Constructing ab initio models of ultra-thin Al–AlOx–Al barriers

The microscopic structure of ultra-thin oxide barriers often plays a major role in modern nano-electronic devices. In the case of superconducting electronic circuits, their operation depends on the electrical nonlinearity provided by one or more such oxide layers in the form of ultra-thin tunnel barriers (also known as Josephson junctions). Currently available fabrication techniques manufacture an amorphous oxide barrier, which is attributed as a major noise source within the device. The nature of this noise is currently an open question and requires both experimental and theoretical investigation. Here, we present a methodology for constructing atomic-scale computational models of Josephson junctions using a combination of molecular mechanics, empirical and ab initio methods. These junctions consist of ultra-thin amorphous aluminium-oxide layers sandwiched between crystalline aluminium. The stability and structure of these barriers as a function of density and stoichiometry are investigated, which we compare with experimentally observed parameters.     

Ion-exchange and potentiometric characterization of Al–cystine and Al–cysteine complexes

The interaction between aluminium and cysteine and cystine was evaluated by means of ion-exchange experiments and potentiometry. Ion-exchange experiments included other ligands with affinity for aluminium and two kinds of resins, either a Na⁺-form or an Al³⁺-form exchanger. The ability of the ligands to keep aluminium in solution in the presence of the Na⁺ exchanger or to withdraw it from the Al³⁺-form resin was evaluated. Aluminium quantification was carried out by either graphite-furnace or flame atomic absorption spectrometry. Aluminium extraction isotherms were linearised using the Scatchard plot, and stability constants were obtained from the curves’ slopes. The experiments showed that the ability of the ligands to withdraw aluminium from the Al³⁺-form resin increased following the order cysteine < oxalate < citrate = cystine < nitrilotriacetic acid < ethylenediaminetetraacetic acid. Potentiometric titrations, carried out in aqueous solution with constant ionic strength and temperature, showed that the predominant species in solution have a metal–ligand proportion of 1:1 for both amino acids. The main species are Al(OH)₃L, with log K of 6.2 for cysteine, and AlL and Al(OH)L, with log K of 10.3 and 1.7, respectively, for cystine. Stability constants obtained from the Scatchard plots showed a linear correlation with the stability constants obtained by potentiometry for cystine and cysteine in this work and those collected from the literature for the other ligands. These results show that cysteine and cystine extract and maintain aluminium in solution, which may explain elevated concentrations of aluminium in parenteral nutrition solutions containing these amino acids.Electronic Supplementary Material Supplementary material is available to authorised users in the online version of this article at .     

Al uptake kinetics in roots of Melastoma malabathricum L. – an Al accumulator plant

The mechanism of Al uptake in melastoma (Melastoma malabathricum L.), which accumulates Al in excess of 10 000 mg kg^–1 in its leaves and roots, was investigated. Al uptake kinetics in excised melastoma roots showed a biphasic pattern, with an initial rapid phase followed by a slow phase. It was indicated that Al uptake in the excised roots occurs mostly through passive accumulation in the apoplast. On the other hand, Al uptake rate in roots of whole melastoma plant was almost double that in excised roots. The difference of Al uptake rate between excised roots and whole plant seems to be due to transpiration-depended Al uptake. Results from a long-term experiment showed that different characteristics of Al accumulation between melastoma and barley was caused by the difference in capacity to retain Al in root symplast, rather than by the difference in uptake rate into symplast. Concentrations of oxalate in root symplastic and apoplastic fractions, and total oxalate in shoots and roots, did not change greatly with time of Al exposure compared to Al concentration, although oxalate is considered as a main Al ligand in tissue of melastoma. On the other hand, oxalate exudation to root apoplast was induced within 24 h of Al exposure; the role of such exudation was discussed.     

Natural bond orbital, nuclear magnetic resonance analysis and hybrid-density functional theory study of σ-aromaticity in Al2F6, Al2Cl6, Al2Br6 and Al2I6

