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However, at least in part because expression of a single GPCR cDNA in heterologous cell systems generally resulted in production of a ligand-binding site with the expected pharmacology a

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Methods to monitor the quaternary structure of

G protein-coupled receptors

Graeme Milligan1and Michel Bouvier2

1 Molecular Pharmacology Group, Division of Biochemistry and Molecular Biology, Institute of Biomedical and Life Sciences,

University of Glasgow, UK

2 Biochemistry, Universite de Montreal, Quebec, Canada

Introduction

In recent times, the view that G protein-coupled

recep-tors (GPCRs) are single polypeptides that function as

isolated monomers has been challenged, and largely

supplanted, by results consistent with the existence of

GPCRs as dimers or higher-order oligomers Data in

support of GPCRs being able to form dimers or

oligo-mers had been scattered throughout the literature [1]

However, at least in part because expression of a single

GPCR cDNA in heterologous cell systems generally

resulted in production of a ligand-binding site with the

expected pharmacology and the capacity to activate

G proteins and hence initiate signal transduction, little

thought was given to potential quaternary structure

This is despite the fact that dimerization of proteins,

as a route to function, is one of the most common

themes in biology [2] This had been well established

previously for other classes of transmembrane recep-tors Key to a broad appreciation of the potential of dimerization for GPCR function was the demonstra-tion that the c-aminobutyric acid (GABA)B-receptor, long recognized as a GPCR, was an obligate hetero-dimer [3,4] Even though the GABABR1 polypeptide

is a seven transmembrane protein able to bind both GABA and a GABAB receptor antagonist [5], when expressed alone this polypeptide is not transported to the cell surface, does not have the expected characteris-tics and affinity for binding of agonists and cannot activate G protein signalling Cell surface delivery and function requires the coexpression of a second, closely related seven transmembrane polypeptide, the GABABR2, which although unable to bind GABAB receptor ligands, allows cell surface delivery of the GABABR1 The heterodimeric complex then functions with pharmacology akin to the native receptor

Subse-Keywords

dimerization; functional reconstitution;

G protein coupled receptor;

immuno-precipitation; resonance energy transfer

Correspondence

G Milligan, Davidson Building, University of

Glasgow, Glasgow, G12 8QQ Scotland, UK

Fax: +44 141330 4620

Tel: +44 141330 5557

E-mail: g.milligan@bio.gla.ac.uk

(Received 16 February 2005, accepted

4 April 2005)

doi:10.1111/j.1742-4658.2005.04731.x

A wide range of approaches has been applied to examine the quaternary structure of G protein-coupled receptors, the basis of such protein–protein interactions and how such interactions might modulate the pharmacology and function of these receptors These include coimmunoprecipitation, var-ious adaptations of resonance energy transfer techniques, functional com-plementation studies and the analysis of ligand-binding data Each of the available techniques has limitations that restrict interpretation of the data However, taken together, they provide a coherent body of evidence indica-ting that many, if not all, G protein-coupled receptors exist and function

as dimer⁄ oligomers Herein we assess the widely applied techniques and discuss the relative benefits and limitations of these approaches

Abbreviations

BRET, bioluminescence resonance energy transfer; DOP, delta opioid peptide; eYFP, enhanced yellow fluorescent protein; FRET,

fluorescence resonance energy transfer; GPCRs, G protein-coupled receptors; G(C,Y)FP, green (cyan, yellow) fluorescent protein;

NEM, N-ethyl maleimide.

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quently, it has become clear that sweet and umami

