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Báo cáo khoa học: Expression and characterization of soluble forms of the extracellular domains of the b, c and e subunits of the human muscle acetylcholine receptor pot

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Our aim was to obtain satisfactory amounts of the ECDs of the non-a sub-units of human muscle AChR for use as starting material for the determin-ation of the 3D structure of the receptor

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extracellular domains of the b, c and e subunits of the

human muscle acetylcholine receptor

Kalliopi Kostelidou1, Nikolaos Trakas1, Marios Zouridakis1,2, Kalliopi Bitzopoulou1,2,

Alexandros Sotiriadis1, Ira Gavra1,2and Socrates J Tzartos1,2

1 Department of Biochemistry, Hellenic Pasteur Institute, Athens, Greece

2 Department of Pharmacy, University of Patras, Greece

The nicotinic acetylcholine receptor (AChR) is a

mem-ber of the superfamily of ligand-gated ion channels,

which also includes the glycine, c-aminobutyric acid A,

and 5-HT3 receptors [1] Its physiological role is to

mediate the fast chemical transmission of electrical

signals in response to acetylcholine released from the nerve terminal to the end-plate

The muscle AChR is a transmembrane glycoprotein ( 290 kDa) located on the postsynaptic membrane of the neuromuscular junction and is composed of five

Keywords

acetylcholine receptor; extracellular domain;

myasthenia gravis; protein expression

Correspondence

S J Tzartos, Department of Biochemistry,

Hellenic Pasteur Institute, GR11521 Athens,

Greece

Fax: +30 210 6478842

Tel: +30 210 6478844 or +30 2610 969955

E-mail: tzartos@mail.pasteur.gr,

tzartos@upatras.gr

(Received 29 March 2006, revised 25 May

2006, accepted 7 June 2006)

doi:10.1111/j.1742-4658.2006.05363.x

The nicotinic acetylcholine receptor (AChR) is a ligand-gated ion channel found in muscles and neurons Muscle AChR, formed by five homologous subunits (a2bcd or a2bce), is the major antigen in the autoimmune disease, myasthenia gravis (MG), in which pathogenic autoantibodies bind to, and inactivate, the AChR The extracellular domain (ECD) of the human mus-cle a subunit has been heterologously expressed and extensively studied Our aim was to obtain satisfactory amounts of the ECDs of the non-a sub-units of human muscle AChR for use as starting material for the determin-ation of the 3D structure of the receptor ECDs and for the characterizdetermin-ation

of the specificities of antibodies in sera from patients with MG We expressed the N-terminal ECDs of the b (amino acids 1–221; b1–221), c (amino acids 1–218; c1–218), and e (amino acids 1–219; e1–219) subunits of human muscle AChR in the yeast, Pichia pastoris b1–221 was expressed at

 2 mgÆL)1 culture, whereas c1–218 and e1–219 were expressed at 0.3– 0.8 mgÆL)1 culture All three recombinant polypeptides were glycosylated and soluble; b1–221 was mainly in an apparently dimeric form, whereas c1–218 and e1–219 formed soluble oligomers CD studies of b1–221 sugges-ted that it has considerable b-sheet secondary structure with a proportion

of a-helix Conformation-dependent mAbs against the ECDs of the b or c subunits specifically recognized b1–221 or c1–218, respectively, and poly-clonal rabbit antiserum raised against purified b1–221 bound to125I-labeled a-bungarotoxin-labeled human AChR Moreover, immobilization of each ECD on Sepharose beads and incubation of the ECD–Sepharose matrices with MG sera caused a significant reduction in the concentrations of auto-antibodies in the sera, showing specific binding to the recombinant ECDs These results suggest that the expressed proteins present some near-native conformational features and are thus suitable for our purposes

Abbreviations

AChR, nicotinic acetylcholine receptor; ECD, extracellular domain; MG, myasthenia gravis; b1–221, amino acids 1–221 of the human AChR b subunit; c1–218, amino acids 1–218 of the human AChR c subunit; e1–219, amino acids 1–219 of the human AChR e subunit.

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homologous subunits in the stoichiometry a2bcd

(embryonic muscle) or a2bed (adult muscle), with the

subunits arranged around a central ion pore [2,3]

Each mature subunit (after cleavage of the signal

peptide) consists of three domains, an extracellular

domain (ECD) (210–220 residues), a

membrane-span-ning domain, and an intracellular domain [3] The

N-terminal ECD of each of the two a subunits

con-tains the major part of the binding site for the

cho-linergic ligands The two sites are nonequivalent, one

being formed at the interface between one a subunit

and the c⁄ e subunits and the other between the second

a subunit and the d subunit [4] The c⁄ e and d subunits

play a major role in shaping the ligand-binding sites

and also in maintaining cooperative interactions

between the a subunits [5–7] The b subunit is an

important determinant in receptor localization, as

shown by studies on the properties of hybrid muscle

AChRs, in which the muscle b subunit was replaced

by its neuronal counterpart [8]

In addition to its physiological function, the muscle

AChR is involved in the pathology of the autoimmune

disease, myasthenia gravis (MG), being the main

anti-gen against which MG autoantibodies are produced

These autoantibodies bind to AChR molecules at the

neuromuscular junction, leading to their loss and

the weakness and fatigability of the voluntary muscles,

the main symptoms of MG [9] A proportion of

patients lacking autoantibodies against the AChR

har-bors antibodies against the muscle-specific kinase,

MuSK [10]

