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Mutation of serine 1072 in the human protein and serine 1094 in the equiv-alent site in the mouse homologue in a consensus binding motif for 14-3-3 abolished 14-3-3 binding to d-catenin

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neurodegenerative disease

Shaun Mackie* and Alastair Aitken

University of Edinburgh, School of Biomedical and Clinical Laboratory Sciences, Edinburgh, Scotland, UK

Dimeric 14-3-3 proteins have important functions in

diverse biological processes [1–3] An optimal motif for

14-3-3 binding was identified as R(S)XpSXP [4] where

Sp is phosphoserine This was later refined to include a

second motif, mode 2, RXXXpSXP [5] A number of

proteins also bind to 14-3-3 at their C-terminus where

the presence of a proline residue may be unnecessary

as the peptide backbone would not be required to loop

out again from the binding pocket Thus in addition

to the well-characterized nonphosphorylated binding

motifs, there may be a third phospho-dependent

14-3-3-binding motif, -pS⁄ pT (X1-2)-CO2H, referred to by

Ganguly and colleagues as ‘mode III’ [6] This motif

has also been characterized structurally in plant proton

ATPases [7] The motif in b-COP (RRSpSV-CO2H)

may also come into this category [8] Unphosphory-lated motifs that interact with 14-3-3 at high affinity have also been characterized [1,2]

Structures of 14-3-3 and the binding site of the phospho- and unphosphorylated motifs have been determined [2,5,6] Phosphorylation of specific 14-3-3 isoforms can also regulate interactions [9]

14-3-3 isoforms are involved in neurodegenerative disorders including Alzheimer’s [10] and Parkinson’s disease [11] We identified four of the seven mamma-lian 14-3-3 isoforms (b, c, e and g) in the spinal fluid (CSF) of patients with Creutzfeldt–Jakob disease (CJD) [12] 14–3-3 g alone was also present in all patients with other dementias, including Alzheimer’s Changes in the localization of 14-3-3 isoforms were

Keywords

14-3-3; d-catenin; IRSp53;

neurodegenerative diseases; yeast

two-hybrid

Correspondence

A Aitken, University of Edinburgh, School of

Biomedical and Clinical Laboratory Sciences,

George Square, Edinburgh, EH8 9XD,

Scotland, UK

Fax: +44 131 6503725

Tel: +44 131 6503721

E-mail: alastair.aitken@ed.ac.uk

*Present address

University of Edinburgh, Psychiatric

Genet-ics Section, Medical GenetGenet-ics Section,

Western General Hospital, Edinburgh,

Scotland

(Received 31 January 2005, revised 13 May

2005, accepted 22 June 2005)

doi:10.1111/j.1742-4658.2005.04832.x

We isolated two novel 14-3-3 binding proteins using 14-3-3 f as bait in a yeast two-hybrid screen of a human brain cDNA library One of these encoded the C-terminus of a neural specific armadillo-repeat protein, d-catenin (neural plakophilin-related arm-repeat protein or neurojungin) d-Catenin from brain lysates was retained on a 14-3-3 affinity column Mutation of serine 1072 in the human protein and serine 1094 in the equiv-alent site in the mouse homologue (in a consensus binding motif for 14-3-3) abolished 14-3-3 binding to d-catenin in vitro and in transfected cells d-catenin binds to presenilin-1, encoded by the gene most commonly mutated in familial Alzheimer’s disease The other clone was identified as the insulin receptor tyrosine kinase substrate protein of 53 kDa (IRSp53) Human IRSp53 interacts with the gene product implicated in dentatoru-bral-pallidoluysian atrophy, an autosomal recessive disorder associated with glutamine repeat expansion of atrophin-1

Abbreviations

CJD, Creutzfeldt–Jakob disease; CSF, cerebrospinal fluid; DRPLA, dentatorubral-pallidoluysian atrophy; IRSp53, insulin receptor tyrosine kinase substrate protein of 53 kDa; SCA1, spinocerebellar Ataxia Type 1.

