Академический Документы
Профессиональный Документы
Культура Документы
Non-metals
Essential
Metalloids micronutrients
Metals
D-block metals
Non-essential
toxic elements
(examples)
Essential for
animals,
beneficial for
plants
www.plantcell.org/cgi/doi/10.1105/tpc.109.tt1009
Outline
• Other micronutrients
• B, Cl, Si, Se
Dennis Hoagland and colleagues developed a soil-
• Summary and ongoing research free system for micronutrient studies. Today,
“Hoagland’s Solution” continues to be used as a
complete plant nutrient solution.
Adapted from Hoagland, D.R., and Arnon, D.I. (1950).The water-culture method for growing plants without soil. Circular. California Agricultural Experiment Station. Volume 347. 2nd edition.
Micronutrients are essential in at least one plant
taxon
“An element is not
considered essen.al unless Or… “the plant can be so severely deficient in
a deficiency of it makes it the element that it exhibits abnormalities
impossible for the plant to in growth, development, or reproduction, i.e.
complete its life cycle” "performance," compared to plants with a
-Arnon and Stout, 1939 Mn lower deficiency”
B -Epstein and Bloom, 2003
Zn
Cu
Fe Mo Cl 1969 Ni
1920 - 1954 Si 1987
1860
1940 (Required for
Equisetum)
Arnon, D.I., and Stout, P.R. (1939). The essentiality of certain elements in minute quantity for plants with special reference to copper. Plant Physiol. 14: 371 – 375; Epstein, E. and Bloom, A.J. (2003). Mineral Nutrition of
Plants: Principles and Perspectives, 2nd Ed., John Wiley & Sons, New York. See also Marschner, P., ed (2012). Marschner’s Mineral Nutrition of Higher Plants. 3rd ed. (London: Academic Press).
Nutrient availability in soil is highly dependent on soil
pH
Aluminum
Adapted from Lin, Y.-F. and Aarts, M.M. (2012). The molecular mechanism of zinc and cadmium stress response in plants. Cellular and Molecular Life Sciences. 69: 3187-3206 and Merchant, S.S., and Helmann, J.D.
(2012). Elemental economy: Microbial strategies for optimizing growth in the face of nutrient limitation. Adv. Microb. Physiol 60: 91 – 210.
Essential micronutrients are normally found in small
amounts
Element Biologically Concentra9on in plant
relevant form in (mg / kg)
plants (These values vary by species, other
nutrient levels etc.)
Deficiency Normal Toxicity
Iron (Fe) Fe2+, Fe3+ < 20 20 – 1000 > 2000
For comparison,
Copper (Cu) Cu+, Cu2+ < 10 10 – 25 > 25
concentrations of
Zinc (Zn) Zn2+ < 10 10 – 120 > 120 macronutrients
Manganese (Mn) Mn2+, Mn3+, Mn4+ < 90 90 – 200 > 200 range from 1000 –
Molybdenum Mo4+, Mo6+ (in < 0.1 0.1 – 90 > 90
450,000 mg / kg)
(Mo) Moco or FeMoco)
Palmer, C.M. and Guerinot, M.L. (2009). Facing the challenges of Cu, Fe and Zn homeostasis in plants. Nat Chem Biol. 5: 333-340. See also Marschner, P., ed (2012).
Marschner’s Mineral Nutrition of Higher Plants. 3rd ed. (London: Academic Press) and Krämer, U. (2010). Metal hyperaccumulation in plants. Annu. Rev. Plant Biol. 61: 517-534.
Metal micronutrients: What’s so special about
metals?
Metal micronutrients
Metals
D-block metals
Most metal micronutrients are important cofactors
for enzymes
Micronutrients
Waldron, K.J., Rutherford, J.C., Ford, D. and Robinson, N.J. (2009). Metalloproteins and metal sensing. Nature. 460: 823-830.
Many metal nutrients are redox active: necessary but
dangerous
e− Fenton reaction
About ¼ of cellular proteins
are metalloproteins (not M(n)+ + H2O2
counting those that make
loose associations with Mg)
M(n)+ M(n+1)+ M(n+1)+ + HO· + OH−
Ferrous
malate Chaperones are small
metal-binding proteins
For example
Fe(OH)3 + 3H+ Fe3+ + 3H2O
Insoluble Soluble
citrate
Iron citrate
Banci, L., Bertini, I., McGreevy, K.S. and Rosato, A. (2010). Molecular recognition in copper trafficking. Natural Prod. Rep. 27: 695-710
Siderophores: Small metal-binding molecules to
facilitate uptake
Siderophores are
structurally diverse. 1. Bacteria and
They are defined other organisms
functionally as a small secrete
molecule that binds siderophores when A siderophore,
metals (the term iron is limiting enterobactin
literally means “iron
carrier”) + Fe3+
2. The siderophore
binds (chelates) the
metal, keeping the
metal in solution
Uptake
3. The siderophore-
metal complex is Fe-enterobactin
imported into the cell
Blindauer, C.A. and Schmid, R. (2010). Cytosolic metal handling in plants: determinants for zinc specificity in metal
transporters and metallothioneins. Metallomics. 2: 510-529 with permission of The Royal Society of Chemistry.
