Frontiers of Materials Science (v.10, #2)

Characterization of decellularized scaffold derived from porcine meniscus for tissue engineering applications by Shuang Gao; Zhiguo Yuan; Tingfei Xi; Xiaojuan Wei; Quanyi Guo (101-112).
Menisci are fundamental fibrocartilaginous organs in knee joints. The injury in meniscus can impair normal knee function and predisposes patients to osteoarthritis. This study prepared decellularized meniscus scaffolds using a 1% (w/w) sodium dodecyl sulfate solution and sufficient rinsing steps. Complete cell removal was verified by hematoxylin and eosin staining and DNA content assay. Decellularized menisci had accordant tension properties to intact ones, but with declined compression properties. This occurred because the collagen fiber was not damaged but glycosaminoglycans was significantly lost during the decellularization process, which was confirmed by biochemical assay and histology staining. In vitro cytotoxicity assay demonstrated that decellularized meniscus scaffolds have no toxicity on L929 murine fibroblasts and porcine chondrocytes. Further experiment showed that porcine chondrocytes could adhere and proliferate on the scaffold surface, and some cells even could infiltrate into the scaffold. All results showed the potential of this decellularized meniscus to be the scaffolds in tissue engineering.
Keywords: meniscus scaffold; decellularization; biomechanical; cytotoxicity; tissue engineering

The multifunctional wound dressing with core–shell structured fibers prepared by coaxial electrospinning by Qilin Wei; Feiyang Xu; Xingjian Xu; Xue Geng; Lin Ye; Aiying Zhang; Zengguo Feng (113-121).
The non-woven wound dressing with core–shell structured fibers was prepared by coaxial electrospinning. The polycaprolactone (PCL) was electrospun as the fiber’s core to provide mechanical strength whereas collagen was fabricated into the shell in order to utilize its good biocompatibility. Simultaneously, the silver nanoparticles (Ag-NPs) as anti-bacterial agent were loaded in the shell whereas the vitamin A palmitate (VA) as healing-promoting drug was encapsulated in the core. Resulting from the fiber’s core–shell structure, the VA released from the core and Ag-NPs present in the shell can endow the dressing both heal-promoting and anti-bacteria ability simultaneously, which can greatly enhance the dressing’s clinical therapeutic effect. The dressing can maintain high swelling ratio of 190% for 3 d indicating its potential application as wet dressing. Furthermore, the dressing’s anti-bacteria ability against Staphylococcus aureus was proved by in vitro anti-bacteria test. The in vitro drug release test showed the sustainable release of VA within 72 h, while the cell attachment showed L929 cells can well attach on the dressing indicating its good biocompatibility. In conclusion, the fabricated nanofibrous dressing possesses multiple functions to benefit wound healing and shows promising potential for clinical application.
Keywords: coaxial electrospinning; core–shell structure; multifunctional wound dressing; anti-bacteria; heal-promoting

Comparative evaluation of a biomimic collagen/hydroxyapatite/β-tricaleium phosphate scaffold in alveolar ridge preservation with Bio-Oss Collagen by Tong Wang; Qing Li; Gui-feng Zhang; Gang Zhou; Xin Yu; Jing Zhang; Xiu-mei Wang; Zhi-hui Tang (122-133).
Bone scaffolds are critical in current implant and periodontal regeneration approaches. In this study, we prepared a novel composite type-I collagen and hydroxyapatite (HA)/β-tricaleium phosphate (TCP) scaffold (CHTS) by incorporating type-I collagen and bovine calcined bone granules, prepared as a mixture of 50% HA and 50% TCP, by freeze drying. We then characterized the CHTS and determined its cytotoxic effects. Additionally, ridge preservation experiments were carried out to evaluate the clinical effects of the CHTS. The results demonstrated that the composite scaffolds had good surface morphology and no cytotoxicity. Additionally, an in vivo experiment in an animal model showed that the CHTS performed equally as well as Bio-Oss Collagen, a widely used bone graft in ridge preservation. These findings revealed that the CHTS, which contained natural constituents of bone, could be used as a scaffold for bone regeneration and clinical use.
Keywords: hydroxyapatite; β-tricaleium phosphate (TCP); collagen; scaffold; ridge preservation

