Graphene oxide (GO), which consists of two-dimensional (2D) sp² carbon hexagonal networks and oxygen-contained functional groups, has laid the foundation of mass production and applications of graphene materials. Made by chemical oxidation of graphite, GO is highly dispersible or even solubilized in water and polar organic solvents, which resolves the hard problem of graphene processing and opens a door to wet-processing of graphene. Despite its defects, GO is easy to functionalize, dope, punch holes, cut into pieces, conduct chemical reduction, form lyotropic liquid crystal, and assemble into macroscopic materials with tunable structures and properties as a living building block. GO sheet has been viewed as a single molecule, a particle, as well as a soft polymer material. An overview on GO as a 2D macromolecule is essential for studying its intrinsic properties and guiding the development of relevant subjects. This review mainly focuses on recent advances of GO sheets, from single macromolecular behavior to macro-assembled graphene material properties. The first part of this review offers a brief introduction to the synthesis of GO molecules. Then the chemical structure and physical properties of GO are presented, as well as its polarity in solvent and rheology behavior. Several key parameters governing the ultimate stability of GO colloidal behavior, including size, pH and the presence of cation in aqueous dispersions, are highlighted. Furthermore, the discovery of GO liquid crystal and functionalization of GO molecules have built solid new foundations of preparing highly ordered, architecture-tunable, macro-assembled graphene materials, including 1D graphene fibers, 2D graphene films, and 3D graphene architectures. The GO-based composites are also viewed and the interactions between these target materials and GO are carefully discussed. Finally, an outlook is provided in this field, where GO is regarded as macromolecules, pointing out the challenges and opportunities that exist in the field. We hope that this review will be beneficial to the understanding of GO in terms of chemical structure, molecular properties, macro-assembly and potential applications, and encourage further development to extend its investigations from basic research to practical applications.

Polymerization of 2-(4-halophenyl)-1,3-butadiene (2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex (1) activated by [Ph₃C][B(C₆F₅)₄] and AlⁱBu₃ shows high cis-1,4-selectivity (>98%) for the polymerization of 2-XPB (2-XPB = 2-FPB, 2-ClPB and 2-BrPB) to afford halogenated plastic poly(dienes) with glass transition temperatures of 30–55 °C. Moreover, the copolymerization of 2-XPB with isoprene (IP) has also been achieved by this catalyst, and the insertion ratios of 2-XPB can be facilely tuned in a full range of 0%–100% simply by changing the 2-XPB-to-IP ratio. Quantitative hydrogenation of cis-1,4-poly(2-XPB) results in perfect alternating ethylene-halostyrene copolymers, and an alternating copolymer of 4-vinylbenzoic acid with ethylene is obtained by a consecutive reaction of ethylene-4-bromostyrene copolymer with ⁿBuLi, CO₂ and HCl.

Flexible strain sensor has promising features in successful application of health monitoring, electronic skins and smart robotics, etc. Here, we report an ultrasensitive strain sensor with a novel crack-wrinkle structure (CWS) based on graphite nanoplates (GNPs)/thermoplastic urethane (TPU)/polydimethylsiloxane (PDMS) nanocomposite. The CWS is constructed by pressing and dragging GNP layer on TPU substrate, followed by encapsulating with PDMS as a protective layer. On the basis of the area statistics, the ratio of the crack and wrinkle structures accounts for 31.8% and 9.5%, respectively. When the sensor is stretched, the cracks fracture, the wrinkles could reduce the unrecoverable destruction of cracks, resulting in an excellent recoverability and stability. Based on introduction of the designed CWS in the sensor, the hysteresis effect is limited effectively. The CWS sensor possesses a satisfactory sensitivity (GF=750 under 24% strain), an ultralow detectable limit (strain=0.1%) and a short respond time of 90 ms. For the sensing service behaviors, the CWS sensor exhibits an ultrahigh durability (high stability>2×10⁴ stretching-releasing cycles). The excellent practicality of CWS sensor is demonstrated through various human motion tests, including vigorous exercises of various joint bending, and subtle motions of phonation, facial movements and wrist pulse. The present CWS sensor shows great developing potential in the field of cost-effective, portable and high-performance electronic skins.

