(''S'')-hydroxynitrile lyase (, ''(S)-cyanohydrin producing hydroxynitrile lyase'', ''(S)-oxynitrilase'', ''(S)-HbHNL'', ''(S)-MeHNL'', ''hydroxynitrile lyase'', ''oxynitrilase'', ''HbHNL'', ''MeHNL'', ''(S)-selective hydroxynitrile lyase'', ''(S)-cyanohydrin carbonyl-lyase (cyanide forming)'', hydroxynitrilase) is an

enzyme An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different mol ...

with

systematic name A systematic name is a name given in a systematic way to one unique group, organism, object or chemical substance, out of a specific population or collection. Systematic names are usually part of a nomenclature. A semisystematic name or semitrivi ...

''(S)-cyanohydrin lyase (cyanide forming)''. This enzyme catalyses the interconversion between

cyanohydrin In organic chemistry, a cyanohydrin or hydroxynitrile is a functional group found in organic compounds in which a cyano and a hydroxy group are attached to the same carbon atom. The general formula is , where R is H, alkyl, or aryl. Cyanohyd ...

s and the

carbonyl In organic chemistry, a carbonyl group is a functional group with the formula , composed of a carbon atom double bond, double-bonded to an oxygen atom, and it is divalent at the C atom. It is common to several classes of organic compounds (such a ...

compounds derived from the cyanohydrin with free

cyanide In chemistry, cyanide () is an inorganic chemical compound that contains a functional group. This group, known as the cyano group, consists of a carbon atom triple-bonded to a nitrogen atom. Ionic cyanides contain the cyanide anion . This a ...

, as in the following two

chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...

s: * an

aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated (in which all ...

(''S'')-hydroxynitrile

\rightleftharpoons

an aliphatic

aldehyde In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

* an

aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...

(''S'')-hydroxynitrile

\rightleftharpoons

an aromatic aldehyde + cyanide In nature, the liberation of cyanide serves as a defense mechanism against

herbivores A herbivore is an animal anatomically and physiologically evolved to feed on plants, especially upon vascular tissues such as foliage, fruits or seeds, as the main component of its diet. These more broadly also encompass animals that eat ...

and microbial attack in

plant Plants are the eukaryotes that form the Kingdom (biology), kingdom Plantae; they are predominantly Photosynthesis, photosynthetic. This means that they obtain their energy from sunlight, using chloroplasts derived from endosymbiosis with c ...

s. Hydroxynitrile lyases of the

α/β hydrolase fold The alpha/beta hydrolase superfamily is a superfamily of hydrolytic enzymes of widely differing phylogenetic origin and catalytic function that share a common fold. The core of each enzyme is an alpha/beta-sheet (rather than a barrel), containing ...

are closely related to

esterase In biochemistry, an esterase is a class of enzyme that splits esters into an acid and an alcohol in a chemical reaction with water called hydrolysis (and as such, it is a type of hydrolase). A wide range of different esterases exist that differ ...

s. All members of the α/β hydrolase fold contain a conserved

catalytic triad A catalytic triad is a set of three coordinated amino acid residues that can be found in the active site of some enzymes. Catalytic triads are most commonly found in hydrolase and transferase enzymes (e.g. proteases, amidases, esterases, aminoac ...

(

nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...

histidine Histidine (symbol His or H) is an essential amino acid that is used in the biosynthesis of proteins. It contains an Amine, α-amino group (which is in the protonated –NH3+ form under Physiological condition, biological conditions), a carboxylic ...

aspartate Aspartic acid (symbol Asp or D; the ionic form is known as aspartate), is an α-amino acid that is used in the biosynthesis of proteins. The L-isomer of aspartic acid is one of the 22 proteinogenic amino acids, i.e., the building blocks of protein ...

). The

in this case is a

serine Serine (symbol Ser or S) is an α-amino acid that is used in the biosynthesis of proteins. It contains an α- amino group (which is in the protonated − form under biological conditions), a carboxyl group (which is in the deprotonated − ...

