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A His6-tagged version of CCR5 was expressed in mammalian cells, purified using the detergent N-dodecyl-b-D-maltoside DDM and reconstitu-ted into preformed liposomal membranes saturarecons

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Functional reconstitution of the HIV receptors CCR5 and CD4

in liposomes

Franc¸ois Devesa, Vida Chams, Premkumar Dinadayala, Alexandre Stella, Aude Ragas, Henri Auboiroux, Toon Stegmann and Yannick Poquet

Institut de Pharmacologie et de Biologie Structurale; CNRS UMR 5089, Toulouse, France

Reconstitution of membrane proteins allows their study in a

membrane environment that can be manipulated at will

Because membrane proteins have diverse biophysical

pro-perties, reconstitution methods have so far been developed

for individual proteins on an ad hoc basis We developed a

postinsertion reconstitution method for CCR5, a G protein

coupled receptor, with seven transmembrane a helices and

small ecto- and endodomains A His6-tagged version of

CCR5 was expressed in mammalian cells, purified using the

detergent N-dodecyl-b-D-maltoside (DDM) and

reconstitu-ted into preformed liposomal membranes saturareconstitu-ted with

DDM, removing the detergent with hydrophobic

polysty-rene beads We then attempted to incorporate CD4, a protein

with a single transmembrane helix and a large hydrophilic

ectodomain into liposomal membranes, together with

CCR5 Surprisingly, reconstitution of this protein was also achieved by the method Both proteins were found to be present together in individual liposomes The reconstituted CCR5 was recognized by several monoclonal antibodies, recognized its natural ligand, and CD4 bound a soluble form

of gp120, a subunit of the HIV fusion protein that uses CD4

as a receptor Moreover, cells expressing the entire fusion protein of HIV bound to the liposomes, indicating that the proteins were intact and that most of them were oriented right side out Thus, functional coreconstitution of two widely different proteins can be achieved by this method, suggesting that it might be useful for other proteins Keywords: membrane protein; reconstitution; liposome

Reconstitution of membrane proteins allows the study of

their behaviour in a membrane in the absence of other

proteins, and the manipulation of their concentration and

environment Unfortunately, no single reconstitution

method is applicable to all membrane proteins, most likely

because their biophysical character varies The most

frequently used method is coinsertion reconstitution, in

which detergent is removed from a mixture of

detergent-solubilized protein and lipid [1,2], a method which has led to

the successful reconstitution of membrane proteins with

diverse structures [3–6] However, no common conditions

are so far known that would allow a standard operating

procedure for reconstitution by this method to be

esta-blished Postinsertion reconstitution is a fundamentally

different method based on the removal of detergent from

detergent-solubilized protein added to a preformed

lipo-some incubated with a detergent at a concentration almost

leading to the onset of membrane solubilization [1]

Although the physical basis for this type of reconstitution

is not clear, a number of proteins have now been reconsti-tuted by this method [2,7–14]

The abundant proteins belonging to the superfamily of G-protein coupled receptors (GPCR) that possess seven transmembrane a helices, have important roles in eukary-otic signalling Few GPCR have been reconstituted, by a variety of coinsertion or postinsertion protocols, with variable results [4,15–17] The b-chemokines RANTES, MIP-1a, and MIP-1b are recognized by the GPCR CCR5 [18–21] Through binding to the chemokine, this receptor plays a crucial role in inflammatory processes CCR5 is also used as a receptor by primary strains of HIV-1 [21–24] When infecting a host cell, the membrane protein complex

of HIV-1, gp120/gp41, first binds to CD4 [25,26], an integral membrane protein with a single transmembrane a-helix Binding induces a conformational change in gp120/ gp41 [27,28], which leads to an increased affinity for CCR5 present in the same host cell membrane [29–31] Further conformational changes induced by the latter interaction then induce fusion between the viral and the cellular membrane, allowing the virus to enter its host cell [32]

In many cell membranes, CCR5 and CD4 are associated, and this association may be important to HIV infection [33]

In this paper, we describe a postinsertion reconstitution method that allows simultaneous incorporation of both CCR5 and CD4, isolated from a mammalian cell in which they were expressed together, into a single proteoliposomal membrane Proteoliposomal membranes containing both proteins recognized the natural ligands for CCR5, a conformation-specific antibody recognized CCR5, the recon-stituted CD4 bound HIV gp120, and the proteoliposomes

Correspondence to Y Poquet, Institut de Pharmacologie et de

Biologie Structurale; CNRS UMR 5089, 205 Route de Narbonne,

31077 Toulouse Cedex, France Fax: + 33 5 61 17 59 94,

Tel.: + 33 5 61 17 54 64, E-mail: yannick.poquet@ipbs.fr

Abbreviations: Cmc, critical micelle concentration; DDM,

N-dodecyl-b- D -maltopyranoside; Egg-PtdEth, egg phosphatidylethanolamine;

Egg-PtdCho, egg phosphatidylcholine; N-NBD-PtdEth,

N-(7-nitro-2,3,1-benzoxadiazol-4-yl)-phosphatidylethanolamine; N-Rh-PtdEth,

N-(lissamine rhodamine B sulfonyl)-phosphatidylethanolamine;

SM, egg sphingomyelin; GPCR, G-protein coupled receptor;

DMEM, Dulbecco’s modified Eagle’s MEM.

(Received 14 June 2002, revised 13 August 2002,

accepted 29 August 2002)

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bound strongly to cells expressing the HIV fusion protein.