taste responses are also generated by obligate

hetero-dimer pairs of T1 taste receptors [6] and both

homo-and heterodimerization of other family C receptors is

firmly established This topic is covered in the

accom-panying review by Pin and colleagues [7] Analysis of

the importance of quaternary structure for function of

the rhodopsin-like family A GPCRs has been more

recalcitrant to analysis, as examples of obligate

hetero-dimerization akin to the GABAB receptor have not

been noted, although there are reports, for example, of

the requirement for heterodimeric interactions to allow

cell surface delivery of certain a1-adrenoceptor

sub-types [8] and olfactory receptors [9] Nevertheless, it is

now generally accepted that family A GPCRs can exist

as dimers and⁄ or higher order oligomers [10–12] A

growing database on the formation of GPCR dimers

prior to membrane delivery [13–15] and the potential

that GPCRs can bind to single heterotrimeric G

pro-teins as dimers [16] is certainly consistent with such

a receptor dimer model However, the importance of

dimerization for receptor function and regulation in

physiological systems remains to be demonstrated

unambiguously A significant number of recent reviews

have covered these topics [11,12,17] and the purpose of

the current piece is to critically evaluate the

approa-ches used to explore dimerization of class A GPCRs

Coimmunoprecipitation

The ability to differentially epitope-tag GPCRs has

been central to the widespread use of

coimmunoprecipi-tation following coexpression of two forms of the same

GPCR in heterologous expression systems Initially

Hebert et al [18] coexpressed c-myc- and HA-tagged

forms of the b2-adrenoceptor in insect Sf9 cells and

demonstrated interaction between the two forms of the

receptor as both were present in immunoprecipitates

generated using either anti-HA or anti-c-myc Igs These

studies also provided a series of key controls (a) in a

lack of cross-reaction between the antibodies and the

alternately tagged form of the receptor and (b) in a lack

of coimmunoprecipitation of the HA-tagged b2

-adreno-ceptor when coexpressed with a c-myc-tagged form of

the M2muscarinic acetylcholine receptor These studies

also noted the resistance to monomerization during

SDS⁄ PAGE of at least a proportion of the

coimmuno-precipitated receptors; this is a commonly observed

feature in many such studies Despite such apparent

receptor dimerization (and indeed multimerization)

being detected following SDS⁄ PAGE resolution of

simple membrane preparations of transfected cells and

even native tissues [19], detection of SDS-resistant

higher-order structures was reminiscent of protein aggregation, a well-appreciated potential artefact resulting from membrane protein solubilization There-fore, the hydrophobicity of the transmembrane domains of GPCRs raised concerns that apparent coimmunoprecipitation might reflect little more than nonspecific aggregation following detergent extraction

of proteins from cells and membranes This resulted in widespread incorporation of mixed samples into co-immunoprecipitation studies to counter this concern

In such experiments detergent extracts of cells or membranes, each expressing only one of the tagged GPCRs, are combined prior to the immunoprecipitation step This is generally considered a sound means to elim-inate nonspecific aggregation as a potential explanation

of spurious coimmunoprecipitation (Fig 1)

Coimmunoprecipitation has been of particular use in efforts to identify heterodimeric interactions between GPCRs [20] However, coimmunoprecipitation studies such as that of Salim et al [21] intimated widespread interactions between coexpressed GPCRs and, assu-ming that interaction between different GPCRs is not

a purely stochastic process, raised further questions about the use of coimmunoprecipitation in the absence

of further supporting evidence of protein–protein

inter-Fig 1 Differentially epitope-tagged forms of the a1b-adrenoceptor have to be coexpressed to be coimmunoprecipitated N-terminally Flag- or c-myc-tagged forms of the hamster a 1b -adrenoceptor were expressed individually (flag, myc) or coexpressed (flag + myc) in HEK293 cells Samples expressing each form of the receptor were also mixed (mix) Lysates of cells were resolved by SDS ⁄ PAGE and immunoblotted to detect expression of each form, or the samples were immunoprecipitated using anti-Flag Ig, resolved by SDS ⁄ PAGE and then immunoblotted to detect c-myc immunoreactivity Coimmunoprecipitation was only observed from samples co-expressing the two forms Data are modified from [35].

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actions A key issue that remains overlooked in many

