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Molecular interaction of neutral trehalase with otherenzymes of trehalose metabolism in the fission yeast Schizosaccharomyces pombe Teresa Soto, Alejandro Franco, S.. In this work we sho

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Molecular interaction of neutral trehalase with other

enzymes of trehalose metabolism in the fission yeast

Schizosaccharomyces pombe

Teresa Soto, Alejandro Franco, S Padmanabhan, Jero Vicente-Soler, Jose Cansado and Mariano Gacto Department of Genetics and Microbiology, Facultad de Biologı´a, University of Murcia, Spain

Trehalose metabolism is an essential component of the stress

response in yeast cells In this work we show that the

prod-ucts of the principal genes involved in trehalose metabolism

in Schizosaccharomyces pombe, tps1+(coding for

trehalose-6-P synthase, Tps1p), ntp1+(encoding neutral trehalase,

Ntp1p) and tpp1+(that codes for trehalose-6-P

phospha-tase, Tpp1p), interact in vitro with each other and with

themselves to form protein complexes Disruption of the

gene tps1+blocks the activation of the neutral trehalase

induced by heat shock but not by osmotic stress We propose

that this association may reflect the Tps1p-dependent

requirement for thermal activation of trehalase Data

reported here indicate that following a heat shock the

enzyme activity of trehalase is associated with Ntp1p dimers

or trimers but not with either Ntp1p monomers or with complexes involving Tps1p These results raise the possibility that heat shock and osmotic stress activate trehalase differ-entially by acting in the first case through an specific mech-anism involving Tps1p–Ntp1p complexes This study provides the first evidence for the participation of the cata-bolic enzyme trehalase in the structural framework of a regulatory macromolecular complex containing trehalose-6-P synthase in the fission yeast

Keywords: neutral trehalase; stress; protein interaction

Synthesis and degradation of the nonreducing disaccharide

trehalose is carried out by several enzymes that are widely

distributed and conserved among prokaryotes and

eukary-otes One probable reason for this conservation is the ability

of trehalose to function as a general stress protectant in

living organisms Recent studies have focused on the role of

trehalose in stabilizing cellular structures under conditions

like desiccation, osmotic or oxidative stresses, and mild heat

shock [1,2] Studies in vitro have confirmed the exceptional

properties of trehalose in protecting biological membranes

or enzymes subjected to different types of extreme

condi-tions [3,4] All these findings suggest that the trehalose

turnover must occur in a coordinated way for this sugar to

play its diverse functional roles during the life cycle

Consequently, the study of the enzymes involved in

trehalose metabolism and the subtle regulation of their

activities at the molecular and cellular level have received a

great deal of attention in the last decade The best known

picture for trehalose synthesis and mobilization in simple

eukaryotes has emerged from studies in the budding yeast

Saccharomyces cerevisiae, where trehalose synthesis is

basically a two-step process: trehalose 6-phosphate synthesis

by trehalose-6-P synthase (TPS1) from UDP-glucose and glucose 6-P as substrates, and dephosphorylation of treha-lose-6-P to trehalose by trehatreha-lose-6-P phosphatase (TPS2) Studies based on two-hybrid analyses and on Western blot analyses of complexes obtained by gel filtration fractiona-tion concluded that TPS1 and TPS2 together with proteins TSL1 and TPS3 (which act as regulators of both synthase and phosphatase activities) form part of a multimeric protein complex of approximate molecular mass 800 kDa called the trehalose synthase complex [5–7] In this complex, TPS1, TPS2, and TPS3 subunits interact with each other and among themselves (as dimers or higher order oligo-mers), whereas TSL1 interacts only with TPS1 and TPS2 [6] Another component of trehalose metabolism is the hydro-lysis of trehalose to glucose This is catalyzed by the enzyme neutral trehalase (NTH1), whose activity is regulated

by phosphorylation of the enzyme protein at serine residues [8,9]

Comparatively much less is known about the regulation

of the trehalose synthesis in the evolutionarily distant yeast Schizosaccharomyces pombe In this fission yeast, the tps1+ gene codes for trehalose-6-P synthase (Tps1p), that synthe-sizes trehalose-6-P as occurs in S cerevisiae [10] However,

in contrast to the behaviour observed in S cerevisiae, Dtps1 strains of S pombe are able to grow on glucose or other readily fermentable carbon sources, although disruption of this gene does prevent spore germination [10] Recently, we characterized a second gene of the trehalose biosynthetic pathway in S pombe, named tpp1+, which codes for trehalose-6-P phosphatase (Tpp1p) and is responsible for the synthesis of trehalose from trehalose-6-P [11] In

S pombe, trehalose degradation is due to the action of a 84-kDa neutral trehalase protein (Ntp1p), encoded by ntp1+ gene [12,13] activated by phosphorylation on

Correspondence to J Cansado, Department of Genetics and

Microbiology, Facultad de Biologı´a, University of Murcia,

30071 Murcia, Spain Fax: + 34 68 363963, Tel.: + 34 68 364953,

E-mail: jcansado@um.es

Abbreviations: EMM2, Edinburgh minimal medium; GST,

glutathi-one S-transferase; Ha6H, hemagglutinin antigen epitope and six

histidines; Ntp1p, neutral trehalase protein; Tps1p, trehalose-6-P

synthase protein; Tpp1p, trehalose-6-P phosphatase protein; TTC,

triphenyltetrazolium chloride

(Received 15 March 2002, revised 6 May 2002, accepted 27 June 2002)

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supplementing cultures with glucose and a nitrogen source.