Therefore, functional reconstitution of different types of

membrane proteins was achieved by our method

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

Materials

Egg phosphatidylcholine (egg-PtdCho), egg

phosphati-dylethanolamine (egg-PtdEth), egg-sphingomyelin (SM),

cholesterol, N-(lissamine rhodamine B

sulfonyl)-phosphati-dylethanolamine (N-Rh-PtdEth), and

N-(7-nitro-2,3,1-ben-zoxadiazol-4-yl)-phosphatidylethanolamine (N-NBD-PtdEth)

were purchased from Avanti Polar Lipids (Birmingham,

Ala.) Detergents were obtained from Sigma, the

chemo-kines MIP-1a and RANTES from R & D Systems

(Wiesbaden, Germany), and 125I-labelled MIP-1a from

NEN Life Science Products (Paris, France) Anti-myc mAb

9E10, fluorescein isothiocyanate (FITC) conjugated goat

anti-mouse Ig, anti-CD4 Q4120 and the anti-His6Ig His1

were purchased from Sigma, horse-radish peroxidase

con-jugated goat anti-mouse Ig from Biorad

(Marnes-la-Co-quette, France), 125I-labelled sheep anti-mouse Ig from

Amersham Pharmacia Biotech (Saclay, France), anti-CCR5

mAb 2D7 from PharMingen Becton-Dickinson (Le Pont

des Claix, France), and anti-CCR5 mAbs 181 (Mab181)

and 182 (Mab182) from R & D Systems Paramagnetic

beads coupled to anti-mouse Ig or anti-CD4 Igs were

purchased from Dynal (Compie`gne, France) NIH

3T3.T4.CCR5 cells and cells expressing a soluble version

of the gp120/gp41 of strain JR-FL (CHO JR-FL gp160,

clone A19) were obtained from the NIH AIDS Research

and Reference Reagent Program, Division of AIDS,

NIAID, NIH through D R Littman and J Arthos,

respectively HeLa cells expressing the gp120/gp41 from

strain ADA was the kind gift of E Bahraoui, Universite´

Paul Sabatier, Toulouse, France

Construction and stable expression of HIV receptor

vectors

Plasmid DNA containing the CCR5 gene was obtained

from the NIH AIDS Research and Reference Reagent

Program, Division of AIDS, NIAID, NIH from N Landau

(ref no 3325) For the construction of a tagged version of

CCR5, an XhoI restriction site was introduced upstream of

the start codon of CCR5 and an ApaI site upstream of the

stop codon by PCR and expanded in pBSK1 plasmid The

resulting XhoI/ApaI fragment was cloned into the

corres-ponding sites in the polylinker region of the

pcDNA3.1-myc-His expression vector (Invitrogen, Groningen, the

Netherlands) in order to obtain a recombinant protein

containing the C-myc epitope followed by six histidines at

the C-terminus A plasmid containing the wild type version

of CCR5 was constructed by introducing the coding

sequence of CCR5 between the ApaI and HindIII

restric-tion sites of a pRC-CMV vector (Invitrogen)

For protein expression, CHO cells grown in Dulbecco’s

modified Eagle’s Medium (DMEM), containing 10% foetal

calf serum (Life Technologies, Cergy-Pontoise, France)

were transfected using Lipofectin Reagent (Life

Technol-ogies) After 3 days of culture, 500 lgÆmL)1of neomycin

(G418, Life Technologies) was added, and resistant cells,

obtained after two weeks of selection, were cloned by limiting dilution The resulting clones were tested for CCR5 cell surface expression by FACS In order to coexpress CCR5 and CD4 on CHO cells, clones expressing CCR5 were also transfected with pcDNA3 containing the CD4 gene This plasmid was made by removing the CD4 cDNA from the pT4b plasmid (obtained from the NIH AIDS Research and Reference Reagent Program, Division of AIDS, NIAID, NIH) between the EcoRI and XbaI sites, and inserting the gene between the corresponding sites into the polylinker of pcDNA3 CD4-his was made by cutting a CD4–His6construct (kindly donated by M Marsh, Medical Research Council Laboratory, University College, London, UK) between two BamHI sites from pSG5 and recloning the gene into the polylinker of pcDNA3 After 2 weeks of culture in the presence of G418, CD4 positive cells were isolated using magnetic beads bearing an anti-CD4 Ig (Dynabeads M-450 CD4, Dynal) After two rounds of selection, cells were cloned by limiting dilution and the clones analysed by FACS for coexpression of CCR5 and CD4

Western blot analysis and35S-labelled CCR5-myc-his detection

CCR5-myc-his containing samples were mixed 1 : 1 with Laemmli sample buffer and loaded on SDS/PAGE gels without heating After migration, proteins were transferred

to nitrocellulose membranes, probed with the anti-myc mAb 9E10 (Sigma) and revealed with horseradish peroxi-dase-conjugated goat anti-mouse IgG and the NEN signal chemiluminescence kit (NEN Life Science Products) For

35S-labelled CCR5-myc-his detection, SDS/PAGE gels were dried in a gel dryer, and exposed for 5–20 h on an Molecular Dynamics (Bondoufle, France) phosphor screen The screen was scanned with a STORM device and data were analysed with IQNT software (Molecular Dynamics)

CCR5-myc-his labelling and purification CHO cells (grown to 90% confluence in 140 mm dishes) were washed twice with NaCl/Pi and incubated with DMEM without methionine and cysteine plus 4% dialysed foetal calf serum for 6h A35S-labelled methionine/cysteine mixture (Easytag, New England Nuclear, Zaventem, Belgium) was added (250 lCi per dish) After overnight incubation at 37C, about 200 millions cells were removed from Petri dishes with NaCl/Pi, containing 10 mMEDTA, and washed with NaCl/Pi After centrifugation, the pellet was suspended in lysis buffer [NaCl/Pisupplemented with 1% Triton X-100, 1000 UÆmL)1DNAse I, 1 mM MgCl2, and the protease inhibitors Chymostatin, Leupeptin, Antipaı¨n, Pepstatin (Sigma), all at 1 lgÆmL)1] After