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observed during neurodegeneration in mice as a result

of scrapie infection [13] 14-3-3 isoforms play a key

role in neurodegeneration in the polyglutamine-repeat

disease spinocerebellar ataxia type 1 (SCA1) [14]

SCA1 is characterized by ataxia, progressive motor

deterioration and loss of cerebellar Purkinje cells

caused by the expansion of a region of the ataxin-1

gene that produces an abnormally long stretch of

glu-tamine In SCA1, 14-3-3 f and e bind to and stabilize

ataxin-1, after phosphorylation by Akt, thus slowing

its normal degradation A number of other inherited

neurodegenerative diseases, including Huntington’s

disease and Dentatorubral-pallidoluysian atrophy

(DRPLA) are caused by proteins that undergo a

simi-lar pathogenic polyGln expansion 14-3-3 and

a-synuc-lein colocalize with the perinuclear inclusions of

huntingtin protein [15]

To identify novel 14-3-3 binding partners in

mamma-lian brain, we performed a two-hybrid screen with

human 14-3-3 f as bait and isolated clones for two

pro-teins involved in distinct neurodegenerative diseases

Results

Identification of d-catenin as a 14-3-3 interacting

protein

The yeast two-hybrid screen of a human brain cDNA

library was carried out with a GAL4 binding domain

14-3-3 fusion protein as bait From 2.54 · 106 trans-formants screened, 35 diploid colonies (D1–D35) grew

up under selective conditions 2 out of 35 colonies specified in-frame coding region cDNAs

BLAST searches showed that one of these, D16, was homologous to the C-terminal region of delta catenin (Primary accession number Q9UQB3 in Swiss-Prot, also known as neural plakophilin related armadillo protein, NPRAP or neurojungin) that is almost exclu-sively expressed in the nervous system [16] d-Catenin

is a member of the p120-catenin (p120ctn) subfamily, defined as proteins with 10 armadillo (ARM) repeats

in characteristic spacing with diverse N- and C-ter-minal flanking sequences [17,18] see Fig 1A The 42-residue repeated Arm motif was originally described

in the Drosophila segment polarity gene, armadillo [19] The ARM domains of d-catenin are necessary and sufficient for adherens junction targeting and for direct interaction with cadherin (Fig 1B)

Clone D16 encoded a putative protein product of

386 amino acids (839–1125) which included 4 of the ARM repeats, a potential 14-3-3 binding site and a PDZ binding motif (Fig 1A)

Both northern blot and in situ hybridization studies indicate that delta-catenin is almost exclusively expressed in the nervous system [16,20] d-Catenin has

a structure similar to that of p0071 and is considered

to be a neural isoform of p0071, which is expressed ubiquitously [21]

β or γ−

catenin

p120ctn or δ-catenin

α-catenin

β or γ−

catenin

p120ctn or

Extracellular

α-catenin

Actin Filaments

Cadherin Receptor

Ca ++

PDZ binding motif

532

RSApSAP N

A

B

D16

2265bp

3’ UTR

14-3-3 phospho-binding site ARM domain

Fig 1 d-Catenin domains (A) Alignment of

d-catenin cDNA and protein domains with

clone D16 PCR amplification of the pACT2

D16 clone identified a  2200 nucleotide

insert Sequence analysis established that

clone D16 encoded the C-terminus of

human d-catenin (GenBank accession

num-ber U96136) and  1 kb of 3¢-untranslated

region The alignment of this fragment is

shown below the full-length human

d-catenin The armadillo, ARM, domains,

predicted 14-3-3 binding site and a PDZ

binding motif are indicated (B) d-catenin

complexes in adherens junction targeting

and interaction with cadherin.