Natural bond orbital (NBO), nuclear magnetic resonance (NMR) analysis and hybrid-density functional theory based method (B3LYP/Def2-TZVPP) were used to investigate the correlation between the nucleus-independent chemical shifts [NICS, as an aromaticity criterion], σ _Al(1)-X2(b) → σ*_Al(3)-X4(b) electron delocalizations and the dissociation energies of Al₂F₆, Al₂Cl₆, Al₂Br₆ and Al₂I₆ to 2AlX₃ (X?=?F, Cl, Br, I). The results obtained showed that the dissociation energies of Al₂F₆, Al₂Cl₆, Al₂Br₆ and Al₂I₆ decrease from Al₂F₆ to Al₂I₆. Like aromatic molecules, these compounds have relatively significant negative NICS_iso(0) values. Clearly, based on magnetic criteria, they exhibit aromatic character and make it possible to consider them as σ-delocalized aromatic species, such as Möbius σ-aromatic species. The σ-aromatic character which is demonstrated by their NICS_iso(0) values decreases from Al₂F₆ to Al₂I₆. The NICS_iso values are dominated by the in-plane σ₂₂ (i.e., σ_yy, the plane containing halogen atoms bridged) chemical shift components. The increase of the NICS_iso values explains significantly the decrease of the corresponding dissociation energies of Al₂F₆, Al₂Cl₆, Al₂Br₆ and Al₂I₆. Importantly, the NBO results suggest that in these compounds the dissociation energies are controlled by the stabilization energies associated with σ _Al(1)-X2(b) →σ*_Al(3)-X4(b) electron delocalizations. The decrease of the stabilization energies associated with σ _Al(1)-X2(b) →σ*_Al(3)-X4(b) electron delocalizations is in accordance with the variation of the calculated NICS_iso values. The correlations between the dissociation energies of Al₂F₆, Al₂Cl₆, Al₂Br₆ and Al₂I₆, σ _Al(1)-X2(b) →σ*_Al(3)-X4(b) electron delocalizations, natural atomic orbitals (NAOs) and NICS_iso values have been investigated.     

Tree fine root Ca/Al molar ratio – Indicator of Al and acidity stress

Many Aloe species are exploited as natural products. Generally, the leaves are unsustainably picked from wild plants to meet the market demand. Basic scientific information on seed biology and the ways of increasing levels of secondary metabolites in seedlings is still lacking for Aloe species. This study investigated seed germination requirements and evaluated levels of secondary metabolites in seedlings of Aloe arborescens, an important species in traditional medicine. The highest percentage germination (78%) and the fastest germination rate (GR) (10% d^? 1) with a mean germination time (MGT) of 9 days were achieved at 20°C under a 16-h photoperiod. At 25°C, maximum percentage germination (67%) (P < 0.05), higher GR (13% d^? 1) and shorter MGT (6 days) were obtained under constant light. These results indicate that temperature and light play a significant role in germination of A. arborescens seeds. Increasing osmotic pressure on seeds decreased percentage germination, whereas buffering the solution to a range of pH values (4–10) did not significantly affect germination. Smoke–water (1:500 v/v), smoke-isolated karrikinolide (10^? 8 and 10^? 9 M) and potassium nitrate (10^? 3 and 10^? 4 M) significantly promoted germination compared with the control at 25°C (supra-optimal temperature) under a 16-h photoperiod. These treatments were also effective in increasing secondary metabolite levels (flavonoids and phenolics) in A. arborescens seedlings.     

‘Variations in phenological and functional traits in Thapsia garganica populations in Al Jebel Al Akhdar,Libya’

Thapsia garganica is a herbaceous perennial in the Apiaceae, distributed around the Mediterranean and traditionally used in North Africa as a remedy for arthritis, herpes, hair-fall, hypertension, rheumatic, eczema and scabies. T. garganica is the source of thapsigargin: known for killing cancer cells. Seven populations were studied in sites differing in aspect and elevation within Al Jebel Al Akhdar in Libya. We studied the within-population size distribution of individuals, the timing of the phenological events, and vegetative and reproductive traits.Thapsia garganica showed high flexibility of functional traits and shifts in the timing of phenological events in response to elevation and aspect (north- or south-facing slopes). Local soil properties, together with effects due to altitude and aspect, could be direct causes of the observed differences in terms of population size and phenological traits. The phenological patterns detected also provide insights into the species response to climate change. Despite this phenotypic flexibility, and good growth in sites at 300–700 m a. s. l. on south-facing slopes, most sites in this study have an unstable size-structure, with few small individuals. This raises concerns about the long-term persistence of the other populations of this species in Al Jebel Al Akhdar.     

In Memory of Yakov Abramovich Al’tman

Chronicle

In Memory of Yakov Abramovich Al’tman     

Answering a century old riddle: brachydactyly type Al

In 1903, Farabee analyzed the heredity of the human digital malformation, brachydactyly, the first recorded disorder of the autosomal dominant Mendelian trait. In 1951, Bell classified this type of brachydactyly as type A1 (BDA1). Over 100 cases from different ethnic groups have so far been reported. However, the real breakthrough in identifying the cause of BDA1 has only taken place in the last few years with the progress of the mapping and identification of one of the genes responsible for this disorder, thus providing an answer for a century old riddle. In this article, we attempt to review the current state of knowledge on the genetic features of BDA1 with its century-old history and signalling pathway of IHH, and also discuss genotype-phenotype correlation not only of BDA1, but also of all types of brachydactyly.     