45 min at 4C, the preparation was centrifuged at

25 000 g for 15 min CCR5-myc-his was purified from the supernatant by immobilized metal ion affinity chromatogra-phy (Ni-nitrilotriacetic acid, Qiagen, Courtaboeuf, France)

or anti-polyhistidine Igs immobilized on agarose beads (Sigma) In both cases, N-dodecyl-b-D-maltopyranoside (DDM) was used at 0.3 mMfinal concentration in all the buffers needed for the various purification steps, thereby replacing the Triton X-100 of the lysis buffer in the purified

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product For purification on the Ni-nitrilotriacetic acid

column, the supernatant was diluted with an equal volume of

binding buffer (Tris 20 mMpH 8, NaCl 500 mM, imidazole

5 mM, DDM 0.3 mM), and passed twice through the column

The column was then washed with Tris 20 mM, NaCl

500 mM, imidazole 25 mM, DDM 0.3 mM, pH 8 and eluted

with a similar buffer containing 200 mM imidazole For

purification on anti-polyhistidine agarose, the supernatant

was passed through the column which was washed with

Hepes 2.5 mM pH 7.4, NaCl 145 mM, DDM 0.3 mM

CCR5-myc-his was eluted with the same buffer, to which

imidazole (200 mM) was added

Liposome preparation and CCR5-myc-his reconstitution

Large unilamellar liposomes (0.1 lm in diameter) were

prepared from dry lipid films containing egg-PtdCho

(55 mol%), egg-PtdEth (27 mol%), SM (8.2 mol%),

cholesterol (8.2 mol%), N-Rh-PtdEth (0.82 mol%),

N-NBD-PtdEth (0.82 mol%) as described previously

[34] For CCR5-myc-his reconstitution, these liposomes

(66 lMof phospholipids) were first incubated with DDM

at 0.2 mM for 30 min at 4C Purified fractions of

CCR5-myc-his in DDM (0.3 mM) were then mixed with

detergent saturated liposomes at a 1 : 3 vol ratio of

protein preparation to liposomes After a 30-min

incu-bation, detergent was removed by the addition of

Biobeads SM-2 (Bio-Rad) A 4-h incubation with

0.5 mg of beads was followed by two 1-h incubations

with an additional 10 mg of beads with continuous

agitation at 4C After detergent extraction, the resulting

proteoliposomes were pelleted three times at 100 000 g

for 30 min All steps were at 4C

MIP-1a binding experiments

CHO cells (1· 106cells in 50 lL) were suspended in Hepes

50 mMpH 7.4, MgCl25 mM, CaCl21 mM, BSA 0.5% at

25C for 1 h in the presence of 0.55 nM[125I]MIP-1a Non–

specific interactions were measured by adding an excess of

unlabeled MIP-1a (500-fold) For MIP-1a binding to

reconstituted CCR5-myc-his, freshly prepared

proteolipo-somes (3 nmol of phospholipids) were incubated for 45 min

at 25C (Hepes 2.5 mM, NaCl 145 mM, BSA 0.1 mgÆmL)1)

in the presence of different concentrations of [125I]MIP-1a

and cold MIP-1a or RANTES (1000 and 500-fold

[125I]MIP-1a quantities) Unbound ligand was removed by

filtration on BSA-presaturated GFB-filters (Whatman), and

the filters were washed twice with Hepes 2.5 mM, NaCl

150 mM, BSA 0.1 mgÆmL)1 The filters were then counted in

a c-counter (Packard)

Anti-CCR5 binding experiments

Freshly prepared proteoliposomes (8 nmol of

phospho-lipids) were incubated for 45 min at 23C in Hepes 2.5 mM

pH 7.4, NaCl 145 mM, BSA 0.1 mgÆmL)1 containing

10 lgÆmL of anti-CCR5 mAb 2D7 (Pharmingen), 181 or

182 (R & D) The proteoliposomes were separated from

unbound antibody by ultracentrifugation (100 000 g,

30 min), the pellet was resuspended in the same

buffer, and incubated with 125I-labelled anti-mouse Ig

(3 lCiÆmL)1) for 30 min at 4C The proteoliposomes

were then washed with the same buffer and pelleted by ultracentrifugation

Protein orientation Proteoliposomes containing CD4, approximately 20 nmol, were incubated in NaCl/Pi for 20 min at 37C, with or without trypsin (0.5 gÆL)1) The proteoliposomes were washed once by ultracentrifugation to remove the protease, and the pellet was resuspended in gel loading buffer for Western blot analysis The blot was revealed by the anti-CD4 mAb Q4120

Co-immunoprecipitation of proteoliposomes

4· 106paramagnetic beads with or without anti-CD4 Igs were incubated overnight at 4C with 20 nmol of CD4-CCR5 proteoliposomes, in Hepes 2.5 mM, NaCl 145 mM, and BSA 1 mgÆmL)1 The beads were then washed in the same buffer five times, and once in the same buffer without BSA Finally the beads were resuspended in sample buffer SDS/PAGE for Western blot analysis

Cell-cell fusion experiments

8· 104cells expressing the gp120/gp41 of strain ADA were seeded per well (1.55 cm diameter) in 24-well plates The following day 18· 104 CHO cells were added and after 3–5 h at 37C, a fusion percentage FI was calculated as

FI¼ [1) (number of cells/number of nuclei)] · 100 A minimum of 500 nuclei were counted for each assay

Binding of a soluble version of the JR-FL gp120/gp41

to proteoliposomes

A35S-labelled preparation of this protein, secreted by CHO JR-FL gp160, clone A19, cells was prepared by radiolabel-ling as described above for CCR5-myc-his Tissue culture supernatant was passed 5–8 times through a 1-mL column

of Galanthus nivalis lectin coupled to Sepharose beads equilibrated with Hepes 2.5 mM pH 7.4, NaCl 145 mM buffer, at approximately 1 mLÆmin)1 The column was then washed with 40 vol of Hepes 2.5 mM pH 7.4, NaCl