published coimmunoprecipitation studies is whether

the samples are fully solubilized prior to the

immuno-precipitation step In many studies, centrifugation after

detergent extraction is limited to a short period in a

bench top microcentrifuge, with force in the region of

15 000 g This is far too limited to ensure production

of a fully soluble fraction and it is suggested that, as

in many other protocols, centrifugation should be for

at least 60 min and > 100 000 g As an alternative,

passage of the detergent-generated extract through a

0.22 lm filter would ensure removal of membrane

frag-ments that might contain both coexpressed forms of a

GPCR that are not actually physically in contact The

addition of alkylating agents such as NEM and

iodo-acetamide in the lysis and solubilization buffers is also

recommended in order to prevent the formation of

spurious intermolecular disulfide bonds that could be

favoured by the oxidizing condition associated with

cell lysis Notwithstanding these caveats, there is no

doubt that coimmunoprecipitation remains as the

starting point and, indeed at the heart, of many GPCR

dimerization studies Indeed, despite the general

pau-city of specific and high affinity anti-GPCR sera,

care-fully controlled coimmunoprecipitation studies remain

the most practical means to explore, in particular,

GPCR heterodimerization in native tissues and can

provide key information to support GPCR

dimeriza-tion⁄ oligomerization

Coimmunoprecipitation of GPCRs, subsequent to

cross-linking with cell-impermeant cross-linking agents

has also provided a useful means to detect GPCR

dimers⁄ oligomers in the plasma membrane The

intro-duction of cysteine residues into specific locations in

transmembrane domains of class A GPCRs, that then

allow cross-linking by bi-functional reagents, is an

extension of the basic cross-linking and

immunopre-cipitation strategy but has the added advantage of

assisting identification of potential protein–protein

interaction sites in GPCR dimers [22,23] and

determin-ing whether ligand-binddetermin-ing modulates the

organiza-tional structure of a GPCR dimer⁄ oligomer Although

the concept of coimmunoprecipitation can be extended

easily to studies that employ cotransfection with three

or more forms of the same GPCR, each incorporating

a different tag, this has only been employed to date in

a limited manner In one such example, where c-myc-,

FLAG- and HA-tagged forms of the M2 muscarinic

receptor were coexpressed in insect Sf9 cells, Park and

Wells [24] were able to immunoprecipitate complexes

containing all three epitope tags, hence providing

evidence for complexes containing at least three GPCR

monomers

Resonance energy transfer studies Fluorescence resonance energy transfer The green fluorescent protein (GFP) from Victoria aequoria has found widespread use in cell biology to monitor the expression and distribution of proteins tagged with this polypeptide Mutation of this protein has produced a range of variants with altered spectral characteristics, and pairs of these are able to function

as fluorescence resonance energy transfer (FRET) part-ners The most widely used pairing is a cyan fluores-cent protein (CFP) as energy donor and a yellow fluorescent protein (YFP) as an energy acceptor, but other pairings are also practical Obvious attractions in the use of FRET for studies of GPCR dimerization⁄ oligomerization include the capacity to monitor pro-tein–protein interactions in intact living cells both in cell populations and single cells It can be combined with cell imaging and photo-bleaching protocols to examine the cellular location of such interactions in specific subcellular compartments [25–27] Photo-bleaching of the energy acceptor construct also provides an important control to demonstrate that FRET-signals actually reflect energy transfer Photo-bleaching of the acceptor should result in increased fluorescence output from the energy donor as well as destruction of signal from the acceptor as no energy transfer can then occur This is a particularly import-ant control as direct excitation of the energy acceptor

by the exogenous light source in sensitization FRET experiments can generate background signals that can

be mistakenly interpreted as real FRET Also, the spectral overlap between the donor and acceptor emis-sion spectra needs to be properly monitored and con-trolled to determine the legitimate FRET signal These are not trivial issues as the contribution of the back-ground signals can vary considerably depending on the relative expression levels of the FRET partners and the band pass width of the fluorescence excitation and emis-sion detection systems

Although some wild-type GFPs have the tendency

to oligomerize, a characteristic that could promote artefactual oligomerization of the proteins attached to them, variants such as CFP and YFP that have lower affinity for one another, have been used successfully to monitor the quaternary structure of several GPCRs FRET between CFP and YFP covalently fused to dis-tinct GPCRs should occur only when the FRET part-ners are brought within 100 A of each other; a distance that falls within the dimensions anticipated for GPCR dimers⁄ oligomers [28] The occurrence of FRET between CFP- and YFP-fused GPCRs has

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therefore been interpreted as strong evidence for the

existence of dimers or oligomers in living cells As with

all approaches based on Fo¨rsters’ principles of

reson-ance energy transfer, the efficiency of transfer is

deter-mined both by the orientation of the energy transfer

partners and by the distance between them [28] The

fact that the efficiency of transfer varies with the

6th-power of the distance between the fluorophores

presents both opportunities and limitations for the

analysis of data (Fig 2) For instance, although the

FRET assays can be extremely sensitive detectors of

conformational changes that can reflect ligand-promoted

alteration in GPCR quaternary structure, the extent of

the D FRET observed for a given change is highly

dependent on the initial distance between the energy

donor and acceptor For example, if constitutive

dime-rization of two GPCR FRET-tagged constructs brings

the energy transfer partners into very close proximity,

the energy transfer efficiency should be close to

maxi-mal and thus, a ligand-induced alteration in distance

between the energy-transfer partners would be poorly

reported (Fig 2) In contrast, if the initial distance

between energy donor and acceptor is within the

region of the FRET R0 (i.e.: the distance between the

donor and acceptor leading to 50% of the maximal

transfer efficiency) where the Denergy transfer ⁄

Ddis-tance is maximal, the same conformational change

would lead to largeDFRET (Fig 2) A range of

fluor-escence-based techniques, including intra- and

inter-molecular FRET, have been used to demonstrate conformational changes in GPCR monomers upon agonist binding [29,30] and recent studies have expan-ded this to show that an agonist bound protomer of the leukotriene B4, BLT1 receptor produces a confir-mation change in the partner GPCR of the homodimer [31] It follows that reports of agonist-induced altera-tions in GPCR quaternary structure based only on res-onance energy transfer studies may simply reflect very small conformational alterations in the GPCR that are amplified by the high sensitivity of the resonance energy transfer responses to distance and orientation [32] (Fig 2) Thus, a large increase or decrease in FRET values observed upon ligand-binding cannot be interpreted, as is too often the case, as an indication of ligand-promoted dimer formation or dissociation The occurrence of FRET between fluorophore-tagged GPCRs could result both from the formation

