive linear liquid crystal polymers (LLCPs) are attractive because of the excellent stimuli-responsibility and the good processability. In this study, a new photoresponsive LLCP containing azoester (PC11AE6) with good mesophase stability was synthesized by ring-opening metathesis polymerization. By introducing photoresponsive azoester mesogenic unit, which has high rigidity and a large length-diameter ratio, the resultant polymer possesses a broad mesophase temperature interval (isotropic temperature = 180 °C). A study on mesophase by 2D-wide angle X-ray diffraction indicated that the mesogens were orientated spontaneously into smectic A phase after annealing. The orientated films and fibres exhibited macroscopic, rapid and reversible deformations under light irradiation as a result of the photoisomerization of azoester as confirmed by UV-Vis absorption spectrophotometry. We anticipate that this work provides a strategy for preparing LLCP with a broad mesophase temperature range, which is positive for potential applications.

Photothermal therapy (PTT) is a minimally invasive treatment that kills cancer cells by converting photon energy into heat. The past few decades have witnessed the booming development of photothermal materials, mainly focusing on precious metal nanomaterials and carbon nanomaterials, such as nanogold and silver and nanocarbon materials for near-infrared (NIR) light-triggered PTT. As precious metals are expensive and potentially harmful to humans, exploration and development of a new type of photothermal materials has become a research hotspot in this field. Herein, we report narrow bandgap conjugated polymer nanoparticles (PDPP NPs) based on pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) with intense NIR absorption at 900 nm, as well as a photothermal energy conversion efficiency of 75%. This polymer nanoparticle is essentially non-toxic, as the cell viability of mouse remained more than 90%, even when the concentration of PDPP NPs was at 0.5 mg·mL⁻¹.

Oleanolic acid (OA) is a pentacyclic triterpenoid compound with extensive biological effects, such as anti-inflammatory and anticancer activities. However, the application of OA in chemotherapy is hampered by its poor solubility and severe adverse effects. To solve the problems, we developed a self-assembled nanoparticle platform based on amphiphilic oleanolic acid polyprodrug, poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly(oleanolic acid methacrylate) (POEGMA-b-POAMA), encapsulating 10-hydroxycamptothecin (HCPT) to achieve efficient cancer therapy. The polyprodrug was prepared via reversible addition-fragmentation chain transfer polymerization (RAFT), and could self-assemble to prepare POEGMA-b-POAMA/HCPT nanoparticles (NPs). The obtained nanoparticles exhibited appropriate particle size, excellent drug stability, good drug loading capacity, and high drug loading efficiency. In vitro drug release indicated that the drug release was prolonged to 132 h. The POEGMA-b-POAMA/HCPT NPs enhanced cell cytotoxicity in 4T1 cells and MCF-7 cells and could be efficiently uptaken by 4T1 cells. Furthermore, in vivo antitumor efficiency showed that the POEGMA-b-POAMA/HCPT NPs had great antitumor efficiency with considerably low adverse effects in the treatment of the 4T1 mouse breast tumor xenograft tumor. Therefore, POEGMA-b-POAMA/HCPT NPs provide great potential as a platform for drug delivery applications.

Highly branched poly(β-amino ester)s (HPAEs) have emerged as one type of the most viable non-viral gene delivery vectors, both in vitro and in vivo. However, the effects of different branching strategies on the gene transfection performance have not yet been explored. Here, using triacrylate (B3) and diamine (B4) as the branching monomers, a series of HPAEs were synthesized via the “A2 + B3 + C2” and “A2 + B4 + C2” strategies, respectively. Results show that the branching strategy plays a pivotal role in dictating the physiological properties of the HPAE/DNA polyplexes and thus leads to obviously different cell viability and transfection efficiency. Comparatively, HPAEs synthesized via the “A2 + B3 + C2” branching strategy are more favorable for DNA transfection than that synthesized via the “A2 + B4 + C2” strategy. This study may provide new insights into the development of HPAEs based non-viral DNA delivery system.

A series of polyimide (PI) films derived from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) were prepared with the employment of chemical pre-imidization, and the pre-imidization degree (pre-ID) was found influential on structures and properties of the films obtained. Specifically, a certain degree of chemical imidization could promote the in-plane orientation of molecular chains inside the film, which then enhanced the mechanical strength and reduced the coefficient of thermal expansion (CTE) of the films. Further, such pre-imidization process could expand the internal space gap inside the films, thereby lowering their dielectric constant and glass transition temperature. Our study provides a new approach for preparing high-performance PI films through chemical imidization.

Yolk-shell nanostructures have recently attracted tremendous research interests in various areas because of their unique structural merits. Currently, there is an urgent need for developing porous shells with multifunctional features to enhance their performance in various applications. Herein, advanced yolk-shell nanospheres have been facilely prepared by encapsulating silver nanoparticles with porous Janus polymer shells that consist of a hypercrosslinked polystyrene (xPS) outer layer and a tethered poly(acrylic acid) (PAA) brush lining. The xPS outer layer possesses well-developed porosity as mass diffusion pathways. More importantly, the tethered PAA brushes with customized carboxyl groups exhibit great affinity toward specific species (e.g., cationic dyes), leading to their enrichment from the bulk solution into the interior cavity. The unusual combination of highly porous outer layers with customizable inbuilt polymer linings in the porous Janus shells endows them with great promise for synergistically catalytic degradation of cationic dyes.

