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Stable and highly receptor-specific BRET signals were obtained in tsA cells transfected with Rluc- and GFP2-tagged CaRs under basal conditions, indicating that CaR is constitutively dimer

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Probing intermolecular protein–protein interactions in the

calcium-sensing receptor homodimer using bioluminescence

resonance energy transfer (BRET)

Anders A Jensen1*, Jakob L Hansen2*, Søren P Sheikh2and Hans Bra¨uner-Osborne1

1

NeuroScience PharmaBiotec Research Centre, Department of Medicinal Chemistry, The Royal Danish School of Pharmacy, Copenhagen, Denmark; 2 Laboratory of Molecular Cardiology, Copenhagen University Hospital, University of Copenhagen, Copenhagen, Denmark

The calcium-sensing receptor (CaR) belongs to family C of

the G-protein coupled receptor superfamily The receptor is

believed to exist as a homodimer due to covalent and

non-covalent interactions between the two amino terminal

domains (ATDs) It is well established that agonist binding

to family C receptors takes place at the ATD and that this

causes the ATD dimer to twist However, very little is known

about the translation of the ATD dimer twist into G-protein

coupling to the 7 transmembrane moieties (7TMs) of these

receptor dimers

In this study we have attempted to delineate the

agonist-induced intermolecular movements in the CaR homodimer

using the newbioluminescence resonance energy transfer

technique, BRET2, which is based on the transference of

energy from Renilla luciferase (Rluc) to the green fluorescent

protein mutant GFP2 We tagged CaR with Rluc and GFP2

at different intracellular locations Stable and highly receptor-specific BRET signals were obtained in tsA cells transfected with Rluc- and GFP2-tagged CaRs under basal conditions, indicating that CaR is constitutively dimerized However, the signals were not enhanced by the presence of agonist These results could indicate that at least parts of the two 7TMs of the CaR homodimer are in close proximity in the inactivated state of the receptor and do not move much relative to one another upon agonist activation However,

we cannot exclude the possibility that the BRET technology

is unable to register putative conformational changes in the CaR homodimer induced by agonist binding because of the bulk sizes of the Rluc and GFP2molecules

Keywords: family C GPCR; CaR; BRET; dimerization; homodimerization

Family C of the G-protein coupled receptor (GPCR)

superfamily consists of eight metabotropic glutamate

receptors (mGluR1-8) [1–3], a calcium-sensing receptor

(CaR) [4], two c-aminobutyric acid type B receptors

(GABABR1-2) [5], several families of putative pheromone

and taste receptors [6,7], and four recently cloned orphan

receptors [8–11] With the exception of the orphan

receptors, all family C GPCRs are characterized by

unusually large extracellular amino terminal domains

(ATDs) of up to 600 amino acid residues to which

agonist binding takes place [12–20] The subsequent translation of the activation signal from the ATD into G-protein coupling to the 7 transmembrane moiety (7TM)

is poorly understood

All family C GPCRs, to which an endogenous ligand has been identified, are believed to exist as dimers Whereas GABABR1 and GABABR2 undergo heterodimerization [21–23], the mGluRs and CaR form homodimers [24,25] The crystal structures of the mGluR1 ATD homodimer have confirmed the findings from immunoblot studies of CaR and mGluRs that the ATD dimer interface is constituted by intermolecular noncovalent interactions and a disulfide bridge [20,26–29] Furthermore, the crystal structures have revealed that the ATD homodimer equili-brates between a resting and an active state, which differs by

a 70 twist in the relative orientation of the two ATDs [20] Agonist binding to one of the ATDs appears to stabilize the active dimer conformation, a principle closely resembling the classical two-state model for family A GPCR function [30,31] Speculating on the following steps in the signal transduction, Kunishima et al have proposed that this activation twist in the relative ATD–ATD conformation could cause a contraction of the two 7TMs in the homodimer thereby creating a newstructural motif recog-nizable to the G-protein [20] A similar signal mechanism has been proposed for certain cytokine receptors signalling through a JAK/STAT pathway [32,33]

Bioluminescence resonance energy transfer (BRET) is the product of nonradiative transfer of energy from a

Correspondence to A A Jensen, Department of Medicinal Chemistry,

The Royal Danish School of Pharmacy, 2 Universitetsparken,

DK-2100 Copenhagen, Denmark.

Fax: + 45 3530 6040, Tel.: + 45 3530 6491,

E-mail: aaj@dfh.dk

Abbreviations: GPCR, G-protein coupled receptor; mGluR,

metabo-tropic glutamate receptor; CaR, calcium-sensing receptor;

GABA B R, c-aminobutyric acid receptor type B; ATD, amino

terminal domain; 7TM, 7 transmembrane moiety; BRET,

biolumi-nescence resonance energy transfer; FRET, fluorescence resonance

energy transfer; Rluc, Renilla luciferase; GFP, green fluorescent

protein; EGFP, enhanced green fluorescent protein; EYFP, enhanced

yellowfluorescent protein; IP, inositol phosphate; WT, wild type;

i1/i2/i3, intracellular loop 1, 2 and 3.