Activation of this enzyme protein appears to be mediated by

protein kinases Pka1p and Sck1p [14,15] In addition,

mRNA levels of ntp1+ rise when S pombe cultures are

subjected to thermal, osmotic or oxidative stresses [12,16]

The increased expression of ntp1+ is accompanied by a

rise in enzyme activity, which is also regulated by the

Pka1p/Sck1p pathway during osmotic and oxidative

stress [16,17] In a previous work, we showed that mutants

of S pombe disrupted in trehalose-6-P synthase function

were unable to increase neutral trehalase activity under heat

shock conditions or after the addition of glucose or

nitrogen source However, these Dtps1 strains still respond

to osmotic stress by increasing trehalase levels [18] Thus, in

S pombe, trehalose-6-P synthase appears to be involved in

the regulation of the thermal- and nutrient-induced

activa-tion of neutral trehalase but not during activaactiva-tion on

osmotic stress These observations raised the question of

whether trehalose-6-P synthase and neutral trehalase would

interact in vivo In this paper we demonstrate that both

Tps1p and Ntp1p interact in vivo and are part of distinct

trehalose-6-P synthase/trehalase complexes Moreover,

trehalose-6-P phosphatase (Tpp1p) is likely a member of

these complexes suggesting that regulation of trehalose

synthesis and breakdown may be integrated mechanisms

These findings indicate a divergence in the molecular designs

controlling trehalose metabolism in S pombe from those in

S cerevisiae

M A T E R I A L S A N D M E T H O D S

Strains and culture media

The S pombe strains employed in this study are listed in

Table 1 They were routinely grown with shaking at 28C

in YES [19] or EMM2 with or without thiamin (5 mgÆL)1)

[12] Culture media were supplemented with adenine,

leucine, histidine or uracil (100 mgÆL)1, all obtained from

Sigma Chemical Co.) depending on the requirements for

each particular strain For sporulation of diploids, MEL

medium was employed [19] Solid media were made by the

addition of 2% (w/v) bacto-agar (Difco Laboratories)

Transformation of S pombe strains was performed by the

lithium acetate method as described elsewhere [19]

Escher-ichia coli DH5aF¢ was employed as a host to propagate

plasmids It was grown at 37C in Luria–Bertani medium

plus 50 lgÆmL)1ampicillin

Construction of Ntp1p-, Tps1p-, and Tpp1p-tagged strains

A 5¢ truncated version of ntp1+ORF was amplified by PCR employing the 5¢ oligonucleotide NTP-1 (CCGCTCGAG TCGAATATCTGCCGGAAG, which hybridizes at posi-tions 701–718 in the ntp1+ORF and contains an internal XhoI site), and the 3¢ oligonucleotide TAG-3 (CTAC GGCGGCCGCCATTTTTATGAATGGAAA, which hybridizes at the 3¢ end of ntp1+ORF and incorporates a NotI site placed immediately upstream of the TAA stop codon) The restriction sites in both oligonucleotides are underlined PCR amplification employing the Expand high-fidelity system (Roche Molecular Biochemicals) generated a 1.6 kb fragment that was cleaved with XhoI and NotI and cloned into plasmids pIH-ura and pIH-LEU These are integrative plasmids derived from plasmid pDS472a [20], without nmt promoter and ars1 sequences, and with ura4+

or LEU2 as selectable markers, which allow the construc-tion of vectors with Ha6H tag fusions at the C-terminus The resulting plasmids were digested at the unique SfiI site within the ntp1+coding region (at position 1665) and the linear fragments transformed into haploid strains MM1 and MM2, to target integration at the ntp1+locus Uracil or leucine prototrophs were selected for strains MM1 and MM2, respectively The identification of strains C3 and C69, with one copy of Ntp1p–Ha6H expressed from the genomic ntp1+ promoter, was verified by Southern blot analysis and immunoblot of whole-cell extracts with

anti-Ha Ig (see below)

To obtain Tps1p-tagged strains, a 5¢ truncated version of tps1+ ORF was amplified by PCR employing the 5¢ oligonucleotide TPSINT-1 (CCGCTCGAGCCTAACGG TGTGGAATAC, which hybridizes at positions 715–732 in the tps1+ORF and shows an internal XhoI site), and the 3¢ oligonucleotide TAF-3 (CTACGGCGGCCGCCCGAGC TAGAATTCATCGA, which hybridizes at the 3¢ end of tps1+ORF and incorporates a NotI site placed immediately upstream of the TAA stop codon) The 0.7 kb amplified PCR fragment was cleaved with XhoI and NotI and cloned into integrative plasmids pIH-ura and pIG-ura (fusion to a GST tag at C-terminus) The resulting plasmids were digested at the unique NcoI site within tps1+(at position 1297) and the linear fragments transformed into haploid strain MM1, to target integration at the tps1+locus Uracil prototrophs were selected and the identification of strains C4 and C5, with one copy of Tps1p–GST or Tps1p–Ha6H

Table 1 S pombe strains used in this study.

