GapMind for Amino acid biosynthesis

 

Definition of L-methionine biosynthesis

As text, or see rules and steps

# Methionine biosynthesis in GapMind is based on MetaCyc pathways
# L-methionine biosynthesis I via O-succinylhomoserine and cystathionine (metacyc:HOMOSER-METSYN-PWY),
# II via O-phosphohomoserine and cystathionine (metacyc:PWY-702),
# III via O-acetylhomoserine (metacyc:HSERMETANA-PWY),
# or IV with reductive sulfhydrylation of aspartate semialdehyde (metacyc:PWY-7977).
# These pathways vary in how aspartate semialdehyde is reduced and sulfhydrylated to homocysteine.
# GapMind does not represent the formation of the methyl donors for methionine synthase,
# such as 5-methyltetrahydrofolate or methyl corrinoid proteins.

# For BRENDA::O63067 -- the paper describes a monofunctional hom but the sequence of uniprot:O63067 is
# much longer and has a close homolog of functional aspartate kinase (due to alternative splicing?).
# In Corynebacterium, aspartate kinase has two subunits, both apparently encoded by the same gene by
# using start codons  (PMID:1956296); Q46133 is the shorter regulatory subunit and lacks the catalytic domain,
# so it does not suffice for activity and is ignored.
asp-kinase	aspartate kinase	EC:2.7.2.4	ignore:BRENDA::O63067	ignore:BRENDA::Q46133
asd	aspartate semi-aldehyde dehydrogenase	EC:1.2.1.11

# Ga0059261_2711 (uniprot:A0A1L6J6Q3) from Sphingomonas koreensis DSMZ 15582
# is distant from characterized homoserine dehydrogenases
# and is confirmed by  fitness data.
# BT2403 from Bacteroides thetaiotaomicron (uniprot:Q8A541_BACTN)
# is a fusion of aspartate kinase and homoserine dehydrogenase.
# The homoserine dehydrogenase portion is somewhat diverged. Its role is confirmed by strong cofitness with
# threonine synthase (the defined media for B. thetaiotaomicron included methionine).
# DvMF_1412 from Desulfovibrio vulgaris Miyazaki F (uniprot:B8DRS3_DESVM) is a somewhat
# diverged homoserine dehydrogenase; it has auxotrophic phenotypes.
# uniprot:A0A168MV81 from Brevundimonas is a somewhat diverged homoserine dehydrogenase (fused to aspartate kinase);
# it has auxotrophic phenotypes.
hom	homoserine dehydrogenase	EC:1.1.1.3	uniprot:A0A1L6J6Q3	uniprot:Q8A541_BACTN	uniprot:B8DRS3_DESVM	uniprot:A0A168MV81

# As discussed in PMID:28581482, many members of the MetA family are
# actually homoserine O-acetyltransferases, and many members of the MetX family
# are actually homoserine O-succinyltransferases.  Fortunately, many
# enzymes of both types have been curated in Swiss-Prot.
metA	homoserine O-succinyltransferase	EC:2.3.1.46

# MetX is often encoded next to a methyltransferase-like protein MetW.
# Because MetW is not consistently required for MetX's activity, it is
# not included in GapMind.  MetW can bind MetX and increase its
# activity (PMID:33604638), and in some bacteria, there is tight
# cofitness between MetX and MetW, which suggests that MetW is
# required for MetX's activity (i.e., Paraburkholderia bryophila, many
# Pseudomonas, Caulobacter crescentus, or Sphingomonas koreensis).
# But in other diverse bacteria, metW mutants can still grow in minimal media
# (i.e., Herbaspirillum seropedicae or Cupriavidus necator), or have
# milder phenotypes than metX mutants (i.e., Burkholderia
# phytofirmans, Acidovorax 3H11, Dechlorosoma suillum PS, Marinobacter
# adhaerens).
metX	homoserine O-acetyltransferase	EC:2.3.1.31

hom_kinase	homoserine kinase	EC:2.7.1.39

# Many metB proteins have some activity as O-succinylhomoserine sulfhydrylase (metZ) as well,
# and many metZ proteins are annotated with this EC number. So this step
# may include both enzymes.
# METI_BACSU (uniprot:O31631) has activity as CGS but is given a more vague EC number.
# uniprot:Q1M0P5 is now thought to be a gamma-lyase instead (see metacyc:HP_RS00540-MONOMER), so it
# is ignored.
metB	cystathionine gamma-synthase	EC:2.5.1.48	curated:SwissProt::O31631	ignore:SwissProt::Q1M0P5

