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Expression of the gene, designated AaBAS, in Saccharomyces cerevisiae, followed by GC⁄ MS analysis, confirmed the encoded enzyme as a b-amyrin synthase.. By manipula-tion of two key enzym

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cerevisiae – b-amyrin synthase from Artemisia annua

James Kirby1, Dante W Romanini2, Eric M Paradise1,3and Jay D Keasling1,3,4,5

1 California Institute for Quantitative Biomedical Research, University of California, Berkeley, CA, USA

2 Department of Chemistry, University of California, Berkeley, CA, USA

3 Department of Chemical Engineering, University of California, Berkeley, CA, USA

4 Department of Bioengineering, University of California, Berkeley, CA, USA

5 Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

Triterpenes belong to the isoprenoid family of

com-pounds and are recognized by their C30 backbones

They are typically synthesized by the cyclization of the

sterol precursor 2,3-oxidosqualene into a multi-ringed

compound with a single alcohol group Fungi and

mammals convert 2,3-oxidosqualene to the triterpene

compound lanosterol in the biosynthetic pathways to

ergosterol and cholesterol, respectively The equivalent

step in plant primary metabolism is the cyclization of

2,3-oxidosqualene to cycloartenol for the production

of membrane sterols Cycloartenol is also the

triter-pene precursor of brassinosteroid phytohormones that

regulate plant growth and development [1,2] Based on

chemical and genetic analyses performed to date, it

appears that plants are more diverse than animals or

fungi in the range of tritepene products synthesized [3]

However, despite the fact that a large variety of

triter-pene compounds have been isolated from plant sources [4], the majority of triterpene synthase genes isolated

to date have encoded either lupeol or b-amyrin synth-ases (EC 5.4.99.–) [1] b-amyrin in particular serves as the olefin precursor to a wide range of downstream products The action of oxidative enzymes (typically cytochrome P450 monooxygenases) and glyco-syltransferases convert b-amyrin to various triterpene saponins in different plant species [5–7] These sapo-nins may perform protective roles in the host plant, acting as antimicrobial [8] and insecticidal [9] agents, and many of these compounds are also of interest from a human health perspective The effect of plant saponins on low-density lipoprotrein cholesterol absorption and arterial atherosclerosis has received much attention, leading to the development of several cholesterol-reducing dietary supplements [10] Saponins

Keywords

Artemisia annua; isoprenoids; metabolic

engineering; Saccharomyces cerevisiae;

b-amyrin synthase

Correspondence

J D Keasling, Berkeley Center for

Synthetic Biology, 717 Potter Street,

Building 977, Mail code 3224, University of

California, Berkeley, CA 94720-3224, USA

Fax: +1 510 495 2630

Tel: +1 510 495 2620

E-mail: keasling@berkeley.edu

(Received 12 December 2007, revised 11

February 2008, accepted 18 February 2008)

doi:10.1111/j.1742-4658.2008.06343.x

Using a degenerate primer designed from triterpene synthase sequences, we have isolated a new gene from the medicinal plant Artemisia annua The predicted protein is highly similar to b-amyrin synthases (EC 5.4.99.–), sharing amino acid sequence identities of up to 86% Expression of the gene, designated AaBAS, in Saccharomyces cerevisiae, followed by GC⁄ MS analysis, confirmed the encoded enzyme as a b-amyrin synthase Through engineering the sterol pathway in S cerevisiae, we explore strategies for increasing triterpene production, using AaBAS as a test case By manipula-tion of two key enzymes in the pathway, 3-hydroxy-3-methylglutaryl-CoA reductase and lanosterol synthase, we have improved b-amyrin production

by 50%, achieving levels of 6 mgÆL)1 culture As we have observed a 12-fold increase in squalene levels, it appears that this strain has the capa-city for even higher b-amyrin production Options for further engineering efforts are explored

Abbreviation

HMGR, HMG-CoA reductase.