C694 h+ade6-M216 leu 1-32 ura4-D18 ntp1 + :Ha6H (LEU2) tps1 + :GST (ura4 + ) This study

C33 h – ade6-M210 leu 1-32 ura4-D18 tpp1 + :Ha6H (ura4 + ) ntp1 + :Ha6H (ura4 + ) tps1 + :Ha6H (ura4 + ) This study

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expressed from the genomic tps1+promoter, was verified

by Southern blot analysis and immunoblot of whole-cell

extracts with anti-GST or anti-Ha Ig, respectively

The double-tagged strain C694 (Ntp1p–Ha6H, Tps1p–

GST) was constructed by mating strains C69 and C4, and

selecting diploids in EMM2 medium without supplements

Sporulation was performed in MEL medium and the spores

purified by glusulase treatment [21] were allowed to

germinate in minimal medium plus adenine Strains with

the double-tagged genotype were identified by Southern and

immunoblot analysis with anti-HA and anti-GST Ig

Double-tagged strain C33 (Ntp1p–Ha6H, Tpp1p–Ha6H)

was constructed by mating strains C3 and MMPI-3b, and

selecting diploids in EMM2 medium with leucine After

spore purification and germination, the double-tagged

strains were identified by Southern and immunoblot

analysis with anti-Ha Ig The triple-tagged strain C335

(Ntp1p–Ha6H, Tps1p–Ha6H, Tpp1p–Ha6H) was obtained

after mating strains C33 and C5, and Southern and

immunoblot analysis of germinated spores, as described

above

Expression of Tps1p–GST and Ntp1p–GST fusions

The tps1+ORF was amplified by PCR with oligonucleotides

which hybridizes at sequences upstream of the ATG start

codon in the tps1+ORF and shows an internal XhoI site),

and TAF-3 The 1.5 kb product was cloned into the XhoI/

NotI sites of plasmid pDS472M, which is a derivative of

plasmid pDS472a with an attenuated version of the nmt1

promoter and LEU2 selectable marker, to create plasmid

pTGST, which expresses trehalose-6-P synthase (Tps1)

fused to GST at the C-terminus under the control of the

medium strength thiamin-repressible promoter pTGST

and control plasmid pDS472M (unfused GST) were

transformed into strains C3, C5 and MMPI-3, and leucine

prototrophs selected in EMM2 medium plus adenine

For Ntp1p–GST expression, ntp1+ORF was amplified

by PCR with oligonucleotides NTP-5 (CCGCTCGAGG

CTATCATTCGTGAATAG,whichhybridizesatsequences

upstream of the ATG start codon in the ntp1+ORF and

shows an internal XhoI site), and TAG-3 The 1.5 kb product

was cloned as above into pDS472M to create plasmid

pNGST, containing an in-frame fusion where the 3¢ end of the

ntp1+ ORF is followed by the GST epitope, and whose

expression is under the control of the medium strength nmt1

thiamin-repressible promoter Both pNGST and control

plasmid pDS472M were transformed into strains C3, C5 and

MMPI-3, and leucine prototrophs were selected

Purification of Ha6H- and GST-tagged proteins

by affinity chromatography

Total cell homogenates were prepared under native

condi-tions employing chilled acid-washed glass beads and lysis

buffer (10% glycerol, 50 mM Tris/HCl pH 7.5, 150 mM

NaCl, 0.1% Nonidet NP-40, plus an specific protease

inhibitor cocktail for fungal and yeast extracts obtained

from Sigma Chemical Co.) The lysate was removed and

cleared by centrifugation at 10 000 g for 30 min

Ha6H-tagged proteins were purified by using Ni2+-nitrilotriacetic

acid-agarose beads (Qiagen Inc.) whereas GST and

GST-tagged proteins were precipitated using glutathione glutathi-one–Sepharose beads (Amersham-Pharmacia) following the procedures described by Shiozaki & Russell [22]

Immunoprecipitation of Ha6H- and GST-tagged proteins For immunoprecipitation of Ha6H-tagged proteins, the extracts were incubated for 12 h at 4C with monoclonal mouse anti-Ha Ig (clone 12CA5, Roche Molecular Bio-chemicals), and the immunocomplexes were adsorbed with protein A–agarose (Roche Molecular Biochemicals) for 4 h

at 4C The immunoprecipitation of GST-tagged proteins was performed with a polyclonal sheep anti-GST Ig (Amersham-Pharmacia) and protein G–agarose (Roche Molecular Biochemicals) In all cases the suppliers’ recom-mendations were followed in terms of incubation times and washing of the complexes

Detection of neutral trehalase activity in gel Affinity purified Ntp1p-Ha and Tps1p–GST proteins were mixed with loading buffer (100 mM Mes pH 6, 15% glycerol and 0.01% bromophenol blue), and resolved at

4C in native 6% polyacrylamide gels (200 V for 8 h), employing Tris/borate pH 7.5 as running buffer The gels were then washed with 100 mMMes pH 6.0 for 10 min, and incubated with 100 mM Mes pH 6 plus 200 mMtrehalose (Sigma Chemical Co.) for 2 h at 30C After washing with distilled water, active neutral trehalase proteins were detected in situ by incubating the gels with 0.1% TTC in 0.5Msodium hydroxide at 80C Color development was stopped with a 7.5% acetic acid solution

