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Cells expressing the unstable CD38 homodimers had diminished expression of CD38 on the plasma membrane and the half-lives of these CD38 mutant proteins on the plasma membrane were signifi

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CD38 is expressed as noncovalently associated homodimers

on the surface of murine B lymphocytes

Miguel E Moreno-Garcı´a1,2, Santiago Partida-Sa´nchez3, Julie Primack3, Adriana Sumoza-Toledo2,

He´le`ne Muller-Steffner4, Francis Schuber4, Norman Oppenheimer5, Frances E Lund3and

Leopoldo Santos-Argumedo2

1

Departamentos de Biologı´a Celular and2Biomedicina Molecular, CINVESTAV-IPN, Mexico;3Trudeau Institute, Saranac Lake, New York, USA;4Laboratoire de Chimie Bioorganique, UMR 7514 CNRS/ULP, Strasbourg-Illkirch, France;5Department of Pharmaceutical Chemistry, UCSF, San Francisco, USA

CD38 is a transmembrane glycoprotein that functions as

an ectoenzyme and as a receptor Based on the structural

similarity between CD38 and ADP-ribosyl cyclase from

Aplysia californica, it was hypothesized that CD38 is

expressed as a homodimer on the surface of cells Indeed,

CD38 dimers have been reported, however, the structural

requirements for their stabilization on the plasma

mem-brane are unknown We demonstrate that the majority of

CD38 is assembled as noncovalently associated

homo-dimers on the surface of B cells Analysis of CD38

mutants, expressed in Ba/F3 cells, revealed that truncation

of the cytoplasmic region or mutation of a single amino

acid within the a1-helix of CD38 decreased the stability

of the CD38 homodimers when solubilized in detergent Cells expressing the unstable CD38 homodimers had diminished expression of CD38 on the plasma membrane and the half-lives of these CD38 mutant proteins on the plasma membrane were significantly reduced Together, these results show that CD38 is expressed as noncova-lently associated homodimers on the surface of murine

B cells and suggest that appropriate assembly of CD38 homodimers may play an important role in stabilizing CD38 on the plasma membrane of B cells

Keywords: B lymphocytes; CD38; homodimer stability; NAD+glycohydrolase; protein structure

CD38 is a type II transmembrane ectoenzyme expressed by

many cell types [1–3] CD38 plays an important role in

calcium signaling as it catalyzes the production of several

calcium mobilizing metabolites including

adenosine(5¢)-diphospho(5)-b-D-ribose (ADP-Rib), cyclic

adeno-sine(5¢)diphospho(5)-b-D-ribose (cADP-Rib) and nicotinic

acid-adenine(5¢)diphosphate (NAADP+) [4,5] In addition

to its role as an enzyme, CD38 can also serve as a receptor

on the plasma membrane of leukocytes and lymphocytes

For example, incubation of B lymphocytes with agonistic

antibodies to CD38 induces calcium mobilization, protein

phosphorylation, proliferation, class switching, rescue from

cell death and induction of apoptosis [1,6–10] In order to

understand the dual receptor and enzyme properties of

CD38, a number of structure/function studies have been

performed These studies have been guided by analyses

of two CD38 homologues, the cytosolic Aplysia

califor-nica ADP-ribosyl cyclase [11,12] and the mammalian

GPI-anchored NAD+ glycohydrolase, CD157 [13,14]

Crystallographic and X-ray diffraction analyses of these two proteins indicated that both proteins form noncova-lently associated homodimers [15,16] Thus, it has been proposed that CD38 is also likely to be expressed as a homodimer on the plasma membrane and, in agreement with this hypothesis, initial reports showed that high molecular mass aggregates of CD38 are formed after incubation of human erythrocytes with NAD+or 2-mercapto-ethanol [17] In addition, it was reported that CD38 formed dimers and oligomers on the membrane of CD38 trans-fected HeLa cells [18] It is not clear, however, whether CD38 is always present in a dimeric form on the surface

of cells as many groups have reported finding only the monomeric form of CD38 [19–21] Furthermore, it remains

to be determined whether CD38 dimers are formed via covalent or noncovalent interactions between monomers For example, it has been suggested that two extracellular cysteines in CD38 (Cys119 and Cys201 in human CD38 or Cys123 and Cys205 in mouse CD38) could form interdi-sulfide bonds between CD38 monomers [22] In agreement with this hypothesis, studies carried out with porcine heart, rat lung and rat hepatocytes showed that under nonreduc-ing conditions CD38 forms dimers, while under reducnonreduc-ing conditions CD38 is present in a monomeric form [23–25]

On the other hand, Umar et al have shown that CD38 oligomers, expressed by retinoic acid stimulated HL60 cells, are covalently stabilized by transglutaminase, suggesting an alternate biochemical mechanism for the stabilization of covalent CD38 oligomers [26] As these previous results are difficult to reconcile with one another, it is still unclear

Correspondence to L Santos-Argumedo, Departamento de

Biomedicina Molecular, CINVESTAV-IPN, Av IPN #2508 Col.

Zacatenco, cp 07360, Me´xico D.F., Me´xico.

Fax: + 52 55 5747 7134, Tel.: + 52 55 5061 3323,

E-mail: lesantos@mail.cinvestav.mx

Abbreviations: BS 3 , Bis(sulfosuccinimidyl)suberate; NP-40,

Nonidet-P-40; IEF, isoelectric focusing.