of dimers or of higher oligomeric structures Unfortu-nately, the currently available FRET techniques do not permit one to distinguish easily between these two possibilities However, recent studies employing atomic force microscopy to visualize the organizational struc-ture of rhodopsin in murine rod outer segment discs have shown higher order arrays of GPCRs [33,34] and analysis of the results of GPCR transmembrane inter-face mapping for both the complement C5a receptor [23] and the a1b-adrenoceptor [35] have suggested ways

in which these GPCRs may organize into higher order structures Although not yet reported in relation to GPCR quaternary structure, three component FRET systems based on serial energy transfer from cyan to yellow to red fluorescent proteins are available [36] These and related systems may be invaluable to explore the potential of higher-order GPCR oligomeri-zation They are, however, likely to suffer from low sensitivity and thus, at least in the short term, the need

to express rather high levels of each component may raise concerns in relation to the specificity of inter-actions observed

Quantitation of the fraction of a GPCR existing as monomer vs dimer or higher-order oligomer remains

a challenging task Efforts to assess this for homo-dimers of neuropeptide Y receptor subtypes were based on FRET efficiency of appropriately tagged GPCRs compared to the FRET signal produced by a positive control generated by fusing together the two FRET partner fluorescent proteins [37] A similar attempt was made for the b2-adrenoceptor homodimer using another resonance energy transfer approach known as bioluminescence resonance energy transfer (BRET, see below) and using theoretical maximal transfer values as the 100% dimer reference [38]

How-Fig 2 Variation in resonance energy transfer efficiency as a

func-tion of distance between energy donor and acceptor Relafunc-tionship

between the energy transfer efficiency (Y-axis) and the distance

between the energy donor and acceptor (X-axis) The distance is

expressed as the ratio of the distance ‘r’ separating the donor and

the acceptor over the distance resulting in 50% of the maximal

efficacy (R0) As indicated by the Fo¨rster equation, the efficiency of

transfer varies inversely with the 6th-power of the distance The

extreme steepness of the relationship results in large changes in

RET for relatively small modifications in distance around the R0 In

contrast, large changes in the distance may not result in any RET

change when the distance is much smaller than the R 0

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ever, the values obtained, which were in the region of

20–40% as dimers for the first study and greater than

85% in the dimeric form for the latter, required a

range of assumptions, including the fact that the

recep-tors existed as dimers and not larger oligomers

There-fore, such estimates must be viewed as extremely

uncertain and require further experimental

confirma-tion As indicated above, pictures of the structural

organization of rhodopsin in the disks from rod outer

segments from mice suggest a much higher level of

dimerization⁄ oligomerization [33] However, the high

concentration of rhodopsin in rods may impose order

and structural organization that is not required for

other class A GPCRs Attempts to explore this by

employing discs from heterozygote rhodopsin

knock-out mice simply resulted in rod knock-outer segments with

reduced volume rather than an alteration in the pattern

of interactions between rhodopsin monomers [34]

Time-resolved FRET

The capacity to image FRET signals in single cells and

in specific cellular compartments, including the plasma

membrane, provides a means to confirm interactions

between GPCR monomers at the surface of individual

cells [25–27] A distinct FRET-based approach to

mon-itor interactions between GPCRs at the cell surface in

cell populations is based on time-resolved FRET using

anti-epitope tag Igs labelled with suitable FRET

accep-tor and donors [39] N-terminally epitope-tagged forms

of GPCRs should only be accessible to such antibodies

in intact cells if they have been delivered successfully

and inserted into the plasma membrane The use of

antibodies labelled with Europium chelates as energy

donor allows the use of ‘time-resolved’ protocols,

where short-lived fluorescence (up to some 50 ls)

derived from excitation of endogenous fluorophores is

allowed to decay before the long lived time-resolved

FRET signal is monitored over the ensuing 100–

200 ls This generates improved signal-to-noise ratios

Although employed in a limited number of studies to

date [40–43], limiting signals to GPCRs at the cell

sur-face using this approach has particular advantages for

analysis of GPCRs expressed in heterologous systems

where a significant fraction of the expressed GPCR(s)

can often be shown to be inside the cell, presumably

within the endoplasmic reticulum or as protein that

has failed to pass cellular quality control mechanisms

and is destined for degradation Time-resolved FRET

pairings have also been used in membrane fractions

generated by sucrose density sedimentation to detect

dimers⁄ oligomers of a1a-adrenoceptors in all

mem-brane fractions containing this GPCR as measured by

[3H]antagonist binding studies [43] As this receptor displays a high level of constitutive, agonist-independ-ent internalization and recycling [44,45], the FRET data are certainly consistent with at least a fraction of the population of this receptor existing as a dimer⁄ oligomer at all stages in its life history The major potential caveats for time-resolved FRET studies relates to the obligatory use of antibodies Appropriate controls need to be performed to make sure that oligo-merization of the partners is not promoted by the bivalent nature of the antibodies In studies assessing the effect of ligand-binding on the quaternary structure

of the receptors, the possibility that the antibodies could inhibit binding to the receptor also needs to

be controlled Finally, the presence of an antibody between the fluorophores and the proteins of interest, increases the uncertainty concerning the minimum and maximum FRET permissive distance

