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. Author manuscript; available in PMC: 2020 Feb 6.
Published in final edited form as: J Am Chem Soc. 2019 Jan 24;141(5):1961–1969. doi: 10.1021/jacs.8b10521

Table 2.

Product distributions catalyzed by engineered mono and bimodular Pik systems.

Enzyme 10-dMLa Narbonolideb Relative
Entry PikAIIITE PikAIII PikAIV 3a + 4a 5a + 6a 7a Activityc
R9 WT -d -d 0.8%e -d -d 100.0e
R10 V753A -d -d 21.1%e -d -d 4.2e
R11 Y755R -d -d N.D.f -d -d N.D.f
R12 Y755V -d -d 42.2%e -d -d 81.5e
R13 WT (apo) -d -d N.D.f -d -d N.D.f
R14 -d WT WT 4.2%e 23.6%e 0.3%e 100.0e
R15 -d V753A WT 7.7%e 21.3%e 0.8%e 92.5e
R16 -d Y755V WT 55.9%e 61.9%e 16.7%e 82.1e
R17 -d WT Y753V 4.4%e 77.2%e 1.3%e 86.8e
R18 -d Y755V Y753V 44.6%e 59.6%e 14.7%e 51.7e
R19 -d WT (apo) WT (apo) N.D.f N.D.f N.D.f N.D.f
a

Percent of 3a + 4a out of all 10-dML products (1, 3a, and 4a). See Scheme 1 for structures of products.

b

Percent of (5a + 6a) or 7a out of all narbonolide products (2, 5a, 6a, and 7a). See Scheme 1 for structures of products.

c

Total activity of each system relative to R9 (for monomodular systems) or R14 (for bimodular systems) is based on total amount of products (sum of 1, 2, 3a, 4a, 5a, 6a, and 7a).

d

Not applicable

e

Error was ± 5% of indicated value

f

N.D. = Not detected