Juglone

Last updated
Juglone
Juglone.png
Juglone-3D-balls.png
Names
Preferred IUPAC name
5-Hydroxynaphthalene-1,4-dione
Other names
  • 5-Hydroxy-1,4-naphthoquinone
  • 5-Hydroxy-p-naphthoquinone
  • Regianin
  • 5-Hydroxynaphthoquinone
  • Nucin
  • NCI 2323
  • Oil Red BS
  • C.I. Natural Brown 7
Identifiers
3D model (JSmol)
1909764
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.006.880 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 207-567-5
PubChem CID
RTECS number
  • QJ5775000
UNII
  • InChI=1S/C10H6O3/c11-7-4-5-9(13)10-6(7)2-1-3-8(10)12/h1-5,12H X mark.svgN
    Key: KQPYUDDGWXQXHS-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C10H6O3/c11-7-4-5-9(13)10-6(7)2-1-3-8(10)12/h1-5,12H
    Key: KQPYUDDGWXQXHS-UHFFFAOYAH
  • O=C\2c1c(c(O)ccc1)C(=O)/C=C/2
Properties
C10H6O3
Molar mass 174.155 g·mol−1
AppearanceYellow solid
Melting point 162 to 163 °C (324 to 325 °F; 435 to 436 K)
Slightly sol.
Related compounds
Related compounds
quinone
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Juglone, also called 5-hydroxy-1,4-naphthalenedione (IUPAC) is a phenolic organic compound with the molecular formula C10H6O3. In the food industry, juglone is also known as C.I. Natural Brown 7 and C.I. 75500. It is insoluble in benzene but soluble in dioxane, from which it crystallizes as yellow needles. It is an isomer of lawsone, which is the active dye compound in the henna leaf.

Contents

Juglone occurs naturally in the leaves, roots, husks, fruit (the epicarp), and bark of plants in the Juglandaceae family, particularly the black walnut ( Juglans nigra ), and is toxic or growth-stunting to many types of plants. [1] It is sometimes used as an herbicide, as a dye for cloth and inks, and as a coloring agent for foods and cosmetics.

History

The allelopathic effects of walnut trees on other plants were observed as far back as the 1st century CE. [2] Juglone itself was first isolated from black walnut in 1856, and was identified as the compound responsible for its allelopathic effects in 1881. [2]

In 1921, a study observed that tomato plants near black walnut trees exhibited wilted leaves, suggesting an adverse interaction. [3] In 1926, instances of apple tree damage caused by both Juglans nigra and Juglans cinerea (butternut) trees were reported in northern Virginia. [4] Certain apple tree varieties displayed varying levels of resistance to walnut toxicity.

In 1926, it was observed that walnut trees in alfalfa fields resulted in crop death, while grass remained unaffected. [5] Subsequent experiments indicated that the toxic compound within walnut trees exhibited limited solubility in water, implying that the compound underwent chemical changes upon leaving the tree. It was only in 1928 that the phytotoxic nature of the compound was identified for other plant species. [6]

The scientific community faced controversy when the harmful effects of walnut trees on certain crops and trees were initially reported, following claims that the trees damaging apple trees in northern Virginia were not walnut trees at all. [7]

In 1942 it was demonstrated that tomato and alfalfa germination and seedling growth were inhibited by contact with pieces of walnut roots, providing additional scientific evidence of juglone's phytotoxicity. [8]

Juglone was used medicinally in America during the early 1900s, prescribed for the treatment of various skin diseases. [9]

Chemistry

Synthesis

Juglone is derived by oxidation of hydrojuglone, 1,5-dihydroxynaphthalene, after enzymatic hydrolysis. [10] It can also be obtained by oxidations of 5,8-dihydroxy-1-tetralone with silver oxide (Ag2O), manganese dioxide (MnO2), or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). [11]

Extraction

Juglone has been extracted from the husk of walnut fruit of which it contains 2–4% by fresh weight. [12] [13]

Degradation

Before oxidization, juglone exists in plants such as walnuts in the form of colorless hydroxyjuglone, the hydroquinone analog. This is rapidly oxidized to juglone once exposed to air. The evidence that hydroxyjuglone is readily degraded is most apparent in the color change of walnut hulls from yellow to black after being freshly cut. [14]

Indigenous bacteria found in the soil of black walnut roots, most notably Pseudomonas putida J1, are able to metabolize juglone and use it as their primary source of energy and carbon. [15] Because of this, juglone is not so active as a cytotoxin in well-aerated soils. [16]