Metals chelators: nicotianamine, phytosiderophores
and others
COOH
3x The enzyme In grasses, phytosiderophores
COOH COOH COOH
nicotiananamine are produced from NA, and
S+ NH2 N NH NH2
synthase (NAS) released from the plant into the
makes Nicotianamine
Adenosyl soil to enhance metal uptake
nicotianamine
(NA) from three Metal-PS
complex COOH COOH COOH
molecules of S-
COOH COOH COOH Yellow= metal
adenosyl Red = oxygen N NH OH
methionine Blue = nitrogen
N NH NH2 Green = carbon Phytosiderophore
Nicotianamine
Grasses have a suite of enzymes
that converts NA to various
compounds in the PS family
NA chelates
Citrate and other small molecules are also metal chelators
metals for HN
transport within N
the plant Citrate O
O−
Metal-NA N
complex + N
Ni H2
O
Purple = metal Metal H2 O−
Ni(His)
N
Red = oxygen HN
Blue = nitrogen Fe(III)-citrate
Blindauer, C.A. and Schmid, R. (2010). Cytosolic metal handling in plants: determinants for zinc specificity in metal transporters and metallothioneins. Metallomics. 2: 510-529.
Phytochelatins and metallothioneins are sulfur-
containing metal binders
Phytochelatins Metallothioniens
Blindauer, C.A. and Schmid, R. (2010). Cytosolic metal handling in plants: determinants for zinc specificity in metal transporters and metallothioneins. Metallomics. 2: 510-529.Rea,
P.A., Vatamaniuk, O.K. and Rigden, D.J. (2004). Weeds, worms, and more. Papain's long-lost cousin, phytochelatin synthase. Plant Physiol 136: 2463-2474; Leszczyszyn, O.I., Imam,
H.T. and Blindauer, C.A. (2013). Diversity and distribution of plant metallothioneins: a review of structure, properties and functions. Metallomics. 5: 1146-1169..
Iron: Abundant, important, and largely insoluble
Al O
Si
Reprinted by permission from Macmillan Publishers Ltd Rasmussen, B., Fletcher, I.R., Bekker, A., Muhling, J.R., Gregory, C.J. and Thorne,
A.M. (2012). Deposition of 1.88-billion-year-old iron formations as a consequence of rapid crustal growth. Nature. 484: 498-501.
Photosynthetic and respiratory electron transport
chains require Fe
Or flavodoxin (Cu)
Respiratory
electron
transport in
Or plastocyanin (Cu)
mitochondria
Photosynthetic
electron
transport in
chloroplasts
Blaby-Haas, C.E. and Merchant, S.S. (2013). Iron sparing and recycling in a compartmentalized cell. Curr. Opin. Microbiol. 16: 677-685
Iron in cells is found in "
heme, Fe-S clusters and other forms
In cells, iron is found in
many forms, including
heme, siroheme, Fe-S
clusters (mainly Fe2S2
and Fe4S4), di-iron
centers, mononuclear
Fe and others (e.g., sulfite reductase,
Ferrodoxin-nitrite reductase)
Balk, J. and Schaedler, T.A. (2014). Iron cofactor assembly in plants. Annu. Rev. Plant Biol. 65: 125-153; Schofield, C.J. and Zhang, Z. (1999). Structural and mechanistic studies on 2-oxoglutarate-dependent oxygenases
and related enzymes. Curr. Opin. Struct. Biol. 9: 722-731; Rocklin, A.M., Tierney, D.L., Kofman, V., Brunhuber, N.M.W., Hoffman, B.M., Christoffersen, R.E., Reich, N.O., Lipscomb, J.D. and Que, L. (1999). Role of
the nonheme Fe(II) center in the biosynthesis of the plant hormone ethylene. Proc. Natl. Acad. Sci. USA 96: 7905-7909; Boucher, I., Brzozowski, A., Brannigan, J., Schnick, C., Smith, D., Kyes, S. and Wilkinson, A.
(2006). The crystal structure of superoxide dismutase from Plasmodium falciparum. BMC Struct. Biol. 6: 20.
