In our present work, a novel controlled radical polymerization system is developed based on xanthene-9-thione (XT). It was found that the radical polymerization of styrene (St) became controlled in the presence of a small amount of XT. At the early stage of the polymerization, the polymerization rate was relatively low and the as-formed polystyrene (PS) had low number-average molecular weight (M_n) and narrow polydispersity (Ð). After XT was consumed, the polymerization rate increased dramatically and the M_n of PS increased gradually with polymerization proceeding. When the polymerization of St was carried out with a proper molar ratio of initiator to XT and at an appropriate temperature, shortened slow polymerization stage and good control over M_n could be achieved. To further improve the regulating ability of XT, a series of substituent groups (―CF₃, ―CH(CH₃)₂, ―N(CH₃)₂) were introduced onto the xanthene ring of XT, and the effects of these derivatives on the polymerization of St were investigated in detail. UV-Vis spectroscopy was carried out to monitor the concentration of XT during the polymerization and the chemical structure of the as-formed PS was fully characterized by ¹H-NMR and ESI-MS analysis. A possible mechanism involving the formation and evolution of the cross-termination products was proposed to interpret the observed polymerization behavior.

Chronic inflammatory responses induced by macrophages play a pivotal role in the progression of atherosclerosis. In the present study, a multifunctional nanocarrier based on poly(ethylene glycol)-block-poly(L-aspartic acid) grafted with diethylenetriamine, lysine and cholic acid (PEG-PAsp(DETA)-Lys-CA₂) polymer was synthesized for co-delivery of andrographolide and siRNA targeting Notch1 gene to alleviate the inflammatory response in macrophages. The nanocarrier exerted low cytotoxicity as well as high performance in drug/siRNA co-delivery. In vitro studies demonstrated the co-delivery of andrographolide and Notch1 siRNA not only significantly inhibited lipopolysaccharide (LPS)-activated interleukin-6 (IL-6) and monocytes chemotactic protein 1 (MCP-1) expression as well as blocked nuclear factor-κB (NF-κB) signal activation, but also interfered the Notch1 gene expression and increased anti-inflammatory cytokines such as interleukin-10 (IL-10) and arginase-1 expression obviously in macrophages. These results suggested that the combination therapy based on Notch1 siRNA and andrographolide co-delivered nanocarrier, i.e. suppressing the expression of pro-inflammatory cytokines while simultaneously increasing anti-inflammatory factors expression, be a feasible strategy for atherosclerosis treatment.

Response speed is one of the most important evaluation criteria for CO₂ sensors. In this work, we report an ultrafast CO₂ fluorescent sensor based on poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly[N,N-diethylaminoethyl methacrylate-r-4-(2-methylacryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole] [POEGMA-b-P(DEAEMA-r-NBDMA)], in which DEAEMA units act as the CO₂-responsive segment and 4-nitrobenzo-2-oxa-1,3-diazole (NBD) is the chromophore. The micelles composed of this copolymer could disassemble in 2 s upon CO₂ bubbling, accompanying with enhanced fluorescence emission with bathochromic shift. Furthermore, the quantum yield of the NBD chromophore increases with both the CO₂ aeration time and the NBD content. Thus we attribute the fluorescent enhancement to the inhibition of the photo-induced electron transfer between unprotonated tertiary amine groups and NBD fluorophores. The sensor is durable although it is based on " soft” materials. These micellar sensors could be facilely recycled by alternative CO₂/Ar purging for at least 5 times, indicating good reversibility.

