• ISSN 1008-9357
• CN 31-1633/O6
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$v.latestStateEn doi: 10.14133/j.cnki.1008-9357.20201130002 Abstract: Bone defects caused by surgery or trauma pose great essential challenges to modern clinical medicine. The donor limits traditional bone graft therapies. Thus, it is essential to find alternative therapies. Polyether ether ketone (PEEK) and its composites which have an elastic modulus similar to natural human bone and good biocompatibility and chemical stability, can be used as implantable material for spinal, trauma and orthopedic applications, thanks to fatigue resistance and penetrating of X-rays. Excellent wear resistance shows great superiority in artificial joint replacement. The stable chemical resistance and potential antimierobial activity make it play an important role in dental restorations as well. It is a potential material for the treatment of bone defects, but its surface hydrophobicity and biological inertia limit its application in biomedical science. Thus, improving the poor surface performances of PEEK and functioning PEEK become the focus of PEEK study at home and abroad. Inspired by bone tissue composition, structure and function, many strategies have been proposed to change PEEK structure and make PEEK surface functional. In order to make it better used in surgical clinical application, researchers adopted two different strategies of mixed modification and surface modification, so that the obtained PEEK-based material has better biocompatibility, osteointegration, antibacterial, angiogenesis, anti-tumor, immune regulation and multiple regulation properties. In this paper, various modification strategies for improving the biological activity of polyether ether ketone and the application status and prospect of PEEK-based materials in the biomedical field are reviewed. The modification strategies are going through single modification to multi-modification. Multi-modification will become the key of clinic applications of PEEK.$v.latestStateEn  doi: 10.14133/j.cnki.1008-9357.20201221001
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Using acrylamide (AM) as monomer, chitosan (CS) and graphene oxide (GO) as functional components, N, N'-methylene bisacrylamide (MBA) as crosslinking agent, a series of PAM/CS/GO composite hydrogels with three-dimensional network structure were prepared by free radical polymerization. The chemical composition, structure, morphology, and mechanical properties of the composite hydrogels were analyzed using Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffractometer (XRD), scanning electron microscope (SEM), and universal testing machine. The experimental results show that GO is uniformly dispersed in the PAM/CS hydrogel matrix. Compared with PAM/CS hydrogels, PAM/CS/GO hydrogels have a tighter porous structure with an average pore diameter of about 55.7 μm. In addition, the mechanical properties of PAM/CS/GO hydrogels have been significantly improved, the largest elongation at break is 2 039%, and the maximum breaking stress reaches 237 kPa. This is due to the fact that GO acts as a physical crosslinking agent in the PAM/CS hydrogel to form good interface bonds. The hydrogel with cross-linked network structure and plenty of hydrophilic groups can be used as the sensing coating of the quartz crystal microbalance (QCM), and the QCM humidity sensor based on the functional hydrogel film is prepared. The moisture absorption behavior of composite hydrogel films was studied using QCM technology under different humidity conditions. As the air humidity increases from 33% RH to 85% RH, the frequency response of the composite hydrogel film modified QCM sensor increases from 12.2 Hz to 22.3 Hz. This research work provides valuable reference for the application of the hydrogel coating in the field of QCM humidity sensors.