Copper: Critical for aerobic life
Sommer, A.L. (1931) Copper as an essential for plant growth.PlantPhysiol.6: 339–45; Image © Ute Krämer (RUB), Josef Bergstein (MPI Golm)
Copper proteins are involved in electron transport
and other rxns
Cu/Zn
Superoxide
Dismutase
Laccase /
multicopper Plastocyanin
Cytochrome c oxidase /
oxidase ferroxidase
Ethylene
receptor
(in ER)
Cu(I) Entry
Chaperone
Cu-metallochaperones
have a “trafficking” role
Cu-metallothioneins
have a “buffering“ role
(like a sponge)
Banci, L., Bertini, I., McGreevy, K.S. and Rosato, A. (2010). Molecular recognition in copper trafficking. Natural Prod. Rep. 27: 695-710
Cells have essentially no “free” copper; it is entirely
bound
Cu-Chaperone Cu-Target
Fe can also be shielded by chaperones but they are less well characterized than Cu chaperones
Banci, L., Bertini, I., McGreevy, K.S. and Rosato, A. (2010). Molecular recognition in copper trafficking. Natural Prod. Rep. 27: 695-710; see also O'Halloran, T.V. and Culotta, V.C. (2000). Metallochaperones, an
intracellular shuttle service for metal ions. J. Biol. Chem. 275: 25057-25060..
Zinc: Deficiency common in plants and people
Barley grown with Zinc is deficient in 50% of the world’s agricultural soils
and without zinc and is recognized as the world’s most critical
micronutrient deficiency in crops. In humans, Zn
deficiency contributes to 800,000 child deaths annually
Soil
Sommer, A.L., and Lipman, C.B. (1926). Evidence on the indispensable nature of zinc and boron for higher green plants. Plant Physiol. 1:
231–249. Alloway BJ. 2007: Zinc in Soils and Crop Nutrition. IZA Publications. International Zinc Association, Brussels
Zn deficiency causes chlorosis, stunting, low yields
and death
Photo credits: South Dakota State University; IPNI; Howard F. Schwartz, Colorado State University, Bugwood.org; IRRI
Ribosomal proteins represent the largest cellular
pool of Zn
Klinge, S., Voigts-Hoffmann, F., Leibundgut, M., Arpagaus, S. and Ban, N. (2011). Crystal structure of the eukaryotic 60S ribosomal subunit in complex with initiation factor 6. Science. 334: 941-948
Zinc-fingers are found in many nucleic acid-binding
proteins
C
C H
Zn stabilizes the Zn-finger domain. In this C2H2
fold, two Cys and two His interact with Zn. Some H
proteins have many Zn fingers Zn
Knight, R. and Shimeld, S. (2001). Identification of conserved C2H2 zinc-finger gene families in the Bilateria. Genome Biology. 2: research0016.0011 - research0016.0018. Laity, J.H., Lee, B.M. and Wright, P.E. (2001).
Zinc finger proteins: new insights into structural and functional diversity. Curr. Opin. Struct. Biol. 11: 39-46 with permission from Elsevier. Nolte, R.T., Conlin, R.M., Harrison, S.C. and Brown, R.S. (1998). Differing
roles for zinc fingers in DNA recognition: Structure of a six-finger transcription factor IIIA complex. Proc. Natl. Acad. Sci. USA.. 95: 2938-2943.
Manganese: Central to the oxygen-evolving reaction
O2 released
Mn cluster
Mn
Symptoms of Mn deficiency
MnSOD is the
dominant SOD in
mitochondria
Iwata, S. and Barber, J. (2004). Structure of photosystem II and molecular architecture of the oxygen-evolving centre. Curr. Opin. Struct. Biol. 14: 447-453; Cheniae, G.M. and Martin, I.F. (1969). Photoreaction of
Manganese Catalyst in Photosynthetic Oxygen Evolution. Plant Physiol. 44: 351-360. http://fyi.uwex.edu/discoveryfarms/2011/06/soil-conditions-and-plant-analysis-for-micronutrient-crop-nutrition/. Page, M.D., Allen,
M.D., Kropat, J., Urzica, E.I., Karpowicz, S.J., Hsieh, S.I., Loo, J.A. and Merchant, S.S. (2012). Fe sparing and Fe recycling contribute to increased superoxide dismutase capacity in iron-starved Chlamydomonas
reinhardtii. Plant Cell. 24: 2649-2665
Four photons are needed to charge the water-
splitting reaction
Vogt, L., Vinyard, D.J., Khan, S. and Brudvig, G.W. (2015). Oxygen-evolving complex of Photosystem II: an analysis of second-shell
residues and hydrogen-bonding networks. Curr. Opin. Chem. Biol. 25: 152-158
In most cells molybdenum functions as Molybdenum
cofactor Moco
+Mo -Mo Mo is functional
when conjugated to
a pterin, as
Molybenum cofactor
(Moco) MoO 2- 4
Arnon, D.I., and Stout, P.R. (1939). Molybdenum as an essential element for higher plants. Plant Physiol. 14: 599-602. Mendel, R.R. (2013). The molybdenum cofactor. J. Biol. Chem. 288: 13165-13172.