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may also find applications in ruminant nutrition [11],

as anticancer agents [12,13], and as vaccine adjuvants

[14]

Although triterpene synthases have been expressed

in microbial hosts such as Saccharomyces cerevisiae,

there has been little effort made so far to engineer the

metabolism of a microbial host for enhanced

produc-tion of triterpenes By contrast, there have been many

considerable efforts to engineer microbes for higher

production of mono-, sesqi- and diterpenes [15] These

projects have mainly focused on the overexpression of

enzymes involved in either of the two pathways

(mevalonate or 1-deoxy-d-xylulose-5-phosphate)

res-ponsible for the biosynthesis of isoprenoids [16–18] In

S cerevisiae, the mevalonate pathway is responsible

for the biosynthesis of isoprenoids and sterols A good

deal is known about regulatory mechanisms within

the pathway, although the majority of studies have

focused on the upper part of the pathway, from

acetyl-CoA to squalene Our knowledge of how the lower

half of the pathway, from squalene to ergosterol, is

regulated remains somewhat limited As the branch

point for triterpene biosynthesis is located in this latter

half of the pathway, the optimal steps to increase their

production in yeast are not immediately apparent

Artemisia annua, or sweet wormwood, has been used

medicinally for centuries, predominantly in China [19]

A sesquiterpene constituent, artemisinin, is one of the

most important drugs used in the treatment of

malaria In an effort to isolate and characterize new

terpene synthases from A annua, we have designed

degenerate primers for use in RT-PCR Here, we

describe the isolation of a b-amyrin synthase gene

from A annua and its expression in S cerevisiae Our

findings on engineering overproduction of b-amyrin in

S cerevisiae should be relevant to the production of

any triterpene

Results

Isolation and verification of a b-amyrin synthase

In order to isolate new triterpene synthase genes from

A annua, several degenerate primers were designed

from an alignment of plant triterpene synthase protein

sequences 3¢ RACE reactions were carried out on

RNA isolated from A annua leaf tissue, and a product

of the expected size was obtained with the primer

TriF1 (Table 1) The fragment was cloned and the

sequence was found to be homologous to triterpene

synthase genes Gene-specific primers were designed

for 5¢ RACE, and a product was obtained that

contained the likely start codon, based on protein

sequence alignments, with 175 nt of the upstream 5¢ UTR sequence The predicted full-length gene encodes a 762 amino acid protein that shares over 70% identity with plant b-amyrin synthases The most closely related protein (AAX14716), sharing 86% sequence identity, is the b-amyrin synthase from Aster sedifolius, a plant which belongs to the asteroi-deae, the same sub-family as A annua (Fig 1)

Published detection methods for triterpenes such as b-amyrin are generally laborious, and are inconvenient when processing a large number of samples [5,20] Therefore, we attempted to streamline the process by eliminating the sample clean-up steps normally per-formed after cell extraction, or the need for derivatiza-tion Cell disruption and saponification was performed

as previously described, using a mixture of EtOH and KOH [20] We found that using the nonpolar solvent dodecane for extraction allowed us to follow this directly with separation by GC⁄ MS, using the highest possible temperature settings for the mass spectrometer ion source and quadrupole This proved to be a sensi-tive and robust method for the detection of b-amyrin and the cell sterol components squalene and ergo-sterol

The coding sequence of the gene, designated AaBAS, was cloned into the high-copy yeast expression vector pESC-URA, under control of the GAL10 promoter, and transformed into S cerevisiae to create the strain bamy1 After induction of AaBAS expression with galactose, sterols were extracted from cells and ana-lyzed by GC⁄ MS A single chromatographic peak was found in extracts from bamy1 cells that was absent in cells containing an empty vector The retention time of this compound was identical to that of a b-amyrin standard, and the corresponding mass spectra were found to match (Fig 2) An in vitro assay using a bamy1 cell extract and the triterpene substrate 2,3-oxidosqualene was also found to result in production

Table 1 Oligonucleotides used The restriction sites used in clon-ing are underlined.

Oligonucleotide Sequence (5¢- to 3¢)

PolyT-anchor GAGCTCGAGATCTAAGCTTGCTTTTTTTTTTTTTT

TTTTTT

AAGGGCGCAATG

CCTGCTTG

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of the b-amyrin product The product was not

observed in the absence of either the substrate or the

AaBASgene (data not shown)

Production of b-amyrin in engineered strains

of S cerevisiae

We attempted to increase production of b-amyrin by

modifying flux through the sterol biosynthetic pathway

of S cerevisiae The enzyme

3-hydroxy-3-methylgluta-ryl-CoA reductase (HMGR, represented by two

iso-zymes: HMG1 and HMG2; Fig 3) is known to act as

a control point in the sterol pathway, with one of

the primary control mechanisms being degradation of

the HMGR protein in response to accumulation of

the squalene precursor farnesyl pyrophosphate [21,22]