The pathophysiological importance of the AChR

necessitates the solution of its 3D structure Current

knowledge of its structure is mainly based on data

from electron images of the AChR found in large

amounts in the electric organ of the marine ray,

Torpedo californica[3] The acquisition of the

crystallo-graphic structure of the mollusc acetylcholine-binding

protein [11] has provided an insight into the

ligand-binding domain of nicotinic receptors However, the

fact that this protein is most closely related to the a7

subunit of the neuronal AChR (24% identity of amino

acids) than each of the muscle AChR subunits (22%

on average) necessitates the solution of the structure of

the mammalian AChR molecule A prerequisite for

this is the availability of large amounts of native,

sol-uble AChR molecules, a target that can be partially

achieved by expression of the ECDs of the AChR

sub-units in heterologous expression systems Several

stud-ies have been carried out on the expression of the

muscle-type a subunit ECD in bacterial systems, in

which the protein is expressed in large amounts, but is

unglycosylated and forms inclusion bodies, requiring

refolding to allow partial renaturation [12–14] Other studies involved the expression of different subunits (whole subunits or ECDs) in mammalian systems, in which the protein has the correct structure, but is only produced in limited amounts because of the inherent difficulty in scaling up expression in cell culture or oocytes [15,16]

In this report, we present the expression and charac-terization of the ECDs of the b, c and e subunits of the human muscle AChR We describe their expression

in a soluble, glycosylated form and in satisfactory amounts using the yeast Pichia pastoris expression sys-tem, which combines the speed of bacterial systems with the advantages of eukaryotic expression systems (e.g post-translational modification) and which had been successfully used in the past by our group to express the ECDs of human muscle a1 [17] and human neuronal a7 [18] CD analysis of amino acids 1–221 of the human AChR b subunit (b1–221) showed that the protein has a b-structure with a contribution from a-helices Two conformation-dependent mAbs (one anti-b and one anti-c) specifically bound to their cog-nate ECDs, whereas autoantibodies in MG sera, the binding of which is highly conformation-dependent [19,20], bound to all three ECDs

As all three ECDs were expressed in satisfactory amounts and were recognized by human MG autoanti-bodies, they may be suitable as starting material for preliminary biophysical and structural studies and for the study of MG

Results

Rationale for the construction and testing

of AChR ECD variants N-Terminal addition of the FLAG peptide (DY-KDDDDK) or addition of the first transmembrane amino acid of the mouse muscle a subunit, a proline, which is conserved in human AChR subunits, results in higher expression of the mouse muscle a ECD [21] To test the effect of these additional epitopes⁄ tags on the yield of the present proteins, we constructed a set of eight human c ECD variants (c, amino acids 1–218) with or without a proline at position 219 and⁄ or the FLAG epitope and⁄ or a 6-His tag (6-HIS) (Fig 1A)

We then performed small-scale cultures for each pro-tein and quantified the amounts of expressed propro-tein in the culture supernatant using dot-blots and a series of supernatant dilutions Expression varied depending on the presence of the different modifications (Fig 1B) The yield of amino acids 1–218 of the human AChR c subunit (c1–218) without additional tags was taken as

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the 100% reference ( 0.3 mgÆL)1, see below)

Addi-tion of the proline residue had no significant effect on

expression (less than 10%) The presence of the FLAG

tag increased expression of c1–218 by almost 20%, but

did not improve expression of c1–219 The presence of

the HIS tag alone reduced the expression of both

con-structs by 30–40% (Fig 1B, bars 2 and 6), and further

addition of FLAG to c1–218HIS gave 100% expression

(construct FLAG⁄ c1–218HIS, bar 4) Strangely, when

both epitopes were present on c1–219, no expression

was observed (Fig 1B, lane 8) We purified two c ECD

variants, FLAG⁄ c1–218HIS and c1–219HIS from 1-L

cultures, obtaining  0.3 mgÆL)1 and 0.2 mgÆL)1

pro-tein, respectively We then constructed b1–221HIS and

FLAG⁄ b1–221HIS and expressed, purified and

quanti-fied them using 2-L cultures The results showed that

expression was increased threefold when the protein

carried the FLAG tag (2 mgÆL)1 protein instead of

0.7 mgÆL)1)

Expression and purification of the b, c and e ECDs

As (a) the presence of the HIS tail on the constructs

greatly facilitates purification, (b) its negative effect on

the yield of c1–128 was considerably counteracted by the addition of the FLAG epitope, and (c) the pres-ence of the proline residue did not improve expression,

we proceeded to large-scale expression of the b, c and

e ECDs using constructs carrying both the FLAG and 6-HIS tags and no additional proline (i.e FLAG⁄ b1– 221HIS, FLAG⁄ c1–218HIS and FLAG ⁄ e1–219HIS) (Fig 2A) The yields ranged from 2 mgÆL)1culture for FLAG⁄ b1–221HIS to 0.3–0.8 mgÆL)1for both FLAG⁄ c1–218HIS and FLAG⁄ e1–219HIS The ECDs were purified using Ni2+⁄ nitrilotriacetate affinity chroma-tography under native conditions Typically, the pro-teins were eluted with 150 mm imidazole, although some protein was eluted at 100 mm (less than 10% of the total) Each protein migrated on SDS⁄ PAGE with

an apparent molecular mass of  35 kDa compared with the estimated molecular mass of 29 kDa, which was apparently due to the glycosylation of the product

in the yeast cell (see below) The proteins were  90% pure, based on quantification of the protein bands on Coomassie Brilliant Blue-stained SDS⁄ polyacrylamide gel (Fig 2B)

