“硼”然心动——硼单质及其化合物*

硼是一种特殊的“准金属元素”,其独特的成键规律和化学性质使得硼及其化合物成为一类特殊的功能材料。介绍了硼单质的发现史,重点围绕硼单质、硼烷及其在国防等领域的应用展开。     

记钙先生参加的一次元素颁奖盛典

钙及其化合物在生产和生活中有着重要的应用。自钙第一次被化学家发现并在实验室合成至今,钙一直伴随在人类左右。而本文将钙拟人化,以"元素世界盛典故事"的形式,回顾了钙的发现史和应用。     

氧化物SrFeO3-δ的可控制备与磁性

应用熔盐路线通过控制温度和时间成功合成了微立方和纳米片层形貌的SrFeO3-δ化合物。X射线衍射、场发射扫描电子显微镜、透射电子显微镜和能量色散X射线光谱(EDS)以及热重分析(TGA)结果表明,微立方形貌化合物SrFeO2.86为四方相,空间群I4/mmm,纳米片层形貌化合物SrFeO2.62是钙铁矿(空间群Ibma)和正交相(空间群Cmmm)的复合物。磁学性能研究表明,SrFeO3-δ形貌对其性能有明显地影响;自旋失挫的减少与铁磁相互作用的增加密切关联;尽管成分几乎相同,但是形貌上的各向异性导致了明显不同的磁学性能。     

渣油加氢反应样品中含铁和含钙化合物溶解性能研究

以某原油及其对应的减压渣油、加氢原料和加氢产品为研究对象,通过柱色谱分离法和溶剂抽提法,对油样中铁和钙化合物在组分中的含量、分布以及存在形态进行了研究。研究结果表明,柱色谱分离过程中,油样中的含铁或钙的化合物在色谱柱上产生吸附,损失了58%的铁化合物和76%的钙化合物;溶剂抽提法能够有效减少组分中金属元素的损失。原油中97%以上的铁和钙分布在减压渣油馏分中,减压渣油中60%-90%的铁和钙分布在胶质、沥青质组分中。渣油加氢反应过程中,铁、钙化合物主要是从胶质中得到脱除,整体脱除率接近30%,铁化合物更易结合在沥青质中而难以脱除。原油经过常减压蒸馏后,油溶性铁相对分布由95.6%降低为64.7%,水溶性铁相对分布由4.4%升高为35.3%。经过加氢反应后,38%左右的油溶性铁在反应中转化为水溶性铁,30%左右的油溶性钙在反应中转化为水溶性钙。     

铝钙包芯线中铝和钙的测定

铝钙包芯线是一种炼钢用的冶炼脱氧剂,由铝粉、铁粉和Ф1mm的钙粒按配比进行物理混匀,然后用薄铁皮包成包芯线。由于钙的化学性质非常活泼,很容易被空气氧化及吸收空气中的水分,使钙的化合物发生变化,按常规操作测定铝和钙,则测定结果与配比(铝20％～30％、钙20％～30％)相差很大,测定结果偏低。本文对铝钙包芯线的取样、制样及分析方法进行探讨,采用分段直接剪取试样、     

宏量元素及化合物对微量元素吸收的影响

钙：当饮水及食物中含钙量高时,可与植酸盐形成植酸钙,在pH为碱性的小肠内形成不溶性复合物而妨碍锌吸收。还有报导指出,高锌尿与高钙尿有关。推测,饮食中钙含量高导致的低锌,不仅系钙能妨碍锌吸收,也由于它能增加锌从尿中的排泄。钙不利于氟的吸收,主要与氟结合成牢固的化合物而减少氟化物的吸收利用。相反食物缺钙可增进氟吸收。应用大剂量的钙治疗氟中毒也是基于钙的这一特点。过量钙存在会阻碍锰和铁的吸收。此外,实验证明高钙饲料可抑制大鼠对铅的吸收。     