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14-3-3 Binds endogenous d-catenin from brain

lysates

To determine whether endogenous d-catenin associated

in brain tissue, we passed sheep brain homogenate

over GST-14-3-3 and control GST affinity columns

d-Catenin specifically bound to a GST-14-3-3 f column

but not to a control GST column (Fig 2A) We

typic-ally detected a doublet by western blot that may be

due to in vivo phosphorylation A doublet has been

observed previously [22] and a splice variant of

d-cate-nin is known, although both forms include the 14-3-3

motif, which is not present in other, more widely

expressed catenins, suggesting that this interaction may

be functionally restricted to neuro-epithelial cells We

also performed immunoprecipitation assays from sheep

and mouse brain homogenates using recombinant

GST-14-3-3 and detected a 160 kDa doublet band with

anti-d-catenin sera, consistent with the expected Mr of

full-length d-catenin The immunoprecipitations were

also probed with a phospho-specific antibody (New

England Biolabs) against the consensus RSXpSXP

14-3-3 binding motif (Fig 2B) This specifically

detec-ted a 160 kDa polypeptide at the same position as the

d-catenin antibody suggesting that phosphorylation at

this site may be functionally important in vivo Other

species were evident which may represent partially degraded, phosphorylated forms of d-catenin

A 14-3-3 binding site on d-catenin Human and mouse d-catenin cDNAs encode proteins

of 1225 and 1247 residues, respectively, and share 95% identity at the amino acid level [22] A predicted 14-3-3 binding motif (RSApSAP) comprises phosphoSer1072 and 1094 and neighbouring residues, respectively Therefore to establish the mode of binding of 14-3-3

to d-catenin, the 386 residue proteins encoded by the wild-type d-catenin clone D16 and the S1072A mutant were expressed as35S-labelled proteins in IVTT 14-3-3 interacted efficiently with wild-type d-catenin but not with the Sfi A mutant (Fig 3) This indicates that the interaction is phosphorylation dependent at this site We also used a synthetic phosphopeptide that

Fig 2 14-3-3 Binds endogenous d-catenin from brain lysates.

Sheep brain homogenate was lysed in NaCl ⁄ P i buffer (including

protease inhibitors) containing 1% Triton-100 or NaCl ⁄ P i ⁄ 1% TX100

plus 0.1% SDS to aid solubilization of brain d-catenin The extract

was clarified by centrifugation at 40 000 g and the supernatant

passed through a GST-affinity column The flow-through was

applied to a GST 14-3-3 f column After extensive washing, bound

proteins were eluted by directly boiling of the

glutathione–Seph-arose beads in SDS ⁄ PAGE sample buffer and analysed by 6%

SDS ⁄ PAGE and blotting with rabbit anti-(d catenin) Ig (Ab62, from

K.S Kosik, Harvard Medical School, Boston, USA) (A) Lane 1,

con-trol GST column (TX100, no SDS); Lane 2, lysate prepared in

1%TX100) and affinity purified on the GST zeta column; Lane 3,

lysate prepared in 1% TX100 plus 0.1% SDS to aid solubilization

and affinity purified on the GST zeta column (B) Samples prepared

as in lanes 1 and 3 above then probed with anti-phospho 14-3-3 BS

monoclonal (NEB, Cell Signaling Technology).

A

B

Fig 3 Mutation of Ser1072 of d-catenin abolishes binding to

14-3-3 (A) Wild-type d-catenin clone D16 (S1072) and the S1072A mutant were expressed as 35 S-labelled proteins in IVTT Lanes 1, 2: Input (2%) of the two constructs; 3 and 4: immunoprecipitation

of wild-type D16 by GST and by GST-14-3-3 5 and 6: immunopre-cipitation of the D16 S1072A by GST and by GST-14-3-3 (B) A simi-lar experiment was carried out in the presence of phosphorylated and unphosphorylated peptides Lanes 1, immunoprecipitation of wild-type D16 by GST-14-3-3; 2, immunoprecipitation of wild-type D16 by GST; 3, immunoprecipitation of D16 S1072A mutant by GST-14-3-3; 4, immunoprecipitation of wild-type D16 by GST-14-3-3

in the presence of Raf-phosphopeptide (300 l M ); 5, immunoprecipi-tation of wild-type D16 by GST-14-3-3 in the presence of the same concentration of unphosphorylated peptide.