Gel filtration

A Superdex-200 column (Amersham-Pharmacia) equili-brated with buffer A (10 mMMes, pH 6.0, 150 mMNaCl) was used for size-exclusion analysis in an AKTA HPLC system (Amersham-Pharmacia) Lower salt concentrations were not used in order to minimize nonspecific electrostatic interactions with the column matrix The column was calibrated using vitamin B12 (1.3 kDa), cytochrome c (12.4 kDa), carbonic anhydrase (29 kDa), ovalbumin (43 kDa), BSA (66 kDa), yeast alcohol dehydrogenase (150 kDa), b-amylase (200 kDa), apoferritin (430 kDa) and thyroglobulin (670 kDa) (all from Sigma Chemical Co.) at the concentrations recommended by the manufac-turer One-hundred microliters (1 mg total protein) of the supernatant from ultracentrifuged extract obtained from triple-tagged strain C335 grown to mid-log phase, after either a heat shock (40C, 1 h) or an osmotic shock (0.75M

NaCl, 2 h) were applied to the column with buffer A plus a yeast protease inhibitor cocktail (Sigma Chemical Co.) A flow rate of 0.4 mLÆmin)1 was used and the elution was tracked by absorbance at 280, 235 and 220 nm Blue Dextran (2000 kDa; Sigma) and vitamin B12were used for void volume (Vo) and total bed volume (Vt) determinations, respectively Molecular masses were estimated from a calibration curve (correlation coefficients‡ 0.98) generated

by linear regressions of the elution volume for each protein using SIGMAPLOT (Jandel Scientific) To determine the fractions containing Ntp1p-, Tps1p-, and Tpp1p–Ha6H tagged proteins, 100 lL of each fraction (0.4 mL) were

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trichloroacetic-acid-precipitated, washed with cold acetone,

air-dried, resuspended in SDS gel sample buffer, and

resolved in SDS/PAGE (10%) gels Immunoreactive bands

were detected by Western blot analysis with anti-Ha Ig (see

below)

SDS/PAGE and Western blotting

Proteins were resolved in 8 or 10% SDS/PAGE gels as

previously described [11], transferred to nitrocellulose filters

(Amersham-Pharmacia), and incubated with mouse

anti-Ha or sheep anti-GST Ig The immunoreactive bands were

revealed with HRP-conjugated secondary Ig [anti-(mouse

IgG) Ig or anti-(sheep IgG) Ig; Sigma Chemical Co.] and the

ECL system (Amersham-Pharmacia)

Enzyme assays and trehalase activation

Trehalase activity was assayed after cell breakage as

described previously [23] Activation of trehalase by heat

treatment or osmotic shock was carried out as indicated

earlier [17] Enzyme activity in eluates was expressed as

nmol glucose produced per min All trehalase

determina-tions were repeated at least three times with consistent

results Representative results are shown Specific activity of

trehalase in slab gels was expressed as enzyme units per mg

protein Protein determination was performed by

absor-bance measurement at 280 and 205 nm according to the

method described in previously [24]

R E S U L T S

Neutral trehalase and trehalose-6-P synthase

associationin vitro

In order to analyse possible interactions between

treha-lose-6-P synthase and neutral trehalase interaction

in vitro, we constructed strains C3 and C69, which

express a C-terminal Ha6H-tagged version of neutral

trehalase (Ntp1p, 84 kDa) under the control of the

genomic promoter These strains showed the same growth

behavior and neutral trehalase activation pattern as the

parental strains MM1 and MM2 for a variety of

conditions Strain C3 was further transformed with

plasmid pTGST, which expresses trehalose-6-P synthase

(55 kDa) fused to a GST epitope (25 kDa) at its

C-terminus under the regulation of an attenuated version

of the thiamin-repressible promoter [20] Several

transfor-mants were cultured in minimal medium plus thiamin,

and then transferred to the same medium without thiamin

to allow synthesis of the Tps1p–GST fusion protein The

cells were collected at mid-log phase of growth, and

Tps1p–GST was affinity-purified employing glutathione

(glutathione)–Sepharose beads As shown in Fig 1 (lane 2),

significant levels of Tps1p–GST were detected employing

anti-GST Ig under these conditions However, if Tps1p

interacts with Ntp1p in vitro, Ntp1p–Ha6H should be

detectable with anti-Ha Ig after Tps1p–GST purification

As shown in Fig 1 (lane 6), this appears to be the case,

and a clear band of the size expected for Ntp1p–Ha6H

fusion was visible after hybridization with anti-Ha Ig

Besides, the Ntp1p–Ha6H signal was absent when strain

C3 was transformed with a control plasmid that expresses

unfused GST (Fig 1, lane 5) Taken together, these results indicate that Ntp1p and Tps1p interact in vitro in

S pombe, and that the nature of this association is specific and independent of the presence of the GST domain fused to Tps1p

Ntp1p–Tps1p association takes place during normal yeast growth and thermal shock, but might not occur when the cells are stressed by an osmotic upshift [18]

To test this possibility, we performed the same experiment described above by subjecting strain C3 plus plasmid pTGST either to osmotic stress or to a thermal one As shown in Fig 1, Ntp1p–Tps1p association was observed not only in control, exponentially growing cells but also for both thermal as well as osmotic stresses (lanes 7 and 8) Thus, in S pombe, Ntp1p–Tps1p interaction does not appear to be transient but is stable, and is maintained even under conditions where the presence of Tps1p is not needed for neutral trehalase activation (osmotic shock) These results, however, do not exclude by themselves the possibi-lity that some Ntp1p might be in a free, nonassociated state (see below)