MoO42- resembles SO42-, Mo and S transporters are
same family
MoO42-
Reversible
chelation MoO42-
CNX Moco
MoO42- resembles SO42- and pathway
high-affinity transport takes MOT2
place through MOT1 and
MOT2, members of the Moco MoO42-
Vacuole
sulfate-transporter family
Moco enzymes
Adapted from Tejada-Jimenez, M., Chamizo-Ampudia, A., Galvan, A., Fernandez, E. and Llamas, A. (2013). Molybdenum metabolism in plants. Metallomics. 5: 1191-1203.
A handful of plant enzymes use Mo
K., Barbier, G.G., Hecht, H.-J., Mendel, R.R., Campbell, W.H. and Schwarz, G. (2005). Structural basis of eukaryotic nitrate reduction: Crystal structures of the nitrate reductase active site. Plant Cell. 17: 1167-1179.
Mendel, R.R. and Hänsch, R. (2002). Molybdoenzymes and molybdenum cofactor in plants. J. Exp. Bot. 53: 1689-1698.See also Schwarz, G., Mendel, R.R., and Ribbe, M.W. (2009). Molybdenum cofactors, enzymes
and pathways. Nature 460: 839 – 847.
Nitrogenase, a bacterial enzyme, uses an Fe & Mo
cofactor, FeMoco
FeMoco
N2 N2
Moco
Nitrogenase Note that FeMoco
NH4+
and Moco are
totally different
NH4+
structures
Buchanan, B.B., Gruissem, W. and Jones, R.L. (2000) Biochemistry and Molecular Biology of Plants. American Society of Plant Physiologists.MacLeod, K.C. and Holland, P.L. (2013). Recent developments in the homogeneous reduction of
dinitrogen by molybdenum and iron. Nat Chem. 5: 559-565; See also Schwarz, G., Mendel, R.R., and Ribbe, M.W. (2009). Molybdenum cofactors, enzymes and pathways. Nature 460: 839 – 847.
Nickel: Necessary but rarely limiting
Urease
% Germination
Ni in urease
active site Other Ni-dependent
proteins are suspected but Ni (ng/g)
have not been identified
Carter, E.L., Flugga, N., Boer, J.L., Mulrooney, S.B. and Hausinger, R.P. (2009). Interplay of metal ions and urease. Metallomics. 1: 207-221; Dixon, N.E., Gazzola, C., Blakeley, R.L. and Zerner, B. (1975). Jack bean
urease (EC 3.5.1.5). Metalloenzyme. Simple biological role for nickel. J. Am. Chem. Soc.. 97: 4131-4133. Ragsdale, S.W. (2009). Nickel-based Enzyme Systems. J. Biol. Chem. 284: 18571-18575; Eskew, D.L., Welch,
R.M. and Caru, E.E. (1983). Nickel: An essential micronutrient for legumes and possibly all higher plants. Science. 222: 621-623 with permission from AAAS; Brown, P.H., Welch, R.M. and Cary, E.E. (1987). Nickel: A
micronutrient essential for higher plants. Plant Physiol. 85: 801-803.
Nickel transporters and chelators
Alyssum lesbiscum, a nickel
Ni uses many of the same transporters as Fe, and hyperaccumulator shows greatly
elevated levels of the amino acid
its toxicity may be due in part to competition with Fe
histidine which is able to chelate Ni
Vacuole
Ni ZIP
Fe
Ni-NA YSL
Fe-NA
IREG2
NRAMP
Adapted from Tejada-Jiménez, M., Galván, A., Fernández, E. and Llamas, Á. (2009). Homeostasis of the micronutrients Ni, Mo and Cl with specific biochemical functions. Curr. Opin. Plant Biol. 12: 358-363; Reprinted
from Kramer, U., Cotter-Howells, J.D., Charnock, J.M., Baker, A.J.M. and Smith, J.A.C. (1996). Free histidine as a metal chelator in plants that accumulate nickel. Nature. 379: 635-638 by permission.
Toxic metals and metalloids
Cadmium interferes
with zinc uptake and Arsenate [As(V)] interferes
activities, affects copper Al inhibits with phosphate uptake and
homeostasis, and root growth function, and arsenite
moves through iron [As(III)] can move through
transporters silicate transporters
Arsenic is toxic to plants and humans and affects
millions
Brammer, H. and Ravenscroft, P. (2009). Arsenic in groundwater: A threat to sustainable agriculture in South and South-east Asia. Environment International. 35: 647-654 with
permission from Elsevier; see also Hasanuzzaman, M., Nahar, K., Hakeem, K.R., Öztürk, M., and Fujita, M. (2015). Arsenic toxicity in plants and possible remediation. In Soil
Remediation and Plants, K.Hakeem, M. Sabir, M. Öztürk and A.Murmet, eds (Amsterdam: Elsevier), pp 433 -501.