$v.latestStateEn doi: 10.14133/j.cnki.1008-9357.20201216001 [Abstract](14) [FullText HTML](8) [PDF 1352KB](2) Abstract: N,N’-di(4-propargyloxyphenyl) phosphoramide (DPPPA) was successfully synthesized by nucleophilic substitution of 4-propargyloxy aniline and phenylphosphonyl dichloride. The structure of DPPPA was characterized by nuclear magnetic resonance (NMR) and Fourier transformation infrared (FT-IR) analyses. DPPPA was used to mix with bisphenol A of dicyanate ester (BADCy) and bisphenol E of dicyanate ester (BEDCy) in solution. The DPPPA modified cyanate esters (BADCy/DPPPA and BEDCy/DPPPA) were obtained after the solvent was evaporated under vacuum. The thermal properties, limited oxygen index (LOI) and mechanical properties of the modified cyanate esters were studied. The results show that the residual yield at 800 ℃ in air of the cured BADCy/DPPPA and cured BEDCy/DPPPA increase from 0 to 33% and 26% in comparison with the cured neat cyanate esters, and the LOI of the cured modified cyanate esters reach 39.4 and 35.4, but the glass transition temperatures of the cured modified cyanate esters decrease by 19 ℃ and 24 ℃, respectively. The flexural and tensile strength of the cured BADCy/DPPPA are 123 MPa and 45 MPa, which are higher than that of the cured BEDCy/DPPPA. The impact strength of the cured BADCy/DPPPA and BEDCy/DPPPA are 11 kJ/m2 and 14 kJ/m2, respectively. The water absorption of the cured neat cyanate esters decreases with blended with DPPPA.$v.latestStateEn  doi: 10.14133/j.cnki.1008-9357.20201215001
[Abstract](16) [FullText HTML](10) [PDF 2052KB](1)
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As a potential substitute of surgical suture for wound closure use, biomedical/tissue adhesives can be widely used in the repair/regeneration of wounds on soft/hard tissue such as skin, viscera, cardiovascular, bone and teeth, possessing a broad market prospect. However, it is still a challenge for the science community to produce strong adhesion to tissues at wet state. To address this problem, scientists developed a series of biomimetic tissue adhesives by imitating the adhesion strategies of various animals and plants in nature. In this review, the development of various polymeric biomimetic medical/tissue adhesives and their applications in surgical wound adhesion, daily wound care, chronic wound regeneration, bone fracture fixation and other soft/hard tissue repair/regeneration, as well as local drug delivery and in situ therapy are summarized in detail. The future development trend of tissue adhesives is also prospected, including their application potential in the field of medical cosmetology.
$v.latestStateEn doi: 10.14133/j.cnki.1008-9357.2021010700 [Abstract](19) [FullText HTML](8) [PDF 722KB](6) Abstract: The power conversion efficiency of polymer solar cells based on bulk heterojunction is gradually increasing. However, to achieve an ideal donor/acceptor morphology with bicontinuous and interpenetrating network structure is still challenge. Recently, Hongliang Zhong group at Shanghai Jiaotong University and the coworkers developed a new post-treatment strategy, namely hot fluorous solvent soaking (HFSS), to optimize the morphology of the active layer. The treatment of HFSS can anneal the active layer quickly and uniformly. When the selected fluorous solvent is miscible with the residue of processing solvent above upper critical solution temperature, the mixed solvent will further promote the reorganization of the donor/acceptor materials in the film, thereby forming a highly ordered fibrous structure. Consequently, the device shows higher carrier mobility and slightly red-shift absorption spectrum, providing a improved photovoltaic performance. This strategy performed with short processing time at relatively temperature is suitable for various combinations of donor/acceptor materials, including polymer/small-molecule systems, all-polymer and all-small-molecule systems. [Abstract](186) [FullText HTML](92) [PDF 579KB](50) Abstract: Although synthetic biomaterials have great potential and diversity, their biomedical applications are still limited by issues such as biocompatibility, biodegradability, and bioresorbability. Because of the inherent advantages of natural materials in terms of biocompatibility, degradability and absorption, they have become viable substitutes for biomedical applications. Among the many natural materials, proteins have attracted great interest as a new type of biological composites, especially functional biomaterials. Proteins display an essential role in numerous natural systems due to their structural and biological properties. Given their unique properties, protein-based biomaterials show the advantages of inherent