Structure of the ultrathin aluminum oxide film on NiAl(110)

The well-ordered aluminum oxide film formed by oxidation of the NiAl(110) surface is the most intensely studied metal surface oxide, but its structure was previously unknown. We determined the structure by extensive ab initio modeling and scanning tunneling microscopy experiments. Because the topmost aluminum atoms are pyramidally and tetrahedrally coordinated, the surface is different from all Al2O3 bulk phases. The film is a wide-gap insulator, although the overall stoichiometry of the film is not Al2O3 but Al10O13. We propose that the same building blocks can be found on the surfaces of bulk oxides, such as the reduced corundum (0001) surface.     

Rhodizite: structure and composition

The mineral rhodizite could not be assigned a chemical formula on the basis of chemical analyses. The solution of the crystal structure reported here reveals that CsB(12)Be(4)Al(4)O(28) is the ideal formula. The oxygen atoms occupy all but four sites per cell of cubic close packing whose period is (1/2)a. The boron, beryllium, and aluminum atoms occupy interstices of this array, the first two in tetrahedral coordination, the last in octahedral coordination. Together these atoms form a continuous network whose composition is B(12)Be(4)Al(4)O(28), which should be neutral. The alkali atom is enclosed in a cage in this network and presumably is not behaving as an ion.     

Kaolinite: synthesis at room temperature

To obtain kaolinite at low temperature and pressure from the system Si(OH)(4)-Al(3+)-H(2)O, the sixfold coordination of aluminum is a necessary prerequisite. Kaolinite was synthesized at pH values from 2 to 9 and with a ratio of SiO(2) to Al(2)O(3) in solution from 1 to 10 by means of the complexation of Al(3+) and fulvic acid.     

酸性土壤中耐铝细菌分离及耐铝性的初步研究

[目的]研究铝离子对5种土壤中细菌的生长情况的影响。[方法]以筛选出的7株细菌为研究对象,分析菌落在不同浓度铝离子下生长状况。[结果]随着Al3＋浓度不断增加,细菌生长受到抑制;细菌中B2、B3、B4、B5耐铝性较好,在Al3＋浓度3 mmol/L时能够生长;7株细菌中,B4的增长率最高,耐铝性最好。[结论]该研究为微生物的耐铝性研究提供了一定的理论依据。     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

Formation of Al13I-: evidence for the superhalogen character of Al13

Al13- is a cluster known for the pronounced stability that arises from coincident closures of its geometric and electronic shells. We present experimental evidence for a very stable cluster corresponding to Al13I-. Ab initio calculations show that the cluster features a structurally unperturbed Al13- core and a region of high charge density on the aluminum vertex opposite from the iodine atom. This ionically bound magic cluster can be understood by considering that Al13 has an electronic structure reminiscent of a halogen atom. Comparisons to polyhalides provide a sound explanation for our chemical observations.     

酸铝对不同速生桉优良无性系叶片内源激素的影响

[目的]分析酸铝处理下4个不同耐铝型速生桉无性系[巨尾桉9号(G9)、巨尾桉12号(G12)、韦赤桉3号(G3)、尾叶桉4号(G4)]叶片内源激素中脱落酸(ABA)、生长素(IAA)、赤霉素(GA3)、玉米素(ZR)的变化趋势,为进一步揭示速生桉对铝毒害的响应机制及选育耐铝型速生桉优良无性系提供参考.[方法]采用砂土培育法对桉树幼苗进行酸铝处理4个月后,应用间接酶联免疫法(ELISA)测定幼苗叶片中ABA、IAA、GA3、ZR 4种内源激素的含量,利用坐标综合评定法对各无性系的抗逆能力进行排序.[结果]酸铝处理对4个桉树优良无性系幼苗ABA产生积累作用,对IAA、GA3和ZR等产生抑制作用,且pH值越低、铝处理浓度越高,作用效果越明显,以120 mg/L Al3++pH 3.0的处理效果最显著;幼苗叶片的ABA/IAA、ABA/GA3、ABA/ZR 3个平衡指标表现出显著的升高趋势,通过内源激素平衡指标综合评定排序,耐铝性最差的尾叶桉4号的平衡指标增加幅度分别是耐铝性最强的巨尾桉9号的9.2、7.3、8.3倍.[结论]4个桉树优良无性系叶片内源激素间的协调能力与耐酸铝抗性成正比关系.巨尾桉9号对酸铝逆境处理的适应性最好,其ABA含量最低,IAA、GA3、ZR含量最高,各指标变化的幅度较小,受到的抑制作用影响最小,而耐铝性最弱的尾叶桉4号内源激素对酸铝处理的敏感性较强,受到抑制作用最大.     

