Alkylation of <Emphasis Type="Italic">p</Emphasis>-cresol with camphene in the presence of aluminum-containing catalysts

Alkylation of p-cresol with camphene was studied in the presence of aluminum-based catalysts (i-PrO)₃Al, AlH₃, AlCl₃, (i-Bu)₂AlH, EtAlCl₂, and LiAlH₄. Aluminum isopropylate was a selective catalyst for the preparation of ortho-isobornylphenol, its activity being close to that of aluminum phenolate.     

Phosphate and calcium uptake in beech (Fagus sylvatica) in the presence of aluminium and natural fulvic acids

In the present study we examine the effects of Al on the uptake of Ca²⁺ and H₂PO^-₄ in beech (Fagus sylvatica L.) grown in inorganic nutrient solutions and nutrient solutions supplied with natural fulvic acids (FA). All the solutions used were chemically well characterized. The uptake of Al by roots of intact plants exposed to solutions containing 0, 0.15 or 0.3 mM AlCl₃ for 24 h, was significantly less if FA (300 mg l⁻¹) were also present in the solutions. The Ca²⁺(⁴⁵Ca²⁺) uptake was less affected by Al in solutions supplied with FA than in solutions without FA. There was a strong negative correlation between the Al and Ca²⁺ uptake (r²=0.98). When the Al and Ca²⁺ (⁴⁵Ca²⁺) uptake were plotted as a function of the Al³⁺ activity (or concentration of inorganic mononuclear Al), almost the same response curves were obtained for the -FA and +FA treatments. We conclude that FA-complexed Al was not available for root uptake and therefore could not affect the Ca²⁺ uptake. The competitive effect of Al on the Ca²⁺ uptake was also shown in a 5-week cultivation experiment, where the Ca concentration in shoots decreased at an AlCl₃ concentration of 0.3 mM. The effect of Al on H₂PO⁻₄ uptake was more complex. The P content in roots and shoots was not significantly affected, compared with the control, by cultivation for 5 weeks in a solution supplied with 0.3 mM AlCl₃, despite a reduction of the H₂PO⁻₄ concentration in the nutrient solution to about one-tenth. At this concentration Al obviously had a positive effect on H₂PO⁻₄ uptake. The presence of FA decreased ³²P-phosphate uptake by more than 60% during 24 h, and the addition of 0.15 or 0.3 mM AlCl₃ to these solutions did not alter the uptake of ³²P-phosphate.     

Form of aluminium for uptake and translocation in buckwheat (Fagopyrum esculentum Moench)

 The forms of Al for uptake by the roots and translocation from the root to the shoot were investigated in a buckwheat (Fagopyrum esculentum Moench, cv. Jianxi) that accumulates Al in its leaves. The Al concentration in the xylem sap was 15-fold higher in the plants exposed to AlCl₃ than in those exposed to an Al-oxalate (1:3) complex, suggesting that the roots take up Al in the ionic form. The Al concentration in the xylem sap was 4-fold higher than that in the external solution after a 1-h exposure to AlCl₃ solution and 10-fold higher after a 2-h exposure. The Al concentration in the xylem sap increased with increasing Al concentration in the external solution. The Al uptake was not affected by a respiratory inhibitor, hydroxylamine, but significantly inhibited by the addition of La. These results suggest that Al uptake by the root is a passive process, and La³⁺ competes for the binding sites for Al³⁺ on the plasma membrane. The form of Al in the xylem sap was identified by ²⁷Al-nuclear magnetic resonance analysis. The chemical shift of ²⁷Al in the xylem sap was around 10.9 ppm, which is consistent with that of the Al-citrate complex. Furthermore, the dominant organic acid in the xylem sap was citric acid, indicating that Al was translocated in the form of Al-citrate complex. Because Al is present as Al-oxalate (1:3) in the root, the present data show that ligand exchange from oxalate to citrate occurs before Al is released to xylem. Received: 10 December 1999 / Accepted: 3 February 2000     