Deglycosylation of b1–221, c1–218 and e1–219 Each recombinant protein carries at least one Asn-X-Ser motif (glycosylation pattern for eukaryotes), b1–221 at Asn141, c1–218 at Asn30 and Asn141, and amino acids 1–219 of the human AChR e subunit (e1– 219) at Asn66 and Asn141 To verify that the recom-binant proteins were glycosylated in the yeast cell (as suggested by the observed difference in the molecular mass of the purified proteins on SDS⁄ PAGE), each protein was deglycosylated with peptide–N-glycosidase

F For each of the three proteins, this resulted in the appearance of a band migrating at the expected mass

of  29 kDa (Fig 2C), confirming that the proteins were glycosylated

Gel-filtration analysis of polypeptides

To examine the solubility and oligomerization state of the recombinant polypeptides, we performed FPLC analysis in detergent-free solution (50 mm phosphate buffer, 300 mm NaCl, pH 8.0) in the presence of trace amounts of 125I-labeled soluble 66-kDa and 29-kDa protein markers To verify that the observed peaks on the FPLC coincided with the presence of our proteins, dot-blots were performed using anti-b (mAb 73) or anti-c (mAb 67) [22] (Fig 3) As the expected molecu-lar mass of a monomer of each of the three ECD pro-teins was 30–32 kDa, the results showed that b1–221 was probably eluted as a dimer with an apparent

A

B

His His

1-219

1-219

His

1-219

His

1-219

His

1-218

1-218

1-218

His

1-218

0

20

40

60

80

100

120

140

1-218 1-218

HIS

FLAG 1-218 FLAG 1-218HIS 1-219 1-219 HIS FLAG 1-219 FLAG 1-219HIS

Recombinant polypeptide

Fig 1 Expression of the c ECD variants (A) Schematic

representa-tion of the various c ECD constructs The drawings depict the

poly-peptides with their tags ⁄ epitopes; the additional amino acid,

proline, is shown as a black bar at the C-terminus of some c

ECD(s) (B) Relative yields of the different c ECD constructs All

yields were expressed as a percentage of the yield of the

non-tagged c1–218 construct, measured as the pixels for the positive

dot-blots of the culture expressing c1–218 The results shown are

the mean from five experiments.

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A γ γ 1-218 His

β

C

6 3

6 3

+ -e s a G

5 5

B

5 5

5 5

5 5

Fig 2 Purification and deglycosylation of the AChR ECDs (A) Schematic representation of the constructs used for expression of the b1–221, c1–218 and e1–219 ECDs of the human AChR in yeast P pastoris The arrowhead indicates the cleavage site of the a-factor peptide after secretion, and the circles indicate putative glycosylation sites (Asn-X-Ser motif) (B) SDS ⁄ PAGE of the proteins purified by Ni 2+ ⁄ nitrilotri-acetate metal affinity chromatography stained with Coomassie Brilliant Blue; the left lane in each panel contains molecular mass markers, and the right lane the test protein (C) Deglycosylation of the b, c, and e ECDs using N-glycosidase F Purified proteins (1 lg) were incubated for 3 h at 37 C in the absence (lane 1) or presence (lane 2) of N-glycosidase F, then the mixture was analyzed by SDS ⁄ PAGE (12% gel) and western blotting using anti-FLAG mAb M2 The arrows indicate the bands corresponding to the glycosylated (upper) and deglycosylated (lower) forms of each protein.

66kDa

29kDa 158kDa

0

500

1000

1500

2000

0

500

1000

1500

2000

ml

β1-221

A

B

–3 )

66kDa

29kDa 158kDa

20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2

1

0

20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2

1

0

ml

γ

γ 1-218 Fig 3 Gel filtration analysis of the

polypep-tides (A) 2.0 mg b1–221 or (B) 2.0 mg c1–218 protein was run on a Superose-12 column (Amersham-Pharmacia) at a flow rate of 0.5 mLÆmin)1, together with 125

I-labeled protein markers of known mole-cular mass (66 and 29 kDa) The fractions were screened for ECD protein by dot-blots using anti-b (mAb 73) or anti-c (mAb 67) The position of the 158-kDa (aldolase) marker is also shown (nonradioactive, obtained from a separate run).

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molecular mass of 60–65 kDa (Fig 3A), whereas

c1–218 was mainly present as an oligomer (possibly

trimers-pentamers) (Fig 3B) e1–219 displayed a

sim-ilar pattern to c1–218 (data not shown), indicative of

an oligomeric state Although these elution patterns

are typical of the proteins produced, occasional

prepa-rations showed a considerable percentage (10–20) of

higher aggregates

CD spectra

When the b subunit ECD was subjected to far-UV CD

analysis to examine its secondary structure, the CD

spectrum in 50 mm phosphate buffer containing

0.15 m NaCl, pH 8.0, was characterized by a positive

Cotton effect in the 190–200 nm region (peak

 196 nm) and a negative effect in the 200–240 nm

region (Fig 4), suggesting a major contribution from a

b-sheet structure However, the quite high negative

dichroism intensity over a relatively wide region

 215 nm is indicative of the presence of bands at 208

and 222 nm, characteristic of a contribution of

a-heli-cal regions [23]

Binding of mAbs to the ECDs using ELISA

ELISAs were performed using the

conformation-dependent mAbs 73 (binds to an epitope on the

extra-cellular side of the b subunit) [22] and 67 (binds to an

epitope on the extracellular side of the c subunit) [22]

and the nonconformation-dependent mAb M2

(anti-FLAG) As a negative control, mAb 25 [24] was used,

which recognizes an epitope on Electrophorus electricus

AChR, but not on mammalian AChR Figure 5 shows that mAbs 73 and 67 specifically recognized their cog-nate proteins, whereas mAb 25 did not bind to any of the three polypeptides, as expected The strong and specific binding of the mAbs to the appropriate ECD suggested the correct folding of at least b1–221 and c1–218 Owing to the unavailability of a conforma-tion-dependent e subunit mAb, only binding of anti-FLAG mAb was tested