Note: *Co-first authors

(Received 19 June 2002, revised 13 August 2002,

accepted 29 August 2002)

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luminescent donor to a fluorescent acceptor protein In the

sea pansy Renilla reniformis the energy from the catalytic

degradation of coelenterazine h by Renilla luciferase

(Rluc) is transferred to green fluorescent protein (GFP),

and the interaction betw een the tw o proteins gives rise to

emission of fluorescence BRET is a derivation technique

of fluorescence resonance energy transfer (FRET), and the

two techniques have been applied repeatedly in studies of

the oligomerization of GPCRs and other protein–protein

interactions [34–40] In these studies, BRET has been

measured using Rluc and enhanced yellowfluorescent

protein (EYFP) as luminescent donor and fluorescent

acceptor, respectively, and coelenterazine h as the

sub-strate Recently, a new BRET2 technology has been

introduced, where the emission of fluorescence caused by

the proximity of Rluc and the GFP mutant GFP2 is

measured using DeepBlueCTM, a modified form of

coelenterazine h, as the substrate (Packard Bioscience)

The BRET2 assay has very recently been applied in a

study of the homo- and heterodimerization of opioid and

adrenergic receptors [41]

In the present study, we have applied the BRET2

technology to investigate the intermolecular arrangement

of the 7TMs in the family C GPCR homodimer, exemplified

by the CaR

E X P E R I M E N T A L P R O C E D U R E S

Materials

Culture media, serum, antibiotics and buffers for cell

culture were obtained from Life Technologies (Paisley,

UK) All other chemicals were obtained from Sigma

(St Louis, MO) The rCaR-pRK5 [42] and pmGluR1a

[43] plasmids were generous gifts from Professor Solomon

H Snyder (The Johns Hopkins University School of

Medicine, Baltimore, MD) and Professor Shigetada

Nakanishi (Kyoto University, Japan), respectively The

pSI and pEGFP-N2 vectors were obtained from Promega

(Madison, WI) and Clontech (Palo Alto, CA), respectively

DeepBlueCTM, pGFP2-N3, pRluc-N1, pRluc-N2 and the

pBRET+ vector (a Rluc/GFP2 fusion protein) were

purchased from Biosignal Packard (Montreal, Canada)

The tsA cells (a transformed human embryonic kidney

(HEK) 293 cell line) [44] and the c-myc- and HA-tagged

GABAB receptors were generous gifts from Penelope

S V Jones (University of California, San Diego, CA) and

Bernhard Bettler, (University of Basel, Switzerland),

respectively All transfections in this study were performed

with Polyfect as a DNA carrier according to the protocol

of the manufacturer (Qiagen, Hilden, Germany) Point

mutations were made using the Quick-Change mutagenesis

kit according to the manufacturer’s instructions (Stratagene,

La Jolla, CA)

Construction of tagged receptors

CaR and mGluR1a were subcloned from their original

vectors as described previously [17] Two different GFP

mutants were used in this study: Enhanced green fluorescent

protein (EGFP) and GFP2, which are the F64L/S65T and

F64L mutants of GFP, respectively [45] CaRD1036-EGFP

and CaRD1036-Rluc were created by subcloning of the

ApaI–XbaI fragment of EGFP-N2 and Rluc-N2 into CaR-pSI digested with ApaI (an endogenous site covering nucleotides 3103–3108 in CaR) and XbaI, respectively (Fig 1) Using the endogenous ApaI site for the constructs results in the truncation of the last 43 amino acid residues in the 212 residues-long carboxy terminal of rCaR CaRD886-EGFP and CaRD886-Rluc were constructed by subcloning

of EcoRI–ApaI digested PCR products into CaRD1036-EGFP and CaRD1036-Rluc digested with EcoRI and ApaI, respectively CaRD1036-V5/His and CaRD886-V5/His were created by subcloning of XhoI–ApaI fragment of CaRD1036-Rluc and CaRD886-Rluc into the pCDNA6-V5/His-A vector (Invitrogen, San Diego, CA) The mGluR1D877-EGFP and mGluR1D877-Rluc plasmids were created by subcloning of BspEI–XbaI digested PCR products of EGFP-N2 and Rluc-N2 into mGluR1a-pSI digested with BspEI (an endogenous site covering nucleo-tides 2627–2632 in mGluR1a) and XbaI Receptor-GFP2 fusion plasmids were created in a similar fashion as described above AT1aD359-GFP2 was created by PCR using the angiotensin II receptor subtype 1a as template and subse-quent subcloning into pGFP2-N3 using HindIII and BamHI

as restriction enzymes The pRluc/EGFP plasmid was created from pRluc/GFP2(pBRET+) by the introduction

of a Ser65fi Thr mutation in the GFP2part of the plasmid For the construction of the c-myc-CaR and HA-CaR constructs, a MluI site was introduced after the signal peptide in CaR (covering nucleotides 55–60) using the QuickChange mutagenesis kit Following digestion with restriction enzymes MluI and NotI, CaR was subcloned into c-myc-GABAB1a-EGFP and HA-GABAB1b-EGFP, respectively The MluI–NotI digestion cut out GABAB 1a-EGFP and GABAB1b-EGFP parts of the original plasmids Hence, c-myc-CaR and HA-CaR consisted of the signal peptide for mGluR5, HA or c-myc and the entire CaR

Fig 1 The Rluc-, GFP2- and EGFP-tagged receptors (A) The topo-logy of the Rluc-, GFP 2 - or EGFP-tagged GPCRs used in the present study (B) The fusion regions of the Rluc- and GFP2/EGFP-tagged receptors GFP 2 and EGFP are given as GFP.