A Novel Aluminum‐Ion Battery: Al/AlCl3‐[EMIm]Cl/Ni3S2@Graphene

Due to an ever‐increasing demand for electronic devices, rechargeable batteries are attractive for energy storage systems. A novel rechargeable aluminum‐ion battery based on Al³⁺ intercalation and deintercalation is fabricated with Ni₃S₂/graphene microflakes composite as cathode material and high‐purity Al foil as anode. This kind of aluminum‐ion battery comprises of an electrolyte containing AlCl₃ in an ionic liquid of 1‐ethyl‐3‐methylimidazolium chloride ([EMIm]Cl). Galvanostatic charge/discharge measurements have been performed in a voltage range of 0.1–2.0 V versus Al/AlCl₄ ^?. An initial discharge specific capacity of 350 mA h g^?1 at a current density of 100 mA g^?1 is achieved, and the discharge capacity remains over 60 mA h g^?1 and coulombic efficiency of 99% after 100 cycles. Typically, for the current density at 200 mA g^?1, the initial charge and discharge capacities are 300 and 235 mA h g^?1, respectively. More importantly, it should be emphasized that the battery has a high discharge voltage plateau (≈1.0 V vs Al/AlCl₄ ^?). These meaningful results represent a significant step forward in the development of aluminum‐ion batteries.     

Aluminium effects on transmembrane potential in cells of fibrous roots of sugar beet

The effect of aluminium (Al) on the electrical transmembrane potential of epidermal and outer cortical root cells of intact seedlings of sugar beet (Beta vulgaris L. cv. Monohill) was studied. The potential difference to the surrounding medium was recorded with microelectrodes inserted into the vacuoles (PD_v) and cytoplasm (PD_c) of intact roots. Both long-term effects of AlCl₃ (100, μM present during cultivation) and immediate effects of AlCl₃ (10, 50, or 100 μM present in the assay medium), were measured. The effect of Al was measured at pH 4.0, 5.0 and 6.5 in order to obtain information on the toxicity of different Al forms existing at different pH values. Low pH and/or the presence of AlCl₃ during cultivation caused large depolarizations of the PD_v. Since the immediate effect of 2,4-dinitrophenol (DNP) on the resting potential of cells from Al-cultivated plants was negligible, it is likely that Al affects the metabolic component of the transmembrane potential. Aluminium also had an immediate effect on the PD in root cells of plants cultivated without Al. Addition of 10 or 50 μM Al to the assay medium caused hyperpolarization of PD_v in the presence of 0.5 mM Ca²⁺ at all pH values studied, depolarization of PD_c at pH 6.5, and hyperpolarization of PD_c at lower pH. At 1 mM Ca²⁺, or in the presence of K⁺ (≥ 2 mM), however, the same Al concentrations had little effect on PD_c. The strongest depolarizing effects of 10 or 50 μM Al in short-term treatments were obtained at pH 6.5, and were probably due to the soluble species Al(OH)₃, which is more frequent at pH 6.5 than at a lower pH. Addition of 50 μM Al caused alkalinization of the root medium at pH 6.5, but not at pH 4.0. Therefore, it is possible that Al at pH 6.5 is bound to, or translocated across, the membrane without the accompanying hydroxide ions. It is likely that most of the Al is bound to the root cells, since removal of Al from the buffer surrounding the roots did not cause the changed PD values to return to the original values. Aluminium also interacts with effects of Ca²⁺ and K⁺ on the membrane potential, since changes in PD, induced by changes in concentrations of Ca²⁺ and K⁺ are different in the absence and presence of Al.     

Aluminum chloride causes 5-fluorouracil resistance in hepatocellular carcinoma HepG2 cells

Chemoresistance is one of the major obstacles in chemotherapy-based hepatocellular carcinoma (HCC) intervention. Aluminum (Al) is an environmental pollutant that plays a vital role in carcinogenesis, tumorigenesis, and metastasis. However, the effect of Al on chemoresistance remains unknown. 5-Fluorouracil (5-FU) is a widely used antitumor drug. Therefore, we investigated the effects of aluminum chloride (AlCl₃) on the chemoresistance of HepG2 cells to 5-FU and explored the underlying mechanisms of these effects. The results demonstrated that AlCl₃ pretreatment attenuated 5-FU-induced apoptosis through Erk activation and reversed 5-FU-induced cell cycle arrest by downregulating p-Chk2^Thr68 levels. In addition, AlCl₃ markedly increased the levels of proteins associated with cell migration, such as MMP-2 and MMP-9. Further investigation demonstrated that an Erk inhibitor (U0126) reversed the AlCl₃-induced decrease in apoptosis, enhancement of cell cycle progression, promotion of cell migration, and attenuation of oxidative stress. In summary, AlCl₃ induced chemoresistance to 5-FU in HepG2 cells. The present study suggests a potential influence of AlCl₃ on 5-FU therapy. These findings may help others to understand and properly address the resistance of HCC to chemotherapeutic agents.     