145 mM, and the protein was eluted with 10 vol of the same buffer containing 250 mM a-methyl-mannopyrano-side The protein was then concentrated by size filtration (Centricon-30, Qiagen) For binding experiments, the labelled protein (10 nM) was added to proteoliposomes (100 lM phospholipid) in Hepes 2.5 mM pH 7.4, NaCl

145 mM, BSA 0.1%, CaCl21 lM, MgCl21 mM

Binding of proteoliposomes to gp120/gp41 expressing cells

200· 103ADA cells per well were seeded in 24-well plates After two days of growth, the cells were washed twice with cold HBSS (Hank’s Balanced Saline Solution, Life Tech-nologies, Cergy-Pontoise, France) and kept for 30 min at

4C About 15 nmol of proteoliposomes were diluted in

200 lL of HBSS, and incubated with the cells for 30 min at

4C The cells were then washed with HBSS to remove unbound proteoliposomes, and incubated for 30 min at

37C After this step, the cells were scraped from the wells

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in NaCl/Piand the fluorescence associated with the cells was

analysed by FACS

R E S U L T S

Functional expression of a Myc-his tagged version

of CCR5, and a his-tagged version of CD4

Because the post-translational modifications of CCR5, such

as tyrosine sulfation appear to be important for its function

[35], we produced the protein in mammalian cells In order

to facilitate the proteins’ purification, a recombinant version

was made containing a C-terminal myc tag followed by a

His6sequence, by cloning the CCR5 gene into a pcDNA3.1

myc-his vector, and transfecting CHO cells with this

construct After G418 selection, clones expressing

CCR5-myc-his were obtained by limiting dilution and analysed by

FACS using the antibody 2D7 (Fig 1), which recognizes

CCR5 [36] Western blot analysis of the cloned protein from

a postnuclear supernatant of lysed cells was carried out

using the 9E10 mAb directed against the myc epitope (none

of the commercially available anti-CCR5 mAbs were able to

recognize wild type- or CCR5-myc-his on blots) Two

proteins were detected by 9E10, one with a molecular mass

of around 38 kDa, close to the estimated molecular mass of

CCR5-myc-his, and a second of 33 kDa (Fig 1) The latter

protein was also detected in untransfected cells Thus, the

tagged version of CCR5 was present on the surface of

transfected cells, and had the expected molecular mass

To test whether the presence of the myc-his tag at the

C-terminus of CCR5 would interfere with the protein’s

ability to function as a chemokine receptor or HIV

coreceptor, we first determined the binding of MIP-1a to

the CCR5-myc-his expressing cells Cells expressing CCR5

or CCR5-myc-his were incubated with [125I]MIP-1a alone

or in the presence of a large excess of cold MIP-1a Specific

binding of the ligand to both cell types was observed

(Fig 2A) Some binding of radioactive MIP-1a to

non-transfected CHO cells, even in the presence of excess cold

MIP-1a was consistently observed, and probably reflects low affinity binding to heparan-like glycosaminoglycans [37]

As the myc-his tag of the protein was present at the C-terminus of the receptor which is located on the inside

of the cell, we then determined if signal transduction by the protein was affected by this modification One of the consequences of signalling is a down-modulation of the expression of CCR5 [38] CCR5-myc-his or wtCCR5 expressing cells were incubated at 37C for 30 min with

10 nMof MIP-1a and then the CCR5 present on the plasma membrane was quantified by FACS analysis using the 2D7 antibody (Fig 2B) It was found that the 60–70% of the myc-his tagged protein was internalized, as much as for wild-type CCR5 in CHO cells [39]

To test the ability of CCR5-myc-his to function as a coreceptor for gp120/gp41 induced fusion, CHO clones coexpressing CCR5-myc-his or wt CCR5 were transfected with pcDNA3.1 containing a His6-tagged version of CD4, CD4-his, as described in Materials and methods After cloning and selection by FACS analysis (not shown) of cells coexpressing CCR5 and CD4, sincytium formation with cells expressing gp120/gp41 from strain ADA was tested The level of fusion obtained with cells expressing tagged or untagged proteins was comparable (Fig 2C) Thus, these results indicated that CCR5-myc-his and CD4-his are functional HIV coreceptor and receptors, respectively Purification of CCR5-myc-his

For the purification of CCR5-myc-his we tested two different methods based on the presence of the six histidines

at the C-terminus of the protein The first involved immobilized metal ion affinity chromatography Cells were lysed with a buffer containing Triton X-100 and spun at

25 000 g for 15 min The supernatant was applied to a Nickel-nitrilotriacetic acid (Ni-nitrilotriacetic acid) column The column was washed with different buffers to remove contaminant proteins and then eluted with a buffer containing 200 mM imidazole and the detergent, as des-cribed in Materials and methods The protein was followed throughout the different purification steps by Western blot, using the anti-myc Ig, and by SDS/PAGE of

35S-labelled protein (Fig 3A) CCR5 was quantitatively retained on the column, and could be eluted with imidazole The protein was unidentifiable by autoradiography in cell lysates, but appeared as the predominant band after purification, although a background of contamination by other proteins was still present The second method involved His1 anti-His6Igs coupled to Sepharose beads A column made of this material also retained CCR5 quantitatively, and elution with 200 mM imidazole resulted in a more highly purified protein than purification on Ni-nitrilo-triacetic acid columns (Fig 3) Ten percent of the total radioactivity present in the lane containing CCR5-myc-his purified on Ni-nitrilotriacetic acid columns was associated with the protein, whereas 36% of the total radioactivity was associated with CCR5-myc-his after purification on an antihistidine column

Reconstitution of CCR5-myc-his

A limited number of protocols for the membrane reconsti-tution of GPCR exist, and there does not seem to be a

Fig 1 CCR5-myc-his expression in CHO cells CHO cells were

transfected with pcDNA3 containing the ccr5-myc-his gene

Expres-sion was measured by FACS, using the 2D7 anti-CCR5 Ig [36].