脯氨酸缓解酸性土壤上小白菜铝毒胁迫的效应及其潜在机制

为了研究不同浓度外源脯氨酸(Pro)对酸性土壤上小白菜铝(Al)毒胁迫的效应及其潜在机制,以小白菜为试验材料,通过酸性土壤盆栽试验,利用不同浓度外源Pro,设置T_1(0 mmol·L~(-1)Al+0 mmol·L~(-1)外源Pro)、T_2(27 mg·kg~(-1)Al+0 mmol·L~(-1)外源Pro)、T_3(27 mg·kg~(-1)Al+10 mmol·L~(-1)外源Pro)、T_4(27 mg·kg~(-1)Al+20 mmol·L~(-1)外源Pro)、T_5(27 mg·kg~(-1)Al+50 mmol·L~(-1)外源Pro)共5个处理,对小白菜生理特性和土壤性质进行研究。结果表明:与T_1相比,Al胁迫下小白菜的产量、抗氧化酶活性以及土壤pH值明显降低,其中,产量降低了约10.6%,土壤pH值降低了0.75个单位;此外,叶片丙二醛和Al含量以及土壤活性Al总量明显升高,其中,小白菜叶片Al含量和土壤活性Al含量分别增加了24.3%和15.3%,对小白菜产生明显胁迫作用,抑制其生长;相对于Al处理,施用不同浓度外源Pro可以明显增加小白菜产量,T_3、T_4和T_5分别增加了29.3%、38.4%和65.2%,抗氧化酶活性也显著提高,而叶片丙二醛和Al含量以及土壤活性Al含量显著降低,T_3、T_4和T_5叶片Al含量分别降低了20.4%、45.6%和49.8%,说明不同浓度外源Pro均能缓解Al对小白菜的胁迫作用。研究表明,外源Pro可缓解Al对小白菜胁迫作用,且缓解效果为T_5T_4T_3,50 mmol·L~(-1)外源Pro缓解效果较好。     

Evidence for a phytotoxic hydroxy-aluminum polymer in organic soil horizons

The toxicity of A1 that has been mobilized in soil, streams, and lakes through acid deposition primarily has been attributed to mononuclear A1 species. Polynuclear A1 species are more toxic than mononuclear species, but they have not been considered to be significant in the environment. Aluminum-27 nuclear magnetic resonance (NMR) spectra of forested spodosol soil horizon samples show the presence of polynuclear A1O(4)A1(12)(OH)(24)(H(2)O)(12)(7+). The AlO(4)A1(12)(OH)(24)(H(2)O)(12)(7+) species accounted for 30 percent of the aqueous A1 observable by NMR, and this could make a significant contribution to the toxicity of the A1 in these soils.     

铝胁迫下不同耐性的小黑麦及其异源亲本活性氧代谢研究

[目的]将耐铝的黑麦(389和390)与不耐铝的四倍体小麦(5020)远源杂交获得耐铝的小黑麦(5020×389和5020×390),比较铝胁迫下小黑麦及其异源亲本活性氧代谢。[方法]通过水培及Al胁迫处理,检测不同处理时间小黑麦及其亲本的膜稳定性、活性氧含量及代谢。[结果]Al Cl3处理后5020、5020×389和5020×390的MDA含量与质膜透性显著增加,铝处理2和12 d,与无铝处理相比增幅为57.7%、11.1%、10.8%和22.8%、17.4%、2.2%。Al促进5020、5020×389和5020×390活性氧含量的显著提高,铝处理2 d时,H2O2含量分别增加了63.2%、47.1%、37%,O2-产生速率分别增加了63.2%、41.1%、37%,且在铝处理12 d时,只有5020活性氧显著增加。5020、5020×389和5020×390的SOD活性在铝处理2和12 d时分别增加了74.5%、63.2%、61.7%和45.1%、31.4%、20.1%。Al处理12 d时,与对照相比5020除了CAT外APX、GPX、GR活性均减小显著减小了74.1%、69%、18%;5020×389和5020×390叶中APX、GPX、GR活性增加显著分别增加了3.56倍、9.54倍与2.96倍、1.22倍与2.4倍、5.74倍。5020、5020×389和5020×390的GSH含量和GSSH含量均在铝处理12 d显著增加分别增加了54.0%、118.2%和25.3%、18.0%和22.0%、12.3%。[结论]小黑麦5020×389和5020×390表现为耐铝,且耐铝性5020×390稍强于5020×389。同时,研究表明不同耐铝品种间叶中APX、GPX和GR活性差异是小黑麦及其异源亲本耐铝性差异显著的原因之一。APX与GPX可能是5020×390耐铝的主要作用酶,GR可能是5020×389耐铝的主要作用酶。     