Magnesium uptake by Al-stressed maize plants with special emphasis on cation interactions at root exchange sites

As aluminium (Al) severely inhibits magnesium (Mg) uptake by many plant species, Mg uptake and Mg-Al interactions in maize (Zea mays L.) were studied in a series of short and long-term experiments. A relationship between Mg uptake and the degree of Mg saturation of exchange or binding sites of the root apoplast (root-CEC) was studied by growing plants in solutions containing: (i) different concentrations of Al, calcium (Ca) and hydrogen (H) ions; and (ii) a number of organic complexes of Al. In short-term experiments, Ca had little effect on the Mg nutrition of maize plants. However, with increasing concentrations of Al and H ions in nutrient solution, there was a decrease in both the degree of Mg saturation of root-CEC and Mg uptake. Effects of pH on cation (H, Al, Mg, Ca) binding at the root apoplasm were pronounced and complicated because of a simultaneous change of H ion concentration, effective root-CEC and Al speciation. The behaviour of Al as organic Al complexes differed from that supplied as aluminium chloride (AlCl₃). In the presence of organo-Al complexes, less Mg was replaced from apoplastic binding sites and Mg uptake was inhibited less severely than with AlCl₃. In a long-term experiment, Al-citrate, in contrast with AlCl₃, was not phytotoxic to maize, expressed by the lack of any inhibition of shoot biomass production.     

Aluminum inhibits phosphatidic acid formation by blocking the phospholipase C pathway

Aluminum (Al³⁺) has been recognized as a main toxic factor in crop production in acid lands. Phosphatidic acid (PA) is emerging as an important lipid signaling molecule and has been implicated in various stress-signaling pathways in plants. In this paper, we focus on how PA generation is affected by Al³⁺ using Coffea arabica suspension cells. We pre-labeled cells with [³²P]orthophosphate (³²Pi) and assayed for ³²P-PA formation in response to Al³⁺. Treating cells for 15 min with either AlCl₃ or Al(NO₃)₃ inhibited the formation of PA. In order to test how Al³⁺ affected PA signaling, we used the peptide mastoparan-7 (mas-7), which is known as a very potent stimulator of PA formation. The Al³⁺ inhibited mas-7 induction of PA response, both before and after Al³⁺ incubation. The PA involved in signaling is generated by two distinct phospholipid signaling pathways, via phospholipase D (PLD; EC: 3.1.4.4) or via Phospholipase C (PLC; EC: 3.1.4.3), and diacylglycerol kinase (DGK; EC 2.7.1.107). By labeling with ³²Pi for short periods of time, we found that PA formation was inhibited almost 30% when the cells were incubated with AlCl₃ suggesting the involvement of the PLC/DGK pathway. Incubation of cells with PLC inhibitor, U73122, affected PA formation, like AlCl₃ did. PLD in vivo activation by mas-7 was reduced by Al³⁺. These results suggest that PA formation was prevented through the inhibition of the PLC activity, and it provides the first evidence for the role of Al toxicity on PA production.     

Reactions of dichloroaluminium acetylacetonate with lewis bases. 1. Ionic complex of Cl2alacac with tetrahydrofurane

The reaction of dichloroaluminium acetylacetonate with THF has been studied. The ionic complex [(acac)₂Al·2THF]⁺[AlCl₄]⁻ was found to result from the reaction. The structure of the complex has been investigated by the variable temperature ¹H NMR technique, as well as by ¹³C and ²⁷Al NMR spectroscopy. The cation complex [(acac)₂Al·2THF]⁺ is predominantly trans in dichloromethane solution (75% trans and 25% cis). In the presence of an excess of THF a fast exchange proceeds at room temperature in the cation complex between the free THF molecules and those present in the complex, which is accompanied by a stereo-chemical rearrangement of the cation complex.     