Western blot analysis was carried out using an anti-myc Ig

Trans-fected cells are marked with +, nontransTrans-fected cells that were used as a

negative control, with - The approximate position of molecular mass

markers (in kDa) is shown on the right.

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generally applicable method Several coinsertion

reconsti-tution methods, involving the preparation of a mixture of

detergent, lipids and protein, followed by removal of

detergent, were first tried for CCR5 CCR5-myc-his

expressing cells were lysed with Triton X-100, and the

protein was immobilized on Ni-nitrilotriacetic acid columns

To exchange the Triton X-100 for other detergents, the

column was then washed with buffer containing another

detergent, imidazole elution was performed in this detergent

and the eluate applied to dry lipid films Several detergents

with a high critical micelle concentration (cmc), such as

b-D-octylglucoside and

3-[(3-cholamidopropyl)-dimethyl-ammonio]-1-propanesulfonate (CHAPS) were tested, and

detergent removal methods tested involved rapid dilution,

dialysis or gel filtration The low cmc detergents

octaethye-leneglycol-mono-N-dodecylether (C12E8) and Triton X-100

were also tested In these cases, detergent was removed by

hydrophobic polystyrene beads (Biobeads SM2) We were

unable to reconstitute the CCR5-myc-his in a lipid bilayer

by any of these methods

Postinsertion reconstitution was therefore attempted

next This involves adding the detergent-solubilized protein

to preformed membranes, followed by detergent removal

Although the physicochemical basis of this type of

recon-stitution is not clear, saturating the membranes with

detergent before protein addition was found to promote

reconstitution in a number of cases [1] One detergent, which

has been used frequently for postinsertion reconstitution, is

DDM This detergent, like other alkyl-glucoside detergents,

also seems to conserve the structure of solubilized CCR5

[40] We first determined how much DDM could be added

to liposomes without solubilizing them To this end,

liposomes containing the lipids egg-PtdCho (55 mol%),

egg-PtdEth (27 mol%), SM (8.2 mol%), cholesterol

(8.2 mol%), and the fluorescent phospholipid analogues

N-NBD-PtdEth and N-Rh-PtdEth (0.82 mol% each) were

produced Resonance energy transfer (RET) between these

probes depends on their membrane concentration; insertion

of detergent into the membrane should result in a gradual

decrease of RET [41,42], and lysis of the liposomes in abrupt

abolition of RET A decrease in RET results in an increase

in NBD fluorescence [43] Addition of DDM at concentra-tions between 0.1 and 0.4 mMto 1.5 mL of a 66-lM(lipid concentration) solution of liposomes at 4C led to gradual increases in NBD fluorescence, which reached stable levels after about 30 min (Fig 4A) In contrast, addition of Triton X-100 (0.5% w/v) at the end of the experiment led to an immediate jump in fluorescence, indicating the lysis of the membranes The cmc of DDM is around 0.25 mM Thirty-five percent fluorescence dequenching was obtained at 0.2 mMDDM Assuming that DDM occupies about half as much volume in the membrane as a phospholipid and that detergent is only incorporated in the outer leaflet, the

Fig 2 The tagged version ofCCR5 binds MIP-1a, is down-regulated

and can serve as a coreceptor for fusion A: CHO cells expressing

CCR5-myc-his, wt CCR5 or CHO cells transfected with pcDNA3

without the ccr5-myc-his gene as a negative control were incubated

with 0.55 n M [ 125 I]MIP-1a or 0.55 n M [ 125 I]MIP-1a in the presence of

250 n M of cold MIP-1a in Hepes 50 m M pH 7.4, MgCl 2 5 m M , CaCl 2

1 m M , BSA 0.5% at room temperature The cells were washed twice

with Hepes 10 m M pH 7.4, NaCl 0.5 M , BSA 0.5% Specific binding

was then calculated by subtracting the cell-associated counts in the

presence of cold MIP-1a from those obtained with radioactive MIP-1a

only B: Downregulation of CCR5 after MIP-1a stimulation Cells

were incubated with (open bars) or without (closed bars) 10 n M

MIP-1a for 30 min at 37 C, and then CCR5 expression on the cell surface

was measured by flow cytometry using 5 lgÆmL)1of antibody 2D7

and an FITC-labelled secondary antibody C: Fusion between cells

expressing different versions of CCR5, or nontransfected cells (CHO)

with HeLa cells expressing gp120/gp41 from strain ADA 8 · 10 5

ADA cells were plated on 35 mm Petri dishes, overlaid with 1.6 · 10 6

CHO cells the following day and incubated for 3 h at 37 C A fusion

index was calculated as described before [55].

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detergent to phospholipid ratio in this leaflet is 1 : 2, close to

the optimal conditions for reconstitution [1,44]

To reconstitute CCR5, we then incubated liposomes

(66 lM) with 0.2 mMof detergent After reaching a stable

level of fluorescence, one-quarter volume of CCR5-myc-his,

purified on a Ni-nitrilotriacetic acid column in 0.3 mMof

DDM, the minimum concentration required to solubilize

the protein, was added (Fig 4B) After 30 min of

coincu-bation at 4C, detergent was removed In postinsertion

reconstitution, usually some detergent is slowly removed

first, with a low amount of hydrophobic biobeads SM2, and

then the rest is removed rapidly by incubation with larger

amounts of beads [1] For initial slow removal, several initial

bead concentrations (from 0.25 to 1.5 mg per mL) and

various incubation times (from 2.5 to 5 h) were tried For

the second step, two additions of 2.5–20 mg per mL for

45 min to 1 h were tested The final protocol involved a 4-h

incubation with 0.5 mg of beads, followed by the addition

of 5 mg of beads, per mL of reconstitution solution After

1 h, these beads were removed from the mixture, and 10 mg

of fresh beads was added for another hour of incubation at

4C The mixture was stirred continuously The removal of

detergent was followed by monitoring the NBD

fluores-cence (Fig 4B) The resulting proteoliposomes were pelleted

by ultracentrifugation, resuspended in detergent free buffer,

pelleted again, and this step was then repeated Using this

protocol, approximately 12% of the purified CCR5

(approximately 3% of the total detergent-solubilized

CCR5) was found in the final pellet, whereas

unincorpo-rated protein was found in the first supernatant (Fig 5)