Bioluminescence resonance energy transfer Conceptually similar to FRET, except that energy is donated to a fluorescent protein energy acceptor by luciferase-mediated oxidation of a substrate, biolumi-nescence resonance energy transfer (BRET) has become almost as popular an approach as FRET The various benefits of BRET compared to FRET, partic-ularly the lack of requirement of a light source to excite the energy donor, have been discussed previ-ously in more specialized articles [28] In particular, we should note that the lack of potential direct excitation

of the energy acceptor that can occur in FRET experi-ments (see above) greatly simplifies controlling for the background signals However, a clear limitation of BRET is that currently it is not sufficiently sensitive to allow high resolution, single cell imaging and analysis and therefore cannot usefully report on the subcellular location of the signal Although single cell BRET signals resulting from the homodimerization of the

b2-adrenoceptor and melatonin MT1 and MT2 homodimers could be detected [32], obtaining subcellu-lar resolution will require the development of more sensitive cameras or of luminescence donors with higher light output In initial BRET studies, the energy transfer pairing was Renilla luciferase and enhanced YFP (eYFP) with h-coelenterazine acting as luciferase substrate However, the overlap between the spectrum generated via this enzymic activity of luciferase and the emission of light from eYFP subsequent to energy transfer is substantial, resulting in a relat-ively high background signal that needs to be carefully controlled As a means to improve this, the Renilla luciferase substrate DeepBlueC, which results in

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emis-sion of light that is substantially blue-shifted in

com-parison to the oxidation of h-coelenterazine, has been

used The wavelength of the light emitted by the

oxida-tion of DeepBlueC is not well aligned for energy

trans-fer to eYFP but is suited for energy transtrans-fer to the

modified fluorescent protein GFP2 and the output

from GFP2 is relatively well resolved from the Renilla

luciferase⁄ DeepBlueC oxidation spectrum [46] (Fig 3)

This results in improved signal-to-noise ratios when

employing BRET2 The major limitation of BRET2 is

the poor quantum efficiency associated with oxidation

of DeepBlueC resulting in much lower absolute signals

that thus necessitates higher GPCR expression levels

With both their limitations and advantages, BRET1 or

BRET2 can be best suited to study specific proteins of

interest Taking advantage of the distinct spectral

char-acteristics of the two BRET generations in the same

experiment, Perroy et al [47] were able to monitor the

interaction between three partners simultaneously in

the same cell population Such combinations between

different types of resonance energy transfer will cer-tainly be increasingly used to examine the stoichio-metry of GPCR complexes

Following the initial report employing BRET that examined interactions between Renilla luciferase- and eYFP-tagged forms of the b2-adrenoceptor [48], BRET has been used, to date, predominantly in ‘single point’ assays In these, single amounts of Renilla luciferase and fluorescent protein-tagged forms of a single GPCR, to study homodimerization⁄ oligomerization, or pairs of GPCRs, to study potential heterodimeriza-tion⁄ oligomerization are cotransfected into host cells However, as with coimmunoprecipitation and FRET studies, the intensity of the signal obtained does not provide a measure of absolute, or even relative, inter-action affinities between the GPCRs linked to the BRET partners, because the extent of BRET signal is dependent upon both distance between the energy donor and acceptor and their orientation The most significant advance in this area since then has been the introduction of ‘saturation’ BRET by Mercier and colleagues [38] Taking advantage of the possibility of expressing differing amounts of energy donor and acceptor-linked GPCRs in heterologous cells, these studies demonstrated that an asymptotic approach to

a maximal BRET signal was obtained with increasing energy acceptor⁄ energy donor ratios Saturation curves

so generated resemble ligand⁄ GPCR binding curves and, as such, the ratio of energy acceptor⁄ energy donor that generates half-maximal BRET signal can provide a useful measure of the relative interaction affinities of the GPCRs linked to the BRET reagents For example, although measurable BRET signals can be recorded following coexpression of a DOP opioid receptor-Renilla luciferase⁄ a1A -adrenoceptor-GFP2 BRET pair in HEK293 cells that is commensur-ate with the signals obtained for each of these two GPCR homodimers, saturation BRET studies indica-ted that the interaction affinity of this heterodimer⁄ oligomer pairing was some 75-fold lower than for the

a1A-adrenoceptor homodimer⁄ oligomer [43] This sug-gests that such a heteromeric pairing would be unlikely

to have physiological significance, even if interactions can be monitored in heterologous expression systems Although it was noted in early studies that hetero-dimeric interactions between structurally homologous receptors were of higher affinity than interactions between more distantly related class A GPCRs [46] it

is not inevitable that homodimer interactions will be of higher affinity than heterodimeric interactions Indeed,

in the studies of Ramsay et al [46] hetero interactions between the closely related KOP and DOP opioid receptors were reported to be at least as high affinity