High tolerance of aluminum in the grass species Cynodon aethiopicus

Concentrations of aluminum (Al) were determined in leaves of native terrestrial plants, macrophytes and fruit parts (watermelon and tomato) using inductively coupled plasma mass spectrometry. Al concentrations in water and soil were determined by inductively coupled plasma optical emission spectrometry. Potamogeton thunbergii (macrophyte) and Cynodon aethiopicus (terrestrial grass) had the highest leaf Al concentrations (2 and 1 g kg^?1 dw, respectively). Transfer factors (mg kg^?1 dw plants/mg kg^?1 dw soil) based on total Al concentrations in soil varied from 2 × 10^?3 to 0.05 and from 1.9 to 78 based on mobile Al concentrations determined after sequential extraction. Bioconcentration factors (mg kg^?1 dw plants/mg L^?1 water) varied from 19 to 9.5 × 10³ L kg^?1 dw. Plants can accumulate high concentrations of Al when growing in neutral pH soils and slightly alkaline lakes in the Ethiopian Rift Valley. Controlled experiments showed that C. aethiopicus can accumulate high levels of Al both in root and shoot. Compared to Arabidopsis thaliana, C. aethiopicus was more tolerant to Al exposure as ≥400 μM AlCl₃ was needed to inhibit root growth compared to 200 μM in A. thaliana. After exposing C. aethiopicus and A. thaliana in 800 μM AlCl_3, alkaline comet assay indicates significant DNA (deoxyribonucleic acid) damage in A. thaliana while C. aethiopicus was unaffected. No significant induction of reactive oxygen species (ROS), in terms of leaf H₂O₂ levels, could be observed in C. aethiopicus. C. aethiopicus has mechanisms to suppress both Al-induced ROS and DNA damage, thereby increasing tolerance of the species to high Al concentrations.     

Induction of Betalain Pigmentation in Hairy Roots of Red Beet under Different Radiation Sources

The effects of aluminum on lipid peroxidation and activities of antioxidative enzymes were investigated in detached rice leaves treated with 0 to 5 mM AlCl₃ at pH 4.0 in the light. AlCl₃ enhanced the content of malondialdehyde but not the content of H₂O₂. Superoxide dismutase activity was reduced by AlCl₃, while catalase and glutathione reductase activities were increased. Peroxidase and ascorbate peroxidase activities were increased only after prolonged treatment, when toxicity occurred. The results give evidence that Al treatment caused oxidative stress and in turn, it caused lipid peroxidation.     

Effects of dietary aluminum source and concentration on mineral status of feeder lambs

A 100 d experiment was conducted to determine the effects of aluminum (Al) source and concentration on mineral status, emphasizing phosphorus (P), of 50 feeder lambs. Six treatments, fed at 10% of the total diet, were formulated using two sources of Al, AlCl₃ and an Al-based water treatment residual (WTR, 11.1% Al), with varying levels of Al and P: (1) control (10% sand, C), (2) low WTR (2.5% WTR and 7.5% sand, L-WTR), (3) AlCl₃ with added P (1% AlCl₃, 9% sand, and 0.4% P, AlCl₃ + P), (4) high WTR (10% WTR, H-WTR), (5) AlCl₃ (1% AlCl₃ and 9% sand, AlCl₃), and (6) high WTR with added P (10% WTR and 0.4% P, H-WTR + P). The total Al varied from 0.037 to 1.2% among diets. Only lambs fed the high WTR diet without P supplementation (H-WTR) decreased feed intakes. These lambs consumed about half as much feed as lambs on all the other treatments, and had lower (P < 0.05) BW from d 84 on. Lambs receiving the H-WTR had the lowest bone Ca, P and Mg concentrations (fresh basis, mg/cm³) and lowest bone mineral content (BMC) as determined by radiographs (mm of Al). Results for the lambs on H-WTR were confounded by the greatly reduced feed intake of animals on this treatment. Plasma P decreased in all lambs consuming Al, regardless of Al source, but the effects were less severe in animals provided additional P supplementation (AlCl₃ + P and H-WTR + P). Apparent absorption of P was affected by concentration and source of Al in two metabolism trials (n = 42) beginning on d 34 and d 70, respectively. In the first trial, d 34, lambs receiving AlCl₃ treatment had reduced apparent P absorption, −17.7% (P < 0.05), when compared to all other treatments. In the d 70 trial, lambs receiving both AlCl₃ and H-WTR treatments were negatively impacted (P < 0.05) compared to the control, −20.9 and −2.5% apparent P absorption, respectively, but were no longer different from one another (P > 0.05). Diets containing 1.2% Al as WTR without P supplementation depressed feed intakes, weight gains, plasma P concentrations (P < 0.05), and BMC. However, given adequate P supplementation, even lambs consuming this amount of Al did not suffer detrimental effects, as lambs on H-WTR + P did not differ from the control (P > 0.05) in feed intakes, weight gains, or BMC.     