过渡金属催化的炔烃复分解反应

综述了过渡金属均相催化的炔烃复分解反应进展,主要分为两部分：一是炔烃复分解反应在炔烃合成中的应用,即从六、七十年代Mortreux催化剂的发现能均相催化炔烃的歧化反应,经过一系列的条件改造,合成了炔醚和二芳基乙炔等化合物,并提出了可能的两种机理：金属卡宾和金属卡拜机理;金属钼和钨的卡拜络合物相继合成,发现此类络合物能够催化官能化的二炔的复分解反应,合成一系列的大环化合物。二是炔烃复分解反应在合成高聚物中的应用,即钙和钨的卡拜络合物被用来催化ROMP和ADIMET反应合成高聚物,改良了的Mortreux催化剂也能催化高聚物的生成,这些高聚物在发光器件、有机"塑料"激光、液晶显示器上都有应用。     

宏量元素及其化合物对微量元素吸收的影响

钙：当饮水及食物中含钙量高时,可与植酸盐形成植酸钙,在pH为碱性的小肠内形成不溶性复合物而妨碍锌吸收。还有报导指出,高锌尿与高钙尿有关。推测,饮食中钙含量高导致的低锌,不仅钙能妨碍锌吸收,也由于它能增加锌从尿中的排泄。钙不利于氟的吸收,主要与氟结合成牢固的化合物而减少氟化物的吸收利用。相反食物缺钙可增进氟吸收。应用大剂量的钙治疗氟中毒也是基于钙的这一特点。过量钙存在会阻碍锰和铁的吸收。此外,实验证明高钙饲料可抑制大鼠对铅的吸收。有人发现澳大利亚南部牧羊需铅量较大,与同时摄入大量的碳酸钙有关。     

近年来有机钙化学的进展

本世纪初即开始了有机钙化合物的研究,但这方面的发展是缓慢的。本文简要地介绍有机钙化合物近年来的进展及其发展缓慢的原因。     

高速逆流色谱技术分离纯化天然产物中黄酮类化合物的研究进展

高速逆流色谱(HSCCC)技术是一种连续高效的新型液-液分配色谱技术,在中药、生化、食品、天然产物化学、环境分析等领域有着广泛的应用.本文综述了部分利用高速逆流色谱技术分离纯化已知和未知黄酮类化合物的文献报道,并介绍了几种新近发展的高速逆流色谱以及其在分离纯化黄酮类化合物和其它化合物中的应用.     

钙与建筑材料

介绍了钙元素的发现以及钙元素在建筑材料领域中的应用历史、工艺变革和重要影响。并通过作者自身的研究工作，简介了钙元素建筑材料与纳米复合材料的结合与发展。     

Anhydrous Amorphous Calcium Oxalate Nanoparticles from Ionic Liquids: Stable Crystallization Intermediates in the Formation of Whewellite

The mechanisms by which amorphous intermediates transform into crystalline materials are not well understood. To test the viability and the limits of the classical crystallization, new model systems for crystallization are needed. With a view to elucidating the formation of an amorphous precursor and its subsequent crystallization, the crystallization of calcium oxalate, a biomineral widely occurring in plants, is investigated. Amorphous calcium oxalate (ACO) precipitated from an aqueous solution is described as a hydrated metastable phase, as often observed during low‐temperature inorganic synthesis and biomineralization. In the presence of water, ACO rapidly transforms into hydrated whewellite (monohydrate, CaC₂O₄ ? H₂O, COM). The problem of fast crystallization kinetics is circumvented by synthesizing anhydrous ACO from a pure ionic liquid (IL‐ACO) for the first time. IL‐ACO is stable in the absence of water at ambient temperature. It is obtained as well‐defined, non‐agglomerated particles with diameters of 15–20 nm. When exposed to water, it crystallizes to give (hydrated) COM through a dissolution/recrystallization mechanism.     

Direct Observation of the Distribution of Gelatin in Calcium Carbonate Crystals by Super‐Resolution Fluorescence Microscopy

Biological organic–inorganic hybrid materials often achieve excellent properties and provide inspiration for the design of advanced materials. The organic phase plays a key role in determining the properties of biogenic materials, and the spatial arrangement of organic and inorganic phases provides direct evidence for interaction between the two phases. Super‐resolution fluorescence microscopy was used to visualize the gelatin distribution in two different crystalline polymorphs of calcium carbonate (vaterite and calcite) and to investigate the process by which gelatin is excluded from the crystals. The results demonstrated that gelatin is distributed through vaterite microspheres in the form of nanoparticles, whereas it tends to accumulate on the edges of the calcite rhombohedra.     