. In contrast to esterases,

serine proteases Serine proteases (or serine endopeptidases) are enzymes that cleave peptide bonds in proteins. Serine serves as the nucleophilic amino acid at the (enzyme's) active site. They are found ubiquitously in both eukaryotes and prokaryotes. Seri ...

lipases In biochemistry, lipase ( ) refers to a class of enzymes that catalyzes the hydrolysis of fats. Some lipases display broad substrate scope including esters of cholesterol, phospholipids, and of lipid-soluble vitamins and sphingomyelinases; how ...

and other enzymes in this family, the nucleophile in hydroxynitrile lyases functions as a proton acceptor. Key

amino acid Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although over 500 amino acids exist in nature, by far the most important are the 22 α-amino acids incorporated into proteins. Only these 22 a ...

residues in this reaction are the

lysine Lysine (symbol Lys or K) is an α-amino acid that is a precursor to many proteins. Lysine contains an α-amino group (which is in the protonated form when the lysine is dissolved in water at physiological pH), an α-carboxylic acid group ( ...

at position 236 and the

threonine Threonine (symbol Thr or T) is an amino acid that is used in the biosynthesis of proteins. It contains an α-amino group (which is in the protonated −NH form when dissolved in water), a carboxyl group (which is in the deprotonated −COO− ...

at position 11. Lys²³⁶ helps to orient the

substrate Substrate may refer to: Physical layers *Substrate (biology), the natural environment in which an organism lives, or the surface or medium on which an organism grows or is attached ** Substrate (aquatic environment), the earthy material that exi ...

while Thr¹¹ serves to block the

oxyanion hole An oxyanion hole is a pocket in the active site of an enzyme that stabilizes transition state negative charge on a deprotonation, deprotonated oxygen or alkoxide. The pocket typically consists of backbone amides or positively charged residues. Sta ...

that would convert the enzyme into an esterase. Commonly studied (''S'')-selective hydroxynitrile lyases include MeHNL from ''

Manihot esculenta ''Manihot esculenta'', commonly called cassava, manioc, or yuca (among numerous regional names), is a woody shrub of the spurge family, Euphorbiaceae, native to South America, from Brazil, Paraguay and parts of the Andes. Although a perennia ...

'' and HbHNL from ''

Hevea brasiliensis ''Hevea brasiliensis'', the Pará rubber tree, ''sharinga'' tree, seringueira, or most commonly, rubber tree or rubber plant, is a flowering plant belonging to the spurge family, Euphorbiaceae, originally native to the Amazon basin, but is now p ...

''. (''R'')-selective hydroxynitrile lyases have also been found to exist in ''

Arabidopsis thaliana ''Arabidopsis thaliana'', the thale cress, mouse-ear cress or arabidopsis, is a small plant from the mustard family (Brassicaceae), native to Eurasia and Africa. Commonly found along the shoulders of roads and in disturbed land, it is generally ...

'' (AtHNL). AtHNL is thought to catalyze this reaction by a different mechanism. Not all hydroxynitrile lyases belong to the α/β hydrolase family. PaHNL ( Prunus amygdalus), (''R'')-selective like AtHNL, uses a flavin cofactor to

catalyze Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...

cyanogenesis In chemistry, cyanide () is an inorganic chemical compound that contains a functional group. This group, known as the cyano group, consists of a carbon atom triple-bonded to a nitrogen atom. Ionic cyanides contain the cyanide anion . This an ...

Natural Substrates of Hydroxynitrile Lyases

Acetone cyanohydrin Acetone cyanohydrin (ACH) is an organic compound used in the production of methyl methacrylate, the monomer of the transparent plastic polymethyl methacrylate (PMMA), also known as acrylic. It liberates hydrogen cyanide easily, so it is used as a ...

has been determined to be the natural substrate of HbHNL, though HbHNL also shows activity with

mandelonitrile In organic chemistry, mandelonitrile is the nitrile of mandelic acid, or the cyanohydrin derivative of benzaldehyde. Small amounts of mandelonitrile occur in the pits of some fruits. Occurrence Mandelonitrile is the aglycone part of the cyano ...

, the natural substrate of PaHNL. The cleavage of mandelonitrile into

benzaldehyde Benzaldehyde (C6H5CHO) is an organic compound consisting of a benzene ring with a formyl substituent. It is among the simplest aromatic aldehydes and one of the most industrially useful. It is a colorless liquid with a characteristic almond-li ...

and

is what produces the characteristic

amaretto Amaretto ( Italian for 'a little bitter') is a sweet Italian liqueur originating from the ''comune'' (municipality) of Saronno. Depending on the brand, it may be made from apricot kernels, bitter almonds, peach stones, or almonds, all of whi ...

smell of almonds. The natural substrate of AtHNL is unknown as no

s have been detected in ''Arabidopis thaliana''.

Unnatural Substrates

In addition to cyanohydrin cleavage, HNLs have been found to catalyze the

nitroaldol reaction The Henry reaction is a classic carbon–carbon bond formation reaction in organic chemistry. Discovered in 1895 by the Belgian chemist Louis Henry (1834–1913), it is the combination of a nitroalkane and an aldehyde or ketone in the presence ...

at low levels.

References

External links

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