Surfactant-free electrochemical synthesis of fluoridated hydroxyapatite nanorods for biomedical applications

Fluoridated hydroxyapatite (FHA) [Ca₁₀(PO₄)₆F_x(OH)_2−x, x = 0–2] is believed to be a promising calcium phosphate (CaP) to replace pure hydroxyapatite (HA) for next-generation implants, owing to its better biocompatibility, higher antibacterial activity, and lower solubility. Notably, the shape and size of the CaP crystals play key roles in their performance and can influence their applications. One-dimensional (1D) FHA nanorods are important CaP materials which have been widely used in regenerative medicine applications such as restorative dentistry. Unfortunately, the traditional synthesis methods for FHA nanorods either employ surfactants or take a relatively long time. In this study, we aimed to propose a facile synthesis route to fabricate FHA nanorods without any surfactants using an electrochemical deposition method for the first time. This study focused on preparing FHA nanorods without the assistance of any surfactant, unlike the traditional synthesis methods, to avoid chemical impurities. FHA nanorods with lengths of 124–2606 nm, diameters of 28–211 nm, and aspect ratios of 4.4–21.8 were synthesized using the electrochemical method, followed by a heat treatment. For the as-synthesized FHA nanorods, the Ca/P ratio was 1.60 and the atomic concentration of F was 2.06 at.%. An ultrastructure examination revealed that each FHA nanorod possessed long-range order, good crystallinity, and a defect-free lattice with a certain crystallographic plane orientation along the whole rod. In short, we propose a novel, surfactant-free, cost-saving, and more efficient route to synthesize FHA nanorods which can be widely applied in multiple biomedical applications, including drug delivery, bone repair, and restorative dentistry.     

Coexistence of three ferroelectric phases and enhanced piezoelectric properties in BaTiO3–CaHfO3 lead-free ceramics

Perovskite ferroelectrics possess the fascinating piezoelectric properties near a morphotropic phase boundary, attributing to a low energy barrier that the results in structural instability and easy polarization rotation. In this work, a new lead-free system of (1-x)BaTiO₃-xCaHfO₃ was designed, and characterized by a coexistence of ferroelectric rhombohedral-orthorhombic-tetragonal (R-O-T) phases. With the increase amount of CaHfO₃ (x), a stable coexistence region of three ferroelectric phases (R-O-T) exists at 0.06 ≤ x ≤ 0.08. Both large piezoelectric coefficient (d₃₃～400 pC/N), inverse piezoelectric coefficient (d₃₃^*～547 pm/V) and planar electromechanical coupling factor (k_p～58.2%) can be achieved for the composition with x = 0.08 near the coexistence of three ferroelectric phases. Our results show that the materials with the composition located at a region where the three ferroelectric R-O-T phases coexist would have the lowest energy barrier and thus greatly promote the polarization rotation, resulting in a strong piezoelectric response.     

Theoretical study of the structural,elastic and thermodynamic properties of chalcopyrite ZnGeP2

The structural, elastic, and thermodynamic properties of ZnGeP₂ with chalcopyrite structure are investigated using the pseudo-potentials plane wave method based on the density functional theory with the generalized gradient approximation. The lattice parameters (a, c and u) are directly calculated and agree well with previous experimental and theoretical results. The obtained negative formation enthalpy shows that ZnGeP₂ crystal has strong structural stability. We have also calculated the bulk modulus B and the elastic parameters (C₁₁, C₁₂, C₁₃, C₃₃, C₄₄, and C₆₆) which have not been measured yet. The accuracy and reliability of the calculated elastic constants of ZnGeP₂ crystal are discussed. In addition, the pressure and temperature dependencies of the lattice parameters, bulk modulus, Debye temperature, Grüneisen parameter, entropy, volume thermal expansion coefficient, and specific heat capacity are obtained in the ranges of 0–20 GPa and 0–1200 K using the quasi-harmonic Debye model. To our knowledge this is the first quantitative theoretical prediction of the thermodynamic properties for ZnGeP₂ compound and still awaits experimental confirmations.     

Enhanced hydrogen generation from Al-water reaction mediated by metal salts

Hydrogen generation by the reaction of micrometer-aluminum powder with water at room temperature is hard to proceed due to the inhibition of alumina layer. In this study, a novel strategy of metal salts mediated Al-water reaction was proposed for more efficient and practical hydrogen generation. The effects of metal salt composition and dosage, and water injection rate and volume on hydrogen generation were investigated. The hydrogen yield of 230.0 mL was achieved in the Al/Ni/Cu/H₂O system within 600 s under the following conditions: 0.24 g aluminum with the molar ratio of Al, Ni and Cu at 10:1:1 and 2 mL water at the injection rate of 2 mL/min, which was equivalent to 70.4% of the theoretical hydrogen yield. Based on the morphology, element composition, crystal structure and electrochemical test results of the obtained composites after reaction, the mechanism of hydrogen production by metal salts mediated Al-water reaction was proposed.     