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corresponds to c-Raf1 amino acids 252–264, a

canon-ical 14-3-3 binding motif previously shown to

dissoci-ate Raf⁄ 14-3-3 complexes [4] By contrast, as a

control, the unphosphorylated version of this peptide

did not interfere with binding

14-3-3 binds to d-catenin expressed in MDCK

cells

As cDNA encoding full-length human d-catenin was

unavailable, we used a mouse cDNA clone for

sub-sequent studies [16] Classical adherens junctions hold

epithelial cells together via cadherin-catenin protein

complex linkages and d-catenin interacts with adhesive

junction proteins both in transfected cells and mouse

brain [22], Fig 1B Cadherins are Ca2+-dependent

cell-cell adhesion receptors involved in a variety of

bio-logical processes including development,

morpho-genesis and tumour metastasis Cadherins on adjacent

cells contact one another through their extracellular

domains The intracellular domains anchor the

junc-tional complex or adherens junction to the actin

cyto-skeleton via the cytoplasmic catenins

Therefore to characterize 14-3-3⁄ d–catenin

inter-actions in a defined culture system where adhesive

junctions are prominent, we used Madin–Darby canine

kidney (MDCK) epithelial cells Lysates were prepared

from cells transfected with untagged (as a control) and

FLAG-tagged d-catenin GST-14-3-3 f

immunoprecipi-tations immunoblotted with anti-FLAG Ig, detected

a 160 kDa doublet which bound specifically to

GST-14-3-3 f Specific interaction was observed with

wild-type full-length d-catenin in both Cos7 and MDCK

cells and was ablated by mutation of serine 1094 to

alanine (Fig 4A,B)

To establish the site of binding of 14-3-3 to

d-cate-nin in MDCK cells, we performed binding assays in

the presence of competitor peptides We again used the

synthetic c-Raf1 phosphopeptide (and the

unphosphory-lated version of this peptide as control, not shown)

and a nonphosphorylated peptide inhibitor of 14-3-3

binding, R18 (FHCVPRDLSWLDLEANMCLP) R18

was originally isolated from a phage display library

with high affinity for the phosphoserine-binding pocket

of 14-3-3 and which disrupts binding of 14-3-3 to

tar-get proteins such as Raf, Ask1 [23] and EXO-S [24]

Both peptides efficiently prevented 14-3-3⁄ d–catenin

complex association in vitro in cell extracts (Fig 5)

These results verified that the interaction between

d-catenin and 14-3-3 is mediated through the

phospho-binding pocket of 14-3-3

The 14-3-3 binding motif is not present in members

of the p120ctn sequence family, which are more

ubi-quitously expressed, suggesting that this interaction may be functionally restricted to neuro-epithelial cells

Interaction of IRSp53 with 14-3-3

We also identified a full-length clone of a 53 kDa SH3 domain-containing adaptor protein originally identified

as a substrate of the insulin receptor kinase (IRSp53) IRSp53 interacts with Rho GTPases to regulate the organization of the actin cytoskeleton and is a

compo-A

B

Fig 4 14-3-3 interacts with full-length d-catenin in cells Cos7 (A) and MDCK cells (B) were transiently transfected with either empty vector (A) or untagged pcDNA wild type delta catenin (B) and Flag tagged delta catenin wild type and Flag tagged d-catenin with a Ser

to Ala substitution at residue 1094 (S1094A) Transfected cell extracts were split and incubated with 20 lg GST and 20 lg GST-14-3-3 for 120 min at 4 C Upper panels: lysate loading controls Lanes: 1, untagged d-catenin; 2, Flag S1094 d-catenin; 3, Flag S1094A d-catenin Lower panels: Immunoprecipitation of Flag tagged d-catenin (western blot with a-Flag) Lanes 1,3,5, GST immunoprecipitation; lanes 2,4,6, GST-14-3-3 f immunoprecipita-tion; Lanes 1,2, Vector (in Cos cells) or no flag tag (MDCK cells); 3,4, Flag S1094 d-catenin; 5,6, Flag S1094A d-catenin.