# BRENDA annotates Q84UD0 with this EC number but it may be a cystine lyase only (PMID:12525491).
# BRENDA annotates Q9EYM7 with this EC but it appears to be a cystathionine beta synthase (PMID:12101301).
# uniprot:Q9SIV0 appears to be specific to glucosinolate biosynthesis.
# CH_088676 is annotated as this but with a different EC number, so it is ignored.
# uniprot:Q4606 is annotated as cysteine desulfidase but is nearly identical to uniprot:Q93QC6, which is
# a cystathionine beta-lyase, so it is ignored.
# XoMetC (uniprot:Q5H4T8) is annotated as a gamma-lyase by BRENDA, but it also has beta-lyase activity
# (PMID:24531493).
metC	cystathionine beta-lyase	EC:4.4.1.13	ignore:BRENDA::Q84UD0	ignore:BRENDA::Q9EYM7	ignore:SwissProt::Q9SIV0	ignore:CharProtDB::CH_088676	ignore:BRENDA::Q46061	curated:BRENDA::Q5H4T8

# METI_BACSU (uniprot:O31631) has activity as OAS but is given a more vague EC number.
# CH_123612, uniprot:Q9WZY4, and uniprot:Q5SK88 are annotated as this but without the EC number.
metY	O-acetylhomoserine sulfhydrylase	EC:2.5.1.49	curated:SwissProt::O31631	ignore_other:O-succinylhomoserine sulfhydrylase	curated:CharProtDB::CH_123612	curated:SwissProt::Q9WZY4	curated:SwissProt::Q5SK88

# No EC number for metZ, so use "O-succinylhomoserine sulfhydrylase", which matches
# uniprot:METZ_PSEAE and uniprot:METZ_MYCTU.
metZ	O-succinylhomoserine sulfhydrylase	term:O-succinylhomoserine sulfhydrylase	ignore_other:EC 2.5.1.49

metE	vitamin B12-independent methionine synthase	EC:2.1.1.14

# In many thermophilic archaea, MetE seems to be split into two pieces (PMC7857596). There
# is experimental support for a protein complex (PMC2668238), and the two pieces
# often appear to form an operon, but there is no experimental evidence that they
# are a methionine synthase. We added the gene from Haloferax volcanii (uniprot:D4GW95) as it is
# diverged but is conserved next to a catalytic component with correct functional residues (uniprot:D4GW90).
split_metE_1	vitamin B12-independent methionine synthase, folate-binding component	predicted:G0EDA1_PYRF1	predicted:D4GW95

# In many thermophilic archaea, MetE seems to be split into two pieces (see PMC7857596).
# The catalytic component has the necessary zinc-binding residues (H219, C221, C307)
# and homocysteine-binding residues (S20, E71, D185).
# We added the gene from Haloferax volcanii (uniprot:D4GW90) as it
# has the correct functional residues and is conserved next to a potential folate-binding component
# (uniprot:D4GW90).
split_metE_2	vitamin B12-independent methionine synthase, catalytic component	predicted:G0EFB7_PYRF1	predicted:D4GW90

# Desulfovibrio have a somewhat diverged MetH, without the activation domain, but confirmed by
# cofitness (DVU1585 = uniprot:Q72BP9_DESVH is cofit with MetF; DvMF_0476 = uniprot:B8DKK4_DESVM is cofit with a RamA-
# like activation protein).
# 3-part split MetH proteins from Phaeobacter are ignored.
metH	vitamin B12-dependent methionine synthase	EC:2.1.1.13	ignore:reanno::Phaeo:GFF1501	ignore:reanno::Phaeo:GFF1318	ignore:reanno::Phaeo:GFF1321	ignore:reanno::Phaeo:GFF1319	ignore:reanno::Phaeo:GFF1582	uniprot:Q72BP9_DESVH	uniprot:B8DKK4_DESVM

# In Phaeobacter and some related bacteria, MetH is split into 3 parts (PMC5764234)
split_metH_1	Methionine synthase component, B12 binding and B12-binding cap domains	curated:reanno::Phaeo:GFF1319
split_metH_2	Methionine synthase component, methyltransferase domain	curated:reanno::Phaeo:GFF1321
split_metH_3	Methionine synthase component, pterin-binding domain	curated:reanno::Phaeo:GFF1582