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except for its signal peptide The c-myc-CaRD1036-Rluc,

c-myc-CaRD886-Rluc receptors were created by subcloning

of the EcoRI–NotI segments of the respective Rluc-tagged

CaRs into c-myc-CaR Analogously, HA-CaRD1036-GFP2

and HA-CaRD886-GFP2were created by subcloning of the

EcoRI–NotI segment of the respective GFP2-tagged CaRs

into HA-CaR

All amplified receptor DNAs were sequenced on an ABI

Prism 310 using Big Dye Terminator Cycle Sequencing kit

(Perkin-Elmer, Warrington, UK)

Inositol phosphate (IP) assay

The tsA cells (3· 105) were split into a 6-cm tissue culture

plate and transfected the following day The day after

transfection, the cells were split into 16 wells of a poly

D-lysine coated 48-well tissue culture plate in inositol-free

DMEM (Dulbecco’s modified Eagle’s medium) with

reduced concentrations of CaCl2 (0.9 mM) and MgCl2

(0.8 mM), supplemented with penicillin (100 UÆmL)1),

streptomycin (100 lgÆmL)1), 10% dialyzed fetal calf serum

and 1 lCiÆmL)1myo-[2–3H]inositol (Amersham,

Bucking-hamshire, UK) Sixteen to twenty-four hours after

applica-tion of the radioligand, the cells were assayed as previously

described [46,47] The pharmacological characterization of

wild type (WT) AT1areceptor and AT1aD359-GFP2 was

performed analogously, except that HEK 293 cells were

used instead of tsA cells

Fluorescence and luminescence measurements

For the measurements of fluorescence and luminescence in

cells cotransfected with Rluc- and GFP2-constructs, tsA

cells (1.5· 105cells per well) were split into wells of a 6

well-culture plate and transfected with 0.4 lg of a GFP2

-construct and 0.4 lg of a Rluc construct the following day

The day after the transfection the medium was changed

The following day, the cells were washed three times in

NaCl/Pi, resuspended in 300 lL NaCl/Piand distributed in

black optiplates (Packard) Fluorescence and luminescence

recordings were performed in a FusionTMreader (Packard)

Fluorescence excitation was performed at 425/20 nm and

emission was measured at 530/10 nm Luminescence was

assayed by addition of coelenterazine h and measured

without any filter

Immunofluorescence studies

The tsA cells (3· 105) were split into a 6-cm tissue culture

plate and transfected with a total of 1.7 lg plasmid

(pCDNA3 or GABAB receptors for the control

experi-ments or various combinations of c-myc- and HA-tagged

CaRs) the following day The day after transfection, the

cells were split into wells of a polyD-lysine coated 24-well

tissue culture plate in DMEM with reduced

concentra-tions of CaCl2(0.9 mM) and MgCl2(0.8 mM)

supplemen-ted with penicillin (100 UÆmL)1), streptomycin

(100 lgÆmL)1) and 10% dialyzed fetal calf serum The

following day the medium was aspirated, the cells were

washed twice with NaCl/Piand fixed by incubation with

500 lL methanol for 5 min The cells were washed

5· 2 min with NaCl/Pi, incubated with 500 lL NaCl/Pi

supplemented with 10% fetal calf serum for 20 min and

labeled with anti-myc (clone 9E10, Roche Molecular Biolabs; 1 : 500) or anti-HA (clone 12CA5, Roche Molecular Biolabs; 1 : 100) monoclonal Igs for 1 h Following 2· 5 min washes with NaCl/Pi and a 5-min incubation with 500 lL NaCl/Pisupplemented with 10% fetal calf serum the cells were incubated for 1 h with secondary Cy3-conjugated affinity-purified goat anti-mouse IgG (Jackson ImmunoResearch Laboratories, West Grove, PA; 1 : 200) Then the cells were washed (2· 5 min) with NaCl/Pi and view ed through a Leica

DM IRB fluorescence microscope

Single cell fluorescence measurements The tsA cells (3· 105) were split into a 6-cm tissue culture plate and transfected with a total of 1.7 lg plasmid

mGluR1D877-EGFP or AT1aD359-EYFP) the following day The day after transfection, the cells were split into poly D-lysine coated 3.5 cm wells containing a glass slide (MatTek Corp., Ashland, MA) in DMEM with reduced concen-trations of CaCl2 (0.9 mM) and MgCl2 (0.8 mM), supple-mented with penicillin (100 UÆmL)1), streptomycin (100 lgÆmL)1) and 10% dialyzed calf serum The follow-ing day, sfollow-ingle cell fluorescence was viewed with an Axiovert 100M confocal microscope (Zeiss, Jena, Germany) using the objective Plan-Achromat 63· 14 W Oil (DiC) and an excitation wavelength of 488 nm The cellular expression of each of the fusion proteins was determined

in at least four individual cells

Emission and excitation spectral measurements For emission spectral measurement of fusion Rluc/GFP proteins Cos7 cells (1· 106) were split into a 10-cm tissue culture plate and transfected with 15 lg plasmid (pRluc-N2, pRluc/GFP2 (pBRET +) or pRluc/EGFP) the following day The day after the transfection the medium was changed The following day, the cells were washed three times in NaCl/Piand resuspended in 500 lL NaCl/Piin a cuvette DeepBlueCTMwas added to a final concentration of

5 lM, and light emission acquisition (340–600 nM) w as performed with a delay 30 s to assure dark adaption using

a SPEX Fluoromax-2 spectrofluorometer (Jobin Yvon Inc., Edison, NJ) with the lamp turned off connected to a

