Effects on the crystallite growth behavior of LaPO4 nanopowders and its mechanical properties

The effects of pH of the reaction solution and the concentration of phosphoric acid on the crystal growth behavior of LaPO₄ crystallites were investigated and the mechanical properties of rare-earth phosphates were compared. As a result, the concentration of phosphoric acid of 10% was beneficial to the crystal growth of LaPO₄ nanocrystalline. When the pH value of the reaction solution was 2, the size of LaPO₄ crystallites increased gradually with the increasing reaction temperature, and the smallest crystallite size of 43.27 nm was obtained after heat-treatment at 1000 °C. Simultaneously, the activation energy for crystal growth of LaPO₄ nanocrystalline was relatively lower (26.82 kJ mol⁻¹). With the decreasing radii of rare-earth ions, the hardness, Young's modulus and fracture toughness of the bulk rare-earth phosphates exhibited a reduced tendency, resulted from the increase of porosity under the same preparation process.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Enhancement in the osteogenesis and angiogenesis of calcium phosphate cement by incorporating magnesium-containing silicates

Based on the good osteogenic and angiogenic effects of silicon and magnesium elements, three types of micro-nano magnesium-containing silicates (MS), including akermanite (Ake, Ca₂MgSi₂O₇), diopside (Dio, CaMgSi₂O₆) and forsterite (For, Mg₂SiO₄), were incorporated into calcium phosphate cement (CPC) to improve its osteogenic and angiogenic performances for clinical application. In this present work, the physicochemical properties, osteogenesis and angiogenesis of MS/CPCs (Ake/CPCs, Dio/CPCs and For/CPCs) were investigated systematically and comparatively. The results showed that all MS/CPCs had good biomineralization and significantly stimulated the osteogenic differentiation of mBMSCs and angiogenic differentiation of HUVECs, respectively. Besides, the stimulating effects were related to not only the category of MS, but also the content of MS. The For/CPCs had a good angiogenic property but their initial setting times were beyond 60 min. The Dio/CPCs showed the lowest biological performance among the three groups of MS/CPCs due to the lower ion release (Si and Mg). The Ake was the ideal modifier that could provide CPC with appropriate physicochemical properties, better osteogenesis and angiogenesis. Simultaneously, a higher addition (10 wt%) of akermanite resulted in the best potential to bone regeneration. Taken together, this research provides an effective approach to improve the overall performance of CPC, and 10Ake/CPC is of great promising prospect in bone repair.     

Human responses to high levels of carbon dioxide and air temperature

In this study, 30 subjects were exposed to different combinations of air temperature (T_a: 24, 27, and 30°C) and CO₂ level (8000, 10 000, and 12 000 ppm) in a high-humidity (RH: 85%) underground climate chamber. Subjective assessments, physiological responses, and cognitive performance were investigated. The results showed that as compared with exposure to T_a = 24°C, exposure to 30°C at all CO₂ levels caused subjects to feel uncomfortably warm and experience stronger odor intensity, while increased mental effort and greater intensity of acute health symptoms were reported. However, no significant effects of T_a on task performance or physiological responses were found. This indicated that subjects had to exert more effort to maintain their performance in an uncomfortably warm environment. Increasing CO₂ from 8000 to 12 000 ppm at all T_a caused subjects to report higher rates of headache, fatigue, agitation, and feeling depressed, although the results were statistically significant only at 24 and 27°C. The text typing performance and systolic blood pressure (SBP) decreased significantly at this exposure, whereas diastolic blood pressure (DBP) and thermal discomfort increased significantly. These effects suggest higher arousal/stress. No significant interaction effect of T_a and CO₂ concentration on human responses was identified.     