# In E. coli and many other bacteria, the MetH protein includes a reactivation domain (pfam:PF02965),
# but other ATP-dependent (ramA-like) activation proteins are also thought to exist.
# Ignore MetH proteins, as they often contain the reactivation domain and this
# creates confusion when checking for reverse hits.
# In Heliobacterium modesticaldum, the missing reactivation domain is probably provided
# by H1S01_RS06050 (very similar to A0A6I3SQJ4), which does not hit the HMM but for PF02965 but is found by PFam-N
# or foldseek, and is usually encoded to next to MetH.
B12-reactivation-domain	MetH reactivation domain	hmm:PF02965	ignore_other:EC 2.1.1.13	predicted:A0A6I3SQJ4

# As of April 2019, all characterized members of the RamA family or PF14574 are involved in the reactivation
# of co(II)balamin. This includes RamA (uniprot:B8Y445), DvMF_1398, PGA1_c15200, and ELI_0370 (part of a O-demethylase).
# Many bacteria contain MetH and probably rely on a distant homolog of RamA for reactivation of B-12.
# pfam:PF14574 describes only the C-terminal putative ATPase domain of RamA, but no other functions are known,
# except for the reactivation of Co(II) corrinoid proteins (i.e. RamQ, uniprot:P0DX10).
ramA	ATP-dependent reduction of co(II)balamin	hmm:PF14574	term:ATP-dependent reduction of co(II)balamin

# In the reductive sulfuration of aspartate semialdehyde, the
# sulfurtransferase component is
# MA1821 or DvMF_1464 (see PMID:25315403 and PMC5764234) or uniprot:Q57564 (from SwissProt).
# Although this reaction has not been biochemically demonstrated, a distant homolog performs a similar
# reaction, converting sulfoacetaldehyde to coenzyme M (see MJ1681 and PMID:30932481).
# (This family was formerly DUF39.)
asd-S-transferase	sulfuration of L-aspartate semialdehyde, persulfide component	curated:SwissProt::Q8TPT4	curated:reanno::Miya:8500721	curated:SwissProt::Q57564

# The NIL/ferredoxin component is MA1822 or DvMF_0262 (see PMID:25315403 and PMC5764234).
# In Methanococcus, the persulfide component (MEVAN_RS03425, uniprot:A6UQ02) is diverged but
# is in a conserved operon with the sulfurtransferase component.
asd-S-ferredoxin	reductive sulfuration of L-aspartate semialdehyde, ferredoxin component	curated:SwissProt::Q8TPT3	curated:reanno::Miya:8499492	predicted:A6UQ02

# The putative persulfide forming component is MA1715 or DvMF_0044 (see PMID:25315403 and PMC5764234).
# A conserved cysetien in MA1821 is modified to a persulfide in vivo (PMID:28165724).
# This component is not 100% required in Methanosarcina acetivorans (possible redundancy).
# In Hippea alviniae, this protein (G415_RS0107280, similar to uniprot:F2LX84) is diverged but is in an operon with the other components.
asd-S-perS	putative persulfide forming protein	uniprot:Y1715_METAC	curated:reanno::Miya:8499265	predicted:F2LX84

# Methanogens have a short homolog of MetE that transfers methyl groups from methylcobalamin
# (not 5-methyltetrahydrofolates) to homocysteine to form methionine (PMID:10469143).
# We named this family of "core" methioine synthases MesA and proposed
# that MtrA (the corrinoid subunit of methyltetrahydromethanopterin:coenzyme M methyltransferase)
# is the physiological methyl donor (PMC7857596).
mesA	Methylcobalamin:homocysteine methyltransferase MesA	curated:SwissProt::P55299

# Another core methionine synthase (distantly related to MesA) has been characterized
# in Dehalococcoides (PMC7005905).
# It probably obtains methyl groups from the iron-sulfur corrinoid protein of the
# Wood-Ljungdahl pathway (CoFeSP), but this is not proven.
# We named this family MesB (PMID:33534785).
mesB	Methylcobalamin:homocysteine methyltransferase MesB	curated:metacyc::MONOMER-21502

# MesC is another family of core methionine synthases, without experimental evidence, but
# with the correct functional residues, and linked to the Wood-Ljungdahl pathway
# by the gene neighbor method
# (PMC7857596). The corrinoid protein of the Wood-Ljungdahl pathway is probably the methyl donor.
mesC	Methylcobalamin:homocysteine methyltransferase MesC	predicted:Q8TUL3_METAC