PC equipped with the Datamax 2.2 software package (emission slit 25 nm, increment 2 nm, integration time 0.5 s)

For excitation and emission spectra measurements of EGFP and GFP2the Cos7 cells were handled as described above, except that they were transfected with pEGFP-N1 or pGFP2-N1 Excitation spectra were recorded from 340 to

520 nm acquiring emission at 530 nm (emission/excitation slit of 1 nm, increment 2 nm, integration time 0.1 s) Emission spectra were recorded from 450 to 600 nm by exciting at 425 nm using the same conditions as above, where background was subtracted using nontransfected cells, and the spectra were normalized

BRET assay The tsA cells (1· 106) were split into a 10-cm tissue culture plate and transfected with 5 lg plasmid the

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following day (5 lg of one plasmid, 2.5 lg of each of tw o

plasmids, or otherwise indicated) The day after

transfec-tion the medium was changed The following day, the cells

w ere w ashed in NaCl/Pi and detached Approximately

1· 106 cells per well were distributed in a 96-well

optiplate in the presence or absence of 20 mM CaCl2

DeepBlueCTMwas added to a final concentration of 5 lM,

and measurements were performed in a FusionTM reader

(Packard Bioscience) (read time 1 s, gain 50, dual bands

410/80 nm and 515/30 nm) BRET ratios was calculated

as (emission515 nm) background515 nm)/(emission410 nm)

background410 nm) The background signal was assessed

in each experiment by measuring the signal of a sample of

nontransfected cells In the BRET measurements using

lyzed tsA cells transfected with various GFP2- and

Rluc-tagged CaRs, the cells were mechanically lyzed

immedi-ately before the measurements by sucking the cell

suspension up and down 12 times with a tuberculin

syringe with a 27 gauge needle

All experiments were performed at least three times, and

the data shown reflects the results of all experiments

R E S U L T S

Pharmacological characterization of

Rluc-and EGFP-tagged CaRs

In excellent agreement with a previous study of

EGFP-tagged CaRs [48], CaRD1036-EGFP, CaRD1036-Rluc,

CaRD886-EGFP and CaRD886-Rluc were all functional

in an IP assay, demonstrating that all of these receptors

were expressed at the cell surface (Fig 2A) However, the

fold responses of particularly CaRD886-Rluc and

CaRD886-EGFP were significantly decreased compared

to that of WT CaR, and Ca2+displayed significant lower

potencies at these two receptors (Fig 2A) The less

efficient G-protein coupling of the Rluc/EGFP-tagged

CaRs compared to WT CaR appeared to arise from an

interference of the Rluc/EGFP molecule in the coupling

process, as CaRD1036-V5/His and CaRD886-V5/His

dis-played WT-like agonist pharmacologies (Fig 2A) The

observation that fusion of a 26 amino acid residue peptide

to residues 1036 and 886 of CaR did not alter the

pharmacological properties of the receptor is in excellent

agreement with a previous study of CaRs truncated in the

carboxy termini [49]

Cellular expression of the GFP- and Rluc-tagged CaRs

To estimate the overall expression levels of Rluc- and

GFP2-tagged CaRs and the control constructs in the cells

and to compare the overall cellular donor/acceptor ratios

within the different experiments, we measured the

fluo-rescence and luminescence in cells cotransfected with

various combinations of GFP2- and Rluc-constructs Cells

were transfected with similar amounts of cDNA of

Rluc-and GFP2-constructs as those used in the BRET

experi-ments

The levels of fluorescence in cells transfected with the

GFP2-tagged receptors were comparable in size, whereas

GFP2was expressed at slightly higher levels (Fig 3A) The

luminescence levels in CaRD1036-Rluc and CaRD886-Rluc

transfected cells were similar, whereas cells expressing Rluc

itself displayed a significantly higher luminescent signal (Fig 3B) These data indicates that the overall cellular expression levels of the Rluc- and GFP2-tagged CaRs and

AT1aRs are similar

To evaluate the cell surface expression, we tagged HA and c-myc epitopes to the N-terminal of the CaR-GFP2and CaR-Rluc fusion proteins, respectively, and visualized these using immunofluorescence microscopy (Fig 4) No fluo-rescence was observed for mock transfected cells, when either anti-HA or antic-myc antibodies were used (data not shown) To validate the reliability of the immunofluores-cence technique further, we took advantage of the well-established heterodimerization of the GABAB receptors [5,21–23] In agreement with a previous study [50], cell surface staining was only observed for c-myc and

Fig 2 Pharmacological characterization of EGFP- and Rluc-tagged CaRs (A) Concentration-response curves of Ca2+-induced IP accu-mulation in tsA cells transfected with WT CaR, CaRD1036-V5/His, CaRD1036-Rluc, CaRD1036-EGFP, V5/His, CaRD886-Rluc and CaRD886-EGFP Data are given as disintegration per minute (DPM) per well (B) Concentration-response curves of angio-tensin II-induced IP accumulation in HEK 293 cells transfected with

WT At 1a R and At1aD359-GFP 2 Data are given fold response [R/

R basal ].