Under these conditions, more than 65% of the total proteins

incorporated in the proteoliposomes was CCR5 If

deter-gent was removed from protein in the absence of liposomes

by this protocol, no protein was pelleted Thus, the proteins present in the pellet were associated with the liposomes Moreover, as judged by the fluorescence quenching of N-NBD-PtdEth by N-Rh-PtdEth in the pelleted proteo-liposomes, the first centrifugation step also removed the remaining detergent from the proteoliposomes (Fig 4B) Similar results were obtained with CCR5-myc-his protein

Fig 3 CCR5-myc-his purification CCR5-myc-his was purified by

immobilized metal ion affinity (A) or immunoaffinity chromatography

using anti-histidine Igs (B) Results were analysed by Western blot as in

Fig 1, or by autoradiography of 35 S-labelled proteins.

Fig 4 Reconstitution ofCCR5-myc-his A: Saturation of liposomes with DDM DDM, at final concentrations between 0.1 and 0.4 m M

was added to liposomes (66 l M of lipid) containing N-NBD-PtdEth and N-Rh-PtdEth at time 0, and the fluorescence of N-NBD-PtdEth was measured and normalized to a scale where 0% representing the initial residual fluorescence of N-NBD-PtdEth before the addition of detergent, and 100% represents the fluorescence of completely dequenched N-NBD-PtdEth, obtained by addition of Triton X-100 (0.5% w/v), corrected for the quenching of NBD by Triton [43] (marked with TX) Note the rapid increase after addition of Triton X-100, and the lack of interaction at DDM concentrations below its cmc B: Reconstitution At time 0, 0.2 m M of DDM was added to liposomes as described above, then protein was added in 0.3 m M of DDM (P), and detergent was removed by addition of 0.5 mg Biobeads SM-2, followed by a second addition of 10 mg of beads These beads were then removed from the mixture, and 10 mg of fresh beads were added (indicated by 0.5, 10 and 10) All incubations were at 4 C Pellet denotes the fluorescence of the same quantity of lipid after purification by ultracentrifugation as described in the text.

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purified on antihistidine coupled agarose beads In

conclu-sion, postinsertion reconstitution produced CCR5

contain-ing liposomes without residual detergent

Characterization of reconstituted CCR5-myc-his

To characterize the membrane orientation and functionality

of the reconstituted protein, we first measured the binding of

antibody 2D7, 181 or 182, which recognize the extracellular

loops of CCR5 [36,45], to the proteoliposomes The

proteoliposomes were incubated with the CCR5

anti-body, pelleted by ultracentrifugation, resuspended,

incuba-ted with a125I-labelled secondary antibody, and washed by

ultracentrifugation Specific binding of monoclonal

anti-CCR5 to anti-CCR5-myc-his proteoliposomes could be

demon-strated (Fig 6) These data demondemon-strated that at least some

of the CCR5 is oriented with its N-terminus toward the outside of the liposomes and the binding of antibody 2D7, known to recognize a conformational epitope on CCR5 [36], indicated that the conformation of the receptor was maintained in the liposomal membrane

Binding of [125I]MIP-1a to the proteoliposomes was then measured Proteoliposomes were incubated with the ligand for 45 min at room temperature, and subsequently filtered

on BSA-presaturated GF-B filters, which were repeatedly washed, after which the filters were counted Specific binding of [125I]MIP-1a to CCR5-myc-his liposomes was demonstrated However, when we attempted to measure the number of binding sites per proteoliposome by adding mixtures of [125I]MIP-1a and increasing concentrations of cold MIP-1a, a strange phenomenon was observed; addi-tion of cold MIP-1a strongly increased the binding of [125I]MIP-1a, in fairly linear manner (Fig 7) Although we have no explanation for this behaviour, nonclassical binding

of MIP-1a has been described before [16] We therefore attempted to use another ligand, RANTES, to compete with MIP-1a for specific binding sites on proteoliposomes; partial competition by RANTES and concentration-dependent specific radioactive MIP-1a binding to proteo-liposomes were observed (Fig 8) However, at the highest concentration of radioactive MIP-1a attainable (4 nM), we did not reach saturation, which could indicate the presence

of a high concentration of CCR5 in the membranes In conclusion, these experiments demonstrate that at least part

of the CCR5 present in proteoliposomes is correctly oriented and still capable of recognizing its natural ligand

Co-reconstitution of CD4 and CCR5 in the same membrane

To preserve potential associations between CD4-his and CCR5-myc-his, these two proteins were then copurified from the same cell line on a Ni-nitrilotriacetic acid column;

as they carried the same hexahistidine tags, optimal conditions for their elution were nearly identical We then attempted to reconstitute the two proteins together in the

Fig 7 Non-classical behaviour ofMIP-1a observed with CCR5 pro-teoliposomes Proteoliposomes (6nmol of phospholipids) were incu-bated with [ 125 I]MIP-1a (open circles) or a mixture of radioactive plus

a 500-fold excess of cold MIP-1a (closed squares) in Hepes 2.5 m M

pH 7.4, NaCl 145 m M , BSA 0.1 mgÆmL)1buffer for 45 min at room temperature, washed on GFB-Whatman filters with the same buffer and then the filters were counted.