We employed a medium-strength thiamin-repressible promoter for Tps1p–GST expression in Ntp1p–Ha6H cells

to achieve low levels of Tps1p–GST synthesis Although Ntp1p–Ha6H was not detectable in the absence of the Tps1p–GST fusion, it was conceivable that the described Tps1p–Ntp1p interaction could be due, in part, to the presence of nonphysiological levels of Tps1p–GST In order

to clarify this point, we constructed the S pombe double-tagged strain C694 This strain expresses Ntp1p and Tps1p fused at their C-terminus to Ha6H and GST epitopes, respectively, and in both cases the synthesis is regulated by their own genomic promoters The Tps1p fusion protein is active because strain C694 synthesizes trehalose at normal level This strain was grown in rich medium to mid-log phase, and after obtaining the corresponding extracts, Tps1p–GST and Ntp1p–Ha6H were immunoprecipitated with anti-GST and anti-Ha Ig, respectively As shown in Fig 2 (lane 2), the Ntp1p–Ha6H band was clearly detected

Fig 1 Ntp1p–Tps1p association takes place in vivo in growing cells of

S pombe, and in cells subjected to heat and osmotic stresses Strain C3, with a Ha6H epitope-tagged version of Ntp1p, was transformed with plasmids pDS472a (unfused GST; lanes 1 and 5) or pTGST (Tps1p– GST fusion; lanes 2, 3, 4, 6, 7 and 8) GST and Tps1p–GST fusions were expressed using the medium-strength thiamin-regulated promoter for 24 h Yeast lysates prepared from exponentially growing cells (lanes 2 and 6), or from either heat- (lanes 3 and 7) or osmotically shocked cells (lanes 4 and 8), were adsorbed with glutathione–Sepha-rose beads After extensive washing in lysis buffer, the proteins bound

to the beads were analyzed by Western blot using anti-GST (lanes 1–4) and anti-Ha Ig (lanes 5–8).

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with anti-Ha Ig in the complexes obtained from Tps1p– GST immunoprecipitation, whereas Tps1p–GST was visi-ble with anti-GST Ig after Ntp1p–Ha6H immunoprecipi-tation (lane 5) In this strain, the existence of Ntp1p–Tps1p interaction was evident not only in growing cells, but also during heat or osmotic stress (not shown) These data strongly suggest the existence of an in vivo association between Ntp1p and Tps1p in S pombe over a variety of environmental conditions

To ascertain the functional significance of this interac-tion, we developed a gel assay for neutral trehalase activity (see Materials and methods) and determined the enzyme activity of Ntp1p bounded to Tps1p in exponen-tially growing cells from double-tagged strain C694 and in cultures subjected to heat or osmotic stress As shown in Fig 2B, affinity-purified Ntp1p–Ha6H from growing cells displayed a typical pattern of neutral trehalase activity, with low level of enzyme activity in unstressed cells that increases strongly upon stress Notably, we were unable to detect in situ any neutral trehalase activity associated to native Tps1–GST protein purified with glutathione– Sepharose beads in samples from either unstressed, osmotic- or heat-shocked cells A quantitative estimation

of neutral trehalase activity gave similar results (Fig 2B, lower panel) Because a significant fraction of Ntp1p protein is bounded in vitro to Tps1p (see Figs 1 and 2A), these results demonstrate that in S pombe the active form

of neutral trehalase exists in a free, non Tps1p-associated state, independently of the environmental condition used for stress

We focussed then our attention on the likelihood that Tps1p or Ntp1p undergo self-association This has been previously reported for the Tps1p homologue in

S cerevisiae [6] Using the same experimental procedure used in Fig 1, we observed that self-association does indeed take place for both proteins As can be seen in Fig 3A (lane 4) and Fig 3B (lane 4), both Ntp1p– Ha6H and Tps1p–Ha6H were detected employing

anti-Ha Ig after Ntp1p–GST and Tps1p–GST purification, respectively These and other results (see below) support

Fig 2 Ntp1p and Tps1p coimmunoprecipitate and associate to form

complexes devoid of neutral trehalase activity (A) The double-tagged

strain C694 (Ntp1p–Ha6H, Tps1p–GST) was grown to mid-log phase,

and Tps1p–GST and Ntp1p–Ha6H were immunoprecipitated from

the corresponding extracts with anti-Ha Ig (lanes 1 and 5) or anti-GST

Ig (lanes 2 and 4) Ig After incubation with protein A–agarose

(anti-Ha immunoprecipitations) or protein G–agarose (anti-GST

immunoprecipitations) and extensive washing, the immunocomplexes

were resolved by SDS/PAGE and analyzed by Western blot using

anti-Ha (lanes 1, 2 and 3) or anti-GST Ig (lanes 3, 5 and 6) Lanes 3 and 6

correspond to negative controls without immunoprecipitation but

incubated with protein A–agarose (lane 3) or protein G–agarose (lane

6) to account for possible nonspecific protein binding to the matrix (B)

Upper panel: Affinity-purified Ntp1p–Ha6H and Tps1p–GST were

prepared from exponentially growing cells of strain C694 prior (lanes 1

and 4) and after osmotic (lanes 2 and 5) or heat stress (lanes 3 and 6).