biological activity, and do not require excessive functional modification and complex synthesis processes, which can better solve the problems of synthetic materials. Protein-based biomaterials in the form of nanoparticles, nanofibers, microfibers, films, coatings, sponges, foams and gels have been widely used in biomedical fields including tissue engineering, bioelectronics, drug delivery, wound healing, nutraceuticals and pharmaceuticals. Different from the other reviews, this paper reviews the animal and plant-derived protein-based biomaterials for clinical and potential preclinical biomedical applications, and the application prospects are also discussed. [Abstract](69) [FullText HTML](52) [PDF 2184KB](19) Abstract: Reactive oxygen species (ROS) is an important class of intermediate products during the metabolism process, which plays a key role to maintain the normal physiological activities in human body. The overexpression of ROS can lead to a series of inflammatory responses, resulting in a range of acute and chronic human inflammatory diseases. In recent years, the antioxidant materials have become a hot spot applied to scavenge ROS for treating inflammatory diseases. Meanwhile, the hydrogel is regarded as one of the promising materials due to its unique biomimic properties and multiple biofunctions. In this review, we strive to summarize the recent advances in antioxidant hydrogels, including the antioxidant mechanism, the fabrication strategies, and related application in biomedical area. The further perspective on this filed is also carefully discussed. [Abstract](104) [FullText HTML](77) [PDF 1435KB](22) Abstract: A composite core/shell Fe3O4@mSiO2 nanoparticles is synthesized by coating mesoporous silica onto a submicrometer-sized Fe3O4 sphere. A Janus silica cage was synthesized by selectively grafting an hydrophilic polymer amine ended PEG-NH2 containing folic acid (FA) and pH responsive polymer of poly (2-diethylaminoethyl methacrylate) (PDEAEMA) onto the exterior and interior sides of the mesoporous SiO2 shell. The chemical composition and microstructure of Janus cages were studied by SEM, TEM, XRD, FT-IR, UV-VIS and TGA. The results show that the prepared Janus cage has a clear chemical partition and the paramagnetic core inside the cavity is responsible for magnetic collection. Oil-soluble substances can be collected in pH responsive Janus cages at pH>7.2, and controlled release can be achieved at pH<7.2. Furthermore, doxorubicin (DOX) is selected as a model drug, the performance as a responsive drug carrier for loading and controlled release of oil-soluble drugs was investigated. The results showed that Janus cages loaded with drugs could achieve responsive drug release in a simulated tumor pH environment. It has good application potential in the field of targeted drug delivery and responsive release.$v.latestStateEn  doi: 10.14133/j.cnki.1008-9357.20201116001
[Abstract](106) [FullText HTML](65) [PDF 1772KB](38)
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Fluorinated benzoxazines with allyl (BOZF-1), phenyl acetylene (BOZF-2) and propargyl (BOZF-3) were synthesized and used to modify silicon-containing arylacetylene (PSA). The effects of the structure and the content of BOZFs on the properties of modified resin (BOZFs/PSA) were investigated. The curing behavior of BOZFs/PSA resins were studied by differential scanning calorimetry (DSC). The micro-morphology of the blend resin casting was analyzed by Scanning Electron Microscope (SEM). The thermal stability and thermal mechanical properties of the cured BOZFs/PSA resin were analyzed by Thermo Gravimetric Analysis (TGA) and Dynamic Mechanical Analysis (DMA). The dielectric property was also studied. Results showed that the addition of BOZFs resins could improve the toughness of PSA resin, and the bending properties of cured products improved with the increase of benzoxazine mass fraction. Among them, the bending strength of modified resin (w(BOZF-1)=30%) could reach to 28.1 MPa, which was increased by 44.1% compared with PSA resin. The heat resistance of modified PSA resin decreased slightly with the addition of BOZF resin, the 5% mass loss temperature of the cured BOZFs/PSA resin (w(BOZFs) = 10%) was 544,604 ℃ and 584 ℃ in nitrogen, and their residual rate at 1 000 ℃ was 84.4%, 89.0% and 88.1%,respectively. With the addition of BOZFs, dielectric constant of modified resin were slightly increased, but still maintained a good dielectric performance. The cross-section morphology observed by SEM showed that the cast cross-section changed from smooth and flat to with many cracks and ductile fracture zones, which proved that the modified resin changed from typical brittle fracture to ductile fracture.
