Tailoring enzymes

In modular systems, tailoring enzymes perform reactions after the inline modifications after the growing NRP/PK chain is released from the assembly line (so also after cyclization by a TE/TD domain). In RiPPs, they are performed before cyclization and also before the proteolytic cleavage, a way around this is to use the PROTEASE or MACROLACTAMFORMATION tailoring enzymes instead of the proteolytic cleavage or cyclization steps. In terpenes, they are performed after the macrocyclization.

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#	Tailoring Enzyme	Reaction performed	Atoms required	Substrate
Group transfer reactions
1	METHYLTRANSFERASE	Methylation	Atom to add methyl group to	None
2	C_METHYLTRANSFERASE	Methylation	Carbon atom to add methyl group to	None
3	N_METHYLTRANSFERASE	Methylation	Nitrogen atom to add methyl group to	None
4	O_METHYLTRANSFERASE	Methylation	Oxygen atom to add methyl group to	None
5	METHYL_MUTASE	Methyl shift	Atom of the methyl group + acceptor atom of the methyl group	None
6	HYDROXYLASE	Hydroxylation	Atom to add hydroxy group to	None
7	EPOXIDASE	Epoxidation of a double bond	Both atoms of the double bond that is epoxidised	None
8	PRENYLTRANSFERASE	Prenylation	Atom to add prenyl group to	Name of prenyl group ("DIMETHYLALLYL", "3_METHYL_1_BUTENYL", "GERANYL", "FARNESYL", "GERANYLGERANYL", "SQUALENE" OR "PHYTOENE")
9	ACETYLTRANSFERASE	Acetylation	Atom to add acetyl group to	None
10	ACYLTRANSFERASE	Acylation	Atom to add the acyl group of fatty acids to	Substrate to add (Name of fatty acids: "PALAMITIC_ACID", "STREARIC_ACID", "DIHYDROXYSTEARIC_ACID", "OLEIC_ACID", "RICINOLEIC_ACID", "LINOLEIC_ACID", "LINOLENIC_ACID", "BEHENIC_ACID" )
11	AMINOTRANSFERASE	Transamination of a keto group	Oxygen of the keto group	None
12	HALOGENASE	Halogenation	Atom to add halogen to	Halogen atom
13	THIOAMIDATION	Thioamide bond formation	Carbon atom of keto group to be transformed	Sulfur atom
Oxidoreduction
14	DOUBLE_BOND_REDUCTASE	Reduction of double bond	Both atoms of the double bond that is reduced	None
15	DOUBLE_BOND_ISOMERASE	Isomerization of double bond	Both atoms of the double bond that is existing at the beginning + both atoms of the new double bond	None
16	DEHYDROGENASE	Formation of double bond	Both atoms of the bond that is oxidized	None
17	KETO_REDUCTION	Reduction of keto group	Oxygen of the keto group	None
18	ALCOHOL_DEHYDROGENASE	Oxidation of hydroxy group to keto group	Oxygen of the hydroxy group	None
Elimination
19	PEPTIDASE	Peptide bond cleavage	Carbon and nitrogen atom of the bond	None
20	PROTEASE	Protein cleavage	Carbon and nitrogen atom of the bond	None
21	MONOAMINE_OXIDASE	Deamination	Nitrogen of the amine group to be removed	None
22	DEHYDRATASE	Dehydration	Carbon with hydroxy group + carbon next to first carbon to remove hydrogen from	None
23	THREONINE_SERINE_DEHYDRATASE	Dehydration of threonine or serine	Oxygen atom of the threonine/serine	None
24	DECARBOXYLASE	Decarboxylation	Carbon atom of the carboxyl group to be removed	None
25	SPLICEASE	Removal of a part of the structure between two atoms (as in spliceotides)	Atoms of both sides of the removed site (the last atoms on both sides to remain)	None
26	ARGINASE	Arginine cleavage to L-ornithine	Secondary nitrogen of arginine	None
Cyclization
27	OXIDATIVE_BOND_SYNTHASE	Oxidative bond formation	Atoms to form bond between (need to possess each at least one hydrogen)	None
28	MACROLACTAM_SYNTHETASE	Macrolactam formation between carboxyl group and N-terminus	Hydroxy oxygen atom of the carboxy group	None
29	CYCLODEHYDRASE	Cyclodehydration of serine, threonine, or cysteine	Sulfur or oxygen atom of the sidechain in serine, threonine, or cysteine	None
30	LANTHIPEPTIDE_CYCLASE	Lanthipeptide cyclization	Sulfur of cysteine or beta carbon of dehydratased serine/threonine (for carbon bridge) + beta carbon of dehydratased serine/threonine	None
31	LANTHIONINE_SYNTHETASE	Lanthionine formation	Sulfur of cysteine or beta carbon of serine/threonine (for carbon bridge) + beta carbon of serine/threonine	None
32	THIOPEPTIDE_CYCLASE	Formation of nitrogen-containing six-membered ring in thiopeptides	Beta carbon of dehydratased serine/threonine for which the upstream amino acid is not used in the 6 membered ring + Beta carbon of dehydratased serine/threonine for which the upstream amino acid is used in the 6 membered ring	None
33	MACROLACTAMIDINATION	Macrolactamidine formation between carbonyl group and primary-amine	Carbon atom of the carbonyl group of ketone or thioketone + nitrogen atom of Lys or N-terminus	None
34	OMEGA_AMIDE	Side chain-side chain linkage between amine group and carbonyl carbon	Nitrogen of amine group of Lys residue (i.e., donor) + the carbonyl carbon of an Asp/Glu residue (i.e., acceptor)	None
35	OMEGA_ESTER	Side chain-side chain linkage between hydroxyl group and carbonyl carbon	Oxygen of hydroxyl group of Ser/Thr residue (i.e., donor) + the carbonyl carbon of an Asp/Glu residue (i.e., acceptor)	None
36	OMEGA_THIOESTER	Side chain-side chain linkage between thiol group and carbonyl carbon	Sulfur atom of Cys residue (i.e., donor) + the carbonyl carbon of an Asp/Glu residue (i.e., acceptor)	None
Epimerization
37	AMINO_ACID_EPIMERASE	Amino acid epimerization	Alpha carbon of the amino acid to be epimerased	None
Bond breakage
38	HYDROLASE	Hydrolysis of bond	Both atoms of the bond to be hydrolysed	None
39	REDUCTIVE_LYASE	Reductive bond breakage	Both atoms of the bond to be lysed	None