Response of the plant root to aluminum stress: Analysis of the inhibition of the root elongation and changes in membrane function

Pea root elongation was strongly inhibited in the presence of a low concentration of Al (5 μM). In Al-treated root, the epidermis was markedly injured and characterized by an irregular layer of cells of the root surface. Approximately 30% of total absorbed Al accumulated in the root tip and Al therein was found to cause the inhibition of whole root elongation. Increasing concentrations of Ca²⁺ effectively ameliorated the inhibition of root elongation by Al and 1 mM of CaCl₂ completely repressed the inhibition of root elongation by 50 μM Al. The ameliorating effect of Ca²⁺ was due to the reduction of Al uptake. H⁺-ATPase and H⁺-PPase activity as well as ATP and PPidependent H⁺ transport activity of vacuolar membrane vesicles prepared from barley roots increased to a similar extent by the treatment with 50 μM AlCl₃. The rate of increase of the amount of H⁺-ATPase and H⁺-PPase was proportional to that of protein content measured by immunoblot analysis with antibodies against the catalytic subunit of the vacuolar H⁺-ATPase and H⁺-PPase of mung bean. The increase of both activities was discussed in relation to the physiological tolerance mechanism of barley root against Al stress.     

Effect of aluminum on cytoplasmic Ca2+ homeostasis in root hairs of Arabidopsis thaliana (L.)

Aluminum inhibition of root growth is a major world agricultural problem where the cause of toxicity has been linked to changes in cellular calcium homeostasis. Therefore, the effect of aluminum ions (Al) on changes in cytoplasmic free calcium concentration ([Ca²⁺]_c) was followed in root hairs of wild-type, Al-sensitive and Al-resistant mutants of Arabidopsis thaliana (L.) Heynh. Generally, Al exposure resulted in prolonged elevations in tip-localized [Ca²⁺]_c in both wild-type and Al-sensitive root hairs. However, these Al-induced increases in [Ca²⁺]_c were not tightly correlated with growth inhibition, occurring up to 15 min after Al had induced growth to stop. Also, in 32% of root hairs examined growth stopped without a detectable change in [Ca²⁺]_c. In contrast, Al-resistant mutants showed little growth inhibition in response to AlCl₃ exposure and in no case was a change in [Ca²⁺]_c observed. Of the other externally applied stresses tested (oxidative and mechanical stress), both were found to inhibit root hair growth, but only oxidative stress (H₂O₂, 10 μM) caused a prolonged rise in [Ca²⁺]_c similar to that induced by Al. Again this increase occurred after growth had been inhibited. The lack of a tight correlation between Al exposure, growth inhibition and altered [Ca²⁺]_c dynamics suggests that although exposure of root hairs to toxic levels of Al causes an alteration in cellular Ca²⁺ homeostasis, this may not be a required event for Al toxicity. The elevation in [Ca²⁺]_c induced by Al also strongly suggests that the phytotoxic action of Al in root hairs is not through blockage of Ca²⁺-permeable channels required for Ca²⁺ influx into the cytoplasm. Received: 24 October 1997 / Accepted: 6 March 1998     

Aluminium polyphosphate complexes in the mycorrhizal basidiomyceteLaccaria bicolor: A27Al-nuclear magnetic resonance study