Expression of a truncated form of the HMG1

(tHMG1) protein circumvents this feedback, which

occurs via the N-terminal transmembrane domain of

the enzyme [23] Furthermore, expression of tHMG1

from an independently-regulated promoter will bypass

any transcriptional control of expression Strain bamy2

contains an integrated copy of tHMG1 under control

of the GAL1 promoter in addition to pESC-AaBAS

In agreement with previous studies [23,24], bamy2

accumulated significantly higher levels of squalene

compared to bamy1 (Fig 4A) However, this eight-fold increase in squalene did not translate into increased yields of b-amyrin; rather the b-amyrin levels from bamy2 were one-third of that produced by bamy1 (Fig 4C) The ergosterol content of the cells remained essentially unchanged in strain bamy2 (Fig 4B), which

is consistent with the view that there is a feedback con-trol mechanism in the pathway between squalene and ergosterol [23] bamy2 grew extremely slowly at first (Fig 4D), as observed previously [23], where it was attributed to accumulation of toxic intermediates such

as farnesyl pyrophosphate

In a separate approach, we tested whether downre-gulation of lanosterol synthase (ERG7; Fig 3) would provide more 2,3-oxidosqualene substrate for AaBAS Other studies have shown that triterpene production can be enhanced by deleting ERG7 completely [20] However, as erg7 strains require feeding with ergo-sterol, this approach is economically limited for indus-trial purposes To enable the downregulation of ERG7,

we modified strain bamy1 by replacing the native ERG7 promoter with the methionine-repressible pro-moter of the MET3 gene [22] Thus, the strain bamy3 contains a PMET3-ERG7 replacement of the native ERG7 gene in addition to pESC-AaBAS Following downregulation of ERG7, strain bamy3 was found to

Fig 1 Pairwise sequence alignment of AaBAS from A annua (upper line) with its closest known relative, b-amyrin synthase from A sedifo-lius (AAX14716, lower line) The position of the primer TriF1 is indicated by the arrow.

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accumulate similar levels of squalene to strain bamy1,

whereas b-amyrin levels were slightly higher (Fig 4) It

is interesting to note that ergosterol levels in the cell

were not reduced in response to ERG7 limitation

Veen et al [25] have shown that, when squalene

epoxi-dase (ERG1) is overexpressed, there is no

accumula-tion of 2,3-oxidosqualene, but rather of lanosterol,

indicating that ERG7 is not a flux-limiting enzyme In

addition, it is likely that regulation of the pathway was

adjusted in response to the reduced ERG7 transcript

levels in order to maintain ergosterol production

Indeed, it was necessary to optimize the relative timing

of AaBAS induction and ERG7 repression to even

maintain the same b-amyrin production levels as strain

bamy1 When induction and repression were

simulta-neous, b-amyrin production levels were actually lower

in strain bamy3 and, thus, it was necessary to delay

repression of ERG7 until 24–48 h after AaBAS

induc-tion in order to allow AaBAS to first accumulate (data not shown) The data shown in the present study were generated by inducing AaBAS at inoculation and repressing ERG7 43 h later by the addition of 1 mm methionine

We next decided to combine the two strategies in order to test whether the feedback regulation that appears to take place in the tHMG1 strain bamy2 may

be overcome by downregulating ERG7 Strain bamy4 was therefore constructed from strain bamy2 by replacing the native ERG7 promoter with the MET3 promoter Again, it was found that optimal results were obtained when ERG7 was repressed by the addi-tion of methionine 24–48 h after inducaddi-tion of AaBAS expression bamy4 did not exhibit the same growth lag phase observed in bamy2, and grew at approximately the same rate as bamy1 (Fig 4D) Interestingly, squa-lene accumulated in bamy4 to even greater levels than

Time (min)

A

BY4742 wt strain

AaBAS in vivo product

β-amyrin standard

β-amyrin standard

HO

AaBAS in vivo product

%

%

m/z m/z

B

Fig 2 Confirmation of b-amyrin production in S cerevisiae by expression of AaBAS (A) Overlaid GC ⁄ MS chromatographs of extracts from strains BY4742 and bamy1 with an authentic b-amyrin standard (with b-amyrin structure shown) (B) Mass spectra extracted from the peaks shown in (A).