川中丘陵区冬作不同品种马铃薯鲜切加工适宜性评价

以四川省川中丘陵区冬作马铃薯10个主栽品种为试验材料,考察了不同品种经鲜切加工后常温贮藏条件下总体感官质量、切片表面色差、褐变度和多酚氧化酶活性。结果表明,不同品种鲜切马铃薯在贮藏过程中各项指标均存在明显差异;中薯2号在贮藏过程中总体感官值相对较高,常温贮藏至第4 d时仍具有一定的商品性,而川芋802在贮藏至第2 d时外观商品性就接近5分(商品临界点);中薯2号和川芋10号的色差变化值相对较小,而川芋50和川芋802变化较大;川芋10号、费乌瑞它和青薯9号贮藏过程中褐变度相对较低;对PPO活性进行聚类分析将10个供试品种分为两个大类;综合多项测试指标表明,中薯2号和川芋10号鲜切加工后常温贮藏过程中产品品质较好,抗褐变能力较强,而川芋802和川芋50较易发生褐变,该研究结果可为马铃薯鲜切加工原料的选择提供参考依据。     

泡辣椒发酵过程中质构劣化规律及其影响因素研究

该研究考察了泡辣椒在发酵过程中质构、微生物数量、理化特性的变化规律，并在此基础上，进一步采用皮尔逊相关性分析法探讨微生物数量、理化特性与产品质构之间的相关性。结果表明，泡辣椒发酵过程中硬度和咀嚼性下降，脆度上升。在发酵前2天，乳酸菌及真菌迅速增殖，pH值迅速下降，总果胶酶活力升高；发酵2 d后，乳酸菌数量、pH值趋于稳定，真菌逐渐消失，总果胶酶活力迅速下降后趋于稳定。在酸和盐的共同作用下，泡辣椒释放自由水，水分含量降低，同时部分自由水逐渐转化为不易移动水，导致产品水分活度（Aw）下降。相关性分析结果表明，泡辣椒硬度、脆度和咀嚼性质构指标的变化主要与总果胶酶活力、水分含量及水分存在状态显著相关。     

High energy storage density and discharging efficiency in La3+/Nb5+-co-substituted (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

In this work, [(Bi_1-xLa_x)_0.5Na_0.5]_0.94Ba_0.06(Ti_1-5y/4Nb_y)O₃ ceramics have been developed by the dual-substitution of La³⁺ for Bi³⁺ and Nb⁵⁺ for Ti⁴⁺ and prepared by an ordinary sintering technique. All ceramics can be well-sintered at 1200 °C. The addition of La³⁺ and Nb⁵⁺ reduces the grain size and improve the dielectric breakdown strength of the ceramics; moreover, after the introduction of La³⁺ and Nb⁵⁺, the remanent polarization of the ceramics is significantly reduced, while the maximum polarization remains the same large value as that of the ceramic without the doping of La³⁺ and Nb⁵⁺. As a result, high energy storage density and discharge efficiency are achieved at x/y = 0.07/0.02, giving the large storage density of 1.83 J/cm³ and high discharging efficiency of 70%. The present work presents a feasible strategy to develop energy storage materials based on perovskite ferroelectrics by the partial substitutions in the A and B sites.     

Low-temperature sintering of (K,Na)NbO3-based lead-free piezoceramics with addition of LiF

Dense Li/Ta-codoped KNN-based piezoceramics with d₃₃^* up to 375 pm/V were successfully fabricated by conventional sintering at a temperature as low as 900 °C by using LiF as a sintering additive. The reduction of densification temperature up to 200 °C was realized by a transient liquid phase sintering mechanism, consequently no grain boundary phase was observed in the sintered samples. It was found that the addition of LiF could further shift down the tetragonal–orthorhombic transition point (T_T-O), indicating that a small amount of Li⁺ could diffuse into the A-site of KNN matrix. The introduction of LiF enhanced the linearity of strain curves of the ceramics, which is unambiguously in favor for the actuator application. The present work reveals that low-temperature sintered LiF-doped KNN-based piezoceramics demonstrates promising potential in multilayer-structured actuator applications.     

NH_3、MNH_2、M_2NH(M=Na/Li)电子结构的理论研究

在MP2/6-311++G(d,p)水平对NH3、MNH2、M2NH(M=Na/Li)的构型进行优化和NPA计算。从空间构型、自然键轨道、NPA电荷、前线轨道等方面进行了分析。MNH2是由M+离子和NH-2组成的离子化合物,M2NH是M+离子和NH2-组成的离子化合物。从HOMO看,从NH3、NaNH2和Na2NH的N端,LiNH2和Li2NH的分子平面上下方进攻N原子的反应当易于进行。从LUMO看,NaNH2和LiNH2的三重态分子中N-H键易于断裂而失去H+。     

Photocatalytic deoxygenation of sulfoxides to sulfides over titanium(IV) oxide at room temperature without use of metal co-catalysts

Deoxygenation of sulfoxides was examined in acetonitrile suspensions of metal-free titanium(IV) oxide (TiO₂) under irradiation of UV light at room temperature. Experimental results indicate that deoxygenation was induced by the TiO₂ photocatalyst and that organic acids such as formic acid and oxalic acid are appropriate as hole scavengers in the photocatalytic reaction. Diphenyl sulfoxide was successfully deoxygenated to diphenyl sulfide with high yields, and the TiO₂ photocatalyst could be repeatedly used for deoxygenation without loss of activity. The present photocatalytic method could be applied for deoxygenation of various sulfoxides to corresponding sulfides, and phenyl vinyl sulfoxide was chemoselectively reduced to phenyl vinyl sulfide without hydrogenation of a CC double bond.