Fig 3 Spectral properties of the energy donor and acceptor for the

two generations of BRET Schematic representation of the

emis-sion spectra for Renilla luciferase (Rluc) using coelenterazine H

(BRET 1 ) or DeepBlue Coelenterazine (BRET 2 ) as substrates and of

the overlap between the emission spectrum of Rluc and the

excita-tion spectrum of the fluorescent energy acceptors YFP for BRET 1

and GFP 2 for BRET 2 The overlap is more complete for BRET 2 than

BRET1favouring a better transfer Also shown are the emission

spectra of GFP 2 and YFP A better separation from the RLuc

emis-sion is obtained with GFP 2 in BRET 2 leading to a better

signal-to-noise ratio Not shown on this figure is the fact that the output

of light is much smaller for DeepBlue Coelenterazine than for

coelenterazine H leading to a lower detection sensitivity for BRET 2

than BRET1[46].

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as KOP receptor homo interactions More recent

studies are also consistent with melatonin MT1⁄ MT2

heterodimers being generated with higher affinity than

MT2 receptor homodimers [49] Such saturation BRET

studies have also been combined with deliberate

varia-tion in expression levels to demonstrate that potential

artefacts arising from physical crowding of GPCRs

and the production of so called ‘bystander’ BRET

(Fig 4) that does not reflect quaternary structure

inter-actions, is only produced with levels of expression in

the region of 25 pmolÆmg)1membrane protein [38] and

thus well beyond the range of expression normally

used in such studies

In the available reports employing saturation BRET, the energy acceptor⁄ energy donor ratio is generally reported simply as a fluorescence : luminescence ratio However, when well validated GPCR radioligands are available, attempts have been made to generate stand-ard curves of GPCR ligand-binding site number against fluorescence or luminescence signals to allow absolute quantitatation of energy acceptor⁄ energy donor ratio [38,43] Although luminescence and fluor-escence signals increase in a linear fashion with ligand-binding site number, surprisingly, the signal per GPCR binding site has not been equal for different GPCRs [38,43] It is not currently possible to establish the

A

B

Fig 4 BRET 2 levels as a function of energy donor and acceptor concentrations (A) BRET2saturation performed in cells coex-pressing a constant level of a GPCR fused

to the energy donor Rluc and increasing concentration of a GPCR fused to the energy acceptor GFP 2 The BRET levels are plotted as a function of the GPCR– GFP : GPCR–Rluc ratio In the case of speci-fic dimerization between the two GPCRs, a classical hyperbolic increase in the BRET signal that rapidly saturates is observed BRET 50 represents the GPCR–

GFP : GPCR–Rluc ratio leading to 50% of the maximal BRET and reflects the relative affinity of the BRET partners for one another In the case of random collisions between the BRET partners, bystander BRET leads to a quasi-linear relationship that will eventually saturate only at very high GPCR-GFP ⁄ GPCR-Rluc ratios (B) BRET 2

measurements performed in cells expres-sing increaexpres-sing concentrations of GPCR– Rluc and GPCR–GFP 2 while maintaining a constant GPCR–GFP 2 : GPCR–Rluc ratio of

1 In the case of specific GPCR dimers,

BRET levels are constant for a wide range

of total concentration since a constant pro-portion of GPCR–GFP2are engaged by a GPCR–Rluc In the case of random collisions between the BRET partners, the bystander BRET should increase as a function of the total receptor concentration for the entire range The increase in BRET observed for very high receptor expression levels > 45 pmolÆmg)1of protein most likely results from random collisions between GPCR dimers Adapted from [38].