浮游植物对溶解态Al的清除作用实验研究

近期黄、东海溶解态Al调查结果显示,赤潮爆发过程中溶解态Al的含量会明显降低,说明浮游植物生长对Al的生物地球化学循环有着重要的影响。本文在此背景下通过实验室培养,初步探讨了不同浓度Al加富条件下部分硅藻（新月菱形藻、中肋骨条藻、威氏海链藻）和甲藻（东海原甲藻）对溶解态Al的清除机制。结果表明：培养液中溶解态Al在硅藻的指数生长期会出现明显的下降,在衰亡期略有回升,而甲藻生长过程对水体中溶解态Al的这种清除相对于硅藻并不明显。采用痕量元素淋洗试剂对浮游植物进行淋洗,以区分细胞内结合态Al和细胞外吸附态Al的含量。淋洗实验结果表明：指数生长期硅藻细胞内结合态Al占浮游植物细胞内总Al含量的比例约为20%-80%,且稳定期的硅藻细胞内结合态Al的比例较指数生长期有不同程度的增加,说明硅藻在生长过程中会主动吸收溶液中的溶解态Al,实验结果对深入认识Al的海洋生物地球化学循环提供了重要的证据。     

Solvent effect on cation–π interactions with Al3+

Cation-π interactions are known to be one of the strongest noncovalent forces in the gas phase, but they rarely occur in a fully solvated environment. The present work used two different ab initio molecular dynamics-based approaches to describe the correlation between the strength of the cation-π interactions and the number of water molecules surrounding the cation. Five different complexes between an aluminum cation and different molecules containing aromatic rings were studied, and the degree of hydration of each complex was varied. Results indicated that cation-π interactions vanish when the aluminum cation is surrounded by more than three water molecules. The results also highlighted the influence of -OH ligands on the interaction strength.     

苜蓿青贮用乳酸菌复合系Al2的组成多样性

苜蓿是高蛋白的饲料作物,青贮是保存青草过冬的主要手段,但苜蓿是难青贮的作物,添加乳酸菌制剂是解决苜蓿青贮难的有效措施。本研究室通过连续的限制性培养筛选到苜蓿青贮用乳酸菌复合系Al2,用变性梯度凝胶电泳(DGGE)、平板分离及建立16S rDNA克隆文库3种手段相结合分析Al2的组成多样性,确认Al2复合菌系由7株菌组成,全部属于Lactobacillus。其中3株菌Al2-1i,Al2-2i,Al2-3i通过平板分离得到,分别属于L.plantarum(99.9%)、L.kimchii(99.4%)、L.farciminis(100%)。在Al2复合菌系的16S rDNA克隆文库中,上述7种菌的组成比例分别为55.21%、19.79%、14.58%、3.13%、3.13%、3.13%、1.03%。     

Phosphorylation sensitizes microtubule-associated protein τ to Al3+-induced aggregation

In Alzheimer’s disease the microtubule-associated protein τ becomes hyperphosphorylated and aggregates into paired helical filaments (PHFs). Although the biochemical basis of the aggregation of τ into PHFs is not very clear, Al³⁺ has been suggested to play some role. Previous studies have shown that Al³⁺ alters the phosphorylation state and causes aggregation of τ in experimental animals and cultured neurons. In this study Al³⁺ inhibited phosphorylation of τ by neuronal cdc2-like kinase and dephosphorylation of phosphorylated τ by phosphatase 2B. These inhibitions are very likely due to Al³⁺-induced aggregations of various proteins present in phosphorylation/dephosphorylation assay mixtures since Al³⁺ caused aggregations of all proteins examined. Furthermore, compared to other proteins, τ displayed only an average sensitivity towards Al³⁺-induced aggregation. However upon phosphorylation, τ’s sensitivity towards Al³⁺ increased 3.5 fold. In the presence of the metal chelator EDTA, Al³⁺-induced aggregates of τ became soluble, whereas Al³⁺-induced phosphorylated τ aggregates were insoluble in the buffer containing EDTA and remained insensitive to proteolysis. Our data suggest that phosphorylation sensitizes τ to Al³⁺ and phosphorylated τ transforms irreversibly into a phosphatase and protease resistant aggregate in presence of this metal ion.     