Samples were resolved by native PAGE and spots developed for

neutral trehalase activity Lower panel: quantitative estimation of

enzyme activity (as trehalase units per mg protein) in each sample.

Fig 3 Ntp1p and Tps1p self-interact in vivo (A) Ntp1p–Ntp1p interaction The Ntp1p–Ha6H epitope-tagged strain C3 was transformed with plasmids pDS472a (unfused GST; lanes 1 and 3) or pNGST (Ntp1p–GST fusion; lanes 2 and 4) GST and Ntp1p–GST fusions were expressed using the medium-strength thiamin-regulated promoter for 24 h Yeast lysates were adsorbed with glutathione–Sepharose beads and after washing

in lysis buffer the proteins bound to the beads were analyzed by SDS/PAGE and Western blotting using anti-GST Ig (lanes 1 and 2) and anti-Ha Ig (lanes 3 and 4) (B) Tps1p–Tps1p interaction The Tps1p–Ha6H epitope-tagged strain C5 was transformed with plasmids pDS472a (unfused GST; lanes 1 and 3) or pTGST (Tps1p–GST fusion; lanes 2 and 4) GST and Tps1p–GST fusions were expressed using the medium-strength thiamin-regulated promoter for 24 h Yeast lysates were processed as described above, and the proteins bound to glutathione beads were analyzed after SDS/PAGE using anti-GST Ig (lanes 1 and 2) and anti-Ha Ig (lanes 3 and 4).

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the existence of a multiprotein complex involved in the

regulation of trehalose synthesis and breakdown in

S pombe

Trehalose- 6P phosphatase (Tpp1) is a member of the

Ntp1–Tps1 complex

Recently a third member of the trehalose metabolism

pathway in S pombe, the tpp1+ gene, which codes for

trehalose-6-P phosphatase, has been isolated and

charac-terized [11] The tpp1+ gene has considerable sequence

homology to S cerevisiae TPS2, which encodes

trehalose-6-P phosphatase S cerevisiae Tps2 has been shown to

interact, among others, with Tps1, and form part of the

trehalose synthase complex in this yeast [6,7] Based on these

precedents, we examined if Tpp1p interacts with both Tps1p

and Ntp1p in S pombe The strain MMPI-3a, that

expresses a Ha6H-tagged version of Tpp1p [11], was

transformed separately with plasmids pTGST and pNGST

(expressing Tps1p and Ntp1p fused to GST, respectively),

and the GST fusions were purified with glutathione–

Sepharose beads In either case (Fig 4A,B), the 100 kDa

Tpp1p–HA6H protein coprecipitated with the purified GST

fusion proteins, whereas it was absent in control

experi-ments (with plasmids expressing unfused GST) These

results clearly suggest that Tpp1p may also participate

in vivoto form Ntp1p–Tps1p complexes However, as for

Tps1p–Ntp1p complexes (see Fig 2B), trehalase activity

was absent in Tpp1p–N tp1p assemblies when assayed on gel

slabs (data not shown)

Analysis of the Ntp1p–Tps1p–Tpp1p complex

by HPLC-gel filtration

The results obtained thus far suggest the existence of

complexes in S pombe formed by mutual interaction

among Ntp1p, Tps1p, and Tpp1p To gain additional

information on their physical nature in terms of size and

composition, we constructed the triple-tagged strain C335

by mating double-tagged strain C33 (Ntp1p–Ha6H,

Tpp1p–Ha6H) and Tps1p–Ha6H tagged strain C5, which

affords simultaneous detection of Tps1p, Ntp1p and

Tpp1p by Western blot analysis using anti-Ha Ig Protein extracts obtained from exponentially growing cells of strain C335 were fractionated in native solution conditions by gel filtration employing a Superdex-200 HPLC column The fractions eluted from the column were subjected to SDS/ PAGE, blotted, and subsequently analyzed by Western blot with anti-Ha Ig As shown in Fig 5A, the elution profiles for Tps1p, Ntp1p and Tpp1p are quite intricate, with Tps1p being detected at higher levels than either Ntp1p or Tpp1p Moreover, Tps1p was detected over a wide range of elution volumes extending from that expected for the monomeric protein (fractions 18–20) to high molecular mass complexes close to 700–800 kDa (fractions 4–5), as well as intermediate-sized complexes Neutral trehalase (Ntp1p) was also detected in virtually all the fractions, but was most pronounced in the 700–800 kDa complex fractions and in those correspond-ing to sizes between 80 kDa (free monomer) and 300 kDa Finally, Tpp1p showed an elution profile similar to Ntp1p and, like Tps1p and Ntp1p, was also found in the 800 kDa complex These data indicate that, in addition to the monomeric forms, at least two distinct complexes exist containing significant amounts of all three proteins One corresponds to the high molecular mass complex (700–800 kDa) and the other to a more diffusely spread population corresponding to lower molecular mass range (80–250 kDa, fractions 12–17) To clarify which of these protein complexes exhibit neutral trehalase activity, we prepared log-phase cultures from strain C335 and subjected them to thermal (40C, 1 h) or osmotic (0.75MNaCl, 2 h) stress The corresponding cell extracts were then fraction-ated by gel filtration under the conditions described above