The aging behaviors and mechanism of fluoroelastomer (FKM) under lubricating oil (FKM-O) and air (FKM-A, as a comparison) at elevated temperatures were studied from both physical and chemical viewpoints. The obvious changes of mechanical and swelling performances indicate that the coupling effect of lubricating oil and temperature causes more serious deterioration of FKM-O compared to that of FKM-A. Meanwhile, much stronger temperature dependence of both bulk properties and micro-structures for FKM-O is found. Three-stage physical diffusion process is defined in FKM-O due to the competition between oil diffusion and elastic retraction of network. FTIR results reveal that the dehydrofluorination reaction causes the fracture of C―F bonds and produces a large number of C＝C bonds in the backbone. The coupling effect of oil medium and high temperature could accelerate the scission of C＝C bonds and generate a series of fragments with different molecular sizes. The TGA results, crosslinking density V_e, and glass transition temperature T_g derived from different measurements coherently demonstrate the network destruction in the initial stage and the simultaneous reconstruction occurring at the final stage. The newly formed local network induced by reconstruction cannot compensate the break of the original rubber network and thus only provides lower tensile strength and thermal stability.

Polyimide (PI) synthesized from aromatic diamine and dianhydrides via two-step poly-condensation method was highly soluble in TGDDM (MY-720) and DGEBA (E-51) at desirable temperature. TGDDM-PI (M-PI) and DGEBA-PI (E-PI) composites within 0.5%−3% PI loading could be prepared without organic solvent. On the cryogenically fractured surfaces of M-PI and E-PI composites, no obvious heterogeneous phase was observed by SEM. The mechanical properties were promoted significantly by PI, especially for impact strength. Adding 2% PI-2W into MY-720 and E-51 composites, the impact strength increased to 21 and 51 kJ/m², the tensile strength increased by 62% and 19%, and the flexural strength by 18% and 13%, respectively, with slight increases in tensile modulus. These results were related to the promotion in plasticity of composites and changes in fragile→ductile fracture mode. Moreover, T_g and thermal stability of M-PI and E-PI were increased effectively.

This study aims to experiment with the mechanical properties of polypropylene (PP)/thermoplastic elastomer/nano-silica/compatibilizer nanocomposite using the melt mixing method. The addition of polyolefin elastomers has proved to be an approachable solution for low impact strength of PP, while it would also reduce the Young′s modulus and tensile strength. That is why reinforcement would be applied to this combination to enhance the elastic modulus. The mechanical properties of the prepared composites were devised to train an artificial neural network to predict these properties of the system in 6256 unknown points. Therefore, the sensitivity analysis was performed and the share of each input parameter on the respective output values was calculated. Additionally, a novel parameter called nanocomposite evaluation criterion (NEC) is introduced to analyze the suitability of the nanocomposites considering the mechanical properties. Accordingly, the formulation with optimal mechanical properties of toughness, elongation at break, tensile strength, Young′s modulus, and impact strength was obtained.

Deformation-induced phase transition of Form II to Form I in polybutene-1 (PB-1) has been investigated by time-resolved Fourier transform infrared (FTIR) spectroscopy over a wide temperature range from 25 °C to 105 °C. The initial film sample containing orientated lamellae is prepared by pre-stretching of PB-1 melt followed by solidification. This is to realize a homogeneity of subsequent deformation at the mesoscale of lamellar stacks by avoiding large-scale spherulites. The deformation induced phase transition is recognized to occur with two stages: first, Form II undergoes the lamellar fragmentation, slipping or local melting after yielding to activate its transition to Form I, which may be realized by releasing the restrictions on chains translational movements in crystalline phase; second, the phase transition proceeds with a continuous dissipation of external work and determines the tensile mechanical response of film. To quantify the relationship between crystalline transition of Form II to Form I and external tensile field, a simple kinetic equation is well established based on FTIR measurement. The equation can describe not only the dependence of crystal transitional degree on applied specific work, but also the retardation effect of elevating temperature on phase transition.

Nanocomposites of high-density polyethylene (HDPE) modified with 0.2 phr graphene-zinc oxide (GN-ZnO) exhibited optimal mechanical properties and thermal stability. Two other nano-materials—GN and nano-ZnO—were also used to compare them with GN-ZnO. Increasing the content of GN-ZnO gradually enhanced the antibacterial and barrier properties, but the addition of 0.3 phr GN-ZnO led to agglomeration that caused defects in the nanocomposites. Herein, we investigated the antibacterial and barrier properties of HDPE nanocomposites infused with different nanoparticles (GN, ZnO, GN-ZnO) of varying concentrations. HDPE and the nanoparticles were melt-blended together in a Haake-Buchler Rheomixer to produce a new environment-friendly nano-material with improved physical and chemical properties. The following characterizations were conducted: tensile test, thermogravimetric analysis, morphology, differential scanning calorimetry, X-ray diffraction, antibacterial test, and oxygen and water vapor permeation test. The results showed that the crystallinity of HDPE was affected with the addition of GN-ZnO, and the nanocomposites had effective antibacterial capacity, strong mechanical properties, high thermal stability, and excellent barrier performance. This type of HDPE nanocomposites reinforced with GN-ZnO would be attractive for packaging industries.

The design optimization of thermal-driven actuators is a challenging task because the performance depends on multiple materials parameters, structural parameters, and working conditions. In this work, we adopted large scale finite element simulation together with machine learning algorithm to fulfill the on-demand design of thermal actuators. Finite element analysis was used to simulate the performance of thermal actuator with two-layer structure, which generated large amount of dataset by considering the variation of parameters including the moduli, thermal expansion coefficient, sample thickness and length, and temperature. Support vector regression (SVR) was adopted to establish the relationship between multiple input parameters and the resulting contact pressure. Thereafter, a simple interior point algorithm was used to achieve the on-demand design based on the SVR model. The contact pressures of thermal actuator constructed from the optimized parameters deviated less than 15% of the target values.