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basis for this but it seems surprising that the enzyme

activity of Renilla luciferase or, even more so, the

fluorescence of variants of GFP should vary markedly

depending on which GPCR they are linked to A

poss-ible explanation would be that the difference in folding

rates between the GFP fluorophore (or luciferase

cata-lytic site) and the binding sites of specific GPCRs

varies from one receptor to another It follows that the

amount of properly folded binding site⁄ folded

fluoro-phore would be an intrinsic property of the individual

GPCR-fusion construct Alternatively, it is certainly

the case that different, but individually well studied,

ligands can generate different Bmaxvalues for the same

GPCR in the same membrane preparation [50] and

thus that the proportion of receptor molecule recognized

by the radioligand may differ for different receptors

Functional complementation

If the coexpression of two nonequivalent and

nonfunc-tional mutants of a GPCR is both able and required

to reconstitute receptor ligand-binding and⁄ or

func-tion, this can provide evidence in favour of direct

pro-tein–protein interactions and quaternary structure for

the active receptor Indeed, coexpression of two forms

of the angiotensin AT1 receptor that were unable to

bind angiotensin II or related ligands due to point

mutations in either transmembrane III or

transmem-brane region V restored ligand-binding [51] Such an

approach has also been used to explore mechanisms of

dimerization Theoretical models of GPCR

dimeriza-tion include both ‘contact’ and ‘domain-swap’ dimers

[52] Class A GPCRs can, at least to some degree,

re-assemble from coexpressed fragments The most

widely used strategy in this regard has been to split

GPCR sequences in two by cleavage within the third

intracellular loop Such experiments have resulted in

the N-terminus and transmembrane regions I–V and

transmembrane regions VI–VII and the C-terminal tail

being considered as units that are able to fold

inde-pendently (reference [53] in this series of reviews)

Indeed, generation of chimeric GPCRs based on this

general strategy provided some of the most elegant

early data in favour of molecular cross-talk between

GPCRs [54] Using the histamine H1 receptor as a

model, Bakker et al [41] showed that although single

point mutations in both transmembrane region III and

transmembrane region VI prevented binding of

antag-onist radioligands (including [3H]mepyramine),

coex-pression of the two mutants resulted in reconstitution

of [3H]mepyramine binding sites with the anticipated

pharmacological characteristics Conceptually this

should not be possible for a contact dimer in which

transmembrane domains are not exchanged but simply appose each other Although these studies provided support for domain swapping in the histamine H1 receptor, the Bmax obtained for [3H]mepyramine in the coexpression studies was only a small fraction of that obtained when the wild-type histamine H1 receptor was expressed [41] This may reflect that domain-swap and contact dimers are not mutually exclusive but can coexist, although domain-swapping may be energetic-ally less favourable The energetics of domain-swap-ping for a src homology 3 domain protein has been discussed recently [55] Domain-swapping may also contribute to GPCR heterodimerization and would be expected, almost as a matter of course, to alter the details of ligand pharmacology This is yet to be explored in significant detail but it is certainly true that, for example, coexpression of pairs of opioid receptor subtypes has been reported to result in the generation of novel pharmacology of ligand-binding and function [56,57] and this is also noted for other GPCR pairs [58] Although these changes could be explained by allosteric interactions between the pro-tomers of a contact dimer they could reflect domain-swap dimer interactions

In addition to the restoration of ligand-binding, studies that have used pairs of nonfunctional mutants

to restore GPCR signalling have produced data consis-tent with GPCR–GPCR interactions By generating mutants of the luteinizing hormone receptor that were either unable to bind ligand or unable to signal, although able to bind the agonist, Lee et al [59] were able to reconstitute agonist-mediated regulation of cAMP levels following coexpression of the two mutants The luteinizing hormone receptor, as with other GPCRs with related ligands, has an extended N-terminal region involved in ligand-binding As such, Lee et al [59] were able to consider the N-terminal exodomain and the seven transmembrane element endodomain as distinct entities in a manner equivalent

to the extracellular and transmembrane elements of class C GPCRs that have allowed elegant chimeric receptor approaches to understand the mechanism of signal transduction through obligate hetero-dimers [7] Interestingly, the pairs of complementary mutants des-cribed above have allowed demonstration of signal transduction through both transmembrane bundles when such mutant receptors do interact, supporting the notion of transactivation within receptor dimers [60] As a modification of the idea of pairs of exo- and endodomains in a single GPCR, Carrillo et al [61] extended the use of GPCR-G protein fusion proteins [62] to study both homo- and hetero dimerization of GPCRs Mutations were introduced to generate pairs