No significant differences in the elution profile of Ntp1p, Tps1p and Tpp1p were found under these circumstances, despite an increase in the overall signal (as the three proteins behave as heat shock proteins) Surprisingly, when the eluted fractions were assayed for neutral trehalase, no enzyme activity was found associated with Ntp1p mono-mers or in fractions corresponding to the high molecular mass trehalose synthase–trehalase complex (fractions 4–5) Instead, the heat-activated neutral trehalase was mainly detected in complexes of about 250 kDa, whereas neutral

Fig 4 Tpp1p associates with Ntp1p and Tps1p in vivo (A) Tpp1p–Tps1p interaction The Tpp1p–Ha6H epitope-tagged strain MMPI-3a was transformed with plasmids pDS472a (unfused GST; lanes 1 and 3) or pTGST (Tps1p–GST fusion; lanes 2 and 4) GST and Tps1p–GST fusions were expressed using the medium-strength thiamin-regulated promoter for 24 h Yeast lysates were then adsorbed with glutathione–Sepharose beads, and after extensive washing the proteins bound to the beads were analyzed by Western blot using anti-GST Ig (lanes 1 and 2) and anti-Ha Ig (lanes 3 and 4) (B) Ntp1p–Tpp1p interaction Strain MMPI-3a was transformed with plasmids pDS472a (unfused GST; lanes 1 and 3) or pNGST (Ntp1p–GST fusion; lanes 2 and 4) GST and Tps1p–GST fusions were expressed using the medium-strength thiamin-regulated promoter for 24 h, purified as described above, and analyzed using anti-GST (lanes 1 and 2) and anti-Ha Ig (lanes 3 and 4).

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trehalase activated by osmotic shock peaked mostly in

fractions corresponding to somewhat lower molecular

masses These enzyme activities fit the expected elution

for trehalase trimers and dimers, respectively

D I S C U S S I O N

Two main lines of evidence lead us to propose that in the

fission yeast S pombe neutral trehalase (Ntp1p) interacts

in vitrowith other proteins involved in trehalose

metabo-lism First, the activation of Ntp1p by heat shock or

nutritional stimuli only takes place in the presence of

trehalose-6-P synthase (Tps1p) [18] Secondly, in contrast

to the neutral trehalase in S cerevisiae [25], all attempts to

activate S pombe Ntp1p in vitro have been unsuccessful to

date Taken together, these results support the idea that in

S pombethe regulation of Ntp1p activity under stress relies

on the existence of some kind of interaction between Ntp1p

and Tps1p, or other elements, that may be lost under the

conditions of the in vitro assay for activation In the present

work, we have performed experiments including affinity

chromatography, immunoprecipitation, and gel filtration to

demonstrate that not only Tps1p, but also Tpp1p, interact

with Ntp1p and that macromolecular complexes, involving

trehalose synthase/phosphatase and trehalase, might indeed

exist in this yeast The demonstration of interactions

between Ntp1p–Tps1p and Ntp1p–Tpp1p (Figs 1, 2 and 4)

is, to our knowledge, the first description of an association

between the hydrolytic enzyme trehalase and proteins

involved in synthesis of trehalose, thus revealing a novel

relationship in trehalose metabolism

In E coli, trehalases are monomeric enzymes [26]

However, in S cerevisiae the functional cytoplasmic neutral

trehalase (NTH1) is probably a dimer, as deduced from gel

filtration experiments with active enzyme [25] No evidence has been reported demonstrating that NTH1 participates in the formation of the well-characterized trehalose synthase complex in the budding yeast [6,7] In S pombe, we find that part of Ntp1p is apparently present as free monomeric protein that does not display trehalase activity in vitro (Fig 5) The elution profile of trehalase activity in gel filtration indicated that after heat or osmotic shock only fractions corresponding to protein sizes between 170 and

300 kDa contain active enzyme On the other hand, Ntp1p eluted mainly in two peaks, either as part of a 700–800 kDa complex, together with Tps1p and Tpp1p, or, as expected,

in the fractions containing trehalase activity, which again showed the coexistence of Tps1p and Tpp1p (Fig 5) Because Ntp1p molecules also associate among themselves (Fig 2), these results alone would not allow us to establish whether trehalase activity correlates with self-assembly of Ntp1p homomultimers or with the formation of hetero-meric complexes involving Tps1p and Tpp1p in addition to Ntp1p However, the observation that Tps1p–(Tpp1p)– Ntp1p complexes lack trehalase activity (Fig 2B) strongly favors the first interpretation Active trehalase might thus arise from the specific self-assembly of a discrete number of Ntp1p molecules to form small oligomers (probably dimers

or trimers, considering the molecular mass of each putative subunit, 84 kDa) An intriguing fact is that there is a small but reproducible shift in the elution behavior of trehalase depending on the nature of the activation stress (Fig 5B) This shift might argue against the participation of a unique set of interactions involving association of Ntp1p molecules and could be taken to indicate a specific event occurring during activation by hyperthermia that is absent in the response elicited by osmotic stress However, the elution pattern of trehalase cannot be exclusively interpreted in

Fig 5 Analysis of Tps1p–Tpp1p–Ntp1p complexes by gel filtration (A) A high-speed supernatant of cell-free extracts from exponentially growing, triple Ha6H-tagged strain C335, was size fractionated by gel filtration through a Superdex-200 column The proteins from 100 lL of each fraction were concentrated by trichloroacetic acid precipitation, separated by SDS/PAGE, transferred to nitrocellulose and incubated with anti-Ha Ig After incubation with an HRP-conjugated secondary antibody [anti-(mouse IgG) Ig], the signals specific for Ha-tagged proteins were visualized with the ECL system V 0 indicates the void volume (B) Elution profile of activated neutral trehalase in S pombe Exponentially growing cultures of strain C335 were subjected to either heat shock (open circles) or osmotic stress (closed circles), and the correspondent protein extracts size fractionated as described for (A) Neutral trehalase activity (expressed as nmol glucose produced per min) was assayed in 250 lL of each fraction.