(Received 17 October 2003, revised 22 December 2003,

accepted 20 January 2004)

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whether CD38 normally forms dimers, and if so, whether

stable CD38 dimer formation is dependent on covalent

bonds between monomers In this report, we show that

CD38 primarily forms homodimers on the plasma

mem-brane of B lymphocytes Furthermore, we demonstrate that

the stability of the CD38 homodimers is highly dependent on

the detergent used to solubilize the cells and is less dependent

on the formation of interdisulphide bonds between CD38

monomers, indicating that the CD38 homodimers in B cells

are likely to be stabilized via noncovalent monomer–

monomer interactions Finally, using Ba/F3 cells stably

transfected with a number of different CD38 mutants, we

identified two domains of the CD38 protein that confer

stability to the homodimeric form of CD38 Functional

analysis revealed that the half-life of these unstable CD38

homodimers on the plasma membrane was significantly less

than wild-type CD38 resulting in reduced plasma membrane

expression Thus, these results suggest that assembly of

CD38 homodimers may influence the stable expression of

CD38 on the plasma membrane of B cells

Materials and methods

Mice, B cell purification and cell lines

Splenic B lymphocytes were purified from 6 to 8-week-old

BALB/c, C3H/HeJ, NMRI, C57BL/6 or C57BL/6-Cd38–//–

[27] mice with magnetic beads coupled with antibodies to

B220 (Miltenyi Biotech, Auburn, CA, USA) All research

mice at CINVESTAV and Trudeau Institute were

eutha-nized by CO2narcosis in accordance with the

recommenda-tions of the Panel on Euthanasia of the AVMA and in

compliance with the CINVESTAV and Trudeau Institute

IACUC guidelines The IL-3 dependent murine pro-B cell

line, Ba/F3 (a generous gift from D Campana, St Jude

Children’s Hospital, Memphis, TN, USA) was cultured in

complete B cell media [21] supplemented with 10% (w/v)

WEHI-3 supernatant (containing IL-3)

Cell lysis, immunoprecipitation, Western blot and

isoelectric focusing

B cells were lysed with 10 mM Tris/HCl (pH 7.3), 2 mM

Na3VO4, 0.4 mM EDTA, 10 mM NaF, 1 mM

phenyl-methanesulfonyl fluoride, 2 lgÆmL)1aprotinin and

leupep-tin and 1% of one of the following detergents: Nonidet-P-40

(v/v) (NP-40), Triton X-100 (v/v) (Sigma), Chaps (w/v)

(Polysciences Inc., Warrington, PA, USA), deoxy-BigChap

(w/v) (Pierce, Rockford, IL, USA), or digitonin (w/v) (Wako

pure chemicals Ltd, Japan) Cell lysates were incubated

over-night at 4C with 5 lg of anti-mouse CD38 monoclonal

antibody (NIM-R5 [1]) or a nonspecific rat IgG2a (Zymed,

San Francisco, CA, USA) together with a 30 lL slurry of

protein G beads (Zymed) Complexes were boiled in

Laemmli buffer containing 2-mercaptoethanol or

dithiotre-itol (Sigma) at the concentration indicated in the text To

analyze the samples under nonreducing conditions, the

samples were suspended in the Laemmli buffer in the absence

of reducing agents and then heated at 50C for 3 min

Immunoprecipitated proteins (25 lL) were loaded into

10% polyacrylamide gels, electrophoresed and transferred

to nitrocellulose (Scleicher and Schuell, Dassel, Germany)

The membranes were blocked with 5% bovine serum albumin (BSA) (Research Organics, Del Mar, CA, USA) and incubated with rabbit polyclonal antibody against CD38 [28] overnight at 4C followed by an anti-rabbit– HRP (DAKO, Carpinteria, CA, USA) for 2 h at room temperature Proteins were developed using chemilumines-cence (Amersham Pharmacia Biotech, Buckingamshire, England)

The two-dimensional isoelectric focusing (IEF) analysis

of immunoprecipitated CD38 was performed as reported by O’Farrel [29]

Preparation of CD38 mutant cDNA constructs and Ba/F3 stable transfectants

Expression vectors containing the full length coding region of murine CD38 (CD38-WT-pME18S/neo) or the CD38 cytoplasmic region mutant (CD38-lATG-pME18S/neo) have been previously described [19,30] CD38-E150L and CD38-G68E were generated by PCR using the CD38-WT expression vector as a template and the primers below Restriction sites are underlined and the altered nucleotides that correspond to the replacement amino acid codons are indicated in lower case italics: CD38-E150L, primer 1: 5¢-(TACTTGGATCCAGGGAAAGATGTTCACCCTG ctGGACACCCTG)-3¢; CD38-E150L, primer 2: 5¢-(CC CTCTAGACCAGATCCTTCACGTATTAAGTCT ACACG)-3¢; CD38-G68E, primer 1: 5¢-(GACATCTTC CTCGagCGCTGCCTCATC)-3¢; CD38-G68E, primer 2: 5¢-(CCCTCTAGACCAGATCCTTCACGTATTAAGTC TACACG)-3¢; CD38-G68E, primer 3: 5¢-(GATGAGGC AGCGCTCGagGAAGATGTC)-3¢; CD38-G68E, primer 4: 5¢-(GGGGAATTCATGGCTAACTATGAATTTAGC CAG)-3¢