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with potential complementary function One of the

pairs had a mutation in the GPCR element of the

fusion that allowed ligand-binding but not G protein

activation, whereas the second fusion had a mutation

in the G protein element that prevented

agonist-media-ted guanine nucleotide exchange Although both were

nonfunctional when expressed individually,

coexpres-sion resulted in reconstitution of agonist-mediated

binding of [35S]GTPcS As [3H]antagonist binding was

unaltered by the mutations, then assays were

per-formed in conditions in which the total number of

GPCR-G protein fusion polypeptides were known and

this allowed estimates of the fraction of the constructs

that produced functional dimers [61] Intermolecular

interactions between the fusion proteins were

respon-sible for the generation of activity, rather than

activa-tion of endogenously expressed G proteins, as similar

results were produced when the pairs of constructs

were expressed in mouse embryo fibroblasts lacking

expression of the appropriate G proteins [61] One

potential caveat to this approach has been provided by

the work of Molinari et al [63] who used a similar

strategy to explore functions of fusions between the

DOP opioid receptor and Gao These workers reported

that the reconstitution of function might simply reflect

the higher concentration of G protein provided in the

membranes by the 1 : 1 GPCR : G protein

stoichio-metry of the fusion proteins allowing the G protein

fused to one receptor to interact with the G protein of

another receptor-G protein fusion that may or may

not be part of the same oligomer This is certainly an

important issue to consider and control However,

Carrillo et al [61] showed that providing extra,

non-GPCR-linked, G protein through attachment to a

truncated GPCR did not permit interaction with the

full length fusion proteins, ruling out the possibility that

the functional recovery resulted from membrane

crowd-ing and random collisions between fusion proteins

Ligand-binding studies

Classic monophasic ligand-binding isotherms as

gen-erally observed for the binding of antagonists is

con-sistent with the ligand-binding to a single class of

noninteracting sites As such, cooperative

characteris-tics of the binding of a antagonist is not compatible

with such a model and may be used to infer

pro-tein–protein interactions between GPCR monomers

This model has been most actively explored for the

M2 muscarinic acetylcholine receptor At least in

cer-tain conditions different 3H-labelled antagonists at

this GPCR display significantly different Bmax values

[64] Assuming that such effects do not reflect trivial

issues such as incorrect measurements of the specific activities of the two ligands, or the binding studies being performed under nonequilibrium conditions, such results are not compatible with the concept of

a single population of noninteracting sites Mathe-matical analysis of this data has been interpreted to suggest that the M2 muscarinic acetylcholine receptor may exist as at least a tetramer and that ligands can bind to the receptor sites in a cooperative manner [64] Related approaches have also been applied to the dop-amine D2receptor expressed in CHO cells Here, when

Na+was eliminated from binding studies, the observed

Bmax for [3H]raclopride was markedly lower than for [3H]spiperone, although this was not observed in the presence of Na+[50] Equally, in the absence of Na+, raclopride appeared to display negative cooperativity

on both its own binding and that of [3H]spiperone These results were modelled based on a GPCR dimer Although of considerable interest, these results may reflect altered interactions with other receptor partners such as the G proteins rather than the existence of dimerization This is particularly important considering that compounds considered as antagonists may display distinct inverse efficacy in the presence or absence of

Na+[65] and that ligand-binding studies using radiola-belled inverse agonists may lead to a different apparent

Bmax as a function of the spontaneous interaction with

G proteins [66] Despite this caveat, as long as they are performed in detail with appropriate controls, such ligand-binding studies offer means to examine GPCR protein–protein interactions in native tissues and with-out the need to manipulate the sequence of GPCRs to add tags required for detection in other types of assays

Conclusions The range of approaches that have been applied to assess the quaternary structure of class A GPCRs is both large and diverse Use of these techniques has led

to a general appreciation that GPCRs can certainly exist as dimers and⁄ or higher order oligomers and that such interactions may be central to delivery of cer-tainly some GPCRs to the cell surface and to their function However, given the nature of each of the widely used approaches it is still possible that observed interactions require the intermediacy and participation

of GPCR-interacting accessory or scaffolding proteins Indeed a very recent study [67] has suggested that MOP and DOP opioid receptor heterodimerization may require G protein interactions It is important that a significant range of different approaches is used

to explore such topics for any particular GPCR,

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because none of those currently in widespread use are

entirely convincing in isolation Key questions that

require further technical advances include the

propor-tion of any specific GPCR that is present as a

mono-mer⁄ dimer ⁄ oligomer and the significance of this for

function Equally, although methods are being

devel-oped and used to explore the relative affinities of

inter-actions between different GPCRs, an issue that is of

particular importance to the likely relevance of

poten-tial GPCR heterodimers in physiology, these are not in

widespread use at this time Also further

documenta-tion of the existence of distinct pharmacology and

functions for GPCR heterodimers should certainly lead

to the development of ligands with selective affinity

and function for such heterodimer pairings and thus

provide ultimate tools to probe the role of

heterodime-rization in vivo

Acknowledgements

Studies on GPCR dimerization in the Milligan and

Bouvier labs are supported by the Biotechnology and

Biosciences Research Council, the Medical Research

Council and the Wellcome Trust to Graeme Milligan

and the Canadian Institute for Health Research and

the Heart and Stroke Foundation of Canada to Michel

Bouvier M Bouvier holds the Canada Research Chair

in Signal Transduction and Molecular Pharmacology

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