Binding of the rabbit anti-b serum to recombinant b1–221 and human AChR

Purified b1–221 was used to raise a rabbit anti-b ECD serum After three immunizations, the antiserum was tested for its ability to bind to the antigen (b1–221) using ELISA The results (Table 1) showed strong and specific binding to b1–221 ( 1.8 absorbance units), with relatively weak cross-reactivity with either a1–210

or yeast proteins ( 0.4 absorbance units) The anti-serum was then tested for its ability to bind to native human TE671 AChR [25] in RIA experiments The high titer of the anti-(b ECD) serum for native AChR (870 nm, Fig 6) further suggests that recombinant b1–221 retains some native-like conformational features

Binding of human MG antibodies to recombinant ECDs

To further examine the structure of the ECDs pro-duced and their potential as tools for MG studies, we tested their capacity to bind the highly conformation-dependent AChR antibodies present in MG sera We had previously identified MG patient sera in which the antibodies are mainly directed against the a subunit

195 200 205 210 215 220 225 230 235 240 245 250

-14

-12

-10

-8

-6

-4

-2

0

2

4

6

8

10

Wavelength (nm)

Fig 4 Far-UV CD spectrum of b1–221.

0 0,5 1 1,5 2 2,5

β1-221 γ1-218 ε1-219 BSA

Recombinant ECD

A450

n

A ti-β n

A ti-γ n

t a

Fig 5 mAb binding to b, c, and e ECDs using ELISA ELISA plates were coated with one of the three ECDs or BSA as a control, and the binding of mAbs tested by ELISA as described in Experimental procedures (duplicate samples) mAb 73, checker-board bars; mAb

67, dark gray bars; FLAG mAb, light gray bars mAb 25 (black bars) was used as the negative control.

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(anti-a sera) and others with a very small proportion

of antibodies against a (nonanti-a sera) [26] We

incu-bated five nonanti-a and one anti-a (82% antibodies

against a) sera with a single ECD (b, c or

e)–Seph-arose or BSA–Sephe)–Seph-arose resin, then measured the

nonbound AChR antibodies in the initial and final

samples If the AChR antibodies in the MG serum

recognized and bound to the recombinant,

immobi-lized proteins, there would be a reduction in the

amount of antibodies in the sample incubated with the

ECD–Sepharose, and this reduction should be

propor-tional to the percentage of subunit-specific antibodies

in each serum The anti-a serum should display little

or no reduction when incubated with any of the test

ECDs Table 2 shows that incubation of each of the five nonanti-a sera (samples 1–5) with different ECD– Sepharose resins resulted in different percentage reduc-tions in AChR antibody titers In contrast, the anti-a serum (sample 6) did not show any significant reduc-tion in titer when incubated with any of the non-a ECDS, as expected, but 82% loss of antibodies when incubated with a ECD–Sepharose Similar results were obtained even when much higher serum quantities were incubated with the ECD–Sepharose resins (data not shown), which suggests that the immunoadsor-bents in this experiment adsorbed all corresponding subunit antibodies As the binding to the AChR of AChR antibodies in MG patient sera is highly confor-mation-dependent, our findings support the presence

of native-like conformational features on all three recombinant ECDs

Discussion

In this paper, we describe the expression of soluble forms of the ECDs of non-a subunits of the human muscle AChR, using the yeast P pastoris system We have successfully used this system for the human muscle a ECD (a1–210) [17] and human neuronal type a7 subunit (a7 1–208) [18] Based on this experi-ence, we embarked on the expression of three of the four non-a ECDs, namely b, c and e The expression

of the d subunit ECD, which is currently under pro-gress, presents major difficulties, which require further investigation

Aiming to improve expression yields, we designed, constructed and tested different variants of the c ECD with and without a 6-HIS tail and⁄ or the FLAG

Table 1 Binding of the rabbit anti-(b ECD) serum to purified b1–

221 in ELISA tests Results shown are the mean from two

experi-ments Recombinant human a ECD (a1–210) was used to test for

nonspecific binding of the rabbit anti-(b ECD) serum to a protein

related to b1–221, rather than to a totally unrelated protein, such as

BSA The purified b1–221 used for immunization was purified from

a P pastoris yeast culture and possibly contained traces of yeast

culture components (e.g peptides originating from yeast protein

degradation and other metabolic by-products) To eliminate the

pos-sibility that rabbit antibodies raised against such components could

lead to spurious ELISA results, a control yeast supernatant sample

was prepared as described in Experimental procedures BSA was

used as a negative control.

Rabbit anti-(b ECD) serum (A450)

Normal rabbit serum (A450)

0

200

400

600

800

1000

1200

Serum Volume (µl)

Fig 6 Binding of the rabbit anti-(b ECD) serum to 125

I-a-bungaro-toxin-labeled native human AChR Various amounts of the rabbit

anti-(b ECD) serum were incubated with 14 fmol intact125

I-a-bung-arotoxin-labeled human AChR, then bound receptor was

precipita-ted with sheep anti-rabbit IgG, and radioactivity was measured.

Samples were processed in duplicate, and the results shown are

the mean of those of three experiments The titer of b antibodies

in the serum was calculated to be 870 n M

Table 2 Adsorption of AChR antibodies from human MG sera by immobilized ECDs AChR antibody titer given in parentheses in n M The reduction in total AChR antibodies present in MG sera observed after incubation of sera with b1–221, c1–218, or e1–219 immobilized on CNBr–Sepharose beads was measured by RIA using 125 I-a-bungarotoxin-labeled native AChR.

