Dissecting the Stereocontrolled Conversion of Short-Lived Sulfenic Acid by Lachrymatory Factor Synthase

ACS Catalysis ◽  
2019 ◽  
Vol 10 (1) ◽  
pp. 9-19
Author(s):  
Takatoshi Arakawa ◽  
Yuta Sato ◽  
Masayuki Yamada ◽  
Jumpei Takabe ◽  
Yoshitaka Moriwaki ◽  
...  
Keyword(s):  
Sulfenic Acid ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase

scholarly journals Enzyme That Makes You Cry–Crystal Structure of Lachrymatory Factor Synthase from Allium cepa

2017 ◽  
Vol 12 (9) ◽  
pp. 2296-2304 ◽  
Author(s):  
Josie A. Silvaroli ◽  
Matthew J. Pleshinger ◽  
Surajit Banerjee ◽  
Philip D. Kiser ◽  
Marcin Golczak
Keyword(s):  
Crystal Structure ◽  
Allium Cepa ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase

GENOME ORGANIZATION OF GENE ENCODING LACHRYMATORY FACTOR SYNTHASE IN ALLIUM CEPA

2012 ◽  
pp. 73-80
Author(s):  
N. Masamura ◽  
J. McCallum ◽  
F. Kenel ◽  
M. Pither-Joyce ◽  
L. Khrustaleva ◽  
...  
Keyword(s):  
Allium Cepa ◽  
Genome Organization ◽  
Gene Encoding ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase

Proton Transfer in a Reaction Catalyzed by Onion Lachrymatory Factor Synthase

2012 ◽  
Vol 76 (9) ◽  
pp. 1799-1801 ◽  
Author(s):  
Noriya MASAMURA ◽  
Morihiro AOYAGI ◽  
Nobuaki TSUGE ◽  
Takahiro KAMOI ◽  
Shinsuke IMAI
Keyword(s):  
Proton Transfer ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase

scholarly journals Structure of Allium lachrymatory factor synthase elucidates catalysis on sulfenic acid substrate

2017 ◽  
Author(s):  
Takatoshi Arakawa ◽  
Yuta Sato ◽  
Jumpei Takabe ◽  
Noriya Masamura ◽  
Masahiro Kato ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Active Site ◽  
Active Sites ◽  
Catalytic Mechanism ◽  
Sigmatropic Rearrangement ◽  
Natural Production ◽  
Lachrymatory Factor ◽  
Biological Decomposition ◽  
Key Residues ◽  
Lachrymatory Factor Synthase

AbstractNatural lachrymatory effects are invoked by small volatile S-oxide compounds. They are produced through alkene sulfenic acids by the action of lachrymatory factor synthase (LFS). Here we present the crystal structures of onion LFS (AcLFS) revealed in solute-free and two solute-stabilized forms. Each structure adopts a single seven-stranded helix-grip fold possessing an internal pocket. Mutagenesis analysis localized the active site to a layer near the bottom of the pocket, which is adjacent to the deduced key residues Arg71, Glu88, and Tyr114. Solute molecules visible on the active site have suggested that AcLFS accepts various small alcohol compounds as well as its natural substrate, and they inhibit this substrate according to their chemistry. Structural homologs have been found in the SRPBCC superfamily, and comparison of the active sites has demonstrated that the electrostatic potential unique to AcLFS could work in capturing the substrate in its specific state. Finally, we propose a rational catalytic mechanism based on intramolecular proton shuttling in which the microenvironment of AcLFS can bypass the canonical [1,4]-sigmatropic rearrangement principle established by microwave studies. Beyond revealing how AcLFS generates the lachrymatory compound, this study provides insights into the molecular machinery dealing with highly labile organosulfur species.Significance statementCrushing of onion liberates a volatile compound, syn-propanethial S-oxide (PTSO), which causes lachrymatory effect on humans. We present the crystal structures of onion LFS (AcLFS), the enzyme responsible for natural production of PTSO. AcLFS features a barrel-like fold, and mutagenic and inhibitory analyses revealed that the key residues are present in the central pocket, harboring highly concentrated aromatic residues plus a dyad motif. The architecture of AcLFS is widespread among proteins with various biological functions, such as abscisic acid receptors and polyketide cyclases, and comparisons with these homologs indicate that unique steric and electronic properties maintain the pocket as a reaction compartment. We propose the molecular mechanism behind PTSO generation and shed light on biological decomposition of short-lived sulfur species.

Inhibition of Platelet Activation by Lachrymatory Factor Synthase (LFS)-Silenced (Tearless) Onion Juice

2013 ◽  
Vol 61 (44) ◽  
pp. 10574-10581 ◽  
Author(s):  
Susan J. Thomson ◽  
Paula Rippon ◽  
Chrissie Butts ◽  
Sarah Olsen ◽  
Martin Shaw ◽  
...  
Keyword(s):  
Platelet Activation ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase

scholarly journals Silencing Onion Lachrymatory Factor Synthase Causes a Significant Change in the Sulfur Secondary Metabolite Profile

2008 ◽  
Vol 147 (4) ◽  
pp. 2096-2106 ◽  
Author(s):  
Colin C. Eady ◽  
Takahiro Kamoi ◽  
Masahiro Kato ◽  
Noel G. Porter ◽  
Sheree Davis ◽  
...  
Keyword(s):  
Secondary Metabolite ◽  
Metabolite Profile ◽  
Significant Change ◽  
Lachrymatory Factor ◽  
Lachrymatory Factor Synthase
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