The techniques of ²⁷Al- and ³¹P-nuclear magnetic resonance (NMR) spectroscopy were used to investigate the interactions of aluminium with intracellular ligands within the mycelium of the ectomycorrhizal basidiomycete Laccaria bicolor (Maire) Orton (S238). The vegetative mycelium was grown on medium containing 0.5 mM AlCl₃ for 0.5 to 3 d. The ²⁷Al-NMR spectra showed that aluminium was rapidly taken up and accumulated into polyphosphate complexes in the vacuole. Comparison with Al-polyphosphate complexes obtained in vitro on model systems indicated that Al forms at least three mixed-solvation complexes with Pi and polyphosphates, that there is more than one complex present under any set of conditions, and that the equilibrium between these complexes shifts dramatically with Al concentration in the medium. The high phosphate concentrations in the growth medium favoured the accumulation of the Al-polyphosphate complexes. When mycelium containing Al-polyphosphate complexes was transferred to Al-free nutrient solution for 9 d, the Alpolyphosphate complexes were not remobilized. The sequestration of Al in the polyphosphate complexes could therefore make a significant contribution to the protection of mycorrhizal plants against aluminium toxicity.Abbreviations NMR nuclear magnetic resonance - PolyP polyphosphate(s) - PP₁ terminal phosphate of PolyP - PP₃ middle phosphate of PolyP We thank Prof. Daniel Canet (Laboratoire de Méthodologie RMN, University of Nancy I, Vandceuvre-lès-Nancy, France) for his constant encouragement and Christine Delaruelle for skilled technical assistance in growing the fungal cultures. This work was supported by a research grant from the Commission of the European Communities (STEP-CT90-0059, Role of Ectomycorrhiza in Stress Tolerance of Forest Trees) to F.M. and a travel grant from the Institut National de la Recherche Agronomique to I.K.; R.C. is a recipient of a Postdoctoral Fellowship from the Natural Sciences and Engineering Research Council of Canada.     

Protective effect of ascorbic acid and glutathione on AlCl3-inhibited growth of rice roots

The effect of AlCl₃ on the antioxidant system of rice roots and the role of applied antioxidants ascorbic acid (AsA) and glutathione (GSH) in AlCl₃-inhibited growth of rice roots were investigated. AlCl₃ treatment resulted in a rapid inhibition of root growth but had no effect on lipid peroxidation and antioxidative enzyme activities in rice roots. AlCl₃ treatment resulted in lower content of H₂O₂, AsA, and GSH than in controls. Exogenous AsA or GSH counteracted growth inhibition of rice roots induced by AlCl₃. AlCl₃ treatment increased syringaldazine peroxidase (SPOX) activities and lignin content in rice roots. Exogenous AsA or GSH prevented the decrease in H₂O₂ content and the increase in SPOX activities and lignin content in rice roots caused by AlCl₃. Results suggest that lignification induced by low AsA or GSH content may explain the mechanism of Al-inhibited growth of rice roots.     

Quantitative 27Al NMR spectroscopic studies of Al (III) complexes with organic acid ligands and their comparison with GEOCHEM predicted values

The toxic inorganic monomeric forms of aluminium (Al) that limit plant growth have been shown to be effectively detoxified by complexation with organic acid ligands released by breakdown of added organic materials. The binding capacity of these acids is dependent on the degree of dissociation of their carboxyl groups and their ability to form bonds with Al. ²⁷Al NMR spectroscopy provides a non-invasive technique to study the bonding of Al with potential ligands without disturbing the equilibrium of the system. In single ligand systems containing oxalic acid, three ²⁷Al resonance peaks were observed at 6.4, 11.4 and 16.0 ppm downfield from the Al³⁺ reference peak at 0 ppm. These were assigned to Alox, Alox₂ and Alox₃ complexes respectively and were observable at pH values down to 3.5. In the presence of the citrate ligand, two ²⁷Al resonance peaks at 6.1 and 11.3 ppm, assigned respectively to the Alcit and Alcit₂ complexes, were observed at pH 3.4. At pH 4.3 and an Al:citrate molar ratio of 1:2, the 6.1 ppm peak was not visible, and the second peak further downfield was split into two unresolved peaks at 10.8 and 12.4 ppm indicating the presence of two forms of the Alcit₂ complex. Distribution of Al between the various species, based on integration of the resonance peaks and equilibrium calculations carried out using GEOCHEM, is discussed in light of the stability constants present in the database of GEOCHEM version (v.) 1.23 and GEOCHEM-PC v. 2.0. Large discrepancies between the computed values and the NMR measured values indicate the need to incorporate more recent literature values in the database for realistic equilibrium calculations in systems containing organic acid ligands. The potential of using quantitative ²⁷Al NMR measurements to calculate stability constants is discussed.     