Serum

Reduction (%) in AChR antibodies in MG serum after incubation with immobilized ECDs

anti-a serum a

Data from [26].

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epitope and⁄ or the first transmembrane amino acid of

the AChR c subunit (proline), which is found at this

position in all human muscle subunits and has been

shown to positively affect expression of the mouse

AChR a subunit [21] Our results showed that the

addition of a Pro residue and the presence of common

epitopes⁄ tags used for purification influenced the

expression yield When the widely used 6-HIS tail was

added to the C-terminus of c1–218, it reduced

expres-sion almost twofold, whereas an N-terminal FLAG, a

peptide sequence rich in charged residues, improved

expression of c1–218 by 20% and that of c1–218HIS

by 40% (Fig 1B) The effect of the hydrophilic FLAG

epitope was most dramatically seen with the b1–221

ECD, its addition leading to an almost threefold

increase in expression Although Yao et al [21]

showed that addition of a Pro to the mouse a ECD

increased expression fourfold, no such effect was seen

with the non-a human ECDs in our system Aiming

simultaneously at easy purification (achievable using

the 6-HIS tail) and high yields, we used the

N-FLA-G⁄ ECD ⁄ HIS-C constructs for the large-scale

expres-sion of the proteins and found that b1–221 was

consistently expressed at a concentration of 2 mgÆL)1

of culture and the c and e ECDs at a concentration of

0.3–0.8 mgÆL)1 These yields are an improvement over

the previous 0.1–0.2 mgÆL)1 expression of the a1–210

protein [17], which, however, was in the monomeric

form, in contrast with the three recombinant proteins

described here Gel-filtration analysis showed that b1–

221 existed mainly as a dimer, whereas both c1–218

and e1–219 were mainly present as oligomers, possibly

trimers–pentamers (Fig 3) The state of the proteins

was confirmed by dynamic light scattering experiments

(data not shown); the proteins appeared polydisperse

with an estimated diameter of 7.5–9.8 nm (b ECD)

and 12.0–13.8 nm (c ECD), suggesting, respectively, a

dimeric or an oligomeric structure and confirming the

FPLC data, considering that the ‘height’ of the ECD

of the AChR is 6 nm [3] This difference in solubility

between the c–e and the b ECDs might be attributed

to the primary structure of the protein: in addition to

the ‘standard’ cysteine pair (residues 128 and 142) [27],

present in all AChR subunit ECDs, both c and e carry

extra cysteine residues at residues 61, 105, and 115 (c)

and 190 (e), which could be involved in the formation

of intramolecular or intermolecular bonds, leading to

oligomer formation However, if ‘free’ cysteines were

the only factors responsible for multimer formation,

then the b ECD should exist as a monomer; as this

was not the case, exposed hydrophobic regions, which

are presumably present in the b ECD, may also

con-tribute to intermolecular association of monomers

The results from a range of experiments suggested that the recombinant polypeptides are, at least to some extent, properly folded Firstly, they were glycosylated, like native AChR [28] (Fig 2C) Even though we lack direct evidence about the site and structure of the glycosylation sites on the ECDs, indirect evidence of correct glycosylation of our ECDs comes from our previous studies on the a ECD [17]: deglycosylation abolished a-bungarotoxin activity, strongly suggesting that glycosylation was at the right site and possibly of correct structure Secondly, the CD spectrum of the b ECD indicated a folded protein consisting mainly of b-sheet (Fig 4) The solved crystallographic structures

of the molluscan Lymnaea stagnalis [11] and Bulli-nus truncatus [29] acetylcholine-binding proteins, which provide the prototypes for the AChR ligand-binding domain, show a predominance of b-sheet, and the CD spectra for these proteins largely resemble our spectra [29] and are also similar to those for mouse a1 expressed in mammalian cells [16] or yeast [21] and the Torpedo a ECD expressed in Escherichia coli [13] These results suggest that the acetylcholine-binding proteins and the b ECD have similar structures and that the secondary structures of a non-a ECD (b) and the a ECD resemble one another, being largely com-posed of b-structure Thirdly, conformation-dependent anti-b and anti-c (mAbs 73 and 67, respectively) bound specifically to their cognate ECD (Fig 5), and

a polyclonal serum raised against the b1–221 polypep-tide specifically bound to native AChR in RIA experi-ments (Fig 6) Finally, AChR antibodies in different

MG sera were specifically adsorbed by matrix-immobi-lized ECDs, with variable concentrations of AChR antibodies being retained on each ECD matrix (up to 89% of b antibodies for MG serum 3; Table 2) The presence of antibodies against several AChR subunits

in a single serum (e.g MG serum 1; Table 2) is inter-esting, although it was not unexpected because of pre-vious indirect information (e.g from competition experiments between mAbs against different subunits and MG sera) [22] The actual autoantigen in anti-AChR-mediated MG is still uncertain It may be intact AChR, AChR subunit(s) or fragments, or an AChR cross-reactive molecule The polyspecificity of the sera may either mean that the autoantigen is an intact AChR or that epitope spreading occurred after initial induction by a single AChR subunit or a cross-reactive molecule The adsorption results also indicated the presence of a considerable percentage (29–39%) of c antibodies in three of the five tested nonanti-a MG sera (e.g MG sera 1, 4 and 5; Table 2) The c subunit, present in the fetal isoform of the AChR, is replaced

by the e subunit in adult muscle; however, this fetal

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isoform is expressed in myoid cells in the thymus

