Rosette‐Shaped Calcite Structures at Surfaces: Mechanistic Implications for CaCO3 Crystallization

Biomineralization is believed to be achieved by the intimate cooperation of soluble macromolecules and an insoluble matrix at the specific inorganic–organic interface. It has been reported that positively charged matrices play an important role in controlling the structure of CaCO₃ at surfaces, although detailed mechanisms remain unclear. In this work, we studied the transformation from amorphous CaCO₃ to calcite crystals on surfaces by using thin films of poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) and its quaternized form. The positively charged PDMAEMA film was found to possess unique properties for CaCO₃ crystallization: individually separated, single calcite crystals were formed on the PDMAEMA film in the absence of poly(acrylic acid) (PAA), while circularly fused calcite crystals were formed in the presence of PAA. The circularly fused (rosette‐shaped) calcite crystals could be changed from a completely packed rosette to a ring‐shaped, hollow structure by tuning the crystallization conditions. A number of factors, such as reaction time, amount of (NH₄)₂CO₃, concentration of PAA, and charge of matrix‐films, were varied systematically, and we now propose a mechanism based on these observations.     

电石制备过程中不同含钙化合物与焦炭的反应行为研究

针对粉状原料-氧热法电石生产新工艺的需求,通过程序升温法研究了多种粉状含钙原料与粉状焦炭直接反应制备电石的过程。结果表明,升温过程中CaCO3释放的CO2、Ca(OH)2和电石渣释放的H2O对焦炭的量和质的影响很小,CaCO3、Ca(OH)2和电石渣均可直接用于电石生产,电石生成反应自1 450℃开始,1 740℃左右达到峰值。CaSO4与焦炭在920℃左右反应形成CaS,在研究的温度范围内CaS不与焦炭反应。     

大豆多糖对尿石矿物草酸钙形成的调控作用

采用水提法从大豆中提取了大豆多糖(SPS),其多糖百分含量为97.38%;平均相对分子质量为115,200,羧基百分含量为13.8%。采用X射线衍射法(XRD)、红外光谱(FTIR)、扫描电子显微镜(SEM)和电感耦合等离子体发射光谱仪(ICP)研究了水溶性大豆多糖(SPS)对草酸钙晶体生长的调控作用。SPS大豆多糖不但可以抑制一水草酸钙(COM)晶体的聚集,而且可以诱导二水草酸钙(COD)晶体形成。当SPS浓度由0增大到0.50g·L-1时,草酸钙晶体由COM完全转变为COD晶体;并且随着多糖浓度的增大,溶解在溶液中的钙离子(可溶性钙)浓度显著增加,草酸钙沉淀的物质的量逐渐减少。这些结果表明,SPS有望成为预防草酸钙结石的一种绿色药物。     

826例儿童发铅、锌、铜、铁、钙含量分析

探讨了东乡县儿童体内微量元素情况。对826例儿童发铅、锌、铜、铁、钙检测结果分各年龄组进行了分析。结果表明,826例儿童中发铅含量超标512例,占61．99％;发锌含量低标604例,占73．1％;发铜含量低标46例,占5．6％;发铁含量低标95例,占11．5％;发钙含量低标116例,占19．6％,占19．6％。5种元素含量与年龄有关,随着年龄增大,发铅、锌、铜、钙含量下降,发铁含量上升。分析表明,儿童铅污染、锌、钙缺乏程度相当普遍且严重。在儿童生长发育期进行常规的微量元素检测非常必要。     

不同尺寸六边形一水草酸钙晶体的合成、表征、性质及其细胞毒性

通过改变反应温度、溶剂、添加剂和搅拌速度,合成了尺寸分别为(1.5±0.4)、(3.5±0.5)、(5.5±0.5)和(9.5±1)μm的4种一水草酸钙(COM)晶体,比较了它们的理化性质差异。加入添加剂Na3Cit,增加搅拌速度,降低反应温度或降低溶剂的介电常数,均有利于获得小尺寸的晶体。X射线衍射(XRD)和傅立叶变换红外光谱(FT-IR)检测表明,这些晶体均为单相的COM晶体;扫描电子显微镜(SEM)观察显示,随着晶体尺寸由1μm增大到9μm,晶体由表面粗糙的圆钝形演变为表面光滑的薄片状,其高电荷密度的(101)晶面增大,晶体表面电荷密度增加,ζ电位绝对值也增大,形成的悬浮液稳定性越高。这些COM晶体对人肾近曲小管上皮细胞(HK-2)的损伤能力与其尺寸成负相关。     

Transport in ionic liquids under pressure. II. Concentrated calcium nitrate-water and magnesium chloride-water solutions