Fig 6 Specific binding ofanti-CCR5 antibody to proteoliposomes.

Proteoliposomes (8 nmol of phospholipids) were incubated for 30 min

with 10 lg/mL of antibody 2D7, 181 or 182, washed once with Hepes

2.5 m M pH 7.4, NaCl 145 m M , BSA 0.1 mgÆmL)1, and then incubated

with 125 I-labelled sheep anti-mouse IgG (5 lCiÆmL)1) for 30 min at

room temperature The proteoliposomes were then washed twice in the

same buffer and bound radioactivity was determined The negative

control consists of incubating the proteoliposomes with the labelled

secondary antibody only.

Fig 5 Analysis ofmyc-his reconstituted into liposomes

CCR5-myc-his proteoliposomes were washed three times by

ultracentrifu-gation The consecutive supernatants S1, S2 and S3 and the final

proteoliposome pellet (PL) were analysed by Western blot and

auto-radiography, and show successful reconstitution of the protein, as well

as the absence of unincorporated protein in the second and third

supernatant.

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same liposomal membrane, simply by applying the protocol

worked out for CCR5-myc-his, in spite of the biochemical

differences between the two proteins To our surprise,

Western blot analysis readily demonstrated the presence of

CD4-his and CCR5-myc-his in the proteoliposomal pellet,

indicating that CD4-his could be reconstituted using a

protocol optimized for a RCPG (Fig 9, Panel A) However,

the proteins could still be present in individual liposomes

To determine whether CD4 and CCR5 were present

together in individual or separate liposomes, these were

immunoprecipitated with paramagnetic beads bearing

anti-CD4 Igs The precipitate analysed by Western blot with an

anti-myc Ig recognizing the myc-his tagged CCR5 As

shown in Fig 9 (Panel B), CCR5-myc-his (the 38 kDa

band) was found to be present in these proteoliposomes

Thus, CD4 and CCR5 were present together in individual liposomal membranes The relative stoechiometry of the two incorporated proteins was estimated by Western blot analysis If we assume that the anti-His6Ig used (anti-tetra-his Ig, QIAGEN) recognizes both His6-tagged proteins with similar affinities, quantifying the relative intensities of each band would lead to an estimate ratio of 5 : 1 for the CD4-CCR5

In order to determine the orientation of CD4 with respect

to the proteoliposomal membranes, proteoliposomes were digested with trypsin, after which the trypsin was removed, and the CD4 quantified by Western blot relative to

Fig 9 Co-reconstitution ofCD4 and CCR5 A: Western blot showing the presence of CD4 and CCR5, after purification by immobilized metal ion affinity from a lysate obtained from CHO cells, coexpressing CD4-his and CCR5-myc-his and reconstitution by the protocol worked out for CCR5-myc-his S1, S2 and S3 represent the three consecutive supernatants obtained after ultracentrifugation, and PL the final pellet (cf Fig 5) The Q4120 antibody (2 lgÆmL)1) was used for detection of CD4, and an anti-myc Ig for CCR5, as described in the legend of Fig 1 B: 20 nmol of proteoliposomes containing CD4 and CCR5 were incubated with 4 · 10 6 paramagnetic beads with (lane A)

or without (lane B) the anti-CD4 Ig After washing the beads they were resuspended in gel electrophoresis sample buffer and analysed by Western blot with the anti-myc Ig Besides the 38 kDa band corres-ponding to CCR5-myc-his which is present in lane a, the heavy and light chains of the anti-CD4 Ig (50 and 25 kDa, respectively, lane a) are also revealed by the anti-mouse IgG secondary antibody, while no CCR5 is detected in lane b.

Fig 8 MIP-1a binds specifically to CCR5 proteoliposomes

CCR5-myc-his proteoliposomes (6nmol of phospholipids) were incubated

with [125I]MIP-1a in Hepes 2.5 m M pH 7.4, NaCl 145 m M , BSA

0.1 mgÆmL)1 for 45 min at room temperature, washed on

GFB-Whatman filters with the same buffer and then the filters were counted.

A: Binding in the presence of radioactive MIP-1a only, or in the

presence of a 500-fold excess of nonradioactive RANTES B: Specific

binding at different concentrations of MIP-1a to CCR5-myc-his

liposomes The proteoliposome-associated counts in the presence of a

500-fold excess of cold RANTES were subtracted.

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untreated controls After digestion, no more CD4 was

detected by Western blot using the anti-CD4 mAb Q4120,

suggesting that the vast majority of CD4 was oriented

right-side out, as the ectodomain of the protein is recognized by

the antibody

In order to test the biological activity of CD4, a

35S-labelled soluble construct, containing the whole

ectodo-main of the gp120/gp41 of strain JR-FL was produced and

purified over a lectin column as described in Materials and

methods It was found that this protein bound specifically to

CCR5/CD4 liposomes As previously described for the

binding of gp120/gp41 to CXCR4-paramagnetic

proteo-liposomes [46], approximately 30% of binding was

dis-placed by a 200-fold excess of cold gp120/gp41 (Fig 10,

Panel A) To determine whether the proteoliposomes could

recognize the complete gp120/gp41 protein, they were

incubated with cells expressing this glycoprotein complex

and the fluorescence of cell-associated proteoliposomes was quantified by FACS analysis (Fig 10, Panel B) The gp120/ gp41 expressing cells were found to bind proteoliposomes containing CCR5 and CD4 specifically These data suggest that CD4 was also inserted right side out into proteolipo-somal membranes, and that CD4 reconstituted in those model membranes remains functional