Corrosion resistance of biodegradable polymeric layer-by-layer coatings on magnesium alloy AZ31 by Lan-Yue Cui; Rong-Chang Zeng; Xiao-Xiao Zhu; Ting-Ting Pang; Shuo-Qi Li; Fen Zhang (134-146).
Biocompatible polyelectrolyte multilayers (PEMs) and polysiloxane hybrid coatings were prepared to improve the corrosion resistance of biodegradable Mg alloy AZ31. The PEMs, which contained alternating poly(sodium 4-styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH), were first self-assembled on the surface of the AZ31 alloy substrate via electrostatic interactions, designated as (PAH/PSS)5/AZ31. Then, the (PAH/PSS)5/AZ31 samples were dipped into a methyltrimethoxysilane (MTMS) solution to fabricate the PMTMS films, designated as PMTMS/(PAH/PSS)5/AZ31. The surface morphologies, microstructures and chemical compositions of the films were investigated by FE-SEM, FTIR, XRD and XPS. Potentiodynamic polarization, electrochemical impedance spectroscopy and hydrogen evolution measurements demonstrated that the PMTMS/(PAH/PSS)5/AZ31 composite film significantly enhanced the corrosion resistance of the AZ31 alloy in Hank’s balanced salt solution (HBSS). The PAH and PSS films effectively improved the deposition of Ca-P compounds including Ca3(PO4)2 and hydroxyapatite (HA). Moreover, the corrosion mechanism of the composite coating was discussed. These coatings could be an alternative candidate coating for biodegradable Mg alloys.
Keywords: magnesium alloy; polyelectrolyte; polysiloxane; corrosion; layer-by-layer

Magnetically active, ordered and stable mesoporous carbons with partially graphitized networks and controllable surface wettability (PR-Fe-P123-800 and PR-Ni-P123-800) have been synthesized through direct carbonization of Fe or Ni functionalized, and ordered mesoporous polymers at 800°C, which could be synthesized from self assembly of resol (phenol/formaldehyde) with block copolymer template (P123) in presence of Fe3+ or Ni2+, and hydrothermal treatment at 200°C. PR-Fe-P123-800 and PR-Ni-P123-800 possess ordered and uniform mesopores, large BET surface areas, good stabilities, controllable surface wettability and partially graphitized framework. The above structural characteristics result in their enhanced selective adsorption property and good reusability for organic pollutants such as RhB, p-nitrophenol and n-heptane in water, which could be easily regenerated through separation under constant magnetic fields and washing with ethanol solvent. The unique magnetically active and adsorptive property found in PR-Fe-P123-800 and PR-Ni-P123-800 will be very important for them to be used as efficient absorbents for removal of various organic pollutants in water.
Keywords: magnetic separation; mesoporous carbon; graphitization; adsorption; high temperature synthesis

Tailoring properties of reticulated vitreous carbon foams with tunable density by Oleg Smorygo; Alexander Marukovich; Vitali Mikutski; Vassilis Stathopoulos; Siarhei Hryhoryeu; Vladislav Sadykov (157-167).
Reticulated vitreous carbon (RVC) foams were manufactured by multiple replications of a polyurethane foam template structure using ethanolic solutions of phenolic resin. The aims were to create an algorithm of fine tuning the precursor foam density and ensure an open-cell reticulated porous structure in a wide density range. The precursor foams were pyrolyzed in inert atmospheres at 700°C, 1100°C and 2000°C, and RVC foams with fully open cells and tunable bulk densities within 0.09–0.42 g/cm3 were synthesized. The foams were characterized in terms of porous structure, carbon lattice parameters, mechanical properties, thermal conductivity, electric conductivity, and corrosive resistance. The reported manufacturing approach is suitable for designing the foam microstructure, including the strut design with a graded microstructure.
Keywords: foam; vitreous carbon; reticulated; cellular structure; pyrolysis

CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.
Keywords: CdSe; optical properties; morphological properties; hybrid solar cells

Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles by Junbo Li; Jianlong Zhao; Wenlan Wu; Ju Liang; Jinwu Guo; Huiyun Zhou; Lijuan Liang (178-186).
In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)]-block-(N-isopropylacrylamide) (PMMPImB-b-PNIPAAm) was first synthesized by reversible additionfragmentation chain transfer (RAFT) and then attached on the surface of gold nanoparticles (Au NPs) via a strong gold-sulfur bonding for preparing hybrid nanoparticles (PMMPImB-b-PNIPAAm-@-Au NPs). The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of (CF3SO2)2N. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature (LCST) because of the space or electrostatic protecting by outer PMMPImB. However, with increasing concentration of (CF3SO2)2N, the micellization of self-assembling PMMPImB-b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB-(CF3SO2)2N surrounded by composite shell of Au NPs-PNIPAAm via the anionresponsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copolymers when phase transition from outer corona polymer.
Keywords: block copolymer; dual stimuli-responsive; gold nanoparticles (Au NPs); self-assembly