In severely arsenic-
affected areas, Eating As-
there are several contaminated
routes to human rice grain
exposure
Burning rice
straw leads to
volatilization and
inhalation
Drinking water
As in soil and from shallow wells
groundwater that are As
moves into plants contaminated
Rahman, M.A., Hasegawa, H., Mahfuzur Rahman, M., Mazid Miah, M.A. and Tasmin, A. (2008). Arsenic accumulation in rice (Oryza sativa L.): Human exposure through
food chain. Ecotoxicology and Environmental Safety. 69: 317-324
Rice is particularly prone to arsenic uptake
accumulation
Inorganic As is mainly
found as arsenate As(V)
and arsenite As(III). In
anaerobic or flooded
soils such as rice
As(OH)3
paddies, As(III)
predominates
As(V) ↑
As(III) As(OH)3
Ma, J.F., Yamaji, N., Mitani, N., Xu, X.-Y., Su, Y.-H., McGrath, S.P. and Zhao, F.-J. (2008). Transporters of arsenite in rice and their role in arsenic accumulation in rice grain. Proc. Natl. Acad. Sci. USA. 105:
9931-9935; Adapted from Zhao, F.-J., McGrath, S.P. and Meharg, A.A. (2010). Arsenic as a food chain contaminant: Mechanisms of plant uptake and metabolism and mitigation strategies. Annu. Rev. Plant Biol. 61:
535-559 and Verbruggen, N., Hermans, C. and Schat, H. (2009). Mechanisms to cope with arsenic or cadmium excess in plants. Curr. Opin. Plant Biol. 12: 364-372.
Strategies to ameliorate As impacts
Increasing synthesis of
phytochelaYns, increased
sequestraYon in the vacuole,
and increased efflux can
contribute to lower As levels in
the rice grain
As(V)
Arsenate PC
reductase synthase
Adding
As(V) Phytochelatin
competing P As(III)
or Si to soil PO42-
interferes with As(III) As(III)-PC
As uptake As(III)
Si
Xylem
Song, W.-Y., Yamaki, T., Yamaji, N., Ko, D., Jung, K.-H., Fujii-Kashino, M., An, G., Martinoia, E., Lee, Y. and Ma, J.F. (2014). A
rice ABC transporter, OsABCC1, reduces arsenic accumulation in the grain. Proc. Natl. Acad. Sci. USA. 111: 15699-15704;
Cadmium is an extremely toxic heavy metal
Cd is usually mixed with zinc and released during the mining process
P-containing
fertilizers are often
It was known as itai-itai Cd-contaminated
(ouch-ouch) disease after the
painful symptoms, which
include bone decalcification, Ni-Cd
batteries
lung and kidney disease
Clemens, S., Aarts, M.G.M., Thomine, S. and Verbruggen, N. (2013). Plant science: the key to preventing slow cadmium poisoning. Trends Plant Sci. 18: 92-99
Breeding for altered transporter activities leads to
low-Cd rice
Uraguchi, S. and Fujiwara, T. (2012). Cadmium transport and tolerance in rice: perspectives for reducing grain cadmium accumulation. Rice. 5: 5; Uraguchi, S., et al. (2011). Low-affinity cation transporter (OsLCT1)
regulates cadmium transport into rice grains. Proc. Natl. Acad. Sci. 108: 20959-20964. See also Uraguchi, S. and Fujiwara, T. (2013). Rice breaks ground for cadmium-free cereals. Curr. Opin. Plant Biol. 16: 328-334.
Ishikawa, S., et al. (2012). Ion-beam irradiation, gene identification, and marker-assisted breeding in the development of low-cadmium rice. Proc. Natl. Acad. Sci. USA 109: 19166-19171.
Aluminium, a damaging element in acidic soils
Aluminum
tolerance is
genetically
determined
Brunner, I. and Sperisen, C. (2013). Aluminium exclusion and aluminium tolerance in woody plants. Front. Plant Sci. 4: 172; Delhaize, E. and Ryan, P.R. (1995). Aluminum Toxicity and Tolerance in Plants. Plant Physiol. 107: 315-321.
One important Al-tolerance strategy is organic acid
(OA) extrusion
Aluminum Aluminum
Al-tolerant varieYes excrete sensitive tolerant
much more organic acid than
sensiYve varieYes
Al3+
Al3+
Al3+ Al3+
Al3+
Al3+ Al3+
Al3+
Delhaize, E., Ryan, P.R. and Randall, P.J. (1993). Aluminum Tolerance in Wheat (Triticum aestivum L.) (II. Aluminum-Stimulated Excretion of Malic Acid from Root Apices). Plant Physiol. 103: 695-702.