The E150L PCR product was digested with BamHI/XbaI and was used to replace the BamHI/XbaI fragment of CD38-WT in pME18S/neo The two PCR products for G68E were digested with XhoI, XbaI and EcoRI and cloned

by three way ligation into the EcoRI and XbaI sites of pME18S/neo The entire CD38 coding sequence was then sequenced in both directions to ascertain that the appropri-ate mutation was introduced and that no polymerase or cloning errors had occurred

Ba/F3 cells (5· 106) were electroporated as described previously [21] and were cultured in Ba/F3 media containing Geneticin (G418, Gibco-BRL, Grand Island, NY, USA)

at 500 lgÆmL)1 After 10 days, the surviving CD38+cells were single cell cloned into a 96-well plate using a FACSVantage-DIVA (Becton-Dickinson, San Jose, CA, USA) At least 20 independent clones from each transfec-tion were stained to determine CD38 expression levels and

at least five individual clones were picked to expand and analyze experimentally

Measurement of cyclase and glycohydrolase activity

in Ba/F3 transfectant cell homogenates Transfected Ba/F3 cells were washed with NaCl/Pi, pelleted, snap frozen and stored at )70 C The mem-brane fraction was obtained and resuspended in 1 mL potassium phosphate buffer (50 mM, pH 6.8) using a Dounce–Potter homogenizer (Wheaton Science Products,

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Milville, NJ, USA) Protein concentration was determined

with the BCAprotein assay (Pierce) The catalytic activity

of CD38 in Ba/F3 cell homogenates was determined

by HPLC using the radiolabeled substrates

[carbo-nyl-14C]NAD and [adenosine-U-14C]NAD+ as described

previously [30] To normalize the enzyme activity of the

cell homogenates from the various Ba/F3 transfectants,

the enzyme activity (Vmax) was multiplied by a correction

factor that compensated for the total protein per cell and

the amount of CD38 expressed per cell This correction

factor was obtained by dividing the amount of protein per

cell (1.54· 10)7mg) by the amount of CD38 expressed

on the membrane of each Ba/F3 cell (mean fluorescence

intensities) and is represented in arbitrary units of CD38

per mg of total protein The protein concentration per cell

was determined by lysing a known number of Ba/F3 cells

and determining protein concentration by Bradford

ana-lysis This was repeated multiple times and the number

represents the average amount of protein (in mgs) per cell

Crosslinking with BS3

B cells were washed, resuspended in 7 mL NaCl/Pi, and

560 lL of a 25 mMsolution of

bis(sulfosuccinimidyl)suber-ate (BS3, Pierce, Rockford, IL, USA) in 5 mMsodium citrate

buffer was added dropwise to the cell suspensions giving a

final concentration of 2 mMBS3 Cells were incubated for 1 h

at 4C with gentle shaking The reaction was stopped with

140 lL 1M Tris/HCl (pH 7.5) Cell suspensions were

washed with NaCl/Piand prepared for lysis

FACS analysis

To measure CD38 expression on Ba/F3 cells, 5· 105cells

were stained with anti-CD38 Ig (NIM-R5-FITC, dilution

1 : 500) (Southern Biotech, Birmingham, AL, USA) for

30 min at 4C The cells were analyzed by cytometry using

a FACSCalibur (Becton-Dickinson, San Jose, CA, USA)

Surface biotinylation of proteins

To analyze the stability of CD38 on the plasma membrane of

the different Ba/F3 mutants, labeling of the surface proteins

with the membrane impermeable reagent

sulfo-NSH-LC-biotin (Pierce) was performed as described [31] and following

the manufacturer instructions Briefly, cultured Ba/F3 cells

(1· 107) or splenic B cells (2· 108) were washed two times

with sterile NaCl/Piand resuspended in 3 mL of NaCl/Pi

containing 0.5 mgÆmL)1of sulfo-NHS-LC-biotin The cells

were incubated for 30 min at room temperature or on ice,

followed by three washings with NaCl/Pi The Ba/F3 clones

were then resuspended in complete Ba/F3 media and splenic

B cells were resuspended in supplemented RPMI media

containing 100 UÆmL)1of IL-4 The cells were cultured at

37C, and 2 · 106Ba/F3 cells or 5· 107splenic B cells were

harvested at 0, 2, 10, 20 and 30 h The cells were lysed with

0.5–1 mL of lysis buffer containing 1% (v/v) NP-40, and

CD38 was immunoprecipitated as described above

Immu-noprecipitated CD38 was analyzed by Western blot using

streptavidin-HRP (Sigma), and then the membrane was

stripped and reanalyzed with rabbit anti-CD38 Ig and

finally anti-rabbit Ig–HRP

Results

CD38 forms homodimers in murine splenic B cells

To address whether murine CD38 is expressed as a homodimer in splenic B cells, we purified these cells from CD38 expressing and CD38 deficient (CD38 KO) mouse strains and lysed them in buffer containing 1% (v/v) NP-40 CD38 was immunoprecipitated with an anti-mouse CD38 monoclonal antibody (NIM-R5), electrophoresed under reducing or nonreducing conditions and then analyzed by Western blot using a polyclonal rabbit anti-mouse CD38 Ig (Fig 1A) Under nonreducing conditions, no CD38 reactive proteins were detected in the immunoprecipitates from CD38 KO cells (Fig 1A, lane 1) In contrast, two distinct

Fig 1 CD38 forms 95 kDa homodimers in B lymphocytes (A)