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HA-tagged GABAB1 receptors, when these were

cotrans-fected with WT GABAB2(data not shown)

The c-myc-CaR/HA-CaR, c-myc-CaRD1036-Rluc/

HA-CaRD886-GFP2 transfected tsA cells all displayed

substantial degrees of cell surface staining both when

labeled with anti-(c-myc) and anti-HA Ig (Fig 4) The

fraction of cells expressing the CaRD1036- and

CaRD886-receptors and that of WT CaR appeared to be similar

The cellular expression patterns of the GFP-tagged

receptors were investigated in greater detail using

confo-cal microscopy The expression patterns of

CaRD1036-EGFP and CaRD886-CaRD1036-EGFP were recorded in several

cells Cells representing the predominant expression

pattern of the respective receptors are depicted in

Fig 5 In agreement with the immunofluorescence

ex-periments and previous studies of similar EGFP-tagged

CaRs, CaRD1036-EGFP and CaRD886-EGFP were

localized in the cell membrane as well as intracellularly

(Fig 5) [48,51]

Cellular expression of GFP- and Rluc-tagged mGluR1 and AT1aR

The receptors mGluR1D877-EGFP, mGluR1D877-GFP2 and mGluR1D877-Rluc were originally constructed as control receptors for the BRET experiments However, confocal microscopy revealed that mGluR1D877-EGFP was trapped in vesicles inside the tsA cell (Fig 5) Hence, the Rluc/GFP-tagged mGluR1D877 constructs were determined to be unsuitable for the BRET experiments, and AT1aD359-GFP2was used instead

Confocal microscopy of cells transfected with AT1aD359-EYFP demonstrated that this receptor was expressed at the cell surface as well as intracellularly (Fig 5) Considering the fewamino acid residues differing

in EYFP compared to GFP2, it is reasonable to assume that the expression pattern of AT1aD359-GFP2 is similar

to that of AT1aD359-EYFP

In the IP assay angiotensin II displayed a potency at AT1aD359-GFP2 not significantly different from that at

Fig 4 Immunofluorescence analysis of and HA-tagged CaRs Visualization of cell surface expression of tsA cells transfected with c-myc-CaR/HA-CaR, c-myc-CaRD1036-Rluc/HA-CaRD1036-GFP2and c-myc-CaRD886-Rluc/HA-CaRD886-GFP2, respectively The transfected tsA cells were prepared as described in Experimental Procedures All cell culture dishes with transfected cells were 80–90% confluent on the day of viewing The upper row of images was labeled with anti-(c-myc) Ig and the bottom row with anti-HA Ig.

Fig 3 Measurements of fluorescence and luminescence in cells cotransfected with GFP 2 - and Rluc-constructs The tsA cells were prepared and assayed as described in Experimental Procedures (A) Fluorescence measurements: excitation was performed at 425/20 nm, and emission was measured at 530/10 nm Data are given as CFU (B) Luminescence measurements performed at 530 nm using a final concentration of 5 l M

coelenterazine h as substrate (C) The ratio between the fluorescence and luminescence signals in the various Rluc-/GFP 2 -combinations The ratio is given as [Fluorescence/Luminescence].

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WT AT1aR, albeit the fold response of the GFP2-tagged

receptor was attenuated compared to that of the WT

receptor (Fig 2B) Furthermore, WT AT1aR and

AT1aD359-GFP2 displayed similar binding characteristics

in a [I125]angiotensin II whole cell binding assay (data not

shown) These observations are in excellent agreement with

the findings of another group [52] and suggest that

AT1aD359-GFP2 is functional and expressed at the cell

surface to a degree comparable to that of WT AT1aR

BRET in living cells

To evaluate the ability of our assay to detect BRET

caused by protein–protein interactions, light emission

spectra were recorded from Cos7 cells transfected with

pRluc-N2 or the two fusion proteins pRluc/GFP2

(pBRET+) and pRluc/EGFP (Fig 6) The

signal-to-noise ratio using DeepBlueCTM as Rluc substrate

turned out to be considerably higher than that reported

for coelenterazine h forms used in other studies [34,40] In

the window of 500–530 nm the emission of Rluc/GFP2

transfected cells was 7.4 times higher than that of Rluc

transfected cells (Fig 6A)

Interestingly, the BRET ratio obtained in Rluc/EGFP

transfected cells was only 20% lower than that in the

Rluc/GFP2transfected cells (Fig 6A,B) At a glance this was intriguing, as the normalized spectral overlap between the donor emission and the acceptor excitation was significantly higher for the Rluc/GFP2 pair than for the Rluc/EGFP pair (Fig 6C) However, this may be explained

by two factors: Firstly, EGFP has a 2.6 times higher excitation coefficient than GFP2(estimatedS (max EGFP)

55 000 cm)1ÆM )1(Clontech) and estimatedS (max GFP2)

21 000 cm)1ÆM )1 (Packard, unpublished data)) Secondly, the spectral overlap for EGFP occurs at higher wavelength, where the electric field drops off more slowly and energy transfer can occur at further distances [53, 54]

BRET experiments with Rluc- and GFP2-tagged receptors

We did not detect any BRET signal in cells transfected exclusively with a Rluc-tagged or a GFP2-tagged CaR A BRET ratio of 0.05 was observed from cells transfected with CaRD1036-Rluc or CaRD886-Rluc (Fig 7B) This signal corresponds to no energy transfer, and this fraction of the BRET ratio is caused by background emission from Rluc into the GFP filter In cells transfected with the GFP2 -tagged receptors alone no luminescence signals were detec-ted (data not shown)

Fig 5 Confocal microscopy of EGFP-tagged receptors Confocal microscopy of tsA cells transfected with CaRD1036-EGFP, CaRD886-EGFP, mGluR1D877-EGFP and AT1aD359-EYFP All images were recorded as described in Experimental Procedures using an excitation wavelength of

488 nm No fluorescence was detected in mock-transfected cells, and the fluorescence in cells transfected with EGFP and EYFP were uniformly distributed over the entire cell (data not shown).