Spectral data

The IR spectrum for juglone shows bands at 3400, 1662, and 1641 cm−1, which are characteristic respectively of the hydroxyl and two carbonyl groups. [17] The 13C-NMR spectrum shows 10 signals, including at 160.6, 183.2, and 189.3 ppm for the hydroxyl and two carbonyl carbons. [17] [11]

Biological effects

Juglone is an allelopathic compound, a substance produced by a plant to stunt the growth of another plant. Juglone affects germination of plants less than it affects growth of the root and stem systems. In below average concentrations, it has increased the rate of germination in some coniferous seeds. [18]

Juglone exerts its effect by inhibiting certain enzymes needed for metabolic function. This in turn inhibits the effects of respiration of mitochondria and inhibits photosynthesis found in common crops such as maize and soy at juglone concentrations that are at or below those common in nature. [19] [20] In addition to these inhibitions, juglone has been shown to alter the relationship between plants and water because of its effect on stomatal functioning. [21]

The rise in popularity of alley cropping with black walnut trees and maize in the American Midwest, due to the high value of black walnut trees, has led to certain studies being conducted about the particular relationship between the two species. Research has shown that juglone affects the yield of maize crops; however, the practice of pruning and usage of root barriers greatly reduce these effects. [22]

Some plants and trees are resistant to juglone including some species of maple (Acer), birch (Betula), and beech (Fagus).[ citation needed ]

It is highly toxic to many insect herbivores. However, some of them, example Actias luna (Luna moth), can detoxify juglone (and related naphthoquinones) to non-toxic 1,4,5-trihydroxynaphthalene. It has also shown anthelmintic (expelling parasitic worms) activity on mature and immature Hymenolepis nana in mice. [23] Naphthoquinonic compounds also exhibit antimicrobial activity. [24] [25] [26]

Uses

Juglone is occasionally used as a herbicide. Traditionally, juglone has been used as a natural dye for clothing and fabrics, particularly wool, and as ink. Because of its tendency to create dark orange-brown stains, juglone has also found use as a coloring agent for foods and cosmetics, such as hair dyes.

See also

Related Research Articles

<span class="mw-page-title-main">Companion planting</span> Agricultural technique

Companion planting in gardening and agriculture is the planting of different crops in proximity for any of a number of different reasons, including weed suppression, pest control, pollination, providing habitat for beneficial insects, maximizing use of space, and to otherwise increase crop productivity. Companion planting is a form of polyculture.

<i>Juglans</i> Genus of trees

Walnut trees are any species of tree in the plant genus Juglans, the type genus of the family Juglandaceae, the seeds of which are referred to as walnuts. All species are deciduous trees, 10–40 metres (33–131 ft) tall, with pinnate leaves 200–900 millimetres (7.9–35.4 in), with 5–25 leaflets; the shoots have chambered pith, a character shared with the wingnuts (Pterocarya), but not the hickories (Carya) in the same family.

<span class="mw-page-title-main">Cover crop</span> Crop planted to manage erosion and soil quality

In agriculture, cover crops are plants that are planted to cover the soil rather than for the purpose of being harvested. Cover crops manage soil erosion, soil fertility, soil quality, water, weeds, pests, diseases, biodiversity and wildlife in an agroecosystem—an ecological system managed and shaped by humans. Cover crops can increase microbial activity in the soil, which has a positive effect on nitrogen availability, nitrogen uptake in target crops, and crop yields. Cover crops reduce water pollution risks and remove CO2 from the atmosphere .Cover crops may be an off-season crop planted after harvesting the cash crop. Cover crops are nurse crops in that they increase the survival of the main crop being harvested, and are often grown over the winter. In the United States, cover cropping may cost as much as $35 per acre.

Chemical ecology is the study of chemically mediated interactions between living organisms, and the effects of those interactions on the demography, behavior and ultimately evolution of the organisms involved. It is thus a vast and highly interdisciplinary field. Chemical ecologists seek to identify the specific molecules that function as signals mediating community or ecosystem processes and to understand the evolution of these signals. The substances that serve in such roles are typically small, readily-diffusible organic molecules, but can also include larger molecules and small peptides.