植物ABC转运蛋白及其在Al胁迫下的功能研究进展

ABC(ATP-Binding Cassette)转运蛋白家族是目前已知最大、功能最广泛的蛋自家族,能利用水解ATP的能量来参与生物体内多种物质的转运,这一基因家族成员在哺乳动物和微生物中已广泛鉴定,在植物中的研究是一个相对较新的研究领域.铝是酸性土壤作物生产的一个主要的限制因素,ABC转运蛋白在植物铝耐受性方面有重要作用.该文主要对ABC转运蛋白的特点、生物学功能及植物ABC转运蛋白在Al胁迫下的作用进行了综述,并分析其存在的问题,展望今后可能开展的研究方向.     

Is the Ca:Al ratio superior to pH,Ca or Al concentrations of soils in accounting for the distribution of plants in deciduous forest?

The distributions of vascular plants in south Swedish deciduous forests were related to exchangeable (exc) and soil solution concentrations of H⁺ (pH), Ca, Al and the Ca:Al ratios within these fractions. Topsoils (0–5 cm) of 172 sites with a pH_KCl of 3.2–3.9 (corresponding to 3.7–4.4 in soil solution) were used. In the soil solution both total Al_t and quickly reacting Al_r were determined. Exchangeable concentrations were generally well related to plant distributions, the highest correlation coefficients usually being given by pH_KCl>Ca_exc>Al_exc.>(Ca:Al)_exc. The (Ca:Al)_exc ratio was clearly inferior. Out of the soil solution variables studied, Ca concentration, followed by pH, was best correlated with plant distributions, Al_t, Al_r, and the Ca:Al ratios having similar and lower coefficients. It is concluded that the use of Ca:Al ratios as a general measure of Al toxicity in controlling plant distributions is rather problematic. It seems difficult to apply evidence for Ca-Al interactions from solution culture experiments to field conditions when measured as exchangeable or soil solution concentrations of the soil.     

Characterization of the lipase immobilized on Mg–Al hydrotalcite for biodiesel

Immobilization of Saccharomyces cerevisiae lipase by physical adsorption on Mg–Al hydrotalcite with a Mg/Al molar ratio of 4.0 led to a markedly improved performance of the enzyme. The immobilized lipase retained activity over wider ranges of temperature and pH than those of the free lipase. The immobilized lipase retained more than 95% relative activity at 50 °C, while the free lipase retained about 88%. The kinetic constants of the immobilized and free lipases were also determined. The apparent activation energies (E_a) of the free and immobilized lipases were estimated to be 6.96 and 2.42 kJ mol^?1, while the apparent inactivation energies (E_d) of free and immobilized lipases were 6.51 and 6.27 kJ mol^?1, respectively. So the stability of the immobilized lipase was higher than that of free lipase. The water content of the oil must be kept below 2.0 wt% and free fatty acid content of the oil must be kept below 3.5 mg KOH g [oil]^?1 in order to get the best conversion. This immobilization method was found to be satisfactory to produce a stable and functioning biocatalyst which could maintain high reactivity for repeating 10 batches with ester conversion above 81.3%.     

单斜Al－（L－丙氨酸）胰岛素初步晶体学研究

用微量气相扩散方法在含酚的柠檬酸缓冲体系中,得到了可供Ｘ射线晶体学分析用的Ａｌ－（Ｌ－丙氨酸）胰岛素晶体,晶体衍射能力为２．５Ａ。经Ｘ射线衍射分析确定,该晶体属于单斜晶系,空间群为Ｐ２_１,晶胞参数：ａ＝６１．５Ａ,ｂ＝６２．２Ａ,ｃ＝４８．３Ａ,α＝γ＝９０．０°,β＝１１０．９°。晶胞中每个结晶学不对称单位含有一个Ａｌ－（Ｌ－丙氨酸）胰岛素六聚体。     

酸性淋溶对赤红壤溶液Ca／Al比的影响

以前对铝的环境化学及生态学效应并未受到应有的重视。近年来随着环境酸化问题的深入研究,发现活性铝是造成树木和植物枯萎、农作物减产和鱼类及其他水生生物大量死亡的直接因素,因此已被认为是一种新的毒性元素。国外研究者认为,土壤溶液中钙、铝两种元素的摩尔比是衡量铝对植物危害的一个有用指标。当Ca/Al比小于1时,铝即能对植物赖以吸收水分和养分的根毛产生损害;当Ca/Al比