Al tolerance can be conferred by elevated
expression of a root cell malate transporter
Barley
engineered
with a malate
transporter
shows
increased Al
tolerance as
compared to
wild type
Schroeder, J.I., Delhaize, E., Frommer, W.B., Guerinot, M.L., Harrison, M.J., Herrera-Estrella, L., Horie, T., Kochian, L.V., Munns, R., Nishizawa, N.K., Tsay, Y.-F. and Sanders, D. (2013). Using membrane
transporters to improve crops for sustainable food production. Nature. 497: 60-66
Mechanisms of aluminium tolerance include
exclusion & sequestration
Organic
acid
TranscripYonal secreYon
responses
Changes in
Vacuolar mitochondrial
sequestraYon metabolism
ROS accumulaYon
and detoxificaYon
Brunner, I. and Sperisen, C. (2013). Aluminium exclusion and aluminium tolerance in woody plants. Front. Plant Sci. 4: 172; See also Nunes-Nesi, A., Brito, D.S., Inostroza-Blancheteau, C., Fernie, A.R. and Araújo,
W.L. (2014). The complex role of mitochondrial metabolism in plant aluminum resistance. Trends Plant Sci. 19: 399-407. See also Delhaize, E., Ma, J.F. and Ryan, P.R. (2012). Transcriptional regulation of aluminium
tolerance genes. Trends Plant Sci. 17: 341-348..
Multiple mechanisms of Al tolerance in rice
FRDL4 exports
citrate which
immobilizes
external Al
ART1 is an
Al-induced
transcription
factor that
Nrat1 is an
upregulates
Al uptake
Al tolerance transporter
genes
(In
Arabidopsis,
START has
the same ALS1
function) imports Al
into the
vacuole
Ma, J., Chen, Z. and Shen, R. (2014). Molecular mechanisms of Al tolerance in gramineous plants. Plant Soil. 381: 1-12; see references therein
Many plants naturally tolerate or accumulate
aluminium
Aluminium
hyperaccumulating
species occur in at least
45 plant families
Yoshida, K., Mori, M. and Kondo, T. (2009). Blue flower color development by anthocyanins: from chemical structure to cell physiology. Natural Product Reports. 26: 884-915; Schreiber, H., Jones, A., Lariviere, C.,
Mayhew, K. and Cain, J. (2011). Role of aluminum in red-to-blue color changes in Hydrangea macrophylla sepals. BioMetals. 24: 1005-1015. Tu7uh; AxelBoldt; Jansen, S., Broadley, M., Robbrecht, E. and Smets, E.
(2002). Aluminum hyperaccumulation in angiosperms: A review of its phylogenetic significance. Bot. Rev. 68: 235-269; Heather Coleman.
Boron is an essential micronutrient
Warington, K. (1923). The effect of boric acid and borax on the broad bean and certain other plants. Ann. Bot. 37: 629-672
Boron is indispensable for cell wall crosslinking
Adapted from Bolaños, L., Lukaszewski, K., Bonilla, I. and Blevins, D. (2004). Why boron? Plant Physiol. Biochem. 42: 907-912; O'Neill, M.A., Eberhard, S., Albersheim, P. and Darvill, A.G. (2001).
Requirement of borate cross-linking of cell wall Rhamnogalacturonan II for Arabidopsis growth. Science. 294: 846-849. Complex Carbohydrate Research Center
Boron influx mutants have developmental and cell
wall defects
Loss of function mutant of B transporter tsl
has cell wall and developmental defects TSL encodes a NIP boron influx
transporter. The mutant phenotype is
rescued by added boron
Durbak, A.R., et al. (2014). Transport of boron by the tassel-less1 aquaporin is critical for vegetative and reproductive development in maize. Plant Cell. 26: 2978-2995; See also Leonard, A., et al. (2014). tassel-less1
encodes a boron channel protein required for inflorescence development in maize. Plant Cell Physiol. 55: 1044-1054; Takano, J., Miwa, K. and Fujiwara, T. (2008). Boron transport mechanisms: collaboration of channels
and transporters. Trends Plant Sci. 13: 451-457
Boron efflux mutants have developmental and cell
wall defects
Chatterjee, M., Tabi, Z., Galli, M., Malcomber, S., Buck, A., Muszynski, M. and Gallavotti, A. (2014). The boron efflux transporter ROTTEN EAR is required for maize inflorescence development and fertility. Plant Cell.
26: 2962-2977. Takano, J., Miwa, K. and Fujiwara, T. (2008). Boron transport mechanisms: collaboration of channels and transporters. Trends Plant Sci. 13: 451-457
Natural variation in B transporter is associated with
B tolerance
Highly expressed
Poorly expressed
Non-functional
Orange shows
countries or
regions where B
toxicity has been
identified
Red allele
is tolerant
Black diamonds indicate predicted sources of the tolerance alleles, with
proposed dispersion shown by black arrows. Red circles show countries
where modern cultivars carrying tolerance alleles have been found.
Pallotta, M., Schnurbusch, T., Hayes, J., Hay, A., Baumann, U., Paull, J., Langridge, P. and Sutton, T. (2014). Molecular basis of adaptation to high
soil boron in wheat landraces and elite cultivars. Nature. 514: 88-91
Boron transport is mediated in part by subcellular
localization of BOR1
Kasai, K., Takano, J., Miwa, K., Toyoda, A. and Fujiwara, T. (2011). High boron-induced ubiquitination regulates vacuolar sorting of the BOR1 borate transporter in Arabidopsis thaliana. J. Biol. Chem. 286: 6175-6183; See
also Zelazny, E. and Vert, G. (2014). Plant nutrition: Root transporters on the move. Plant Physiol. 166: 500-508.