[Abstract](462) [FullText HTML](270) [PDF 1362KB](46)
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$v.latestStateEn doi: 10.14133/j.cnki.1008-9357.20200718001 [Abstract](256) [FullText HTML](185) [PDF 1653KB](59) Abstract: With the increasing demand for energy resources, the development of efficient electrocatalysts has attracted much attention on energy storage and conversion. As a kind of inorganic-organic hybrid materials, recently crystalline metal-organic frameworks (MOF) have been used as electrocatalysts in electrocatalytic reactions due to their abundant metal nodes and organic linkers, high porosity and large surface area. Particularly, the MOF with the form of thin film form are crucial to achieve effective reactions due to their fast charge transfer and sufficient catalytic sites. Particularly, MOF thin films are coordinated on substrate surfaces by liquid phase epitaxial (LPE) layer by layer (LBL) growth method (called surface-coordinated MOF thin films, SURMOF), which recently have been studied in various fields due to their controlled thickness, preferred growth orientation and homogeneous surface. In this review, the background of electrocatalysis, MOF and SURMOF are briefly introduced at the beginning of this review, then the preparation and electrocatalytic applications of SURMOF and their derived thin films (SURMOF-D) are summarized respectively. Owing to the SURMOF based thin films possess tunable structures, controllable thickness and growth orientation, strong coordination interaction between MOF and substrate surface, and compact film, they can provide abundant catalytic sites and fast charge transfer for efficient electrocatalytic activities in oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CRR), supercapacitor, tandem electrocatalysis and so on. At the end of the review, SURMOF and SURMOF-D for the electrocatalytic applications are also discussed on the current research challenges and problems to be solved. [Abstract](393) [FullText HTML](220) [PDF 1339KB](18) Abstract: Heparin is a kind of glycosaminoglycan with complex structure, which is composed of glucuronic acid and glucosamine. Even though heparin has been used as anticoagulant in clinic for years, growing evidence have indicated its potent capability in anti-metastasis. In recent years, heparin-based anti-tumor drug delivery system has been widely reported. And in these systems, heparin not only enhances the anti-tumor effect of anticancer drugs, but also exhibits its own anti-metastasis function, realizing synergistic anti-tumor and anti-metastasis effects between drugs and drug vesicles. Generally, the heparin-based drug delivery system can be divided into nano-based drug delivery system, micro-based drug delivery system and hydrogel. And this work reviews the rational design of these systems, and possible challenges were also discussed. Column Display Method: 2021, 34(1): 1-4. doi: 10.14133/j.cnki.1008-9357.20200903001 [Abstract](714) [FullText HTML](461) [PDF 681KB](106) Abstract: Organic two-dimensional (2D) materials have become one of the emerging topics, due to their potential unique physical and chemical properties. The preparation of 2D polymers with large area, controllable thickness and long-range ordering features remains challenge. Many new organic 2D materials have been reported in the past few years. However, many organic 2D materials possess obvious disadvantages, including poor crystallinity, limited ordering size. Recently, Xinliang Feng's group at Dresden University of Technology reported the controllable preparation to crystalline two-dimensional polymer by surfactant-monolayer-assisted interfacial synthesis (SMAIS). The key of this method is the surfactant monolayers at the gas-liquid interface can limit molecules or precursors to the 2D interface, for further polymerization. The regulation of the repeating structure and crystallinity of as-prepared 2D polyaniline (2DPANI), 2D polyimide (2DPI) and 2D polyamide (2DPA) were very well studied. This method provides a new strategy for preparation of crystalline organic 2D polymers. 2021, 34(1): 5-25. doi: 10.14133/j.cnki.1008-9357.20200716001 [Abstract](334) [FullText HTML](266) [PDF 1636KB](31) Abstract: Two-dimensional porous polymers (2DPPs) have planar architecture along with numerous attributes, including optical anisotropy, high mobility, reversible redox properties, intrinsic porosity, etc. These features render them promising materials for gas storage and separation, as membranes for fuel cells and as thin-film electrodes for batteries and supercapacitors. 2DPPs can be generally classified as 2D metal-organic frameworks, 2D covalent organic frameworks, graphitic carbon nitride, graphdiyne, and sandwich-like porous polymer nanosheets. Among these, the 2DPPs with sp2-hybridized carbon (\begin{document}${\rm C}_{\rm {sp}^2} $\end{document}) bonding are of great interest. Compared with 2DPPs linked by B―O, C―N, or C=C bonds, \begin{document}${\rm C}_{\rm {sp}^2} \$\end{document}-linked 2D porous polymers have unique optical/electrical properties as well as high chemical-/photo-stability and tunable electrochemical performance due to their fully conjugated feature and tunable bandgap properties. Furthermore, such 2DPPs are one of the best precursors for the fabrication of 2D porous carbons with atomically dispersed transition-metal active sites. In this review, rational synthetic approaches for 2D porous polymers with sp2-C bonding are summarized. Their applications in optoelectronic devices, gas separation, luminescent sensing and imaging, batteries and supercapacitors, and photocatalysis are also discussed.