生物炭对铝富集酸性土壤的毒性缓解效应及潜在机制

【目的】红壤铝毒是土壤改良持续关注的问题之一。生物炭因其自身的理化和生物学特性,为探索解决该难题提供了新的思路和途径。论文通过在红壤中添加外源铝并种植作物,研究生物炭对铝富集土壤铝毒的缓解效应及潜在机制。【方法】选用酸性红壤做盆栽试验,种植小白菜,添加花生壳生物炭和外源铝,设置CK(0C+0Al)、C(2%C)、Al(1 mmol·L~(~(-1))Al)、C+Al(2%C+1 mmol·L~(~(-1))Al)4个处理,分析生物炭对铝富集红壤不同活性铝及作物生长的影响。【结果】铝毒会显著抑制小白菜的出苗,且加重红壤小白菜生长受抑制的情况,降低小白菜的生物量,同时,铝毒会显著提高小白菜铝含量。而施用生物炭能缓解铝毒对小白菜的抑制影响,显著改善小白菜的生长状况,降低小白菜铝含量,C+Al处理小白菜铝含量较Al处理降低89.4%。铝毒会显著降低红壤的pH,Al处理红壤pH较CK处理降低了0.36个单位,而施用生物炭能显著提高土壤pH,C+Al处理土壤pH较Al处理上升0.62个单位。Al处理较CK处理土壤活性铝含量上升276.4μg·g~(-1),远大于添加量(27μg·g~(-1)),而施用生物炭能显著降低土壤活性铝含量,C+Al处理较Al处理下降14.9%。此外,Al处理交换性Al~(3+)含量较CK处理上升23.1%,施用生物炭后,C+Al处理交换性Al~(3+)含量较Al处理下降46.5%。CK与Al处理土壤活性铝形态主要以具有生物毒害性的交换性Al~(3+)为主,C与C+Al处理土壤活性铝形态主要以单聚体羟基铝离子、胶体Al(OH)30为主。【结论】添加外源铝降低了土壤pH,加重铝的毒害,抑制作物的生长发育。此外,外源铝的添加对红壤中活性铝有较强的激发效应,使得交换性Al~(3+)含量显著升高。然而,生物炭能显著提高酸性土壤pH,且改变不同活性铝的含量,但其对4种不同形态活性铝的效应有较大差异,其主要通过降低具有生物毒性的Al~(3+)含量来缓解铝毒,从而改善作物生长状况。     

模拟酸雨和铝添加对茶树生长及生理生化特性的影响

以茶树(Camellia sinensis)种子实生苗为材料,研究了模拟酸雨和铝添加对茶树生物量、抗氧化酶及一些抗性指标的影响.结果表明,适量的铝和适度的酸雨有利于茶树生物量的积累,较高的铝和较高酸度酸雨不利于茶树生物量的积累.随着铝处理浓度的增加,茶树叶片超氧化物歧化酶(SOD)、过氧化物酶(POD)、过氧化氢酶(CAT)和抗坏血酸过氧化物酶(APX)先增加后下降.随着酸雨强度的增加,SOD、POD、CAT和APX总体上增加,在较低浓度铝处理下,酸雨加剧SOD、POD、CAT和APX的增加,存较高铝浓度(30 mg/L)处理下,酸雨加剧SOD、POD、CAT和APX的下降.10 mg/L铝浓度处理茶树叶片超氧阴离子产生速率(O2-)和丙二醛(MDA)含量与无铝处理的相比没有明显差异,随着铝处理浓度的增加其O2-产生速率和MDA含量增加.酸雨强度对茶树叶片O2-产生速率和MDA含量没有明显影响.酸雨加剧铝引起茶树叶片O2-产生速率和MDA积累的增加.随着铝处理浓度的增加,茶树叶片脯氨酸含量增加.而酸雨单独作用对脯氨酸含量没有明显影响,但酸雨加剧铝对茶树叶片脯氨酸积累的增加.随着铝处理浓度的增加,茶树叶片可溶性糖含量先增加后下降.pH 3.0的酸雨明显提高茶树叶片可溶性糖含量.结果表明,茶树可通过提高抗氧化酶活性和一些渗透调节物质(脯氨酸和可溶性糖)增强对酸雨和低浓度铝的适应性和耐受能力.高浓度的铝(30 mg/L)损伤茶树抗氧化系统,减少一些抗性物质的合成,影响其生长,而酸雨加剧高铝对茶树的伤害.     