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Significant BRET signals were obtained for all

CaR-GFP2and CaR-Rluc combinations (Fig 7B) BRET ratios

between 0.11 and 0.17 were obtained for every combination

including CaRD1036-Rluc or CaRD1036-GFP2, w hereas

the CaRD886-Rluc/CaRD886-GFP2combination gave rise

to a BRET signal of substantial higher intensities (BRET

ratios between 0.31 and 0.47)

No changes in the BRET signal were observed for any of

the combinations by addition of Ca2+(Fig 7B) In these

experiments Ca2+was unable to reach the intracellular pool

of receptors Hence, in order to investigate whether

exposure of all receptors in the cell to Ca2+would result

in an increased BRET signal, experiments were also

performed on mechanically lyzed tsA cells transfected with

various combinations of GFP2- and Rluc-tagged

CaRD1036 and CaRD886 However, the BRET ratios

in these experiments were comparable to the similar experiments using whole cells, and no Ca2+-induced BRET could be detected (data not shown) It was also verified that the BRET2 assay itself was not sensitive to Ca2+ concentration changes (Fig 7A)

Several experiments were performed in order to confirm that the BRET signals obtained in CaR-Rluc/CaR-GFP2 transfected cells were receptor-specific Co-expression of CaRD886-GFP2 and pRluc-N2 did not give rise to any BRET signal, and coexpression of CaRD886-Rluc and pGFP2-N3 elicited only a weak signal (Fig 7C) No significant BRET was recorded in cells expressing CaRD886-Rluc and the angiotensin II receptor 1a tagged with GFP2 (AT1aD359-GFP2) either (Fig 7C) Further-more, the BRET signal obtained with CaRD886-Rluc and CaRD886-GFP2was reduced considerably by coexpression

Fig 6 Spectral properties of DeepBlueCTMillumination (A) Light-emission acquisition spectrum of Cos7 cells transfected with Rluc/EGFP, Rluc/ GFP2(pBRET+) and pRluc-N2 Cells were incubated with 5 l M DeepBlueCTM, and light-emission acquisition was measured with a delay of 30 s The normalized luminescence is given (B) BRET ratios in Cos7 cells transfected with Rluc/EGFP, Rluc/GFP 2 (pBRET+) and Rluc-N2 The BRET ratio is given as emission500)530 nM/emission370)450nM (C) Excitation and emission spectra measurements of EGFP and GFP 2 Cos7 cells were transfected with pEGFP-N1 or pGFP2-N1 Excitation spectra were recorded from 340 to 520 nm acquiring emission at 530 nm Emission spectra were recorded from 450 to 600 nm by exciting at 425 nm The recording of the light-emission spectrum of Rluc is described above.

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of WT CaR, CaRD1036-V5/His and CaRD886-V5/His

(Fig 7D) In contrast, the signal was not diminished by

coexpression of CaRD886-Rluc and CaRD886-GFP2with

family A GPCRs such as the muscarinic acetylcholine

receptor m1 and the histamine H1 receptor or with the

family C GPCR GABAB2(Fig 7D) Finally, no significant

BRET signal could be detected, when CaRD886-Rluc

transfected cells and CaRD886-GFP2transfected cells were

mixed, indicating that the donor and acceptor molecules

had to be present in the same cell in order to elicit BRET

(Fig 7C)

Another important factor to consider was the ratio

between the fluorescence signal and the luminescence signal

for the various GFP2/Rluc-combinations As can be seen

from Fig 3C, this ratio was higher for the CaRD886-Rluc/

GFP2 and CaRD886-Rluc/AT1D359-GFP2 combinations than for the CaRD886-Rluc/CaRD886-GFP2 and CaRD1036-Rluc/CaRD1036-GFP2 combinations This indicated that the overall expression of the fluorescent acceptor molecule was at least as favourable for the formation of BRET in the control experiments as in the regular BRET experiments (Fig 7B,C) This further sup-ports that the BRET signal is caused by specific homo-dimerization of CaR rather than nonspecific interactions due to overexpression of the proteins

BRET experiments with Rluc- and EGFP-tagged receptors Similar BRET patterns were observed for the various Rluc/ EGFP combinations as for the Rluc/GFP2 combinations