2021, 34(1): 26-48.   doi: 10.14133/j.cnki.1008-9357.20200615001
[Abstract](834) [FullText HTML](446) [PDF 2082KB](87)
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Hyaluronan (hyaluronic acid, HA) is a linear polysaccharide with disaccharide repeats of D-glucuronic acid and N-acetyl-D-glucosamine. As one of the most important glycosaminoglycans, HA is widely distributed in the human body including the extracellular matrix of the vitreous of the eye and cartilage tissue. The physiological functions of HA in the human body to maintain moisture, regulate osmotic pressure, lubricate joints and absorb shock are closely related to their physicochemical properties and rheological properties. The applications of HA-based functional materials mainly include the following three aspects: (1) Various HA-based derivatives and hydrogels are prepared based on the chemical modifications of hydroxyl, carboxyl, and acetamido groups. (2) HA and its derivatives have been widely used as drug carriers for targeted drug delivery based on HA interacting with receptors on the surface of cancer cells (such as CD44, RHAMM and LYVE-1 receptors). (3) HA hydrogels have been widely used in tissue engineering based on the close relationship between HA and human physiological activities. The HA-based biomaterials and their applications in the biomedical field (such as cancer targeted therapy, wound healing, postoperative adhesion, cartilage regeneration and osteoarthritis treatment) have been summarized in this review.
2021, 34(1): 49-65.   doi: 10.14133/j.cnki.1008-9357.20200713001
[Abstract](937) [FullText HTML](474) [PDF 2096KB](51)
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Polymer stabilized liquid crystals (PSLCs) can help stabilize a variety of microscopic liquid crystalline structures. Generally formed by polymerization in the liquid crystals (LCs), the polymer network can replicate the liquid crystalline order of the LCs. A rich selection of reactive monomers, of isotropic or anisotropic molecular shape, can be utilized for fabricating PSLCs. The presence of polymer networks can stabilize the disclination defects, broaden the temperature range of the LC phase, and improve the electro-optic properties of the devices. PSLCs present excellent performances in the applications such as display, sensing, temperature control, light modulator and smart windows. As a category of smart materials, PSLCs have demonstrated great potential for future smart life, therefore has attracted lots of attention in related research fields. This review introduces the PSLCs materials with different phases, including nematic, cholesteric, ferroelectric, blue phase, and other LC phases. The characteristics and optical performances of PSLCs are described in detail, with the function of polymer networks in different PSLCs specially emphasized and explained. The research progress of in the field is reviewed, and the opportunities and challenges faced by PSLCs materials are pointed out, aiming to promote the development and utilization of polymeric functional materials.