D I S C U S S I O N

Postinsertion or coinsertion protocols have been used for the reconstitution of membrane proteins [1,47] Co-insertion involves the removal of detergent from mixtures of free and micellar detergent and mixed protein/detergent and lipid/ detergent micelles Upon removal of detergent, the protein will likely become insoluble and either self-aggregate, or associate with lipids if these also become insoluble at this point In the latter case, a membrane containing the protein may be formed However, protein aggregates may be formed on the one hand and lipid membranes with little incorporated protein on the other [48] The success of this method thus probably depends on the relative affinities of interaction of the protein and lipid with the detergent As it is not always possible to predict these parameters, a variety of detergents and detergent removal protocols have to be tested for every individual protein, and successful reconstitutions

by these methods have involved a variety of lipid/detergent combinations and detergent removal protocols [3,5,6] Postinsertion reconstitution involves mixing detergent-solubilized protein with detergent-saturated liposomes, followed by detergent removal The physicochemical basis

of postinsertion reconstitution is not clear, but whether proteins will aggregate or associate with the lipid bilayer probably also depends on the relative affinities of the protein for a membrane or itself Most successful reconsti-tutions by this method were with transporter proteins, over-expressed in bacteria, containing 6–12 transmembrane

a helices [2,9–11,49] These proteins are robust and have large hydrophobic domains, facilitating reconstitution, and their production can easily be scaled up, making the efficiency of reconstitution less critical

No GPCR over-expressed in mammalian cells had previously been reconstituted by postinsertion protocols, although some had been successfully reconstituted by coinsertion methods [4,15,17,50] CCR5 and the related CXCR4, isolated from mammalian cells in which they were expressed at relatively high levels, were recently reconstitu-ted by an innovative method involving paramagnetic beads [16,46] After extraction with a detergent, the proteins were immunoprecipitated with antibodies coupled to the beads and then lipid membranes were formed around these An advantage of this method is that the antibodies can orient the GPCR However, the immobilization on beads may affect the protein’s behaviour

In order to develop a postinsertion reconstitution proto-col, the choice of the detergent is crucial DDM, b-D-octylglucoside or Triton X-100 are among the deter-gents which seems most suited for this type of reconstitution [11,49] Interestingly, both CD4 and CCR5 are associated with membrane raft microdomains [51,52], known to be solubilized preferentially by alkyl-glucoside type detergents [53] As the native conformation of CCR5 was well preserved in DDM [40], probably because of its structural

Fig 10 Binding ofsoluble gp 120 or cells expressing gp120/gp41

to proteoliposomes containing CD4 and CCR5 A: Binding of the

35 S-labelled soluble version of gp120/gp41, strain JR-FL to

CD4-CCR5 or only CD4-CCR5 containing proteoliposomes containing CD4 and

CCR5, in the absence or presence of a 200-fold excess (200x) of cold

protein, as described in Materials and methods Error bars are one

standard deviation B: FACS analysis of cells expressing gp120/gp41

(ADA strain), incubated with about 15 nmol of proteoliposomes

(PL, thick line) or liposomes (L, thick line) The thin line corresponds

to the auto-fluorescence of the cells.

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resemblance to raft glycolipids, this detergent was chosen.

Efficient reconstitution is strongly dependent on detergent

concentration for a given lipid/protein ratio [44] The

optimal detergent concentration was frequently found to be

close to that at the onset of liposome solubilization [2], and

the most critical steps in postinsertion usually are the

(stepwise) addition of the detergent to the membranes

without causing their solubilization, followed by detergent

removal [1] Saturation of liposomes with detergent is

mostly measured by techniques [1,54] that require high lipid

concentrations and do not give quantitative information on

the concentration of detergent present in the membrane As

expression of proteins in mammalian cells leads to the

isolation of lg rather than mg of receptors, small quantities

of liposomes can be produced only In this paper, detergent

insertion was therefore followed by resonance energy

transfer measurements using fluorescent phospholipid

ana-logues present in the liposomal membrane [41,42]

Satura-tion with 0.2 mM of DDM was found to suffice to

destabilize membranes for reconstitution, leading to a bulk

solution lipid/detergent molecular ratio of about 3 : 1 in

solution Usually, at higher lipid concentrations, a 1 : 1

ratio is attained [10] Besides differences in the nature of the

detergent, this could be a consequence of the lipid

concen-tration, because the detergent partitions between the

solution, protein and membrane, but only the concentration

in the membrane determines the outcome of reconstitution

Therefore, an advantage of the resonance energy transfer

method is that the membrane concentration of the detergent

can be estimated At less than 0.2 mM DDM, poor

reconstitution of proteins was observed, and at higher

concentrations liposomes were solubilized In the latter case,

if detergent was removed with beads, no reconstitution of

protein was observed at all The resonance energy transfer

assay also allowed direct observation of the removal of

detergent from the membrane in real time, and therefore the

efficient comparison of a number of protocols Initial slow

detergent removal and biobeads quantity were found to be

crucial for the recovery of high concentrations of functional

proteins in proteoliposomes An initial four-hour

incuba-tion time with 0.25 mg of biobeads per ml led to optimal

protein incorporation Studies of molecular interactions

between CD4 and CCR5 reconstituted in proteoliposomes

could lead to an understanding of the constitutive

associ-ation of CCR5 and CD4 in vivo, recently suggested to be

important for HIV entry [33]

In conclusion, two rather different proteins, one largely

hydrophobic with seven transmembrane helices and a small

ecto- and endodomain (CCR5), and one with a large

hydrophilic ectodomain and a single transmembrane

seg-ment (CD4), were reconstituted into proteoliposomal

membranes by the same protocol, using the same detergent,

DDM These data suggest that the protocol might be

applicable to membrane proteins in general Moreover, it

might be useful for the reconstitution of other membrane

proteins usually available only in small quantities from

mammalian cells

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

This research was supported by the Re´gion Midi-Pyre´ne´es, the Agence

Nationale pour la Recherche sur le SIDA (ANRS), the Fondation pour

la Recherche Me´dicale (FRM), the Association pour la Recherche sur

le Cancer (ARC), and the comite´ scientifique SIDACTION of the FRM.

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