B lymphocytes (5 · 10 7 ) were isolated from the indicated mouse strains, including CD38 deficient mice (CD38-KO [27]) The cells were lysed with 1% (v/v) NP-40 and CD38 was immunoprecipitated with monoclonal antibody to CD38, NIM-R5 The samples were prepared either in the absence (lanes 1–5) or presence of 5% (v/v) 2-mercapto-ethanol (lanes 6–10) and CD38 was detected by Western blot as des-cribed in Materials and methods The relative molecular mass markers are indicated on the left of each figure The nonspecific IgH band present in all of the reduced samples (including the CD38-KO sample)

is indicated with an asterisk (B) Immunoprecipitated CD38 from BALB/c B cell lysates was boiled in the presence of 2-mercaptoethanol (lanes 1–3) or dithiothreitol (lanes 4–6) at the concentrations shown

in the figure (C) CD38 was immunoprecipitated from splenic B cell lysates, resolved by 2D isoelectric focusing (IEF) and detected by Western blot IEF spots of monomeric and dimeric forms of CD38 are indicated by arrows b-ME, 2-mercaptoethanol; DTT, dithiothreitol.

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molecular mass forms of CD38 were observed in the

immunoprecipitates from CD38-expressing cells; a 42 and a

95 kDa protein (p42 and p95) (Fig 1A, lanes 2–5) The

42 kDa protein is the expected size of glycosylated

mono-meric CD38 [19] while the 95 kDa protein is the

approxi-mate size of a CD38 dimer When the samples were boiled

and reduced in 2-mercaptoethanol, we observed nonspecific

bands of 68 kDa (corresponding to the immunoglobulin

heavy chain present in B lymphocytes) and  200 kDa

(data not shown) in all immunoprecipitates, including the

sample from the CD38 KO mice (Fig 1A, lane 6) In

addition to observing the nonspecific bands, we still detected

the p42 and p95 forms of CD38 in the CD38-expressing cells

(Fig 1A, lanes 7–10) This indicates that p95 was partially,

although not fully, resistant to reduction by

2-mercapto-ethanol Interestingly, even addition of higher

concentra-tions of 2-mercaptoethanol or another reducing agent,

dithiotreitol, did not completely ablate the p95 form of

CD38 (Fig 1B)

To determine the structural composition of the p95 form

of CD38, we first ruled out the possibility that the p95 form

was composed of a CD38 monomer associated with the

immunoglobulin heavy chain from the precipitating

anti-CD38 Ig (data not shown) Next, we showed that the p95

form of CD38 was easily detected when iodoacetamide was

included in all of the buffers in order to block any reactive

free cysteines (data not shown) This ruled out the possibility

that p95 was formed during the lysis and

immunopreci-pitation process Finally, we compared p42 and p95 for their

pattern of isoelectric points by IEF and 2D polyacrylamide

gel electrophoresis For p42 we observed two dominant

isoelectric points of 7.7 and 7.2 and two minor points at 7.4

and 7.1 (Fig 1C) Analysis of p95 revealed isoelectric points

of 7.7, 7.2 and 7.1 (Fig 1C) These points were located at

similar positions to the corresponding points in the p42

monomeric form We did not detect a protein spot at 7.4 in

p95; however, this protein species only represented a minor

form even in the CD38 p42 monomer Taken together, the

data indicate that the p95 form of CD38 appears to

represent a homodimeric form of CD38 as it is recognized

by both monoclonal and polyclonal antibodies against

CD38, and has essentially identical IEF points as the p42

monomer form of CD38

CD38 homodimers are expressed on the surface

of splenic B cells and are destabilized when solubilized

with type B surfactants (steroid-based detergents)

To determine whether CD38 is normally expressed in the

homodimeric form on the plasma membrane of B cells, we

purified splenic B cells from normal and CD38 KO mice

and treated them for 1 h with a nonpermeable chemical

crosslinker, BS3, in order to stabilize the CD38 homodimers

during the lysis and immunoprecipitation steps As

expec-ted, no CD38 protein was detected in the CD38 deficient

cells (Fig 2A, lanes 2 and 5) Similarly to the previous

results, the majority of CD38 protein was of monomeric size

(p42) in the cells that were not treated with BS3(Fig 2A,

lanes 1 and 4) In contrast, in cells that had been treated

with crosslinker, CD38 was found predominantly in the

p95 homodimeric form (lanes 3 and 6) As the ratio of

homodimers to monomers was approximately five-fold

increased when the crosslinker was used (Fig 2A, compare lanes 1 and 3 or lanes 4 and 6), these results indicate that

a large proportion of the total CD38 is expressed in a

Fig 2 CD38 is found as homodimers on the surface of splenic

B lymphocytes and the stability of the dimers depends on the detergent used to solubilize the cells (A) Purified B cells were incubated with the nonpermeable crosslinker BS 3 for 1 h at 4 C (lanes 2, 3, 5 and 6) or left untreated (lanes 1 and 4) Crosslinked cells were lysed and CD38 was immunoprecipitated from cells expressing CD38 (CD38-WT, lanes 1, 3, 4 and 6) or lacking CD38 (CD38-KO, lanes 2 and 5) Immunoprecipitated proteins were treated with (lanes 4–6) or without 5% (v/v) 2-mercaptoethanol (lanes 1–3) and CD38 was detected by Western blot (B) Splenic B cells were solubilized with 1% (v/v) NP-40 (lanes 1, 2, 5 and 6) or Chaps (lanes 3, 4, 7 and 8) and CD38 was immunoprecipitated The samples were heated in the presence (lanes 5–8) or absence (lanes 1–4) of 5% (v/v) 2-mercaptoethanol and CD38 was detected by Western blot (C) B cells were solubilized with 1% (v/v) NP-40 (lane 1), Triton X-100 (lanes 2 and 3), digitonin (lanes 4 and 5), Chaps (lanes 6 and 7) or deoxy-BigChap (lanes 8 and 9) Lysates were immunoprecipitated with antibody to CD38 (NIM-R5) and CD38 was detected by Western blot The nonspecific IgH band present in all samples, including samples immunoprecipitated with an isotype control antibody (IgG2a), is indicated with an asterisk b-ME, 2-mercaptoethanol.