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terms of changes in the complex composition Because gel

filtration is responsive to Stokes radius, one should also

consider that the conformation has merely changed upon

activation depending on the triggering stimulus while the

composition is unaltered

Tps1p is probably the most abundant protein related to

trehalose metabolism present in S pombe (Fig 5), although

we can not exclude that the differential relative expression of

Ntp1p, Tps1p and Tpp1p in eluted extracts might be an

experimental artifact arising from differences in the

acces-sibility of the antibody to the Ha tag However, there is a

parallel in S cerevisiae, where the Tps1p homologue (TPS1)

is also present at levels higher than those of the other

constituents of the trehalose synthase complex [7] In

S cerevisiae, trehalose is synthesized by the 800 kDa

trehalose synthase complex as well as by free TPS1 [7] It

is unknown whether Tps1p activity in S pombe is present in

the high molecular mass trehalose synthase–trehalase

com-plex or linked to forms of lower molecular mass as for

neutral trehalase, although accumulation of trehalose by

ntp1-deleted strains seems to indicate that Tps1p function

does not require association with Ntp1p In any case, our

data suggest the existence of different types of Ntp1p

complexes in S pombe that might be specifically activated

as a function of the external stimulus If so, an attractive

explanation for the above results would be that S pombe

harbors at least two forms of Ntp1p that are capable of

being activated, one as a Ntp1p–Ntp1p homodimer

( 170 kDa), that becomes activated during osmotic shock,

and the other as a Tps1p–(Tpp1p)–Ntp1p heterocomplex

( 250 kDa) activated during heat shock Apparently,

trehalase requires association with Tps1p while being

activated by heat shock acquires enzymatic activity only

when detached from the heat-induced activation complex

Other possibilities may exist, but some experimental data

are consistent with this hypothesis For instance, in contrast

to heat shock, Ntp1p activation during osmotic shock is

independent of the presence of Tps1p [18] Also, the

activation of neutral trehalase induced by heat shock is

largely a post-translational event that exhibits considerably

faster kinetics than the osmotically induced activation

[17,23] In the latter case, the Pka/Sck1p-mediated

activa-tion of Ntp1p appears to occur at the level of the enzyme

synthesized de novo [17] Finally, the Tps1p–Ntp1p

associ-ation can occur under any growth condition or stress

treatment (Fig 1), which lends physiological significance to

this association In this context it should be mentioned that

Tpp1p disruption mutants show heat-shock activation of

Ntp1p [11], which supports the view that Tpp1p, but not

Tps1p, may be dispensable for this activation of trehalase

The advantages of a complex bearing enzymes separately

implicated in synthesis and breakdown of trehalose could

provide improved control efficiency of the respective

enzymatic activities as has been suggested in the case of

the synthesizing Tps1–Tps2 complex in S cerevisiae [7] On

the other hand, although this work has demonstrated the

existence of Tps1p–(Tpp1p)–Ntp1p complexes, one or more

of these may also interact with, as yet, unknown elements to

form the final complex In this context, an exhaustive search

for homologues to Tps1p, Tpp1p and Ntp1p in the

databases of the S pombe sequencing project (Sanger

Center, Cambridge, UK), revealed the existence of three

putative ORFs (SPAC3G6.09c, SPAC2F8.05 and

SPACUNK.16c) encoding proteins that show amino acid identity with Tps1p and Tpp1p ranging from 34 to 42%, and that may be good candidates for additional interac-tions More remarkably, the degree of identity of these ORF products is also high with respect to TSL1 and TPS3, two members of the trehalose synthase complex in S cerevisiae that regulate both trehalose synthase and phosphatase activities In particular, the protein sequence deduced from ORF SPAC2F8.05 indicated 37% identity with TSL1, whereas that of SPACUNK.16c showed a 38% of identity with TPS3 Hence, as described for the TPS1–TPS2 complex in S cerevisiae, it is tempting to speculate that in

S pombe these ORFs code for proteins that somehow regulate trehalose metabolism by interacting with some members of the enzyme proteins described here The data presented in this report reveal a crucial difference between the two organisms Unlike previously reported for

S cerevisiae[25], both the anabolic and catabolic enzymes might be integrated in some instances into a regulatory complex in S pombe

A C K N O W L E D G E M E N T S

T S and A F contributed equally to this work We thank Prof F J Murillo for generous access to the HPLC equipment and F Garro for expert technical assistance We are indebted to Profs M Yamamoto,

S L Forsburg and A Duran for kindly providing plasmids and strains A F is a predoctoral fellow of PFPI from the University of Murcia This work was supported in part by grant BMC2001-0135 from MCYT, Spain.

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