In this study we report design of stimuli-responsive coating based on poly(2-methyl-2-oxazoline-random-glycidyl methacrylate) (PMOXA-r-GMA) comb copolymer and poly(acrylic acid)-block-poly(glycidyl methacrylate) (PAA-b-PGMA) block copolymers and scrutinize its ability to control protein adsorption. Firstly, PMOXA/PAA based coatings were prepared by simply spin coating the mixture of PMOXA-r-GMA and PAA-b-PGMA copolymer solutions onto silicon substrates followed by annealing at 110 °C. Then coatings were rigorously characterized by X-ray photoelectron spectroscopy (XPS), the static water contact angle (WCA) test, ellipsometry and atomic force microscopy (AFM). After that, the relationship of switchable behavior of PMOXA/PAA based coatings with PAA content and chain length was investigated through the change of thickness and WCA upon pH and ionic strength (I) trigger, which indicated that the change in thickness and WCA was triggered when PAA contents were increased as well as by increasing chain length of PAA in PMOXA/PAA based coatings. Finally, real-time adsorption/desorption of lysozyme (Lyso) on PMOXA/PAA based coatings was monitored using quartz crystal microbalance with dissipation monitoring (QCM-D). The results showed that the Lyso adsorption amount was increased upon increasing chain length and contents of PAA in PMOXA/PAA based coatings. The adsorbed Lyso was then efficiently desorbed by changing pH and I of medium with the maximum desorption (> 90% desorption percentage) observed for the suitable ratio of PMOXA and PAA while chain length of PAA was kept longer than that of PMOXA. Furthermore, the prepared coatings were found to repeatedly adsorb and desorb Lyso for four successive cycles of adsorption/desorption, which confirmed the stability of prepared coatings.

Imidazolium-based elastomeric ionomers (i-BIIR) were facilely synthesized by ionically modified brominated poly(isobutylene-co-isoprene) (BIIR) with different alkyl chain imidazole and thoroughly explored as novel toughening agents for poly(lactic acid) (PLA). The miscibility, thermal behavior, phase morphology and mechanical property of ionomers and blends were investigated through dynamic mechanical analyses (DMA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), tensile and impact testing. DMA and SEM results showed that better compatibility between the PLA and i-BIIR was achieved compared to the PLA/unmodified BIIR elastomer. A remarkable improvement in ductility with an optimum elongation at break up to 235% was achieved for the PLA/i-BIIR blends with 1-dodecylimidazole alkyl chain (i-BIIR-12), more than 10 times higher than that of pure PLA. The impact strengths of PLA were enhanced from 1.9 kJ/m² to 4.1 kJ/m² for the PLA/10 wt% i-BIIR-12 blend. Toughening mechanism had been established by systematical analysis of the compatibility, intermolecular interaction and phase structures of the blends. Interfacial cavitations initiated massive shear yielding of the PLA matrix owing to a suitable interfacial adhesion which played a key role in the enormous toughening effect in these blends. We believed that introducing imidazolium group into the BIIR elastomer was vital for the formation of a suitable interfacial adhesion.

A series of cross-linked poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/octavinyloctasilasesquioxane (PHBV/OVS) composites were obtained by a simple melt reactive processing technique. Dicumyl peroxide (DCP) and OVS were employed as a free radical initiator and a cross-linking agent, respectively. The chemical structure of these produced composites were identified by ¹H/¹³C/²⁹Si-nuclear magnetic resonance spectroscopy (¹H/¹³C/²⁹Si-NMR) and Fourier transform infrared spectroscopy (FTIR). The melting behavior, non-isothermal crystallization, spherulite morphology and thermal stability property of PHBV/OVS composites were also investigated. The nucleation behaviors and crystallization rate of PHBV/OVS were significantly enhanced with the formation of cross-linked networks with different side-chains and cross-linking points. The red shift of crystalline peak temperature with addition of a small amount of OVS content evidenced the higher crystalline ability compared with the neat PHBV. However there was a threshold content, beyond which the crystallization rate weakened again. Additionally, the cross-linked structure of PHBV/OVS composites could be adjusted by changing the amount of OVS.

Multilayer graphene was prepared by mechanical exfoliation of natural graphite with dioctyl phthalate (DOP) as milling medium without solvent. The obtained mixture could be directly mixed with poly(vinyl chloride) (PVC) for melt-forming, with DOP acting as plasticizer and graphene acting as conductive filler for antistatic performance. The composite showed surface resistance of 2.5 × 10⁶ Ω/□ at 1 wt% carbon additive, significantly lower than approx. 7 wt% of raw graphite required for achieving the same level. This value is low enough for practical antistatic criterion of 3 × 10⁸ Ω/□. The effect of filler addition on mechanical performance was minimal, or even beneficial for the milled carbon in contrast to the case of raw graphite.