<span class="mw-page-title-main">Allelopathy</span> Production of biochemicals which affect the growth of other organisms

Allelopathy is a biological phenomenon by which an organism produces one or more biochemicals that influence the germination, growth, survival, and reproduction of other organisms. These biochemicals are known as allelochemicals and can have beneficial or detrimental effects on the target organisms and the community. Allelopathy is often used narrowly to describe chemically-mediated competition between plants; however, it is sometimes defined more broadly as chemically-mediated competition between any type of organisms. The original concept developed by Hans Molisch in 1937 seemed focused only on interactions between plants, between microorganisms and between microorganisms and plants. Allelochemicals are a subset of secondary metabolites, which are not directly required for metabolism of the allelopathic organism.

<i>Juglans nigra</i> Species of tree

Juglans nigra, the eastern American black walnut, is a species of deciduous tree in the walnut family, Juglandaceae, native to North America. It grows mostly in riparian zones, from southern Ontario, west to southeast South Dakota, south to Georgia, northern Florida and southwest to central Texas. Wild trees in the upper Ottawa Valley may be an isolated native population or may have derived from planted trees.

<i>Centaurea diffusa</i> Species of flowering plant

Centaurea diffusa, also known as diffuse knapweed, white knapweed or tumble knapweed, is a member of the genus Centaurea in the family Asteraceae. This species is common throughout western North America but is not actually native to the North American continent, but to the eastern Mediterranean.

Autotoxicity, meaning self-toxicity, is a biological phenomenon whereby a species inhibits growth or reproduction of other members of its species through the production of chemicals released into the environment. Like allelopathy, it is a type of interference competition but it is technically different: autotoxicity contributes to intraspecific competition, whereas allelopathic effects refer to interspecific competition. Furthermore, autotoxic effects are always inhibitory, whereas allelopathic effects are not necessarily inhibitory–they may stimulate other organisms.

<span class="mw-page-title-main">Lawsone</span> Chemical compound

Lawsone (2-hydroxy-1,4-naphthoquinone), also known as hennotannic acid, is a red-orange dye present in the leaves of the henna plant, for which it is named, as well as in the common walnut and water hyacinth. Humans have used henna extracts containing lawsone as hair and skin dyes for more than 5,000 years. Lawsone reacts chemically with the protein keratin in skin and hair via a Michael addition reaction, resulting in a strong permanent stain that lasts until the skin or hair is shed. Darker colored staining is due to more lawsone–keratin interactions occurring, which evidently break down as the concentration of lawsone decreases and the tattoo fades. Lawsone strongly absorbs UV light, and aqueous extracts can be effective sunless tanning agents and sunscreens. Lawsone is a 1,4-naphthoquinone derivative, an analog of hydroxyquinone containing one additional ring.

Antibiosis, also referred to as antagonism, a process of biological interaction between two or more organisms that is detrimental to at least one of them; it can also be an antagonistic association between an organism and the metabolic substances produced by another. Antibiosis can occur through a variety of mechanisms, with "injury, death, reduced longevity, or reduced reproduction of the pest" being common. The process of antibiosis is either reversible or irreversible, and is caused by the production of volatile organic compounds by plant-growth-promoting rhizobacterium (PGPR). Antibiosis is one of two forms of amensalism, the other form being competition. Primary examples of antibiosis include "antibacterial activity against bacteria, fungus, nematodes, insects, and occasionally against plants and algae".

<i>Juglans australis</i> Species of tree

Juglans australis, the nogal criollo, is a species of plant in the Juglandaceae family. This large, fast-growing tree can grow to 20 m (66 ft) tall at elevations of 0.5—1.5 km in the Southern Andean Yungas, montane cloud forests on the eastern slopes of the Andes in Tucumán, Salta, and Jujuy provinces of Argentina and Tarija and Chuquisaca departments of Bolivia. It is threatened by habitat loss.

<i>Juglans neotropica</i> Species of plant

Juglans neotropica is a species of plant in the Juglandaceae family. It is found in Colombia, Ecuador, and Peru. It is threatened by habitat loss. Common names include Colombian walnut, Ecuadorian walnut, Andean walnut, nogal, cedro negro, cedro nogal, and nogal Bogotano.

<i>Juglans mandshurica</i> Species of tree

Juglans mandshurica, also known as monkey nuts, or tigernut, is a species of deciduous tree in the walnut family Juglandacea, native to the Eastern Asiatic Region. It grows to about 25 m.