Li-rich Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNC) powders were synthesized by a gel-combustion method. The related microstructure, electrochemical performance and electrochemically induced phase evolution were characterized. The 900°C calcined powders have a hexagonal layered structure with high ordered degree and low cationic mixing level. The calcined materials as cathode electrode for Li-ion battery deliver the high electrochemical properties with an initial discharge capacity of 243.5 mA•h•g–1 at 25 mA•g–1 and 249.2 mA•h•g–1 even after 50 cycles. The electrochemically induced phase evolution investigated by a transmission electron microscopy indicates that Li+ ions deintercalated first from the LiMO2 (M = Mn, Co, Ni) component and then from Li2MnO3 component in the LMNC during the charge process, while Li+ ions intercalated into Li1–xMO2 component followed by into MnO2 component during the discharge process.
Keywords: Li[Li0.2Mn0.54Ni0.13Co0.13]O2 ; gel-combustion synthesis; phase evolution; Li-storage capacity; electrochemical reaction

Hydrothermal synthesis of blue-emitting YPO4:Yb3+ nanophosphor by Guangfa Wang; Linhui Gao; Hongliang Zhu; Weijie Zhou (197-202).
The blue-emitting YPO4 phosphors doped with Yb3+ were prepared by a simple hydrothermal method. All the products were characterized by XRD and TEM, which revealed that they were zircon structure with leaf-like morphology. According to the analysis of photoluminescence spectra, upon ultraviolet (275 nm) excitation, the Yb3+ doped YPO4 phosphor showed an intense blue emission composed of two main bands at 420 and 620 nm assigned to charge transfer state (CTS) → 2F5/2 and CTS → 2F7/2, respectively. Moreover, the optimum doping concentration of Yb3+ in YPO4 phosphor was 1%, which exhibited the maximum emission intensity. The possible physical mechanism of concentration quenching was discussed, and the critical transfer distance determined to be 23.889 Å. In particular, the color purity of the as-synthesized Yb3+ doped YPO4 phosphor was as high as 83%, which made it an excellent candidate for blue-emitting materials.
Keywords: blue-emitting nanophosphors; hydrothermal synthesis; luminescence; Yb3+ doped YPO4

Effects of Cr2O3 doping on the microstructure and electrical properties of (Ba,Ca)(Zr,Ti)O3 lead-free ceramics by Xiang Xia; Xiangping Jiang; Chao Chen; Xingan Jiang; Na Tu; Yunjing Chen (203-210).
Lead-free ceramics (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3x wt.%Cr2O3 (BCZT-xCr) were prepared via the conventional solid-state reaction method. The microstructure and electrical properties of BCZT-xCr samples were systematically studied. XRD and Raman results showed that all samples possessed a single phased perovskite structure and were close to the morphotropic phase boundary (MPB). With the increase of the Cr content, the rhombohedral-tetragonal phase transition temperature (T R-T) increases slightly, and the Curie temperature (T C) shifts towards the low temperature side. XPS analysis reveals that Cr3+ and Cr5 + ions co-existed in Cr-doped BCZT ceramics, indicating the different impact on the electrical properties from Cr ions as “acceptor” or “donor”. For the x = 0.1 sample, relative high piezoelectric constants d 33 (∼316 pC/N) as well as high Q m (∼554) and low tanδ (∼0.8%) were obtained. In addition, the AC conductivity was also investigated. Hopping charge was considered as the main conduction mechanism at low temperature. As the temperature increases, small polarons and oxygen vacancies conduction played important roles.
Keywords: lead-free ceramics; electrical properties; BCZT; XPS analysis

Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1–x/TiO2 by Xujuan Chen; Xiaoliang Sun; Cairong Gong; Gang Lv; Chonglin Song (211-223).
Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4 + (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature (< 200°C) and the E-R mechanism at high temperature (> 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.
Keywords: CuCe0.25Zr0.75/TiO2 ; catalyst; selective catalytic reduction (SCR); diffuse reflectance infrared transform spectroscopy (DRIFT); reaction mechanism