[30,31], and c expression persists into adulthood in

mouse and bovine ocular fibers [32,33], justifying the

presence of c antibodies in adult MG sera The

major-ity of AChR antibodies in MG sera are directed

against various nonlinear, conformation-dependent

epitopes on the extracellular part of the AChR

mole-cule, a fact that has prevented their characterization

using synthetic peptides or denatured recombinant

polypeptides obtained using prokaryotic expression

systems [20,34] In addition, the immune responses

against the non-a AChR subunits have not been

exam-ined as carefully as those against the a subunit, even

though the differential expression of the different

sub-units may be highly significant in the pathogenesis of

MG [35]

All four ECDs of the Torpedo AChRs have

previ-ously been expressed as soluble proteins using

baculo-virus-infected insect cells [36], and the proteins showed

proper folding, but the amounts produced were

insuffi-cient for crystallization trials Moreover, the a ECDs

of Torpedo and human AChR, which have been

pro-duced as inclusion bodies in bacteria in quantities

suf-ficient for structural studies [13,14], require denaturing

conditions for solubilization of the protein and

refold-ing and also do not undergo post-translational

modifi-cations In the present study, we obtained stable

Pichia clones expressing satisfactory amounts of three

non-a ECDs (b1–221, c1–218 and e1–219) which were

in a soluble, secreted form and probably correctly

folded, a fact that may permit preliminary

crystalliza-tion trials Crystallizacrystalliza-tion trials require protein

sam-ples of concentration  10 mgÆmL)1, purity of at least

95%, and monodispersity Based on the yields of our

yeast cultures (0.5–2 mgÆL)1), a medium-scale

expres-sion would suffice to provide material that, after

puri-fication and gel filtration, should be sufficiently

concentrated The risk in this case would be the

puta-tive formation of aggregates that would render the

sample unusable for downstream processing, especially

for the recombinant c1–218 and e1–219, which were

already in the form of oligomers; this approach,

how-ever, could possibly be applicable to b1–221, which is

dimeric, stable on concentration (data not shown),

and exhibits the highest expression yield For the c

and e ECDS, improvement in their solubility is

required before attempts at structural trials We are

working towards this by constructing mutant forms of

the proteins Nevertheless, these polypeptides, together

with the already produced a1–210 [17], were all

specif-ically recognized by human AChR antibodies in MG

sera, allowing their immediate use for the detailed

study of the specificities of the antibodies in MG sera

and the development of antigen-specific therapeutic approaches

Experimental procedures

Bacterial and yeast strains, growth conditions, plasmids and DNA manipulations

The E coli K-12 strain TOP10F¢ (Invitrogen, San Diego,

CA, USA) was used for replication of plasmid DNA Clo-ning of the ORFs encoding the b1–221, c1–218 and e1–219 ECDs was performed by standard techniques [37] Luria– Bertani broth and agar were used for amplification of transformed bacteria Ampicillin (100 lgÆmL)1) was used in liquid or solid media

The vector pPIC9 (Invitrogen) was used to clone the ORFs in-frame with a leader sequence allowing secretion

of the produced protein after cleavage of the secretion signal An oligonucleotide, 5¢-GTAGATTACAAGGATG ACGATGACAAAG-3¢ encoding the FLAG sequence, DYKDDDDK, was introduced into the vector between the unique SnaBI and EcoRI sites This allowed the subsequent in-frame cloning of our PCR products with a 5¢-EcoRI site

in such a way that the cloned ORF was expressed as a polypeptide carrying the FLAG peptide at its N-terminus The resulting plasmid was named pPIC9⁄ FLAG

Cloning using PCR

We used PCR to amplify the extracellular region of each of the b, c and e subunits, using the plasmid templates, pcDNA3.1⁄ Beta, pcDNA3.1⁄ Gamma and pcDNA3.1⁄ Epsilon (cDNA clones of the human b, c and e AChR sub-units in pcDNA3.1 respectively; all kindly provided by D Beeson, University of Oxford, UK) [38] PCR was per-formed on the appropriate template for each subunit on a Perkin-Elmer (Boston, MA, USA) thermal cycler; 5 min denaturation at 94C was followed by 25 cycles of 94 C for 20 s, 58C for 30 s, and 72 C for 90 s, and a final 5-min extension step at 72C The reaction mix consisted

of 10 ng template, 50 mm each dNTP, 20 pmol each pri-mer, and 1 U Taq DNA polymerase in a volume of 50 lL 10-fold diluted reaction buffer (Promega, Madison, WI, USA) For b1–221, the forward primer was 5¢-GCGGA ATTCTCGGAGGCGGAGGGTCGAC-3¢ and the reverse primer 5¢-ATAGTTTAGCGGCCGCTCAATGGTGATGG TGATGGTGCTTGCGGCGGATGATGAG-3¢ For the c1–218 variants (some with an additional C-terminal Pro giving c1–219), the forward primer 5¢-GGTGTAGA ATTCCGGAACCAGGAGGAGCGC-3¢ was used in all cases, together with the reverse primer (a) 5¢-ATA GTTTAGCGGCCGCTTACTTGCGCTGGATGATGAG CAGG-3¢ for c1–218, (b) 5¢-ATAGTTTAGCGGCCGC TTAGTGATGGTGATGGTGATGCTTGCGCTGGATG