Aluminum Ions Induce Oat Protoplasts to Produce an Extracellular (1-->3)beta-d-Glucan

Aluminum chloride induced mesophyll protoplasts of oat (Avena sativa) to produce an extracellular polysaccharide (EPS). EPS induced by AlCl₃ appeared identical to that produced in response to the phytotoxin victorin (JD Walton, ED Earle [1985] Planta 165: 407-415). Al ions at 1 millimolar were toxic to protoplasts, but maximum EPS production occurred at a sublethal concentration of 200 micromolar, assayed at pH 6.0. As measured by incorporation of [¹⁴C]glucose, AlCl₃ stimulated EPS production 10- to 15- fold. Pretreatment of protoplasts with cycloheximide prevented EPS production but not cell death in response to AlCl₃, indicating that protein synthesis was necessary for EPS production but not for the phytotoxicity of Al ions. The trivalent salts of Y, Yb, Gd, and In also induced EPS production but those of Sc, Fe, Ga, Cr, and La did not. Mesophyll protoplasts from an acid-soil tolerant oat cultivar, Coker 83-23, produced less EPS in response to AlCl₃ than the acid-soil sensitive cultivar Fla 501. EPS was also produced by wheat (Triticum aestivum) and barley (Hordeum vulgare) protoplasts in response to AlCl₃. An Al-tolerant cultivar of wheat, Atlas, produced less EPS than an Al-sensitive cultivar, Scout, but an Al-tolerant cultivar of barley, Dayton, produced more than the Al-sensitive cultivar Kearney. Therefore, production of EPS by protoplasts in response to Al ions did not appear to be related to Al ion tolerance at the level of whole plants. EPS fluoresced in the presence of Calcofluor and Sirofluor and was degraded by purified laminarinase [(1→3)β-d-glucanase] but not pectinase (polygalacturonase). EPS was composed solely of glucose in 1→3 linkages; hence it is a (1→3)β-d-glucan (callose).     

Importance of hydrogen ions and aluminium in regulating the structure and function of stream ecosystems: an experimental test

1. Experiments simulating spring acidic snowmelt episodes were conducted to determine the effects of short-term inputs of H⁺ and Al on the chemistry and biology of a poorly buffered mountain stream. HC1 and A1C1₃ were added in separate experiments to first- to third-order reaches of a New Hampshire stream. 2. Cation exchange and Alⁿ⁺ dissolution reactions neutralized experimentally added H ⁺, whereas groundwater dilution was insignificant. Mobilized Ca⁺⁺, Mg⁺⁺ and Alⁿ⁺ concentrations progressively increased from third- to first-order reaches during HC1 additions. Mobilization of Ca⁺⁺ and Mg⁺⁺ was greater during A1C1₃ than HC1 addition. 3. Total phosphorus was mobilized from stream sediments during both HCI and A1C1₃ addition. Dissolved organic carbon (DOC) decreased during A1C1₃ addition in the second-order but not in the third-order reach. DOC concentration decreased during HCI addition only when Al^{n +} mobilized from the stream bottom was >0.28 mg AI 1¹. 4. Production of foam at the water surface during AlCl₃ addition to a second-order and HCl addition to a first-order reach indicated a reduction in surface tension of the streamwater and may be related to complexation reactions between Al and DOC at low pH (4–5). 5. Mayfly nymphs and blackfly and chironomid larvae drifted at greater rates from HCl- and AlCl₃treated sections of first- and second-order streams than from corresponding reference areas. 6. When stream pH was lowered to 5.25–5.5 by HCI alone (15 μg monomeric inorganic Al l^?1), the behaviour of aquatic invertebrates did not change, but pH reduced to the same range during Al additions (280μg Al 1^?1) did affect it. Therefore, fluctuating aluminium concentrations in low-order streams at a pH range of 4.5–5.5 may alter the biology and geochemistry of poorly buffered waters.