Fig 7 BRET in tsA cells transfected with Rluc- and GFP2-tagged receptors The experiments were performed as described in Experimental Procedures, and the BRET ratio is given as (emission 515 nm ) background 515 nm )/(emission 410 nm ) background 410 nm ) All the experiments were performed at least three times Data shown are from a single experiment (A) BRET in tsA cells transfected with the fusion proteins pBRET+ (Rluc/GFP 2 ) or Rluc/EGFP in absence and presence of 20 m M CaCl 2 (B) BRET in tsA cells transfected with Rluc- and GFP 2 -tagged CaRs (C) Receptor specificity of the BRET In [1], BRET obtained in tsA cells transfected with CaRD886-Rluc or CaRD886-GFP 2 and pRluc-N2, pGFP 2 -N3 or AT1aD359-GFP2were recorded In [2], two 10 cm culture dishes of tsA cells were transfected with 2.5 lg CaRD886-Rluc and 2.5 lg CaRD886-GFP 2 , respectively, and cells from the two dishes were mixed immediately prior to the BRET recording The mixture of the two population of cells is indicated with brackets around each cell line The two experiments depicted in Fig 7C were performed independently of each other (D) Competitive inhibition of BRET by coexpression of receptors not tagged with GFP2or Rluc Cells were transfected with 0.5 lg CaRD886-Rluc, 0.5 lg CaRD886-GFP2and 4 lg of various plasmids (pSI, CaR-pSI, CaRD1036-V5/His, CaRD886-V5/His, m1-pCD, H1-pCDNA3 and GABA B 2-pCDNA3) and assayed as described in Experimental Procedures.

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(compare Figs 7 and 8) In agreement with the experiments

with the GFP2-tagged receptors, no agonist-induced BRET

was detected for any of the Rluc/EGFP–tagged receptor

combinations (data not shown)

D I S C U S S I O N

Evaluation of the BRET2assay

The present study is the second publication, where

dimerization between Rluc- and GFP2-tagged proteins

has been demonstrated using the modified form of

coelenterazine h DeepBlueCTM as the substrate [41] The

emission of DeepBlueCTM catalyzed by Rluc takes place

at a lower wavelength than that of coelenterazine h (390–

400 nm and 475–480 nm, respectively), which gives rise to

a significant increase in spectral resolution (Packard

Bioscience) Because of the higher degree of separation

between the wavelengths of Rluc and Rluc/GFP2 in the

presence of DeepBlueCTM than between Rluc and Rluc/

EYFP using coelenterazine h as substrate, the Rluc/

DeepBlueCTM/GFP2system provides better signal-to-noise

ratios than the Rluc/coelenterazine h/EYFP system

(Fig 6) [34,40] Interestingly, the intensity of the BRET

signal caused by proximity of Rluc and EGFP was

comparable to that elicited by Rluc and GFP2 in this

system (Figs 6–8) Thus, GFP2 and EGFP are both

suitable acceptor molecules in the BRET2assay The fact

that EGFP, the most widely used GFP variant, can be used as fluorescent acceptor in this BRET2 assay in contrast to the original BRET assay using Rluc/coelen-terazine h [34,40], may hold some practical advantages for future studies of GFP fusion proteins

As the obtained BRET signal patterns using GFP2and EGFP as fluorescent acceptor proteins were similar, GFP will be used as a common reference point in the following sections

Receptor specificity of BRET Numerous observations support that the BRET signals obtained in tsA cells transfected with the Rluc- and GFP-tagged CaRD1036 and CaRD886 were the result of specific protein–protein interactions between the receptors, rather than nonspecific diffusive lateral motion or clustering of overexpressed receptors First, the lifetime of an excited Rluc molecule is in the range of 5 nsec (Packard Bioscience), which limits the contribution of diffusive lateral motion to negligible levels Secondly, CaR-Rluc or CaR-GFP recep-tors expressed alone or together with GFP and Rluc, respectively, did not give rise to any significant signal (Fig 7B,C) Thirdly, CaR-Rluc and CaR-GFP had to be present in the same cell in order to elicit BRET (Fig 7C) Fourthly, the fact that coexpression of CaRD886-Rluc with AT1aD359-GFP2 did not give rise to any BRET further underlines the specificity of the CaR homodimerization process (Fig 7C) However, this does not exclude the possibility that CaR could heterodimerize with other GPCRs, and recently heterodimerization between CaR and mGluRs has been reported [55] Fifthly, the BRET signal in cells transfected with CaRD886-Rluc/CaRD886-GFP was significantly reduced by cotransfection with WT CaR, CaRD1036-V5/His or CaRD886-V5/His (Fig 7D)

We were unable to suppress the BRET signal to the extent previously shown in a study of the thyrotropin-releasing hormone receptor [35] The most likely explanation for the insuppressible fraction of the BRET signal is that the cellular distribution patterns of WT CaR, CaRD1036-V5/ His and CaRD886-V5/His are somewhat different from those of CaRD886-GFP and CaRD886-Rluc Hence, BRET could arise from interactions between intracellular CaRD886-GFP and CaRD886-Rluc proteins in cellular compartments not expressing WT CaR or the V5/His-tagged CaRs

Constitutive homodimerization of CaR This study provides the first evidence of dimerization of CaR or any other family C GPCR in living cells The finding that CaR exists as a homodimer under basal conditions is hardly a surprise The crystal structure of the mGluR1 ATD homodimer has strongly suggested that mGluR1 is constitutively dimerized, and several groups have demonstrated CaR homodimerization using coimmunoprecipitation techniques [20,25,26,56] However, incomplete solubilization of the receptors prior to the coimmunoprecipitation step in these experiments could cause aggregation, which in turn could be misinterpreted as receptor dimer formation Hence, this study supplements the findings from the coimmunoprecipitation studies of CaR dimerization

Fig 8 BRET in tsA cells transfected with Rluc- and EGFP-tagged

receptors The experiments were performed as described in Experimental

Procedures, and the BRET ratio is given as (emission 515 nm )

back-ground 515 nm )/(emission 410 nm ) background 410 nm ) All data shown

are measured under basal conditions (in the absence of agonist) All the

experiments were performed at least three times Data shown is from a

single experiment In the experiments depicted in the two last bars, the

tsA cells were transfected with 0.5 lg CaRD886-Rluc, 0.5 lg

CaRD886-EGFP and 4 lg pSI (vector alone) or CaR-pSI (WT CaR),

respectively, and assayed as described in Experimental Procedures.