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nent of signaling pathways that control the formation

of lamellipodia and filopodia [25]

A number of splice variants of human and mouse

IRSp53 are known, comprising mainly of a 12 residue

longer C-terminus and a 40 residue insertion around

residue 300 [26] In this study we isolated the longer

form that is mainly expressed in brain A ‘Scansite’

search [27] revealed a number of potential suboptimal

14-3-3 binding motifs in IRSp53 conserved across

mammalian species (Fig 6) The best motif was the

medium stringency site at Ser512, RSVS512SG, which

would explain loss of binding of construct 1–366 but

motif(s) near the N-terminus must also be important

(e.g RYLS117AA and⁄ or RKKS148QG) A

nonphos-phorylated Ser immediately following Arg within the

first mode and a Pro two residues C-terminal to the

phosphorylated Ser or Thr in both motifs is strongly favoured, but not an essential requirement for binding

to 14-3-3 [3]

As it was not clear which region or potential motif(s) in IRSp53 might be involved in 14-3-3 associ-ation we attempted to identify the site(s) of interaction

by deletion analysis The constructs depicted in Fig 7

A were coexpressed with HA-14–3-3f in Cos7 cells The results in Fig 7B clearly indicate that deletion of either the C-terminal region or the N- terminus caused loss of 14-3-3 interaction This may be due to a requirement for binding through two sites to a 14-3-3 dimer and this type of tandem 14-3-3 binding has been clearly shown to be functionally important in cases such as Raf kinase [3,28] and the Forkhead transcrip-tion factor FOXO4 [29]

It is also probable that the interaction between 14-3-3 and IRSp53 is not phosphorylation dependent

as treatment with lambda phosphatase of Cos7 cell lysates, into which Flag-IRSp53 and HA-14-3-3 zeta had been co transfected, did not reduce interaction (Fig 8A)

Immunoprecipitation experiments with a construct with mutations in essential residues of the phospho-peptide binding pocket, HA-14-3-3 zeta (R56A, R60A), that was transfected in Cos7 cells showed that much less IRSp53 was immunoprecipitated This veri-fied that IRSp53 interacts with 14-3-3 in the binding pocket

Discussion

One of the 14-3-3 interacting clones that we identified

in the 2-hybrid analysis encoded the armadillo repeat protein named delta-catenin, NPRAP (neural plako-philin-related arm-repeat protein) or neurojungin [16]

Fig 5 14-3-3 Binding peptides prevent 14-3-3 ⁄ d–catenin

associ-ation MDCK cells expressing d-catenin constructs were lysed and

extracts incubated in the absence or presence of 300 m M Raf

phos-phopeptide or nonphosphorylated peptide, R18, at 4 C for 60 min

20 lg GST-14-3-3 was added for 120 min GST fusions were

recov-ered on GSH–Sepharose beads and washed four times with 0.5 mL

lysis buffer Samples were separated by 6% SDS PAGE and assayed

for associated d-catenin by anti-Flag immunoblots Lanes 1–4, lysate

loading controls Lane 1, no Flag; 2–4, Flag d-catenin; 5, no Flag, no

peptide; 6, Flag d-catenin, no peptide; 7, Flag d-catenin, plus Raf

phosphopeptide; 8, Flag d-catenin, plus R18.

Fig 6 Alignment of IRSp53 cDNA and domains in the yeast two-hybrid clone, D6 (A) Domain alignment of full-length human IRSp53 cDNA The SH3 domains (residues 377–435) which bind atrophin-1; an autoinhibitory region (AIR) that regulates Cdc42 binding to the CRIB motif and a Cdc42 binding motif (residues 238–292) and potential 14-3-3 binding sites are indicated (B) PCR amplification of the pACT2 D6 clone identified a 2.4 kb insert that encoded the complete IRSp53 cDNA insert and  1 kb of 3¢-untranslated region.