Preparation and characterization of calcium phosphate cement with enhanced tissue adhesion for bone defect repair

Anti-washout and tissue adhesion properties are essential for the clinical application of injectable bone materials. In this study, we prepared calcium phosphate cement (CPC) with anti-washout and tissue adhesion properties and attempted to build covalent bonds between CPC and the amino groups in bone tissue under a self-regulating pH system in the CPC (acidic to basic). The results of push-out tests demonstrated that a significant enhancement (from 6.42 ± 0.76 N to 61.5 ± 4.09 N) in tissue adhesion was obtained with the addition of 6% (w/w) oxidized sodium alginate (OSA) in CPC. The FTIR, XRD, anti-washout test, XPS, pH test, and SEM results suggested that the synergistic effect of OSA-citric acid (CA) led to the formation of a three-dimensional gel network structure in the CPC, and the Schiff base reaction between aldehyde and amino groups induced adhesion between CPC and the bone tissue. Further, the addition of less OSA had no significant negative effect on the hydration properties of CPC. Our work aims to promote the development of injectable bone material in clinical applications.     

Catalytic supercritical water oxidation of tri-n-butyl phosphate: Process optimization by response surface methodology and cytotoxicity assessment

Catalytic supercritical water oxidation (SCWO) of an organophosphate flame retardant, namely tri-n-butyl phosphate (TNBP) was studied. Firstly, copper oxide nanoparticles (NPs) were synthesized in SCW and their properties were characterized by various analyses. Afterwards, their catalytic performance was investigated under different conditions including reaction temperature (400–500 °C), TNBP volume percentage in the feed (1–4%), oxidant ratio (0–2) and reaction time (50–150 min) based on response surface methodology (RSM). The synthesized CuO NPs had an average particle size of 30 nm with a narrow distribution. According to RSM analysis, the reaction temperature and time are the most significant factors; whereas, the impact of the other factors, especially TNBP volume percentage in the feed, was found to be negligible. Overall, excellent performance was achieved under optimal conditions found by the RSM, which was reaction temperature of 500 °C, TNBP volume percentage of 4%, oxidant ratio of 1.5, and reaction time of 90 min. The TOC removal efficiency as an indicator of TNBP degradation was about 99%. Finally, in vitro cell viability assays for the cytotoxicity evaluation of fresh and SCW-treated solution were applied. The results of MTT showed that SCWO converts TNBP into by-product that did not induce any cytotoxicity.     

露天转地下联合开采技术探讨

针对复杂型锰矿开采提出了由露天转地下联合开采技术，与其它采矿方法相比较，这种方法提高了回采率，降低了采矿成本。     

磷酸酯类离子液体在燃油深度脱硫中的应用

研究了3种磷酸酯类离子液体,即1,3-二甲基咪唑磷酸二甲酯盐([MM im]DM P)、1-乙基-3-甲基咪唑磷酸二乙酯盐([EM im]DEP)和1-丁基-3-甲基咪唑磷酸二丁酯盐([BM im]DBP)的制备过程,考察了这3种磷酸酯类离子液体对模型油中3-甲基噻吩、苯并噻吩和二苯并噻吩的脱除效果及磷酸酯类离子液体的电化学再生方法。实验结果表明,这3种磷酸酯类离子液体的脱硫能力强弱顺序为:[EM im]DEP>[BM im]DBP[MM im]DM P;且对二苯并噻吩的脱除效果最好,对苯并噻吩的脱除效果次之,对3-甲基噻吩的脱除效果较差。以[EM im]DEP为萃取剂,油剂质量比为1∶1时,经5次萃取后,二苯并噻吩的脱除率可达到99.5%。利用电解法对[EM im]DEP进行了再生,在5~10V电压下电解10h,[EM im]DEP的脱硫率可以达到新鲜[EM im]DEP的90%以上。     

在二(2-乙基己基)磷酸钠的微乳液中金属萃合物对水增溶的影响

测算了由二（2－乙基己基）磷酸钠，金属盐（CoSO4,NiSO4,ZnSO4,MgCl2或Cr(NO3)3)水溶液，正辛醇和正辛烷组成的微乳液中正辛醇从连续油相到界面的ΔGo→i^o和水的极限增容量φ'H2O。用金属萃取络合物反胶束的形成及其亲油性解释了金属离子对φ'H2O和ΔGo→i^o的影响。     

论城市可持续性发展与地下空间利用

本文分析了目前制约我国城市可持续发展的最主要因素是低效率的土地利用方式 ,若使地上、地面、地下空间协调发展 ,合理科学的规划好地下空间 ,珍惜地下空间资源 ,健全地下空间法律法规 ,统一地下空间管理机构 ,则可高效率的利用土地。