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homodimeric form on the surface of live B lymphocytes and

suggest that most of the CD38 dimers must fall apart when

the cells are solubilized in detergent Crosslinkers like

disuccinimidyl suberate, that have the same reactivity and

spacer arm length as BS3(11.4 A˚) also stabilized the CD38

homodimers However, crosslinkers such as

3,3¢-dithio-bis(sulfosuccinimidyl propionate), sulfo-disulfosuccinimidyl

tartarate and

sulfo-bis[2-(sulfosuccinimidooxycarbonyl-oxy)ethyl]sulfone, that have the same reactivity as BS3but

have different spacer arm lengths (12, 6.4 and 13 A˚,

respectively), were unable to stabilize the homodimers (data

not shown) These results suggest that the stabilization

of CD38 homodimers by crosslinkers depends strongly

on the conformation and orientation between the CD38

monomers

It has been reported that NP-40 and Triton X-100

stabilize noncovalent hetero- or homo-dimerization of

proteins, while detergents like Chaps and octylglucoside

disrupt these interactions [32,33] Up to now, in all our

experiments, the cells were solubilized in NP-40, a

deter-gent that might help to stabilize or protect the CD38

dimers from dissociating during the solubilization process

In sharp contrast, when the B cells were solubilized with

Chaps we found significantly less CD38 homodimers,

whether under reducing (Fig 2B, lanes 5–8) or

nonreduc-ing (Fig 2B, lanes 1–4) conditions This demonstrates that

the detergent used to solubilize the cells influenced the

amount of CD38 homodimers that could be

immuno-precipitated

To analyze whether the stabilization of CD38 dimers

was a property of the family of detergents utilized, we used

several different detergents to solubilize the cells As

shown in Fig 2C, CD38 dimers were precipitated when

the cells were solubilized with NP-40 or Triton X-100;

detergents that belong to the polyoxyethylene family

(Fig 2C, lanes 1–3) In contrast, when the cells were

solubilized with Chaps, digitonin or deoxy-BigChap,

members of the steroid-based detergent family, only

CD38 monomers were detected (Fig 2C, lanes 4–9)

These results suggest that CD38 homodimer stability is

dependent on noncovalent interactions between CD38

monomers

Structural requirements for CD38 homodimerization

To investigate the structural requirements for dimer stabilization, we determined whether different CD38 mutants were capable of forming homodimers when transfected into Ba/F3 cells Ba/F3 cells, stably transfected with full length wild-type CD38 (CD38-WT) or with different CD38 mutants, were solubilized in NP-40 lysis buffer and CD38 was immunoprecipitated, run on SDS/ PAGE under nonreducing conditions, and detected by Western blot Asummary of the results, presented in Table 1, indicates that CD38 homodimers were present in the lysates of most of the transfectants expressing CD38 mutants, including, CD38-E150L, a CD38 active site mutant (Table 2, [34]) and CD38-C123K, a mutant that

is unable to form the postulated interdisulphide bond between two CD38 monomers [22] These data indicate that CD38 homodimers can be formed even when the active site is altered and the putative interdisulphide bridge formed betweeen CD38 monomers is disrupted Interestingly, however, CD38 dimers were absent in lysates from two of the other mutant Ba/F3 transfectants

Table 1 Expression of CD38 homodimers in different CD38 mutants expressed in Ba/F3 pro-B cells Each of the mutant CD38 cDNAs listed, was stably expressed in Ba/F3 cells (Materials and methods) or A20 cells as described previously [30] The cells were solubilized in 1% (v/v) NP-40 CD38 was immunoprecipitated, run on SDS/PAGE gels under nonreducing conditions and then analyzed for the presence (Y)

or absence (N) of the p42 monomer and p95 homodimer by Western blot WT, wild-type.

Table 2 NAD+glycohydrolase activity of membrane homogenates from Ba/F3 transfectants Each of the mutant CD38 cDNAs listed, was stably expressed in Ba/F3 cells and the enzyme activity (V max ) of the membrane homogenates was determined as described previously [30] The V max was adjusted to reflect differences in CD38 expression levels between the various mutants and is reported as nmol of product formed per minute per arbitrary unit of CD38 Briefly, the total amount of protein per Ba/F3 cell was determined by the Bradford method The average amount of CD38 expressed on the membrane of each Ba/F3 cell was determined by FACS and is reported as mean fluorescence intensity (Fig 3C shows values of each of the clones) The relative enzyme activity of each of the mutants is given in parentheses It was determined by setting the V max adjusted activity of CD38-WT to 100% and then calculating the percentage activity of each of the mutants relative to CD38-WT MFI, mean fluorescence intensity; WT, wild-type.