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d-Catenin was originally identified by its ability to bind

to the loop region of presenilin-1, encoded by the gene

most commonly mutated in familial Alzheimer’s disease

[30] Presenilin-1 interacts with complexes including

d-catenin to modulate Wnt signaling which is

respon-sible for a variety of signaling events that lead to neural

plate formation and patterning decisions⁄ development

in the embryonic nervous system [20]

Although there is no evidence that 14-3-3 zeta

bind-ing plays a role in this pathway, it nevertheless suggests

another link between 14-3-3 and neurodegenerative

disease Wnt signaling also regulates neuronal

cytoskeleton structure, cerebellar synaptic

differentia-tion, apoptosis and degenerative processes in the aging

brain The latter establishes a link to pathogenesis

in Alzheimer’s disease Mutations in presenilin 1

(PS1) gene are the most common cause of early onset

familial Alzheimer’s disease d-Catenin expression is

decreased in presenilin-1 deficient mice [30]

The other novel 14-3-3 interacting protein in our study was identified from a full-length clone of the insulin receptor tyrosine kinase substrate protein of

53 kDa (IRSp53) IRSp53 is an SH3 domain-contain-ing adaptor protein originally identified as a substrate

of the insulin receptor kinase [25] IRSp53 interacts with Rho GTPases to regulate the organization of the actin cytoskeleton and is a component of signaling pathways that control the formation of lamellipodia and filopodia [31] Human IRSp53 was isolated as

a protein which interacts with the gene product implicated in DRPLA, an autosomal recessive disorder caused by CAG⁄ glutamine repeat expansion of atro-phin-1 [32] While the DRPLA gene is ubiquitously expressed, neuron death occurs in specific anatomical areas of the brain

In a yeast two-hybrid screen of a human foetal brain cDNA library with a fragment of atrophin-1 (residues 335–1185, containing 10 CAG repeats) clones isolated included IRSp53, hDVL1, d-Catenin and 14-3-3 [33]

A proline rich region near the polyGln tract of atro-phin-1 bound to the SH3 domain of IRSp53 in vitro Our results therefore expand the range of interacting proteins and diversity of neurodegenerative disorders

A

B

Fig 7 Domains of IRSp53 interacting with 14-3-3 (A) Schematic of

the constructs of flag tagged IRSp53 (B) The ability of the N- and

C-terminal constructs of flag tagged IRSp53 to be

immunoprecipi-tated by HA-tagged 14-3-3 f The constructs of flag tagged IRSp53

depicted in A were cotransfected with HA-14-3-3 f in Cos7 cells

and immunoprecipitated with anti-HA-Ig as described in

Experimen-tal procedures Lane 1, HA-14-3-3 f + IRSp53; 2, HA-14-3-3 f +

IRSp53-FLAG; 3, HA-14-3-3 f + D 1–125 IRSp53-FLAG; 4,

HA-14-3-3 f + D 1–179 FLAG; 5, HA-14-3-3 f + D 1–366

IRSp53-FLAG Upper panel, expression levels of the constructs Middle

panel, expression levels of HA-14-3-3 f Lower panel, western blot

of IP with anti-Flag Ig.

A

B

Fig 8 IRSp53 interacts with 14-3-3 in the binding pocket but may

do so in a nonphospho-dependent manner (A) Flag-IRSp53 and HA-14-3-3 zeta were co transfected into Cos7 cells as described in Fig 4 and Experimental procedures The cell lysates were treated with lambda phosphatase and immunoprecipitated with anti-HA Ig The IPs were western blotted with anti-Flag Ig Lane 1, input; 2,

no phosphatase treatment; 3, treatment with lambda phosphatase (B) Flag-IRSp53 and HA-14-3-3 zeta constructs were co transfected into Cos7 cells as described in Fig 4 and Experimental procedures The cell lysates were immunoprecipitated with anti-HA Ig The pellets were western blotted with anti-Flag Ig Lane 1, input; 2, immunoprecipitation with wild-type HA-14-3-3 zeta; 3, immunopre-cipitation with HA-14-3-3 zeta (R56A, R60A) mutant construct.