High-density electron anions in a nanoporous single crystal: [Ca24Al28O64]4+(4e-)

We removed approximately 100% of clathrated oxygen ions from the crystallographic cages in a single crystal of 12CaO.7Al2O3, leading to the formation of high-density (approximately 2 x 10(21) cm-3) electrons highly localized in the cages. The resulting electron forms a structure that we interpret as an F+ center and migrates throughout the crystal by hopping to a neighboring cage with conductivity approximately 100 siemens per centimeter, demonstrating that the encaged electron behaves as an anion. The electron anions couple antiferromagnetically with each other, forming a diamagnetic pair or singlet bipolaron. The resulting [Ca24Al28O64]4+(4e-) may be regarded as a thermally and chemically stable single crystalline "electride."     

X-ray diffraction study of the ultrathin Al2O3 layer on NiAl110

Ultrathin Al2O3 layers on alloys are used as templates for model catalysts, tunneling barriers in electronic devices, or corrosion-resistant layers. The complex atomic structure of well-ordered alumina overlayers on NiAl110 was solved by surface x-ray diffraction. The oxide layer is composed of a double layer of strongly distorted hexagonal oxygen ions that hosts aluminum ions on both octahedral and tetrahedral sites with equal probability. The alumina overlayer exhibits a domain structure that can be related to characteristic growth defects and is generated during the growth of a hexagonally ordered overlayer (Al2O3) on a body-centered cubic (110) substrate (NiAl).     

铝逆境下植物根系有机酸的分泌及其解铝毒机理

铝元素是限制酸性土壤中作物产量的一个重要因子,本文根据铝逆境下植物根系有机酸的分泌及其解铝毒机理研究现状,详细地论述了铝逆境下植物有机酸的分泌方式及其解铝毒机理,并对铝胁迫下植物根系分泌的有机酸种类及调控其分泌的主要因素等做了介绍,提出了铝逆境下植物有机酸解铝毒的研究方向。     

Al^3＋对蚯蚓和家兔乙酰胆碱酯酶的毒性研究

[目的]探讨Al3＋对蚯蚓和家兔乙酰胆碱酯酶的毒性。[方法]通过体外试验,分别研究了Al3＋对蚯蚓乙酰胆碱酯酶（AChE）和家兔脑部AChE的毒力（IC50）和双分子速率Ki的影响。[结果]Al3＋对蚯蚓AChE和家兔脑部AChE的IC50分别为5.4和4.2 mmol/L;4.2mmol/LAl3＋对家兔大脑AChE的双分子速率Ki值为5.4mmol/LAl3＋对蚯蚓AChE双分子速率Ki值的1.02倍,表明家兔脑部AChE对A l3＋的敏感性较蚯蚓AChE对Al3＋的敏感性强。[结论]为从整个动物界层面阐明铝对AChE的毒性性质以及利用AChE快速检测铝的污染提供了理论依据。     

Solvated electrons in high-temperature melts and glasses of the room-temperature stable electride [Ca₂₄Al₂₈O₆₄]⁴⁺·4e⁻

Solvated electrons in alkali metal-ammonia solutions have attracted attention as a prototype electronic conductor and chemical reducing agent for over a century. However, solvated electrons have not been realized in a high-temperature melt or glass of an oxide system to date. We demonstrated the formation of persistent solvated electrons in both a high-temperature melt and its glass by using the thermally stable electride [Ca(24)Al(28)O(64)](4+)·4e(-) (C12A7:e(-)) and controlling the partial pressure of oxygen. The electrical and structural properties of the resulting melt and glass differ from those of the conventional C12A7:O(2-) oxide, exhibiting metallic and hopping conduction, respectively, and a glass transition temperature that is ~160 kelvin lower than that of C12A7:O(2-) glass. Solvated electrons reside in cage structures in C12A7:e(-) and form a diamagnetic paired state.     