2021, 34(1): 66-73.   doi: 10.14133/j.cnki.1008-9357.20200810001
[Abstract](627) [FullText HTML](270) [PDF 1612KB](42)
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Photocatalytic water splitting to produce hydrogen is one of the effective ways to achieve solar energy utilization, in which the key point is to develop efficient and cheap photocatalysts. Conjugated microporous polymers (CMPs), allowing the fine synthetic control over their chemical structures and electronic properties, have become a new type of photocatalysts due to their diverse synthetic modularity. In order to investigate the effects of molecular structures on the photocatalytic performance of CMPs, four triazine-based conjugated microporous polymers (TCMPs) were designed and synthesized by Suzuki coupling reaction in this work, among which, TTCMP1 and TTCMP2 contain thiophene units, and TFCMP1 and TFCMP2 possess fluorene units. These TCMPs have high specific surface areas and appropriate optical band gaps. Through optical analysis of these TCMPs, it is found that the structural change of functional units and the length of linkers can tune the energy band gap, thereby influencing the hydrogen production performance of the polymers. Results show that TFCMPs containing fluorene units show better photocatalytic hydrogen production performance. And TFCMP2 with longer linking units shows the highest hydrogen release rate of 244 μmol/(h·g) under visible light (λ ≥ 420 nm). This work provides a promising strategy for exploring the relationship between the structure and performance of CMPs for photocatalytic hydrogen evolution.
2021, 34(1): 74-79.   doi: 10.14133/j.cnki.1008-9357.20200624001
[Abstract](415) [FullText HTML](221) [PDF 781KB](187)
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The proanthocyanidin (PC)-enhanced polyethylene glycol (PEG)-lysozyme (LZM) hydrogel (PEG-LZM-PC) was prepared based on PEG-LZM hydrogel by post-soaking with PC. The morphology, structure and mechanical properties of PEG-LZM-PC were characterized by scanning electron microscope (SEM), Fourier-transformed infrared (FT-IR) spectroscopy and universal testing instruments. Antibacterial ability of PEG-ZEM-PC was evaluated by plate coating method. The effect of PEG-LZM-PC on the expression of inflammatory factors in immune cells was evaluated by quantitative reverse transcription PCR (RT-qPCR). The results showed that the strength and toughness of PEG-LZM-PC were significantly improved compared with PEG-LZM; the antibacterial performance of PEG-LZM-PC in vivo and in vitro was pretty good; and the inflammatory response caused by lipopolysaccharide (LPS) stimulation was inhibited by PEG-LZM-PC, which is expected to promote wound healing.
2021, 34(1): 80-88.   doi: 10.14133/j.cnki.1008-9357.20200801001
[Abstract](256) [FullText HTML](137) [PDF 1891KB](15)
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In this study, rod like hydroxyapatite (HAp) with a length of 25—35 nm and a width of 10—20 nm was synthesized by chemical precipitation method. Then the HAp was doped in situ into the nano-disk osteogenic Laponite (LP) matrix. A type of injectable composite with high bioactivity was prepared by a single-step ultrasonic mixing method by leveraging Laponite’s good water solubility and in situ gelation property. The prepared gel material showed good injectability and thixotropic properties. A comparative study was conducted between pure LP injectable material (LIM) and LP/HAp injectable material (LHIM). The results of X-Ray Energy Spectrum showed that the HAp in the LHIM was well dispersed. The results of Scanning Electron Microscope (SEM) showed that the introduction of HAp increased the surface roughness of LHIM compared with LIM. The results of rabbit bone marrow mesenchymal stem cells (rBMSCs) in vitro showed that both LHIM and LIM had good cytocompatibility, and more rBMSCs adhered to the surface of LHIM in one day. The results of transwell showed that compared with LIM, LHIM could further improve the migration ability of rBMSCs. The results of osteogenic activity in vitro showed that LHIM can increase rBMSCs alkaline phosphatase (ALP), Runt-related transcription factor 2 (Runx2) and osteocalcin (OCN) activity. LHIM has the advantages of simple preparation, rapid gelation, no cross-linking agent, easy storage and good osteogenic activity. Therefore, LHIM is expected to be a bone repair material for clinical use. The current study provides a potential therapeutic tool for bone repair and regeneration.