Self-healing hydrogels with the shear-thinning property are novel injectable materials and are superior to traditional injectable hydrogels. The self-healing hydrogels based on 2-ureido-4[1H]-pyrimidinone (UPy) have recently received extensive attention due to their dynamic reversibility of UPy dimerization. However, generally, UPy-based self-healing hydrogels exhibit poor stability, cannot degrade in vivo and can hardly be excreted from the body, which considerably limit their bio-application. Here, using poly(l-glutamic acid) (PLGA) as biodegradable matrix, branching α-hydroxy-ω-amino poly(ethylene oxide) (HAPEO) as bridging molecule to introduce UPy, and ethyl acrylate polyethylene glycol (MAPEG) to introduce double bond, the hydrogel precursors (PMHU) are prepared. A library of the self-healing hydrogels has been achieved with well self-healable and shear-thinning properties. With the increase of MAPEG grafting ratio, the storage modulus of the self-healing hydrogels decreases. The self-healing hydrogels are stable in solution only for 6 h, hard to meet the requirements of tissue regeneration. Consequently, ultraviolet (UV) photo-crosslinking is involved to obtain the dual crosslinking hydrogels with enhanced mechanical properties and stability. When MAPEG grafting ratio is 35.5%, the dual crosslinking hydrogels can maintain the shape in phosphate-buffered saline solution (PBS) for at least 8 days. Loading with adipose-derived stem cell spheroids, the self-healing hydrogels are injected and self-heal to a whole, and then they are crosslinked in situ via UV-irradiation, obtaining the dual crosslinking hydrogels/cell spheroids complex with cell viability of 86.7%±6.0%, which demonstrates excellent injectability, subcutaneous gelatinization, and biocompatibility of hydrogels as cell carriers. The novel PMHU hydrogels crosslinked by quadruple hydrogen bonding and then dual photo-crosslinking of double bond are expected to be applied for minimal invasive surgery or therapies in tissue engineering.

A series of semi-aromatic polyesters named as Poly(PO-CHO-PA) were facilely synthesized via ring-opening terpolymerization of bio-based cyclohexane oxide (CHO)/propylene oxide (PO)/phthalic anhydride (PA) using economical U1/PPNCl as dual catalyst. The proportion of CHO-PA and PO-PA segments in polymer can be readily altered by changing the feed ratio of CHO/PO because the reactivity ratios of CHO and PO with PA calculated by Fineman-Ross method are comparable. All synthesized amorphous polyesters with various compositions show one T_g ranging from 62 °C to 133 °C. Significantly, the mechanical, thermal and barrier properties of these amorphous semi-aromatic polyesters are also adjustable and investigated for the first time. The results indicate the semi-polyesters exhibit superior thermostability (T_5% ranging from 306 °C to 323 °C) and high tensile strength (40.21−55.7 MPa) that is comparable with polystyrene (PS). Furthermore, Poly(PO-CHO-PA) films possess a promising prospect as packaging materials because of its colorless and highly transparent nature, along with low oxygen and water vapor transmission rate. All above performances may guarantee its potential alternative to commercial PS.

Flexible electrochromic (EC) materials have an urgent demand in the current electronic equipment market due to their technological interest and applications. However, at present, few flexible EC devices developed by industry exist due to some problems and challenges still to be solved such as flexibility. In this work, we have successfully synthesized a novel thiophene-furan (TFu) monomer via Stille coupling reaction, and facilely electrochemically polymerized in a neutral Bu₄NPF₆-CH₂Cl₂ electrolyte system to afford the corresponding poly(thiophene-furan) (PTFu) polymer film with good flexibility. The electrochemical and photoelectrochemical analyses of the as-prepared PTFu demonstrate that it has achieved the improved EC performance compared with pure polyfuran and polythiophene polymers, and as a result it possesses favorable EC parameters manifested as a reasonable ΔT (32.1%), faster response (1.38 s), excellent coloration efficiency (CE, 300.9 cm²·C⁻¹), and after a continuous redox process up to 2000 s, its optical stability can be maintained at 96%, and even after 3000 s, it can still be maintained at 80%. In addition, the successful assembly of the electrochromic device of PTFu film can easily realize the reversible conversion of the color from orange to gray. All these systematic studies suggest that the as-prepared flexible PTFu film is a promising candidate for EC materials and has great potential interest for versatile EC applications.