Silicon is essential for some plants, beneficial for
many
Silicon (Si) is the Equisetum arvense In 1969 Chen and
second most abundant Lewis showed Si to be
element in the earth’s essential for growth of
crust after oxygen the common horsetail,
Equisetum arvense
It is often found as
silica SiO2 (insoluble
quartz sand), and in
biological systems as Diatoms form cell walls from silicon
silicic acid Si(OH)4
See Chen, C.-h., and Lewin, J. (1969). Silicon as a nutrient element for Equisetum arvense. Can. J. Bot. 47: 125-131; Painting by
Carl Axel Magnus Lindman; MPF. Norris, D.J. (2007). Materials science: Silicon life forms. Nature 446: 146 – 147
Silicon contributes to plant resistance to biotic &
abiotic stress
Powdery mildew on
control plant
Ma, J.F. and Yamaji, N. (2006). Silicon uptake and accumulation in higher plants. Trends Plant Sci. 11: 392-397; Heckman, J. (2013) Silicon: A beneficial substance. Better Crops 97: 14 – 16.
Rice grown with low Si is susceptible to herbivores &
pathogens
The mechanisms of Si-conferred
resistance remain unclear:
• Physical barrier?
• Enhancement of defense
responses?
• Priming of defense responses?
Ma, J.F. and Yamaji, N. (2006). Silicon uptake and accumulation in higher plants. Trends Plant Sci. 11: 392-397 and Cooke, J. and Leishman, M.R. (2011). Is plant ecology more siliceous than we realise? Trends Plant Sci. 16: 61-68. See also Vivancos,
J., Labbé, C., Menzies, J.G. and Bélanger, R.R. (2015). Silicon-mediated resistance of Arabidopsis against powdery mildew involves mechanisms other than the salicylic acid (SA)-dependent defence pathway. Mol. Plant Pathol. In press Van
Bockhaven, J., De Vleesschauwer, D. and Höfte, M. (2013). Towards establishing broad-spectrum disease resistance in plants: silicon leads the way. J. Exp. Bot. 64: 1281-1293.
Uptake and transport of silicon in rice; Arsenic uses
the same pathway
exodermis
Image by J. Ma. See Mitani, N., Chiba, Y., Yamaji, N. and Ma, J.F. (2009). Identification and characterization of maize and barley Lsi2-Like silicon efflux transporters reveals a distinct silicon uptake system from that in
rice. Plant Cell. 21: 2133-2142. Ma, J.F., Yamaji, N., Mitani, N., Xu, X.-Y., Su, Y.-H., McGrath, S.P. and Zhao, F.-J. (2008). Transporters of arsenite in rice and their role in arsenic accumulation in rice grain. Proc. Natl.
Acad. Sci. USA. 105: 9931-9935; see also Van Bockhaven, J., De Vleesschauwer, D. and Höfte, M. (2013). Towards establishing broad-spectrum disease resistance in plants: silicon leads the way. J. Exp. Bot. 64:
1281-1293; See Ma, J.F., Tamai, K., Yamaji, N., Mitani, N., Konishi, S., Katsuhara, M., Ishiguro, M., Murata, Y. and Yano, M. (2006). A silicon transporter in rice. Nature. 440: 688-691; Ma, J.F., Yamaji, N., Mitani, N.,
Tamai, K., Konishi, S., Fujiwara, T., Katsuhara, M. and Yano, M. (2007). An efflux transporter of silicon in rice. Nature. 448: 209-212.
Chlorine is an essential micronutrient
Broyer, T.C., Carlton, A.B., Johnson, C.M., and Stout, P.R. (1954). Chlorine, a micronutrient element for higher plants. Plant Physiol. 29: 536 -532; Chloride deficiency photo used by permission of R.E. Engel.
One of chloride’s main roles is to regulate cell turgor
Potassium
transporters
Other roles: O2-evolving complex and several special
metabolites
Eupachlorin
acetate, isolated
from Eupatorium
rotundifolium, is a
Cl-containing
sesquiterpenoid
with cytotoxic
properties
Iwata, S. and Barber, J. (2004). Structure of photosystem II and molecular architecture of the oxygen-evolving centre. Curr. Opin. Struct. Biol. 14: 447-453 ; Guskov, A., Kern, J., Gabdulkhakov, A., Broser, M., Zouni, A.