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Agonist-induced rearrangement of the 7TMs

in the CaR homodimer?

One of the goals of the present study was to investigate,

whether the activating twist in the ATD dimer of the family

C GPCR homodimer could be detected as agonist-induced

alterations in the BRET signal intensity, reflecting the

7TM)7TM contraction suggested by Kunishima et al [20]

Because CaR is constitutively dimerized, a certain degree of

constitutive agonist-independent BRET was to be expected

For us to be able to record agonist-induced BRET, the Rluc

and the GFP molecules would have to be sufficiently

separated in the resting state of the CaR homodimer

compared to in the activated state

We have not been able to detect agonist-induced BRET

in cells transfected with any of the combinations of

GFP-and Rluc-tagged CaRs (Figs 7 GFP-and 8) The recent

demonstration of agonist-induced BRET for the insulin

receptor, which is also constitutively dimerized, proves the

validity of this technique in studies of conformation

changes in dimeric receptor complexes [57] However, the

intermolecular distances in the CaR homodimer are most

likely quite different from those in the insulin receptor

dimer

One explanation for the lack of agonist-induced BRET

for CaR is that the chromophore/fluorophore of the Rluc

and GFP molecules are positioned so close in the resting

conformation of the homodimer that maximal BRET

intensity already has been achieved In an attempt to

probe other intermolecular distances in the CaR

homo-dimer, we have also studied CaRs with Rluc and GFP

molecules tagged to the intracellular loop 1 (i1) (Jensen,

Hansen, Sheikh and Bra¨uner-Osborne, unpublished data)

However, as these fusion proteins were retained in vesicles

inside of the cells, we were not able to use them in the

BRET studies It would have been interesting to tag Rluc

and GFP molecules to the i2 and i3 of CaR as well

However, as truncations in these regions of CaR have

been demonstrated to reduce the cell surface expression of

the receptor dramatically [58], we have not made these

constructs

An alternate interpretation of the lack of agonist-induced

BRET observed in this study is that the translation of

agonist binding to the ATDs of the family C GPCR

homodimer into G-protein coupling of the 7TM)7TM

moiety is mediated by another mechanism than that

proposed by Kunishima et al [20] A couple of

pharmaco-logical observations support this speculation: the trivalent

cation Gd3+has been show n to activate CaR directly at its

7TM [18], the somatic Ala843fi Glu mutation in TM7 of

CaR causes constitutive activity in the receptor [59], and the

splice variants of mGluR1 and mGluR5 with long carboxy

termini are constitutively active [60,61] All these

pheno-mena originate exclusively from the 7TM of the family C

GPCR and are unlikely to be accompanied by a

conform-ational change in the ATD dimer Furthermore, a recent

study of the GABABreceptor heterodimer has suggested a

model for signal transduction through the family C GPCR,

where the activation signal is translated by a direct

interaction between the ATDs and the 7TMs of the receptor

dimer [62]

In conclusion, this study represents the first

demonstra-tion of family C GPCR dimerizademonstra-tion in living cells We have

demonstrated that CaR is constitutively dimerized How-ever, we have not been able to demonstrate agonist-induced alterations in BRET signal intensities reflecting 7TM dimer rearrangement as a result of the activating twist in the ATDs

of the CaR homodimer Further investigations into the signal transference from the ATDs to the G-protein coupling areas of the receptor homodimer are clearly needed in order to gain a better understanding of the signal transduction through the family C GPCRs From a technical perspective, we have demonstrated that interac-tions between Rluc- and GFP2/EGFP-tagged proteins can

be recorded using DeepBlueCTM as the substrate The BRET2assay appears to have a higher signal-to-noise ratio than previously reported BRET assays and may represent a small step forward in the study of protein–protein interactions

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

Søren G F Rasmussen and Professor Ulrik Gether are thanked for the use of the SPEX Fluoromax-2 spectrofluorometer, and Birger Brodin for technical assistance with the single cell fluorescence measurements Mette B Hermit is thanked for developing the protocol used for the immunofluorescence experiments.

This work was supported by grants from the Danish Medical Research Council and the Novo Nordisk Foundation (AAJ, JLH, SPS and HBO), by the Lundbeck Foundation (AAJ) and by the Danish Heart Foundation no 01-1-2-22–22895 and no 00-2-2–24 A-22838, the Villadsen Family Foundation, the Birthe and John Meyer Foundation, and the Foundation of 17.12.1981 (JLH and SPS).

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9 Bra¨uner-Osborne, H & Krogsgaard-Larsen, P (2000) Sequence and expression pattern of a novel human orphan G-protein-cou-pled receptor, GPRC5B, a family C receptor with a short amino-terminal domain Genomics 65, 121–128.

10 Robbins, M.J., Michalovich, D., Hill, J., Calver, A.R., Medhurst, A.D., Gloger, I., Sims, M., Middlemiss, D.N & Pangalos, M.N (2000) Molecular cloning and characterization of two novel retinoic acid-inducible orphan G-protein-coupled receptors (GPRC5B and GPRC5C) Genomics 67, 8–18.

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