Recently, hollow filler as an emerging concept is attracting more attention in preparation of mixed matrix membranes (MMMs). Herein, poly(ethylene glycol) microcapsules (PMC) are synthesized via distillation precipitation polymerization and embedded into the polyetherimide (Ultem^®1000) matrix to fabricate MMMs for CO₂ capture. The PMC exhibits a preferential hollow structure within the Ultem matrix to furnish highways within membrane, and thus achieve high gas permeability. Meanwhile, the favorable affinity of poly(ethylene glycol) (PEG) microcapsule with ether oxygen group (EO) towards CO₂ enhances the CO₂ solubility selectivity. Such integration of physical and chemical microenvironments in the as-designed PEG microcapsule affords highly enhanced CO₂ separation performance. Compared to pristine Ultem^®1000, the membrane with 2.5 wt% PMC loading exhibits 310% increment in CO₂ permeability and 22% increment in CO₂/N₂ selectivity, which shows the promising prospects of designing PEG-containing microcapsules as the filler of MMMs for CO₂ capture.

The correlation between aggregates and bound rubber structures in silicone rubbers (S(phr)) with various silica fractions (Φ_Si) has been investigated by contrast matching small-angle neutron scattering (SANS), swelling kinetics, and low-field nuclear magnetic resonance (NMR). Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix (S_MP(phr)) and the filler (S_MS(phr)), respectively. All the data consistently suggest that: (i) There is a critical threshold Φ_Si^c between 10 and 30 phr; below Φ_Si^c, the isolated aggregates are dominant, while beyond Φ_Si^c, some rubber fraction is trapped among the agglomerate; (ii) Φ_Si-independent thicknesses around 7.5 nm (NMR) and 8.6 nm (SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber; (iii) S_MS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less Φ_Si is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated.

The integration of high strength and toughness concurrently is a vital requirement for elastomers from the perspective of long-term durability and reliability. Unfortunately, these properties are generally conflicting in artificial materials. In the present work, we propose a facile strategy to simultaneously toughen and strengthen elastomers by constructing 3D segregated filler network via a simple latex mixing method. The as-fabricated elastomers are featured by a microscopic 3D interconnected segregated network of rigid graphene oxide (GO) nanosheets and a continuous soft matrix of sulfur vulcanized natural rubber (NR). We demonstrate that the interconnected segregated filler network ruptures preferentially upon deformation, and thus is more efficient in energy dissipation than the dispersed filler network. Therefore, the segregated filler network exhibits better reinforcing effects for the rubber matrix. Moreover, the excellent energy dissipating ability also contributes to the outstanding crack growth resistance through the release of concentrated stress at the crack tip. As a result, the strength, toughness and fatigue resistance of the nanocomposites are concurrently enhanced. The methodology in this work is facile and universally applicable, which may provide new insights into the design of elastomers with both extraordinary static and dynamic mechanical performance for practical applications.

We adopt Langevin dynamics to explore the stress-structure relationship of telechelic reversible associating polymer gel during start-up shear flow, with shear strengths varying from W_i=12.6 to W_i=12640. At weak shear flow W_i=12.6, the shear stress proportionally increases with shear strain at short times, followed by a strain hardening behavior and then passes through a maximum (σ_max, γ_max) and finally decreases until it reaches the steady state. During the evolution of stress, the gel network is only slightly broken and essentially maintains its framework, and the strain hardening behavior originates from the excessive stretching of chains. On the other hand, the stress-strain curve at intermediate shear flow W_i=505.6 shows two differences from that at W_i=12.6, namely, the absence of strain hardening and a dramatic increase of stress at large strains, which is caused by the rupture of gel network at small strains and the network recovery at large strains, respectively. Finally, at very strong shear flow W_i=6319.7, the gel network is immediately broken by shear flow and the stress-strain curve exhibits similar behaviors to those of classical polymeric liquids.