<span class="mw-page-title-main">Plumbagin</span> Chemical compound

Plumbagin or 5-hydroxy-2-methyl-1,4-naphthoquinone is an organic compound with the chemical formula C
11
H
8
O
3
. It is regarded as a toxin and it is genotoxic and mutagenic.

A root barrier is an underground wall placed to block plant roots. This is often for the purpose of protecting structures or other plants, but root barriers are also used to preserve soil moisture.

<span class="mw-page-title-main">Walnut</span> Nut of any tree of the genus Juglans

A walnut is the edible seed of any tree of the genus Juglans, particularly the Persian or English walnut, Juglans regia. They are accessory fruit because the outer covering of the fruit is technically an involucre and thus not morphologically part of the carpel; this means it cannot be a drupe but is instead a drupe-like nut.

<span class="mw-page-title-main">Leptospermone</span> Chemical compound

Leptospermone is a chemical compound produced by some members of the myrtle family (Myrtaceae), such as Callistemon citrinus, a shrub native to Australia, and Leptospermum scoparium (Manuka), a New Zealand tree from which it gets its name. Modification of this allelopathic chemical to produce mesotrione led to the commercialization of derivative compounds as HPPD inhibitor herbicides.

<span class="mw-page-title-main">Mycorrhizal network</span> Underground fungal networks that connect individual plants together

A mycorrhizal network is an underground network found in forests and other plant communities, created by the hyphae of mycorrhizal fungi joining with plant roots. This network connects individual plants together. Mycorrhizal relationships are most commonly mutualistic, with both partners benefiting, but can be commensal or parasitic, and a single partnership may change between any of the three types of symbiosis at different times.

<span class="mw-page-title-main">Husk</span> Outer shell or coating of a seed

Husk in botany is the outer shell or coating of a seed. In the United States, the term husk often refers to the leafy outer covering of an ear of maize (corn) as it grows on the plant. Literally, a husk or hull includes the protective outer covering of a seed, fruit, or vegetable.

<i>Medicago rigidula</i> Species of plant

Medicago rigidula, the Tifton burclover, is a species of annual herb in the family Fabaceae. They have a self-supporting growth form and compound, broad leaves. Individuals can grow to 0.50m tall. It is a secondary wild relative of the cultivated crop Barrel Clover, and a tertiary wild relative of cultivated Alfalfa.

References

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  3. Cook, M.T. (1921). "Wilting caused by walnut trees". Phytopathology. 11: 346.
  4. Schneiderhan, F.J. (1926). "Apple disease studies in northern Virginia". Virginia Agricultural Experiment Station Bulletin. 245: 1–35.
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  10. Gerald Booth "Naphthalene Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a17_009.
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  16. Fisher, R.F. (1987). "Juglone inhibits pine growth under certain moisture regimes". Soil Sci. Soc. Am. J. 42 (5): 801–803. doi:10.2136/sssaj1978.03615995004200050030x.
  17. 1 2 Suchard, Oliver; Kane, Ronan; Roe, Bernard J.; Zimmermann, Elmar; Jung, Christian; Waske, Prashant A.; Mattay, Jochen; Oelgemöller, Michael (2006). "Photooxygenations of 1-naphthols: An environmentally friendly access to 1,4-naphthoquinones". Tetrahedron. 62 (7): 1467. doi:10.1016/j.tet.2005.11.021.
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  22. Jose, Shibu; Gillespie, Andrew R. (1998). "Allelopathy in black walnut (Juglans nigra L.) alley cropping. I. Spatio-temporal variation in soil juglone in a black walnut–corn (Zea mays L.) alley cropping system in the midwestern USA". Plant and Soil. 203 (2): 191–197. doi:10.1023/A:1004301309997. S2CID   41384254.
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  24. Dama L.B.; Poul B.N.; Jadhav B.V. (1998). "Antimicrobial activity of Napthoquinonic compounds". J. Ecotoxicol.Environ. Monit. 8: 213–215.
  25. Dama L.B.; Poul B.N.; Jadhav B.V; Hafeez MD. (1999). "Effect of "Juglone" on Development of the plant parasitic nematode (Meloidogyne Spp.) on Arachis hypogaea L". J. Ecotoxicol. Environ. Monit. 9: 73–75.
  26. Dama L.B. (2002). "Effect of naturally occurring napthoquinones[sic] on root- knot nematode Meloidogyne spp". Indian Phytopathology. 55 (1): 67–69.