[Quinone.com] Health / Bioactivation / Medicine

Applications, physical properties and features

Health / Bioactivation / Medicine

1.Medicine and quinones

The chemical compounds having the quinone structure are widely distributed in the nature. Those quinone compounds have various bioactivities and play important roles in the nature.
For example, coenzyme Q represented by the ubiquinone has the quinone structure, exists widely in animals, plants and microorganisms, exhibits important roles by electron transport action in their bodies. quinone:Medicine and quinones

    Among a lot of quinone compounds including naturally occurring compounds, especially the naphthoquinone derivatives have wide variety of bioactivities.
    Some natural health promotion medicines including naphthoquinone derivatives as a main component has been taken for a long time, naphthofuandiones are one of their components.
    The most representative natural naphthoquinones with bioactivities is vitamin K (phylloquinone, menaquinone) known as antihemorrhage vitamin. Nanomycin is the antibiotic having the 5-hydroxy-1,4-naphthoquinone structure.
    The antibiotics of the anthracycline group known as daunomycin and adriamycin also have a same structure, and have powerful antitumor activity (anticancer action), and many related chemical compounds have been developed as anticancer drug.
    Lapachol is known as anti-microbe and anti-protozoal for a long time, and a lot of its derivatives have been developed.
    Atovaquone

is the antimalarial developed from them, and it also has the anti-HIV activity.
    Other compounds with naphthoquinone structure have been developed as key composition of wide variety of medicines.
Also potency as anti-inflammatory agent, anti-allergic agent, anti-asthma medicine, anti-dragon gore medicine, anti-psoriasis medicine, bronchodilator, thrombus prevention and hypotension are found in their derivatives.
    They can be also utilized for the infection drugs as anti-fungal agents, anti-virus medicines and antibacterial agents against gram-positive bacteria, gram-negative bacteria, etc. In the field of animal drugs, menadion (2-methyl-1,4-naphthoquinone) is used as a hemostatic, a feed additive.
    Naphthoquinones can be utilized for antiprotozoal agents as the infection therapeutic agents of protozoiasis such as coccidiosis, theileriasis, mycoplasmosis, and antibacterial agents for the animals effectively against drug resistance strains.

2.Agricultural chemicals and quinones

Agricultural chemicals are agents that protect the crops by ridding of pathogenic fungi, harmful insect, weeds and rats, and raise the productivity of the farm products by improving or controlling their physiological functions. There are some types such as insecticides, fungicides, herbicides, plant growth regulators (PGR medicine), anti-fouling agent, bird repellents.
Delan

(2,3-dicyano-1,4-dithia-9,10-anthraquinone) that was developed by Merck & Co., Inc. in Germany is a famous fungicide used practically for a long time. It is effective on a fruit tree and a vegetable. It is hard to break out the resistant microbes, and it is used in all over the world at present.
Mogeton

(2-amino-3-chloro-1, 4-naphthoquinone) is representative of a herbicide, and it is used practically for a long time, too.
It is reported that the herbicidal activity rises when such substituents as amino group, chloro group or thioalkyl group are introduced at the 2 or 3 position of the naphthoquinone same as Mogeton.
The insecticide is the agent preventing the noxious insect, contains the miticide. quinone:Agricultural chemicals and quinones

quinone:Agricultural chemicals and quinones

    Recently, we developed a new industrial production method of the miticide, Acequinoscyl (2-acetoxy-3-dodecyl-1,4-naphthoquinone) starting from 2-hydroxy-1,4-naphthoquinone
( Lawsone ). We also developed a convenient production process of high purity Lawsone from 1,4-naphthoquinone.
    We were awarded the Society Prize (technical) in 1999 from the Society of Synthetic Organic Chemistry, Japan, because the manufacturing technology of Acequinocyl was evaluated high. The action mechanism of the miticide,Acequinocyl, is as follows in the figure.
    The main active structure is 2-hydroxy-3-dodecyl-1,4-naphthoquinone, a hydorolyzed metabolite of Acequinocyl.
    It combines with the ubiquinol oxidation site of the enzyme complex and inhibits the electronic flow of the respiratory chain electron transport system, and inhibits the ATP production.
    That is to say, it is the first miticide which affects the enzyme complex

in a mitochondria and its action mechanism is deferent from the conventional one. So it is there seems to be seldom the cross resistance with the conventional miticide.
The miticide ( the trade name is "kanemite

") .is formulated from Acequinocyl by AGRO-KANESHO Co., Ltd.
The quinone derivatives show various activities as agricultural chemical. There are large number of patents about the application such as fungicide, insecticide, herbicide and underwater anti-fouling.

pesticide, fungicide, insecticide, herbicide, miticide, bioactivation, kanemite, ADNQ, dithianon, Mogeton, dichlone