Mutant

V max

(nmolÆmin)1Æmg)1protein)

Protein per cell (mg protein per cell · 10)7)

CD38 per cell arbitrary units CD38 per cell (1/MFI · 10)4)

V max adjusted (nmolÆmin)1per arbitrary units of CD38 · 10)10)

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In one of the mutants (CD38-lATG), the 22 amino acid

cytoplasmic region of CD38 was replaced with a 4 amino

acid tail (Met-Lys-Val-Lys), and in the second mutant

(CD38-G68E), the glycine at position 68 was replaced by

the polar residue glutamate The G68 residue is within the

a1-helix that has been previously postulated to be a dimer

interface site in the Aplysia enzyme [16] As shown in

Fig 3A(lanes 2 and 5), CD38 homodimers were

preci-pitated from Ba/F3 transfectants expressing CD38-WT or

expressing a mutant form of CD38 in which a single

residue in the active site was mutated (CD38-E150L) However, no CD38 homodimers were detected in immunoprecipitations from transfectants expressing the CD38-G68E or CD38-lATG mutant proteins (Fig 3A, lanes 3 and 4) This result suggests that the cytoplasmic region and first a-helix interface region of CD38 are important for dimer stability

To determine whether these two regions were necessary for CD38 dimer stabilization on the plasma membrane of the Ba/F3 cells, the transfectants expressing CD38-lATG

Fig 3 The stability and membrane expression of CD38 homodimers is dependent on at least two separate domains of CD38 (A) Ba/F3 cells transfected with control vector, CD38-WT, CD38-G68E, CD38-lATG or CD38-E150L were lysed with 1% (v/v) NP-40 and CD38 was imu-noprecipitated, run on SDS/PAGE under nonreducing conditions and detected by Western blot (B) The Ba/F3 transfectants listed above were treated (as described in Fig 2) with the crosslinker BS3(lanes 2, 4, 6, 8 and 10) or left untreated (lanes 1, 3, 5, 7 and 9) CD38 was detected by Western blot as in Fig 2A (C) Ba/F3 mutants were analyzed for expression of CD38 on the plasma membrane by FACS using the antibody, NIM-R5, conjugated to FITC Dead cells were excluded by propidium iodide incorporation Light line histograms, nontransfected Ba/F3 cells; dark line histograms, Ba/F3 transfectants The mean fluorescence intensity of the cells from each of the transfectants is listed above the histogram (D) Post-nuclear supernatants were prepared from Ba/F3 clones lysed with 1% (v/v) NP-40, the protein concentration was determined and equivalent amounts of protein were run on SDS/PAGE gels under reducing conditions CD38 and actin expression were analyzed by Western blot using rabbit polyconal anti-CD38 Ig and mouse monoclonal antibody to actin, followed by HRP-labeled anti-rabbit IgG and anti-mouse IgG, respectively (E) Comparison of plasma membrane and total CD38 expression levels in the Ba/F3 clones To determine the relative plasma membrane expression levels of CD38 between the different Ba/F3 clones the mean fluorescence intensity for each of the clones was determined (C) and the relative levels were normalized to that of the CD38-WT transfectant which was set at 100% To quantitate the total CD38 expression levels for the various Ba/F3 transfectant clones, densitometric analysis of CD38 and actin Western blots (D) were performed using SIGMAGEL LNK The CD38 levels for each clone were first normalized to actin by dividing the densitometric value of CD38 by the densitometric value of actin Then the relative total CD38 expression levels for each clone were normalized to CD38-WT which was set at 100%.

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or CD38-G68E were crosslinked with BS3, solubilized in

NP-40 lysis buffer, and CD38 was detected by

immuno-precipitation and Western blot (Fig 3B) As we have

previously observed, homodimers of CD38 were absent in

the immunoprecipitates from the noncrosslinked

CD38-lATG and CD38-G68E transfectants (lanes 5 and 9)