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those found in bamy2, corresponding to a 12-fold

increase over those in bamy1 (Fig 4A) In this case,

however, b-amyrin production levels were also

signifi-cantly enhanced, resulting in a 50% increase in yield

over bamy1 (Fig 4C)

Discussion

We have shown that it is possible to engineer increased production of tritepenes in S cerevisiae without the need for feeding with exogenous sterols The 50% increase in b-amyrin levels demonstrated in the present study should be considered in the light of the fact that triterpene production may not be as amenable to engi-neering efforts as the volatile sesquiterpenes and mono-terpenes that readily diffuse out of the cell However,

it is apparent that further progress can be made and there are some clues as to what these next steps may comprise We have achieved a 12-fold increase in squa-lene levels over the initial bamy1 strain, and a logical course of action would be to find a way to convert this squalene into b-amyrin

M’baya et al [26] demonstrated that ERG1 activity

is reduced in the presence of excess sterols through a mechanism other than enzyme inhibition, most likely transcriptional repression Not a great deal is known about how the latter half of the sterol pathway is regu-lated and exactly what role ERG1 plays in this pro-cess However, the fact that we observe a further increase in squalene upon downregulation of ERG7 in strain bamy4 would indicate that 2,3-oxidosqualene can act as a repressor of ERG1 Tight regulation at ERG1 would make sense as it marks the beginning of the oxygen-dependent reactions in the pathway If the feedback regulation is transcriptional in nature, then it

Acetyl-CoA

HMG-CoA

Mevalonate

HMG1,2

Squalene

2,3-oxidosqualene

ERG1

Lanosterol

ERG7

β-amyrin

AaBAS

Ergosterol Fig 3 The yeast sterol pathway with the branch point for b-amyrin

synthesis Multiple steps are indicated by dashed lines.

0

2

4

6

8

10

12

Time (h)

βamy1 βamy2 βamy3 βamy4

0 5 10 15 20 25 30

Time (h)

0

1

2

3

4

5

6

7

Time (h)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Time (h)

Fig 4 Determination of (A) squalene, (B) ergosterol, (C) b-amyrin, and (D) D600for strains bamy1 (BY4742, pESC-AaBAS), bamy2 (BY4742, pESC-AaBAS, P GAL1 -tHMG1), bamy3 (BY4742, pESC-AaBAS, P MET3 -ERG7), and bamy4 (BY4742, pESC-AaBAS, P GAL1 -tHMG1, P MET3 -ERG7 ) Error bars represent the SD for three independent cultures per strain.

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should be possible to circumvent it by overexpressing

ERG1 under the control of an independent promoter

Veen et al [25] overexpressed ERG1 and tHMG1

together and observed a 50% increase in sterol

concen-trations

We have subsquently tested this hypothesis by

trans-forming the strain bamy4 with a high-copy expression

vector harboring ERG1 under control of the GAL1

promoter (to create strain bamy5) A comparison

between these two strains showed that b-amyrin

pro-duction levels were essentially unchanged whereas

squalene levels actually increased slightly in strain

bamy5 (data not shown) This would indicate that flux

from squalene to b-amyrin is not limited by ERG1

transcription levels, but the possibility remains that

there is regulation of ERG1 at the protein level It also

is likely that there are other factors contributing to the

lack of flux from squalene to b-amyrin In particular,

the availability of squalene for conversion by ERG1

may be limited by its biochemical state In cases where

tHMG1 has been overexpressed in yeast, squalene

accumulates predominantly in an insoluble form that is

not immediately available to the sterol pathway [25,27]

The sterol-acyl transferases ARE1 and ARE2 are

responsible for esterification of excess squalene for

storage in insoluble lipid particles [27] Thus, it appears

that attenuation of this process would be the next

logi-cal step for further engineering triterpene production in

S cerevisiae Additional studies into the possible

regulation of ERG1 by 2,3-oxidosqualene at either

post-translational or enzyme kinetic levels may also be

warranted

Experimental procedures

Isolation of a triterpene synthase gene from

A annua

Leaf tissue from A annua was collected predominantly

from new growth at branch tips and immediately frozen in

liquid nitrogen The tissue was ground to a fine powder

using a cooled mortar and pestle, and RNA was purified by

the Qiagen Plant RNeasy extraction method using RLC

buffer as supplied (Qiagen, Valencia, CA, USA) RNA was

quantified and checked for integrity using the Bioanalyzer

2100 (Agilent, Foster City, CA, USA) A single

triterpene-specific primer (TriF1; Table 1) was designed from an

align-ment of various plant triterpene synthase protein sequences

For 3¢ RACE, two primers were used in conjunction with

TriF1: a poly(dT) primer with a 5¢ ‘anchor’ sequence that

has a melting temperature matching that of TriF1; and a

primer composed of only the anchor sequence (Table 1)

cDNA was synthesized from 3 lg of leaf total RNA using

the polyT-anchor primer and Superscript II (Invitrogen,

followed by RNase H treatment Touchdown PCR was car-ried out on the cDNA using the TriF1 and anchor primers