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in which isoforms of 14-3-3 are implicated, including

another polyglutamine expansion disease, DRPLA

The key feature of all these diseases is the

accumula-tion in specific areas of the brain of abnormal forms

of proteins which results in neurodegeneration The

proteins that accumulate (due to their misfolding

and⁄ or genetic mutation) are specific to each disease

However, a common feature that is now emerging is

the involvement of specific isoforms of 14-3-3

Deter-mining the component proteins and role of 14-3-3

complexes, may lead to advances in understanding of

how these protein complexes regulate brain functions

Experimental procedures

Two-Hybrid ScreencDNA encoding the 14-3-3 f ORF was

cloned into the NdeI⁄ BamHI sites of the vector pGBKT7

(Clontech, Basingstoke, UK) to create an in-frame fusion

with the DNA binding domain of GAL4 Plasmid

pGBKT7⁄ 14-3-3 f was transformed into yeast strain

SFY526 and combined with a pretransformed Matchmaker

cDNA library (Clontech) using standard yeast mating

pro-cedures Diploid colonies were selected for activation of

his-tidine (His) and adenine (Ade) reporter genes by growth on

SD medium lacking Ade, His, Leu and Trp for 7–10 days

Clones that survived repeated auxotrophic selection were

assayed for b-galactosidase activity by use of

5-bromo-4-chloro-3-indolyl-b-d-galactopyranoside (X-gal) as a

sub-strate Plasmid DNA was isolated from 39 positive clones

and library inserts were amplified by PCR using pACT2

vector specific primers

Plasmids and constructs

Mouse d-catenin in pcDNA3.1 was from W Franke

(Ger-man Cancer Research Center, Heidelberg, Ger(Ger-many)

Plasmids pGEX-2T 14-3-3 f and HA tagged 14-3-3 f

(pcDNA.1 Zeo) have been described previously [35] The

d-catenin ORF was amplified by PCR and the product

inser-ted into Not1⁄ Xho1 cut pCMV TAG4A (Invitrogen, Paisley,

UK) to generate a C-terminal FLAG tagged construct

Site-specific mutations were introduced into the d-catenin ORF

using the QuikChange Site Directed Mutagenesis System

(Stratagene, Cleveland, OH, USA) according to the

manu-facturer’s instructions and confirmed by DNA sequencing

PCR amplification of DNA fragments was carried out using

Pfu Turbo DNA polymerase (Stratagene) and integrity of

cloned inserts were confirmed by DNA sequencing

The construct with mutations in essential residues of the

phosphopeptide binding pocket, HA-14-3-3 zeta (R56A,

R60A) was generated by Stratagene Quickchange site

direc-ted mutagenesis according to the manufacturers instructions

In vitrotranscription and translation (IVTT) was carried

out using TnT expression kits (Promega) as described [34]

Transfection of cultured cells Cos7 and MDCK cells (ATCC) were maintained in high glu-cose Dulbecco’s modified Eagle’s medium (Sigma) supple-mented with 10% foetal bovine serum (Life Technologies), 1· nonessential amino acid supplement, 1· glutamine, peni-cillin and streptomycin (Life Technologies) in air plus 5%

CO2 with constant humidity Cells were transfected at 80–90% confluence using Lipofectamine 2000 (Invitrogen) according to the manufacturer’s instructions and harvested 24–30 h later

Protein extracts Transfected cells (100 mm plates) were washed once with NaCl⁄ Pi, scraped into 1.8 mL lysis buffer (50 mm Tris-Cl

pH 7.5, 150 mm NaCl, 1% TX-100, I mm EDTA, 1 mm dithiothreitol, 1 mm NaVO4, 10 mm NaF and protease inhibitor cocktail without EDTA (Roche Molecular Bio-chemicals), incubated on ice for 15 min and clarified by centrifugation for 20 mins at 16 000 g in a refrigerated microfuge For brain extract preparation, adult sheep brain was briefly rinsed in lysis buffer (50 mm Tris⁄ Cl pH 7.5,