# Genetic evidence shows that ACIAD3523 and Ga0059261_2929 are methionine synthases,
# see PMC2290942 and PMID:33534785.
# They require mesX (ACIAD3524 or Ga0059261_2928) and oxygen for activity, but not
# 5-methyltetrahydrofolates or cobalamin.
mesD	oxygen-dependent methionine synthase, methyltransferase component MesD	uniprot:Q6F6Z8	curated:reanno::Korea:Ga0059261_2929
# MesX is required for the activity of MesD, see PMC2290942.
mesX	oxygen-dependent methionine synthase, putative oxygenase component MesX	uniprot:Q6F6Z7	curated:reanno::Korea:Ga0059261_2928

aspartate-semialdehyde: asp-kinase asd

# Reductive sulfhydrylation of aspartate semialdehyde to homocysteine is carried out by
# a multi-component system (see PMID:25315403 and PMC5764234)
asd-sulfhydrylation: asd-S-transferase asd-S-ferredoxin asd-S-perS

homoserine: aspartate-semialdehyde hom

# Transsulfuration is the conversion of homoserine to homocysteine, with the sulfur being obtained from cysteine.
# It is thought to occur with any
# of the activated forms of homoserine (O-acetyl-, O-succinyl-, or O-phospho-homoserine).
transsulfuration: metA metB metC
transsulfuration: metX metB metC
transsulfuration: hom_kinase metB metC

# Homocysteine can be formed by reduction of aspartate semialdehyde, direct sulfurylation of activated homoserine,
# or transsulfuration of (activated) homoserine.
# Activated forms of homoserine include O-acetylhomoserine, O-succinylhomoserine, or O-phospho-homoserine.

homocysteine: aspartate-semialdehyde asd-sulfhydrylation
homocysteine: homoserine metX metY
homocysteine: homoserine metA metZ
homocysteine: homoserine transsulfuration

# MetH occasionally oxidizes the vitamin B12 cofactor from Co(I) to Co(II), so
# a reductase is needed to maintain its activity.
B12-reactivation: B12-reactivation-domain
B12-reactivation: ramA

# Besides MetH (with B-12 reactivation) or 3-part MetH as in Phaeobacter (PMC5764234), or MetE,
# or MetE split into two parts (PMC7857596),
# GapMind also includes the folate-independent systems MesA, MesB,
# MesC, and MesD/MesX (PMC7857596).
# It is possible that the corrinoid-dependent methionine synthases (MesA, MesB, or MesC) would require B12 reactivation,
# but this is not proven, and some methanogens with MesA seem to lack RamA, so
# B12 reactivation is not included.
# The role of split MetE or MesC lacks experimental evidence, and is based on
# gene neighborhoods and functional residues only (PMC7857596).
methionine_synthase: metH B12-reactivation
methionine_synthase: split_metH_1 split_metH_2 split_metH_3 B12-reactivation
methionine_synthase: metE
methionine_synthase: split_metE_1 split_metE_2
methionine_synthase: mesA
methionine_synthase: mesB
methionine_synthase: mesC
methionine_synthase: mesD mesX

all: homocysteine methionine_synthase 

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About GapMind

Each pathway is defined by a set of rules based on individual steps or genes. Candidates for each step are identified by using ublast (a fast alternative to protein BLAST) against a database of manually-curated proteins (most of which are experimentally characterized) or by using HMMer with enzyme models (usually from TIGRFam). Ublast hits may be split across two different proteins.

A candidate for a step is "high confidence" if either:

where "other" refers to the best ublast hit to a sequence that is not annotated as performing this step (and is not "ignored").

Otherwise, a candidate is "medium confidence" if either:

Other blast hits with at least 50% coverage are "low confidence."

Steps with no high- or medium-confidence candidates may be considered "gaps." For the typical bacterium that can make all 20 amino acids, there are 1-2 gaps in amino acid biosynthesis pathways. For diverse bacteria and archaea that can utilize a carbon source, there is a complete high-confidence catabolic pathway (including a transporter) just 38% of the time, and there is a complete medium-confidence pathway 63% of the time. Gaps may be due to:

GapMind relies on the predicted proteins in the genome and does not search the six-frame translation. In most cases, you can search the six-frame translation by clicking on links to Curated BLAST for each step definition (in the per-step page).

For more information, see:

If you notice any errors or omissions in the step descriptions, or any questionable results, please let us know

by Morgan Price, Arkin group, Lawrence Berkeley National Laboratory