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.     

碳酸钙/镍复合导电材料的原位合成及其抗静电性能

利用胶棉膜作为活性模板,制备出方解石型碳酸钙组装球,在其表面上将镍进行原位还原反应,首次成功获得了碳酸钙/镍复合导电材料,通过TEM、XRD、FT-IR和TG-DTA等测试技术对产物结构及性能进行了表征,并将产物应用于抗静电领域,制备成的抗静电涂料与用纯镍粉制备的涂料具有同等抗静电性能(电阻率为1.2×106 Ω·cm),并可以节省60%的镍。 该复合材料在导电和抗静电等领域具有应用前景,能够节省对镍的消耗。     

微波法研制碱土金属氧化物负载型MCM-48碱性介孔材料

以立方相介孔分子筛MCM-48为载体,用微波辐射分散MgO或CaO和醋酸镁溶液浸渍等方法研制碱性介孔材料。MCM-48能经受微波辐射,负载碱性客体之后也保持介相结构。异丙醇分解探针反应表明:载体本身没有碱催化活性,而碱性MCM-48介孔材料的活性随温度升高而提高。本文还对介孔材料在微波分散和碱性催化方面的特点进行分析。     

Characterization of a Novel CaCO3-Forming Alkali-Tolerant Rhodococcus erythreus S26 as a Filling Agent for Repairing Concrete Cracks

Biomineralization, a well-known natural phenomenon associated with various microbial species, is being studied to protect and strengthen building materials such as concrete. We characterized Rhodococcus erythreus S26, a novel urease-producing bacterium exhibiting CaCO₃-forming activity, and investigated its ability in repairing concrete cracks for the development of environment-friendly sealants. Strain S26 grown in solid medium formed spherical and polygonal CaCO₃ crystals. The S26 cells grown in a urea-containing liquid medium caused culture fluid alkalinization and increased CaCO₃ levels, indicating that ureolysis was responsible for CaCO₃ formation. Urease activity and CaCO₃ formation increased with incubation time, reaching a maximum of 2054 U/min/mL and 3.83 g/L, respectively, at day four. The maximum CaCO₃ formation was achieved when calcium lactate was used as the calcium source, followed by calcium gluconate. Although cell growth was observed after the induction period at pH 10.5, strain S26 could grow at a wide range of pH 4–10.5, showing its high alkali tolerance. FESEM showed rhombohedral crystals of 20–60 µm in size. EDX analysis indicated the presence of calcium, carbon, and oxygen in the crystals. XRD confirmed these crystals as CaCO₃ containing calcite and vaterite. Furthermore, R. erythreus S26 successfully repaired the artificially induced large cracks of 0.4–0.6 mm width.     

Hydrothermal synthesis followed by post heat-treatment: A novel route for the fabrication of KCa2Nb3O10 layered compound

Due to unique properties, KCa₂Nb₃O₁₀ compound has received great attention worldwide. High-temperature solid-state reaction is the common route for the synthesis of this compound. In order to propose a new low-temperature method (i.e. hydrothermal synthesis), which could improve the final properties of KCa₂Nb₃O₁₀, this study has been planned and performed. The preliminary experiments in KOH-Nb₂O₅ and Ca(OH)₂-Nb₂O₅ systems revealed that KCa₂Nb₃O₁₀ could be hydrothermally synthesized from a KOH-Ca(OH)₂-Nb₂O₅ system using an alkaline condition (i.e. 5 M < KOH <10 M). However, the experimental results showed that the product only consisted of KNbO₃ and Ca₂Nb₂O₇ phases. To initiate the reaction between KNbO₃ and Ca₂Nb₂O₇, the obtained KNbO₃-Ca₂Nb₂O₇ mixture was heat-treated in an air atmosphere. The results showed that KCa₂Nb₃O₁₀, with a high crystallinity and good purity, has been successfully obtained at 800 °C. This temperature is the lowest temperature, reported for the synthesis of KCa₂Nb₃O₁₀ compound so far. The SEM investigations revealed that the obtained KCa₂Nb₃O₁₀ powder has plate-like morphology due to its layered structure.