However, when the crosslinker was added, CD38

homo-dimers could be visualized (lanes 6 and 10) Indeed, similar

ratios of homodimers to monomers were observed in the

crosslinked CD38-G68E and CD38-lATG mutants

com-pared to crosslinked CD38-WT and CD38-E150L (compare

lanes 4, 6, 8 and 10) Therefore, the cytoplasmic region and

a1-helix domains are not critical for CD38 dimer

stabiliza-tion in B cells, however, the two domains must contribute to

the overall stability of CD38 homodimers because the

mutated dimers fell apart even under permissive

solubili-zation and nonreducing conditions

CD38-G68E and CD38-lATG are less efficiently

expressed and have a reduced half-life

on the plasma membrane

The previous results indicated that CD38-lATG and

CD38-G68E are not obligatory for dimer stabilization

but do contribute to the overall stability of the dimers,

particularly upon detergent solubilization It has been

reported that inappropriate folding of proteins or

inappro-priate assembly of multimeric protein complexes can

influence the surface and overall expression of these proteins

in cells and can also alter the half-life of the misfolded or

disorganized protein complexes [35,36] Given that the

stability of CD38-lATG and CD38-G68E homodimers is

reduced when the proteins are solubilized in permissive

detergents, immunoblotting and FACS experiments were

performed in order to analyze the total and surface levels of

CD38 in all the Ba/F3 transfectants (Fig 3C–E) These

experiments revealed that the total amount of CD38 (as

assessed by immunoblotting), as well as the amount of

CD38 expressed on the plasma membrane (as assessed by

FACS) was similar in the CD38-WT and CD38-E150L

transfected Ba/F3 cells (Fig 3C,D) In contrast, CD38

expression levels (both total and plasma membrane levels) in

transfectants expressing CD38-G68E and CD38-lATG

were significantly decreased relative to CD38-WT

(Fig 3C,D) Similar results were obtained upon analysis

of multiple independent Ba/F3 clones expressing

CD38-lATG or CD38-G68E (data not shown) Upon

densito-metric analysis of the immunoblots it became clear that the

amount of CD38 expressed on the plasma membrane and

the total amount of CD38 expressed by the various

transfectants correlated very well with one another

(Fig 3E), strongly suggesting that the reduced cell surface

expression of CD38 by the CD38-lATG and CD38-G68E

transfectants was not due simply to inefficient transport of

the protein to the plasma membrane In addition, confocal

microscopic analysis of CD38 expression in Ba/F3

trans-fectants revealed that neither CD38 nor any of the CD38

mutant proteins were present in intracellular compartments

(data not shown) Therefore, we next considered the

possibility that the reduced plasma membrane expression

of the CD38-lATG and CD38-G68E mutant proteins

could be due to a faster turnover rate for these mutant

molecules on the plasma membrane [35] To analyze this possibility, we performed pulse-chase experiments using normal B cells and the Ba/F3 transfectants To first determine whether the surface half-life of CD38 in Ba/F3 cells is comparable to that of splenic B cells, we biotinylated the surface of splenic B cells and Ba/F3 clones (CD38-WT and lATG) and compared the plasma membrane half-life

of CD38 In these experiments the biotinylation was carried out for 30 min on ice in order to avoid any potential internalization of biotin or biotinylated proteins The cells were then washed to remove the reactive biotin and cultured for up to 30 h The amount of cell surface biotin-labeled CD38 at various timepoints was determined by immuno-precipitating with anti-CD38 and immunoblotting with SA-HRP to detect the cell surface biotinylated-CD38 and anti-CD38 to detect the total CD38 pool The plasma membrane expression of CD38 on CD38-WT Ba/F3 transfectant cells and on normal B cells was quite stable over time with a half-life of approximately 28 h on both cell types (Fig 4A,B), indicating that the turnover rate of CD38

in both cell types is similar and comparable In contrast, the surface half-life of CD38-lA TG was less than half that observed for CD38 expressed by normal B cells or Ba/F3 transfectants, suggesting that this mutant protein is less stably expressed on the plasma membrane (Fig 4A,B) To confirm these results, we repeated the biotinylation experi-ment using Ba/F3 transfectants expressing other CD38 mutant proteins The plasma membrane expression of both CD38-WT and CD38-E150L was quite stable over time with a half-life of approximately 28 h (Fig 5A,B) In striking contrast, the half-lives of plasma membrane bound CD38-G68E and CD38-lATG were less than half that observed with CD38-WT (Fig 5A,B) Thus, both of the CD38 mutant proteins that form unstable homodimers also have significantly reduced stability on the plasma mem-brane, suggesting that appropriate assembly or stabilization

of CD38 into homodimers may be required for its extended expression on the plasma membrane

Enzyme activity is not dependent on the presence

of stable homodimers

As the mutations in the cytoplasmic region and the a1-helix

of CD38 affected dimer stability upon solubilization, plasma membrane expression levels and surface half-life, it was also possible that these mutations would affect the enzyme activity of the proteins To test the enzyme activity

of the CD38 mutants, membrane homogenates from the various Ba/F3 transfectants were prepared and NAD+ glycohydrolase activity in the membranes was measured by HPLC As shown in Table 2, the enzyme activity of the active site mutant, CD38-E150L was greatly decreased compared to CD38-WT Interestingly, the glycohydrolase activities of CD38-G68E and CD38-lATG were also less than CD38-WT As the membrane expression levels of CD38-lATG and CD38-G68E were reduced compared to CD38-WT (Fig 3C,D), we performed a calculation to adjust the enzyme activity (Vmax adjusted) to reflect the amount of total protein and CD38 protein expressed on

a per cell basis Upon adjusting the enzyme activity to compensate for the membrane CD38 expression levels, we found that the enzyme activity of CD38-lATG was at least

Trang 8

as high as CD38-WT (Table 2) These data indicate that the

catalytic activity of CD38 is not dependent on the formation

of stable CD38 homodimers Interestingly, however, even

when expression levels of CD38-G68E were accounted for,

the NAD+glycohydrolase activity of CD38-G68E was only

27% of CD38-WT This result shows that a single point

mutation in the first a-helix of CD38, a residue that is far

removed from the active site of CD38, can significantly

influence CD38 enzyme activity

Discussion

In this work we show that homodimers of CD38 are expressed on the surface of B lymphocytes Although CD38 dimers that are sensitive to reducing agents have been previously reported [22–25], we found that the stability of CD38 dimers expressed in B cells correlated better with the type of detergent used to solubilize the cells (Fig 2) than the presence or absence of reducing agents (Fig 1) Previous reports have shown that heterodimerization of proteins such

as Bax with Bcl-2 or Bax with Bcl-XLare dependent on the detergent used to solubilize the cells [32,33] Thus, NP-40 and Triton X-100, detergents that form large micelles, stabilized the hydrophobic interactions between Bax and its partners, while Chaps and octyl glucoside, detergents that form small micelles, could not accommodate the hetero-dimers Interestingly, we found the same pattern with CD38 homodimers in that they were stabilized in the

polyoxy-Fig 5 The mutants expressing unstable CD38 homodimers present a reduced CD38 half-life on the plasma membrane (A) Ba/F3 transfectant cells expressing CD38-WT or each of the different mutants were sur-face labeled with sulfo-NHS-LS-biotin for 30 min at room tempera-ture The cells were washed and then cultured at 37 C for an additional 30 h 2 · 10 6

cells were harvested at 0, 2, 10, 20 and 30 h after biotin labeling Cell viability, as measured by trypan blue exclu-sion, was over 95% at each time point Immunoprecipitation and Western-blotting was performed as described in Materials and methods and Fig 4 (B) Densitometric analyses using the program

SIGMAGEL.LNK were performed to compare the relative amounts of biotin-labeled CD38 in each Ba/F3 clone Densitometry was per-formed as described in Fig 4.