and Saenger, W. (2009). Cyanobacterial photosystem II at 2.9-A resolution and the role of quinones, lipids, channels and chloride. Nat Struct Mol Biol. 16: 334-342. Engvild, K.C. (1986). Chlorine-containing natural
compounds in higher plants. Phytochemistry. 25: 781-791; USDA
Chloride transporters contribute to salinity tolerance
(salt exclusion)
Henderson, S.W., Baumann, U., Blackmore, D.H., Walker, A.R., Walker, R.R., and Gilliham, M. (2014). Shoot chloride exclusion and salt tolerance in grapevine is associated with differential ion transporter expression in roots. BMC Plant Biol. 14:
273.See also Teakle, N.L. and Tyerman, S.D. (2010). Mechanisms of Cl- transport contributing to salt tolerance. Plant Cell Environ. 33: 566-589 and Jossier, M., Kroniewicz, L., Dalmas, F., Le Thiec, D., Ephritikhine, G., Thomine, S., Barbier-
Brygoo, H., Vavasseur, A., Filleur, S. and Leonhardt, N. (2010). The Arabidopsis vacuolar anion transporter, AtCLCc, is involved in the regulation of stomatal movements and contributes to salt tolerance. Plant J. 64: 563-576. USDA, USDA
Selenium is an essential micronutrient for animals
Selenium deficiency
25 human genes encode selenoproteins, in which
affects many systems
the “21st amino acid” Se-Cys (abbreviated U) is
and can cause death
incorporated into the polypeptide
Thyroid
Muscle
Heart
Reproductive
tissues
Lu, J. and Holmgren, A. (2009). Selenoproteins. J. Biol. Chem. 284: 723-727; Labunskyy, V.M., Hatfield, D.L. and Gladyshev, V.N. (2014). Selenoproteins: Molecular pathways and physiological roles. Physiol. Rev. 94:
739-777. Hatfield, D.L., Tsuji, P.A., Carlson, B.A. and Gladyshev, V.N. (2014). Selenium and selenocysteine: roles in cancer, health, and development. Trends Biochem. Sci. 39: 112-120.
The amount of Se in soils has a direct effect on
dietary levels
Dark = High Keshan
Light = Low County
Pink = High
Very low Se levels in Gray = Low
northeast China
contributed to many
deaths from Se-
deficiency, aka
Keshan disease.
Blazina, T., Sun, Y., Voegelin, A., Lenz, M., Berg, M. and Winkel, L.H.E. (2014). Terrestrial selenium distribution in China is potentially linked to monsoonal climate. Nat Commun. 5: 4717. See also Lyons, G.,
Stangoulis, J. and Graham, R. (2003). High-selenium wheat: biofortification for better health. Nutrit. Res. Rev. 16: 45-60. Zhu, Y.-G., Pilon-Smits, E.A.H., Zhao, F.-J., Williams, P.N. and Meharg, A.A. (2009). Selenium
in higher plants: understanding mechanisms for biofortification and phytoremediation. Trends Plant Sci. 14: 436-442. USGS
Selenium can be found in several different forms in
plants
Selenate
Selenocysteine Selenocysteine can be
Selenate (SeO42-) is the major (SeCys) introduced into selenoproteins
assimilated form in most or converted into other forms
plants. It resembles sulfate including volatile forms
and is taken up through
sulfate SO42- transporters
Cystseine
Sulfate (Cys)
Se metabolism and bioremediation involves S
assimilation genes
Uptake as selenate Manipulation of these
[Se(VI)] through sulfate pathways can contribute to
transporters or as either biofortification and
selenite [Se(IV)] through phytoremediation efforts;
phosphate transporters for example, increasing
expression of APS or SMT
leads to increased
accumulation of Se
Se is incorporated into
organic form through S
assimilation pathway
Malagoli, M., Schiavon, M., Dall'Acqua, S. and Pilon-Smits, E.A.H. (2015). Effects of selenium biofortification on crop nutritional quality. Front. Plant Sci. 6: 280; Zhu, Y.-G., Pilon-Smits,
E.A.H., Zhao, F.-J., Williams, P.N. and Meharg, A.A. (2009). Selenium in higher plants: understanding mechanisms for biofortification and phytoremediation. Trends Plant Sci. 14: 436-442.
Van Hoewyk, D. (2013). A tale of two toxicities: malformed selenoproteins and oxidative stress both contribute to selenium stress in plants. Ann. Bot. 112: 965-972.
Summary and ongoing research
Non-metals
Metalloids
Metals
D-block
Essential
micronutrients
Non-essential
toxic elements
(examples)
www.plantcell.org/cgi/doi/10.1105/tpc.109.tt1009
Transporters and chelators contribute
to homeostasis
Clemens, S., Palmgren, M.G. and Krämer, U. (2002). A long way ahead: understanding and engineering plant metal accumulation. Trends Plant Sci. 7: 309-315
The study of plant
micronutrients helps
ensure:
1) Optimal crop yields,
particularly in nutrient
-poor soil,
2) Adequate dietary Cd
iron and zinc so that
children and adults
can thrive, and
3) Helps to protect
people from the toxic
effects of arsenic and
cadmium
IRRI; CIAT; Water.org; Centre for Food Safety, Government of Hong Kong