3.Cosmetic and quinones

    Since early times people have dyed their hair by using various natural dyestuffs.
    For example, it is found out from the analysis of the mummy hair that the ancient     Egyptians used to dye their hair by using plant dyes made of leaves and stems of the tree called the henna (Eugenia Lythraceae Lawsonia inermis genus) came from North Africa or Southwest Asia originally.
    The henna is used as a dye of the tattoo beside the hair dye, the tattoo is the traditional custom of women in Maghreb (North Africa) at present, and they are friendly to the tattoo that is one of the makeup methods to fascinate men.
    The main component of the henna is Lawsone (2-hydroxy-1,4-naphthoquinone ) that of naphthoquinone derivatives. quinone:Cosmetic and quinones

And, it is reported that the mixture of Lawsone with other materials have effectiveness of absorbing an ultraviolet and a visible ray by putting on the skin, to prevent suntan in the stratum corneum.
    Especially, there are many reports that above mixture shows the effectiveness for sunlight hypersensitivity patients.
    Some reports say the effectiveness of naphthoquinone for the prevention and the improvement of not only suntan by the ultraviolet ray but also pigmentation, spots, freckles, etc. after the suntan.
    The bisnaphthoquinon derivative (2,2'-Ethylidene bis(3-hydroxy-1,4-naphthoquinone) isolated from the extract of garden balsam (Impatiens balsamina L.) as Balsaminaceae has the effectiveness of the skin darkening-inhibitor and various bio-activities.
    The spots and the freckles by the suntan are caused by the deposition of melanin     pigment in the skin.
    The melanin pigment absorbs ultraviolet ray in order to protect the inside of the skin.     This mechanism is as follows.
    The stimulation such as ultraviolet ray is transmitted to the pigment cell called a melanocyte, then the pigment cell makes melanin from tyrosine.
    The enzyme of the tyrosinase in pigment cell mainly controls the melanogenesis process, in this biosynthetic pathway.
    The bisnaphthoquinone affects the tyrosinase and inhibits to produce the melanin.

Dyestuff, henna, hair dye, naphthoquinones, Lawsone, 2-hydroxy-1,4-naphthoquinone, ultraviolet ray, small wavelength region, visible ray, suntan, pigmentation, spot, freckle, balsam, bisnaphthoquinones, skin darkening-inhibitory effect, bioactivation, melanin,

4.Photosynthesis and quinones

    One of the most well known quinones which functions in living bodies are a series of quinones called plastoquinones that work as electron transferring materials in photosynthesis.
    Blue algae (cyanobacteria) acquired new photosynthesis capability which produces oxygen from water by getting a photo energy from 2 reaction centers 20~30 billion years ago, and build up the today's environment we mankind live.
    When a chlorophyll called P680 absorbs a photon, an electron is excited, and the electron moves into the pheophytin a from P680, and into the plastoquinone in turn in a photosystem

.
The plastoquinone receives the electron, and it is reduced to hydroquinone form from quinone form, but the electron does not return to the P680 from the plastoquinone by separating from the reaction center. The P680 lost the electron becomes a strong oxidizing agent, and it consequently pulls off the electron from the water molecule, and an oxygen generates.
And the electron moves to cytochrome b/f from the plastoquinone, and to the plastocyanin, at that time ATP is synthesized by its electron energy.
Blue algae has a chlorophyll a called P700 which constitutes another photosystem

. The electron of P700 excited by photon absorption passes through the other chlorophyll, the quinone, the iron/sulfur cluster and the ferredoxin, and is finally used for ;the synthesis of NADPH.
The P700 receives the electron by moving from the photosystem

and this electron is excited and is used again.
The above is called the light reaction. In the light reaction, the stronger oxidizing power is obtained because energy of two photons can be utilized at one time, so it became possible that the water was utilized as the supply source of electron. The water is changed into the oxygen by taking the electron.
By the way, they say that blue algae appeared by the symbiosis of two bacteria, because two photosystems respectively resemble the photosystems of two kinds of photosynthetic bacteria.
The mechanism of the photosynthesis of the oxygen evolution type is shown in the figure called the Z scheme.
Further, the glucose is made from carbon dioxide and H of NADPH by the work of the ATP in the dark reaction.

The figure of the Z scheme in the photosynthesis

5.Generation suppression of the hydrogen sulfide and quinones

    The sulfate-reducing bacteria decompose the organic substance utilizing sulfate ion as the oxidizing agent, and the resulting energy is used for their life support.
    As a result, sulfate ion is reduced and hydrogen sulfide is formed. This hydrogen sulfide is not only dangerous for human body, but it causes the corrosion of concrete because the air oxidizes it and hydrogen sulfide becomes to sulfuric acid.
    Anthraquinone acts against the sulfate-reducing bacteria, and inhibits the generation of the hydrogen sulfide by disturbing the electron transport of enzyme cytochrome C₃.     Kawasaki Kasei Chemical Co. makes fine slurry of the anthraquinone for this purpose, and it is sold in the name of Sulf Control (SC

Sulfate respiration of Sulfate-Reducing Bacteria


Absorbing Sulfate ion	Energy	Exhaling Hydrogen Sulfide

Generation of Hydrogen Sulfide	Decrease of Sulfate ion

The results of suppression test of the hydrogen

sulfide generation by SC

H₂S suppression mechanism of anthraquinone in the sulfate-reducing bacteria.