30 cycles of amplification with an annealing temperature of

based on the average length of a triterpene synthase gene and a plant 3¢ UTR) was cloned into the TOPO TA vector (Invitrogen) and sequenced to reveal an ORF that appeared

to encode a triterpene-synthase-like protein The 5¢ end of the cDNA was recovered using the GeneRacer kit (Invitro-gen) according to the manufacturer’s guidelines, with the gene-specific primer TriRaceR1 The complete coding sequence of the candidate triterpene synthase gene was con-firmed by cloning and sequencing three PCR products, amplified using PFU Turbo (Stratagene, La Jolla, CA, USA) from three independent cDNA preparations The sequence has been submitted to Genbank and is available under accession number EU330197

Expression of the candidate triterpene-synthase gene in S cerevisiae

The full-length coding sequence of the candidate triterpene synthase gene was amplified using the primers TricdsF and TricdsR, which contain the 5¢ restriction sites EcoRI and SacI, respectively The sequence AACA was included immediately 5¢ to the start codon in TricdsF to provide a favorable translation start context [28] The PCR product was cloned into the EcoRI and SacI sites of the yeast expression vector pESC-URA (Stratagene) under control of the GAL10 promoter and ADH1 terminator to create pESC-AaBAS Following sequence verification, the plasmid was transformed into S cerevisiae BY4742 by the lithium acetate method [29], and transformants were selected on synthetic complete minus uracil agar (SC-URA) Synthetic

nitrogen base (Becton, Dickinson & Co., Sparks, MI, USA)

to a complete supplemental mixture (MB Biomedicals, Solon, OH, USA) of vitamins, minerals and amino acids, with the appropriate amino acid dropped out Transformed yeast strains were maintained on SC medium with 2%

Modification of the sterol biosynthesis pathway

in S cerevisiae

A strain containing a soluble, truncated form of HMG-CoA reductase 1 (HMG1) under control of the GAL1 pro-moter was constructed by transformation of BY4742 with the integrating plasmid pd-tHMGR and selection for loss

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of the URA3 selection marker using 5-fluoroorotic acid, as

described previously [17]

The native promoter for the S cerevisiae lanosterol

syn-thase gene, ERG7, was replaced with the

The strategy used essentially follows that described by

Gardner and Hampton [21] Genomic DNA from strain

BY4742 served as a template for amplification of the first

422 bp of the ERG7 cds using the primers ERG7F and

ERG7R (Table 1) The amplified fragment was cloned into

the NcoI and ClaI restriction sites of the vector pRS-ERG9

[17], thus replacing the ERG9 cds fragment with the ERG7

cds fragment, 3¢ to the MET3 promoter For integration

into S cerevisiae, the vector was digested at the unique

BbvCI site in the ERG7 cds to facilitate homologous

recom-bination with the native ERG7 gene Upon transformation

into S cerevisiae, the successful promoter replacement was

ERG7 reverse primer

Extraction, identification, and quantitation

of b-amyrin and sterols

A single method was developed to extract and quantify

b-amyrin and the native yeast sterols squalene and

ergos-terol Yeast culture (1 mL) in a microfuge tube was

centri-fuged for 1 min at 17 900 g to pellet cells The cells were

an internal standard The cells were boiled for 5 min in this

solution in 2 mL screw-cap tubes After cooling, the sterols

and b-amyrin were extracted by vortexing with 0.6 mL

dodecane (Sigma, St Louis, MO, USA) for 5 min at room

temperature The dodecane phase was transferred to a glass

model 5973 inert, Agilent) An aliquot of the sample (1 lL)

was injected into a DB5-MS column (Agilent) operating at

of 40–440 For quantification of metabolites, samples were

run in selected ion mode, detecting ions 203, 218, and 426

Standard curves for b-amyrin, squalene and ergosterol were

run at the start and end of each batch of samples

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