外源一氧化氮对铝胁迫下烟草叶片呼吸作用和活性氧代谢的影响

为探明外源一氧化氮(NO)提高烟草耐铝性的生理机制,采用水培法研究了NO供体硝普钠(SNP)对铝胁迫下2个不同耐铝性烟草品种云烟100(耐铝)和云烟105(敏感)植株生长、叶片活性氧(ROS)含量、呼吸作用和线粒体抗氧化酶活性的影响。结果表明,铝胁迫显著降低了烟草叶片总呼吸速率、细胞色素呼吸速率、交替呼吸速率、细胞色素氧化酶(COX)活性和丙酮酸含量,导致叶片O—·2产生速率升高和H2O2大量积累,植株生物量显著下降,且云烟105变幅高于云烟100;外源NO处理显著缓解铝对烟草植株生长的抑制,提高叶片总呼吸速率、细胞色素呼吸速率、交替呼吸速率、COX活性和丙酮酸含量,降低叶片O—·2产生速率和H2O2含量,且对云烟105的缓解效果显著高于云烟100。此外,外源NO处理进一步提高铝胁迫下烟草叶片线粒体超氧化物歧化酶(SOD)和抗坏血酸过氧化物酶(APX)活性,且云烟105增幅显著大于云烟100。综上所述,外源NO处理可通过提高烟草叶片呼吸作用和线粒体抗氧化酶活性来清除线粒体内ROS含量,从而缓解铝对烟草的毒害作用,且对敏感基因型的缓解效应较耐铝基因型更为明显。     

Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy

The anion-exchange ability of layered double hydroxides (LDHs) has been exploited to create materials for use in catalysis, drug delivery, and environmental remediation. The specific cation arrangements in the hydroxide layers of hydrotalcite-like LDHs, of general formula Mg2+(1-x)Al3+(x)OH2(Anion(n-)(x/n)).yH2O, have, however, remained elusive, and their elucidation could enhance the functional optimization of these materials. We applied rapid (60 kilohertz) magic angle spinning (MAS) to obtain high-resolution hydrogen-1 nuclear magnetic resonance (1H NMR) spectra and characterize the magnesium and aluminum distribution. These data, in combination with 1H-27Al double-resonance and 25Mg triple-quantum MAS NMR data, show that the cations are fully ordered for magnesium:aluminum ratios of 2:1 and that at lower aluminum content, a nonrandom distribution of cations persists, with no Al3+-Al3+ close contacts. The application of rapid MAS NMR methods to investigate proton distributions in a wide range of materials is readily envisaged.     

外源一氧化氮对铝胁迫下烟草叶片光能利用和光保护系统及活性氧代谢的影响

以云烟100(耐铝)和云烟105(铝敏感)为材料,采用水培法研究外源一氧化氮(NO)对铝胁迫下烟草植株生长、叶片活性氧含量、光合特性、叶绿素荧光参数、光呼吸和抗氧化酶活性的影响。结果表明,铝胁迫显著降低了烟草叶片叶绿素含量、净光合速率(Pn)、最大光化学效率(Fv/Fm)、PSII光合电子传递量子效率(FPSII)和光化学猝灭系数(q P),提高了反应中心PSII过剩激发能,从而导致叶片超氧阴离子(O_2·)和过氧化氢(H_2O_2)含量升高,植株生物量下降。外源NO可显著提高铝胁迫下烟草叶片叶绿素含量、Pn、Fv/Fm、FPSII、q P和植株生物量,降低反应中心PSII过剩激发能和叶片O_2·、H_2O_2含量,且云烟105变化幅度高于云烟100。此外,外源NO还显著提高了铝胁迫下烟草叶片非光化学猝灭系数、光呼吸速率、超氧化物歧化酶和抗坏血酸过氧化物酶活性,说明NO可通过提高烟草叶片光化学反应能力、热耗散、光呼吸以及抗氧化酶活性来降低反应中心PSII过剩激发能,防止或清除叶绿体内产生的活性氧,缓解铝对烟草的毒害,这种缓解效应在敏感基因型云烟105中表现更明显。