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AGCAGG-3¢ for c1–218HIS (c1–218 with a 6-HIS tag

at its 3¢ end to facilitate purification), (c) 5¢-ATAG

TTTAGCGGCCGCTTAGGGCTTGCGCTGGATGAGCA

GG-3¢ for c1–219, or (d) 5¢-ATAGTTTAGCGGCC

GCTTAGTGATGGTGATGGTGATGGGGCTTGCGCT

GGATGAGCAGG-3¢ for c1–219HIS For the e1–219

variants (e1–220 with additional Pro), the forward

pri-mer 5¢-GGTGTAGAATTCAAGAACGAGGAACTGCG-3¢

was combined with (a) 5¢-ATAGTTTAGCGGCCG

CTTACTTCCGGCGGATGATGAGCGAG-3¢ for e1–219,

(b) 5¢-ATAGTTTAGCGGCCGCTTAGTGATGGTGATG

GTGATGCTTCCGGCGGATGATGAGCGAG-3¢ for e1–

219HIS, (c) 5¢-ATAGTTTAGCGGCCGCTTACGGCTT

CCGGCGGATGATGAGCGAG-3¢ for e1–220, or (d)

5¢-ATAGTTTAGCGGCCGCTTAGTGATGGTGATGGTGA

TGCGGCTTCCGGCG-GATGATGAGCGAG-3¢ for e1–

220HIS (underlined EcoRI and NotI) The PCR products

were purified (Qiagen PCR clean-up kit; Qiagen, Hilden,

Germany), EcoRI–NotI digested, repurified, and cloned

into the EcoRI–NotI-digested pPIC9 or pPIC9⁄ FLAG

plas-mid Each PCR product was cloned into both plasmids

Sequencing was used to verify the identity of the inserts

Yeast transformation and dot-blot screening

of positive clones

Plasmids (10 lg) encoding the b1–221 ECD (with or

with-out the FLAG epitope) and the various c1–218 and e1–219

ECDs were linearized using SacI (for b1–221) or SalI or

SacI (for c1–218 and e1–219) and electroporated into

freshly made competent GS115 P pastoris cells Selection of

positive transformants (cells able to grow in the absence of

histidine) was achieved by plating on regeneration dextrose

plates (1 m sorbitol, 2% dextrose, 1.34% yeast nitrogen

base, 4· 10)5% biotin, 0.005% l-glutamic acid, l-lysine,

l-methionine, l-leucine, and l-isoleucine, 2% agar) without

histidine Small-scale cultures of single colonies were tested

after growth overnight in 3 mL BMGY medium (1% yeast

extract, 2% peptone, 100 mm potassium phosphate, pH 6.0,

1.34% yeast nitrogen base, 4· 10)5% biotin, 1% glycerol)

and resuspension of the cells in 3 mL BMMY medium to

induce expression (BMMY medium is identical with

BMGY, but contains 0.5% methanol instead of glycerol)

(day 0) Methanol was added to 0.5% every 24 h to

main-tain induction, and 0.75 mL liquid medium was removed

every 24 h after day 0 to test for the expression and

secre-tion of the produced protein The cleared supernatant was

tested on dot-blots using mAb 73, mAb 67, or anti-FLAG

mAb M2 (Sigma, St Louis, MO, USA) to test for the

expression of b, c or all ECDs, respectively After the initial

screening, phosphate buffers with a pH of 6.5 or 7.0 were

also tested, and the pH 7.0 buffer was finally adopted for

large-scale expression Expression levels of the different c or

e variants were estimated by quantification of the positive

signal on dot-blots of culture supernatant (at serial dilu-tions) using imagej software (http.//rsb.info.nih.gov/ij/)

Large-scale expression and purification of proteins

The best expressing clone was selected for each protein A 0.1-mL sample of a small overnight culture of 20 mL BMGY medium was used to inoculate 1 L fresh BMGY medium After growing to an A600 of 3 ( 18–20 h), the cells were spun down, washed, and resuspended in 3 L BMMY medium to induce expression On day two, the cul-tures were cleared of cells by centrifugation for 20 min at

2500 g (Jouan 11175372 M4 rotor), and the supernatant concentrated using a Millipore (Bedford, MA, USA) ultra-filtration system (filter cut-off 10 kDa); these steps and all subsequent steps were performed at 4C The concentrate was dialyzed overnight against 50 mm phosphate buffer,

2 m NaCl, pH 8.0, for the c and e ECDs or 50 mm phos-phate buffer, 0.5 m NaCl, pH 8.0, for the b ECD before binding of the protein to 1.5 mL pre-equilibrated Ni2+⁄ ni-trilotriacetate⁄ agarose (Qiagen) The protein was purified under native conditions following the manufacturer’s instructions Eluates were analyzed by SDS⁄ PAGE (12% gel) and Coomassie blue staining or western blotting using mAb 73 (for the b ECD) or anti-(FLAG M2) (Sigma) The purity of the protein was estimated from Coomassie Brilli-ant Blue-stained gels and quBrilli-antification of the bands using imagejsoftware, and protein concentration was determined using the Bradford method (Bio-Rad, Hercules, CA, USA)

In vitro deglycosylation

A sample (1 lg) of purified protein was deglycosylated by incubation for 3 h at 37C with 1000 U N-glycosidase F (New England Biolabs, Frankfurt, Germany) in a final vol-ume of 50 lL under the conditions recommended by the manufacturer for a nondenatured protein The protein was then precipitated by the addition of 200 lL methanol⁄ acet-one (1 : 1, v⁄ v), incubation at)20 C for 20 min, centrifu-gation for 15 min, and resuspension in 15 lL distilled water The samples were analyzed by SDS⁄ PAGE and western blotting using FLAG mAb M2

FPLC analysis of polypeptides

To determine the size of b1–221, c1–218 or e1–219, FPLC analysis on a Superose-12 column (Amersham-Pharmacia, Munich, Germany) was performed in 50 mm sodium phos-phate buffer⁄ 300 mm NaCl, pH 8.0, at a flow rate of 0.5 mLÆmin)1 Samples of each fraction (normally 1 and