150 mm NaCl, 1% TX-100, 2 mm EDTA, 10% glycerol,

2 mm dithiotreitol, 2 mm NaVO4, 50 mm NaF, 20 mm b-glycerophosphate, 1 mm PMSF and 2x protease inhibitor cocktail without EDTA) and homogenized in the same buffer Lysates were precleared at 13 000 g for 30 min at

4C Supernatant from the lysates was further clarified by centrifugation at 40 000 g for 60 min at 4C Supernatants were filtered through 0.2 lm syringe filters (Nalgene) before application to GST or GST 14-3-3 f affinity columns Treatment of cell lysates with lambda phosphatase (New England Biolabs) was with 400 units phosphatase for 60 min at 30C, according to the manufacturers instructions

Immunoprecipitation Equal amounts of GST or GST 14-3-3 f fusion protein (20 lg) were incubated overnight at 4C on a rotary wheel with lysates prepared from 10 cm dishes of confluent Cos7

or MDCK cells Complexes were captured by incubation with glutathione Sepharose beads for 2 h at 4C After centrifugation, beads were washed four times with lysis buf-fer Bound proteins were eluted with SDS sample buffer and subjected to SDS PAGE and immunoblotting For immunoprecipitations, 5 lg anti-HA7 monoclonal Ig (Sig-ma) was incubated for 4 h or overnight at 4C with con-trol or HA expressing lysates Immunocomplexes were incubated with protein A⁄ G beads (Pierce) for 2 h at 4 C and captured by centrifugation Immunocomplexes were washed as above before immunoblot analysis SDS PAGE and western blotting were performed by standard methods

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Anti-FLAG M2 peroxidase conjugate and Anti-HA7 Igs

were from Sigma and signals were detected using ECL,

chemiluminescence detection (Amersham Pharmacia

Bio-tech, Buckinghamshire, UK)

Recombinant protein purification

Protein expression was induced in E coli strain BL21(DE3)

(Novagen, Merck Biosciences, Nottingham, UK) carrying

plasmid pGEX-2T or pGEX-2T 14-3-3 f Briefly, cultures

were grown overnight at 37C in Liquid Broth medium (Life

Technologies, Inc., Paisley, UK) containing 50 lgÆmL )1

ampicillin and diluted the following day (1⁄ 10) in the same

medium Culture growth continued at 30C until the

absorb-ance (600 nm) reached 0.8 to 1.0 Expression of the tagged

protein was induced by the addition of 0.5 mm isopropyl

b-d-thiogalactopyranoside for 3 h at 25C The fusion

proteins were purified by affinity chromatography on

gluta-thione-Sepharose beads (Amersham Pharmacia Biotech.)

For large-scale preparation of GST and GST 14-3-3 f affinity

columns, fusion protein lysates prepared from 2.5 L of

induced bacterial culture ( 7 mg fusion protein) were used

to saturate 2 mL columns of glutathione-Sepharose beads

Peptide competition studies: dissociation

of 14-3-3⁄ d-catenin complexes in vitro

Cell extracts were incubated with 300 lm synthetic

phos-phopeptide corresponding to a c-Raf1 14-3-3 binding motif

(residues 252–264, SQRQRSTpSTPNVH) as well as with

the control peptide of the same sequence but

unphosphory-lated or with 300 lm of a nonphosphoryunphosphory-lated peptide (R18,

FHCVPRDLSWLDLEANMCLP [23]

Acknowledgements

The work was funded by a MRC programme grant to

AA We thank Bengt Hallberg for the R18 peptide

Mouse d-catenin in pcDNA3.1 was a kind gift from

the laboratory of Dr W Franke; Rabbit anti-(d

cate-nin) Ig (Ab62), raised against residues 434–530 was a

kind gift from the laboratory of Dr Kenneth Kosik

HA tagged 14–3-3f (pcDNA.1 Zeo) was from Preeti

Kerai and Thierry Dubois

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