The interpretations of transport properties of concentrated aqueous solutions by the physics of glass-forming liquids approach recently applied to normal pressure measurements is extended by analysis of the pressure dependence of the electrical conductance of Ca(NO₃)₂ and MgCl₂ solutions. The conductance of these solutions has been determined to 3 kbar over the temperature range 20–100°C for compositions 9–20 mole% Ca(NO₃)₂ (5.6–13.9 m) and 80–200°C for MgCl₂ solutions of composition 12.4 and 14.2% MgCl₂. Using high-pressure-data determination of the glass-transition temperature to eliminate one adjustable parameter, it is found that the pressure dependence of the conductance of these solutions can be adequately described by ascribing all the pressure dependences to a single parameter, the ideal glass temperature T_o(P) of the Vogel-Tammann-Fulcher (VTF) equation known to describe temperature dependences of transport in viscous liquids. The results are discussed in terms of the Adam-Gibbs entropy theory and the Angell-Rao bond lattice model. The latter relates the pressure dependence of conductance to the volume change involved in configurational excitations of the liquid quasi-lattice, for which a mean volume increment of 1.6 cm³/mole is obtained.     

Hydrogen Storage Properties of Ca(BH4)2–LiNH2 System

Ca(BH₄)₂ is one of the promising candidates for hydrogen storage materials because of its high gravimetric and volumetric hydrogen capacity. However, its high dehydrogenation temperature and limited reversibility has been a hurdle for its practical applications. In an effort to overcome these barriers and to adjust the thermal stability, we make a composite system Ca(BH₄)₂–LiNH₂. Interaction of Ca(BH₄)₂ and LiNH₂ leads to decreased dehydrogenation temperatures and increased hydrogen desorption capacity in comparison to pristine Ca(BH₄)₂. More than 7 wt % of hydrogen can be detached at a temperature as low as approximately 178 °C from the cobalt‐catalyzed Ca(BH₄)₂–4 LiNH₂ system.     

In situ synthesis of calcium pimelate as a highly dispersed β-nucleating agent for improving the crystallization behavior and mechanical properties of isotactic polypropylene

The reaction precursors pimelic acid (Pi) and calcium stearate (CaSt) were added in situ during extrusion of isotactic polypropylene (iPP) to generate self-dispersed calcium pimelate (CaPi[IS]). The results reveal that the nucleating agents (NAs) synthesized in situ obviously affected the nucleation effect in iPP. The crystallization, mechanical properties and melting behavior of nucleated iPP were investigated. The crystallization temperature (T_c) of iPP modified with CaPi(IS) increased by 4–5°C when compared to that of pure iPP. Especially, when the addition amount of CaPi(IS) in iPP was 0.30 wt%, the relative β-crystal concentration of iPP/CaPi(IS) reached the highest level of 96.47%, 22.71% higher than that of iPP/CaPi. However, Pi and CaSt has hardly impact on the nucleation effect in iPP. The mechanical properties of iPP show that CaPi and CaPi(IS) have excellent toughening effect on iPP while Pi and CaSt greatly improved the stiffness of iPP. Furthermore, the dispersion of these NAs in iPP was investigated by scanning electronic microscope (SEM). It can be clearly seen that the CaPi(IS) particles are uniformly distributed in the iPP after magnification.     

用OP作增感剂原子吸收光谱法测定微量钙

研究以表面活性剂OP作增感剂。火焰原子吸收光谱法测定微量钙的方法。试验发展OP的加入可使吸光度增加70％,分析灵敏度得到提高。同时,以0．5mg.ml^-1钾、6．0mg.ml^-1镧盐及2．0mg.ml^-18－羟基喹啉作消电离剂、释放剂和保护剂消除基体物质的干扰。据此建立了标准加入法直接测定铝酸钠溶液中微量钙的分析方法。其线性范围为0－7．5mg.L^-1。灵敏度为0．05mg.L^-1/1%。方法灵敏度高,操作简便,结果准确度和精密度满足分析要求。     

Microwave‐Assisted Hydrothermal Rapid Synthesis of Amorphous Calcium Phosphate Mesoporous Microspheres Using Adenosine 5′‐Diphosphate and Application in pH‐Responsive Drug Delivery

Herein we report a rapid and green strategy for the preparation of amorphous calcium phosphate mesoporous microspheres (ACP‐MSs) using adenosine 5′‐diphosphate disodium salt (ADP) as an organic phosphorus source by a microwave‐assisted hydrothermal method. The effects of the pH value, the reaction time, and temperature on the crystal phase and morphology of the product are investigated. The ADP biomolecules used in this strategy play an important role in the formation of ACP‐MSs. The as‐prepared ACP‐MSs are efficient for anticancer drug delivery by using doxorubicin (Dox) as a model drug, and the Dox‐loaded ACP‐MSs show a high ability to damage cancer cells. Moreover, the ACP‐MSs drug delivery system exhibits a pH‐responsive drug‐release behavior due to the degradation of ACP‐MSs at a low pH value, thus, it is promising for applications in pH‐responsive drug delivery.