10 lL of each 0.5-mL fraction) were tested for the presence

of the specific protein by dot-blotting with FLAG mAb M2

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Radioactive labeling of protein markers and

a-bungarotoxin

a-Bungarotoxin (24 lg) or 2 lg either bovine erythrocyte

carbonic anhydrase ( 29 000 Da) or BSA ( 66 200 Da)

(both from Fluka; Sigma-Aldrich, Athens, Greece) was

labeled, respectively, with 2 mCi or 0.1 mCi 125I, using the

chloramine T method [39], loaded on to a G50-Fine column

(Amersham-Pharmacia), and the labeled protein collected

and stored at )20 C Approximately 100 000 c.p.m of

each of the 125I-labeled protein markers was loaded on

every FPLC run as size markers

Preparation of rabbit anti-(b subunit) serum

An 8-week-old female New Zealand White rabbit was

injec-ted subcutaneously with  0.5 mg purified b1–221 protein

in 50% (v⁄ v) complete Freund’s adjuvant, followed by

three injections at monthly intervals in 50% incomplete

Freund’s adjuvant One week after the last injection,

anti-serum was collected, aliquoted, and stored at)20 C in the

presence of 0.05% sodium azide Use of experimental

ani-mals abides by law 2015/27-2-1992 of the Greek Republic

and Presidential Decree 160/3-5-1991 in accordance with

directive 86/609EOK of the Council of Europe for

protec-tion of vertebrates/animals used for experimental or other

research purposes

CD spectra

CD spectra were measured at 20C using a Jasco model

J-715 spectropolarimeter (located at NCSR, Demokritos,

Athens, Greece) in semi-automatic slit adjustment mode

The scan speed was set at 50 nmÆmin)1, the response time

at 2 s, and the scan range at 180–260 nm Optical activity

was expressed as the mean residue ellipticity (Q), in

degree-sÆcm2Ædmol)1, based on a mean residue weight of 115 for

the b ECD polypeptide The derived spectrum represents

the mean of eight scans and was corrected for light

scatter-ing by buffer subtraction The protein concentration was

optimized as 0.2 mgÆmL)1, and the quartz cell path length

was 1 mm All samples were optically homogeneous

ELISA

ELISA plates (Maxi-Sorb; Nun Roskilde, Denmark) were

coated, as described previously [14], using 0.25 lg purified

recombinant protein (b1–221, c1–218 or e1–219) per well

Control wells were coated with BSA (0.25 lg) Additional

control wells were coated with 0.25 lg a ECD (a1–210) or

100 lL yeast culture supernatant prepared as follows:

100 mL of a culture of P pastoris GS115 strain was spun,

and the supernatant filtered, concentrated 40-fold, and

dia-lyzed against 50 mm phosphate buffer, pH 8.0

The plates were washed with phosphate-buffered saline,

pH 7.5 (NaCl⁄ Pi) and blocked for 30 min at 37C with blocking solution (5% nonfat milk in NaCl⁄ Pi), then incu-bated for 1 h at 25C with primary antibody in blocking solution; mAbs were used at a 1 : 100 dilution (the concen-tration of the undiluted mAb ‘stock solution’ was 0.1– 0.5 mgÆmL)1), and the rabbit antiserum was used at dilu-tions of 1 : 100–1 : 10 000 After three washes with block-ing solution, the plates were incubated for 1 h at 25C with secondary antibody [horseradish peroxidase-conju-gated rabbit anti-rat IgG (Dako, Glostrup, Denmark) in the case of the mAbs and sheep anti-rabbit IgG (Dako)] at

a 1 : 500 dilution in blocking solution No secondary anti-body was used when the FLAG mAb M2 was used, as the antibody was supplied in its horseradish peroxidase-conju-gated form (Sigma) The ELISA plate was developed using 3,3¢,5,5¢-tetramethylbenzidine ready-to-use substrate (MBI-Fermentas, St Leon-Rot, Germany), stopping the reaction with 0.2 m H2SO4 The plate was read at 450 nm on a microtiter plate reader

Preparation of ECD–Sepharose beads ECD (0.25 mg) mixed with BSA (1.25 mg, as carrier) were bound to 0.25 g CNBr-activated Sepharose beads (Pharma-cia, Munich, Germany) according to the manufacturer’s protocol as described previously [26] The beads were then diluted in NaCl⁄ Pi⁄ 2% BSA ⁄ 0.05% NaN3 so that 120 lL

of the mixture contained 1 lg recombinant protein Control beads were prepared using 1.5 mg BSA

Use of the ECD–Sepharose matrix for binding AChR antibodies in MG sera

Depending on the AChR antibody titer, different dilutions

of sera were prepared: the MG sera were diluted 1 : 10 (for serum titer 5 nm) to 1 : 500 (for titer 290 nm) supplemented with normal human serum to a final serum dilution of

1 : 10 This guaranteed that the amount present in the untreated sample would immunoprecipitate  50% of the labeled AChR A 40-lL portion of the dilution was incuba-ted for 2 h at 4C with 120 lL Sepharose–ECD or Seph-arose–BSA matrix (final volume 160 lL), and then duplicate 40-lL samples of supernatant (containing 1 lL serum) were tested in the RIA described below

RIA for MG sera or rabbit anti-(b1–221) serum

We tested the ability of MG sera to precipitate a-bungaro-toxin-labeled human AChR prepared from either TE671 cells or a mixture of CN21⁄ TE671 cells (CN21 cells express the e and c AChR subunits at a ratio of approximately

2 : 1 [40], whereas TE671 cells express only the c subunit AChR [25]) The TE671-derived AChR was used when sera

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