Light polymeric soundproofing materials (density = 63 kg/m³) of interest for the transportation industry were fabricated through electrospinning. Blankets of electrospun polyvinylpyrrolidone (average fiber diameter = (1.6 ± 0.5) or (2.8 ± 0.5) µm) were obtained by stacking disks of electrospun mats. The sound absorption coefficients were measured using the impedance tube instrument based on ASTM E1050 and ISO 10534-2. For a given set of disks (from a minimum of 6) the sound absorption coefficient changed with the frequency (in the range 200–1600 Hz) following a bell shape curve with a maximum (where the coefficient is greater than 0.9) that shifts to lower frequencies at higher piled disks number and greater fiber diameter. This work showed that electrospinning produced sound absorbers with reduced thickness (2–3 cm) and excellent sound-absorption properties in the low and medium frequency range.

The achievement of both robust fire-safety and mechanical properties is of vital requirement for carbon fiber (CF) composites. To this end, a facile interfacial strategy for fabricating flame-retardant carbon fibers decorated by bio-based polyelectrolyte complexes (PEC) consisting of chitosan (CH) and ammonium polyphosphate (APP) was developed, and its corresponding fire-retarded epoxy resin composites (EP/(PEC@CF)) without any other additional flame retardants were prepared. The decorated CFs were characterized by SEM-EDX, XPS and XRD, indicating that the flame-retardant PEC coating was successfully constructed on the surface of CF. Thanks to the nitrogen- and phosphorous-containing PEC, the resulting composites exhibited excellent flame retardancy as the limiting oxygen index (LOI) increased from 31.0% of EP/CF to 40.5% and UL-94 V-0 rating was achieved with only 8.1 wt% PEC. EP/(PEC8.1@CF) also performed well in cone calorimetry with the decrease of peak-heat release rate (PHRR) and smoke production rate (SPR) by 50.0% and 30.4%, respectively, and the value of fire growth rate (FIGRA) was also reduced to 3.41 kW·m⁻²·s⁻¹ from 4.84 kW·m⁻²·s⁻¹, suggesting a considerably enhanced fire safety. Furthermore, SEM images of the burning residues revealed that the PEC coating exhibited the dominant flame-retardant activity in condensed phase via the formation of compact phosphorus-rich char. In addition, the impact strength of the composite was improved, together with no obvious deterioration of flexural properties and glass transition temperature. Taking advantage of the features, the PEC-decorated carbon fibers and the relevant composites fabricated by the cost-effective and facile strategy would bring more chances for widespread applications.

Despite the good biodegradable and mechanical properties, poly(lactic acid) still suffers from a highly inherent flammability, which restricts its applications in the electric and automobile fields. In order to improve the flame retardancy of PLA, in this work, melamine polyphosphate (MPP) and zinc bisdiethylphosphinate (ZnPi) were firstly incorporated into PLA, and the synergistic effect of them on flame retardance of PLA was investigated using limiting oxygen index (LOI), UL-94 vertical measurement, scanning electron microscopy (SEM) and cone calorimeter tests etc. The results showed that PLA composite with 15 wt% of MPP/ZnPi (3:2) had the best flame-retardant efficiency with LOI value of 30.1 and V0 rating in UL-94 tests, which was far better than using MPP or ZnPi alone. What is more, although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical properties of PLA. On the premise of maintaining good flame-retardant performance, we improved the toughness of flame-retardant PLA composite, and the impact strength of flame-retardant PLA composite was more than tripled (8.08 kJ/m²) by adding thermoplastic urethanes (TPU). This work offers an innovative method for the design of the unique integration of extraordinary flame retardancy and toughening reinforcement for PLA materials.

The mesoscopic simulation technique was applied to describe the phase separation behavior of polyimide blends and used for design of immiscible polyimide/BN blend films with enhanced thermal conductivity. The simulation equilibrium morphologies of different poly(amic acid) (PAA) blend systems were investigated and compared with optical images of corresponding polyimide blend films obtained by experiment. The immiscible polyimide blend films containing nano-/micro-sized BN with vertical double percolation structure were prepared. The result indicated that the thermal conductivity of polyimide blend film with 25 wt% nano-sized BN reached 1.16 W/(m·K), which was 236% increment compared with that of the homogenous film containing the same BN ratio. The significant enhancement in thermal conductivity was attributed to the good phase separation of polyimide matrix, which made the inorganic fillers selectively localized in one continuous phase with high packing density, consequently, forming the effective thermal conductive pathway.