Fig 4 The half-life of CD38 is the same in splenic B cells and

CD38-WT Ba/F3 transfectants Purified splenic B cells, CD38-CD38-WT and

CD38-lATG Ba/F3 transfectants were labeled with

sulfo-NHS-LS-biotin for 30 min on ice The cells were washed and then cultured at

37 C for an additional 30 h 2 · 10 6

Ba/F3 cells or 5 · 10 7

splenic

B cells were harvested at 0, 10, 20 and 30 h after biotin labeling Cell

viability, as measured by trypan blue exclusion, was over 95% for the

Ba/F3 transfectants at each time point and was 97, 90, 87 and 75% for

splenic B cells at 0, 10, 20 and 30 h after biotinylation, respectively.

(A) At each timepoint, the cells were lysed in 1% (v/v) NP-40, CD38

was immunoprecipitated with anti-CD38 Ig, and the

immunoprecipi-tated protein was analyzed by SDS/PAGE and Western blotting The

amount of plasma membrane associated (biotinylated-CD38) and

total CD38 was determined by immunoprecipitation, SDS/PAGE and

Western blotting Plasma membrane biotinylated-CD38 was detected

with streptavidin-HRP (left) Total immunoprecipitated CD38 was

detected using the polyclonal rabbit antibody to CD38 (right).

(B) Densitometric analyses using the program SIGMAGEL LNK were

performed to compare the relative amounts of biotin-labeled CD38

(membrane CD38) in each Ba/F3 clone To determine the relative

amount of biotin-labeled CD38 present in each clone, the

densito-metric value of biotin-CD38 was divided by the densitodensito-metric value of

total CD38 The ratio of cell surface CD38 to total CD38 at time 0

was set at 100% and all other time points were compared relative to

this.

Trang 9

ethylene detergents (i.e NP-40 and Triton X-100) and were

destabilized with detergents such as digitonin, Chaps

and deoxy-BigChap (Fig 2) Importantly, these differences

could not be attributed to differences in the ability of the

various detergents to solubilize CD38 (data not shown)

Furthermore, when we used the crosslinker, BS3, the

majority of CD38 was captured in the homodimer form

indicating that CD38 must be dimerized via noncovalent

interactions that were partially disrupted when the cells were

solubilized in detergent However, it is also clear that

conformation and folding of the individual CD38

mono-mers is strongly influenced by the five known

intradisul-phide bonds present in each monomer and their reduction is

also expected to greatly influence the stability of the

noncovalently associated CD38 homodimers

As CD38 dimers appear to be stabilized via noncovalent

interactions between monomers, a reasonable assumption is

that mutations within the potential interface domains might

alter the formation or stability of CD38 homodimers When

cells expressing two different mutant forms of CD38, a

cytoplasmic region mutant and an a1-helix mutant, were

solubilized under nonreducing conditions in a permissive

detergent such as NP-40, we were unable to detect the

presence of CD38 homodimers (Fig 3A), suggesting that

these two domains play an important role in homodimer

stability Because homodimers of G68E and

CD38-lATG were observed when the cells were crosslinked with

BS3(Fig 3B), these data suggest that these domains are not

obligate for the stabilization of the dimers, but rather must

contribute to the overall stability of the dimers

Crystallo-graphic analysis of the Aplysia cyclase indicates four

putative oligomerization sites including the a1, a4 and a10

helices and residues between 242 and 248 [16] Thus, we

propose that multiple contact points contribute in an

additive or synergistic manner to CD38 homodimer

stabil-ization Although the mutants described here are not

sufficient, in themselves, to control CD38 homodimer

stabilization, the results clearly demonstrate a role for the

a1-helix and the cytoplasmic region in stabilizing the

solubilized homodimers

The mutations in the cytoplasmic tail and a1-helix of

CD38 not only affected the stability of the CD38

homo-dimer upon solubilization, but also significantly diminished

the expression of the CD38 homodimer on the plasma

membrane Indeed, we were never able to isolate

CD38-G68E expressing transfectants expressing levels of CD38

comparable to CD38-WT, despite screening more than 25

individual clones (data not shown) As a whole, these data

suggest that CD38-G68E and CD38-lATG mutants were

either inefficiently assembled and transported to the

mem-brane or were less stable on the surface Our pulse-chase

experiments (Figs 4 and 5) clearly showed that the plasma

membrane half-life of these CD38 mutants was significantly

less than CD38-WT, suggesting that extended plasma

membrane expression of CD38 may depend on the presence

of stable CD38 homodimers Although further experiments

will be needed to prove this hypothesis, similar results were

obtained analyzing mutants of the dipeptidylpeptidase IV

CD26 [36] The close correlation between surface expression

of CD38 and total expression of CD38 suggests that the

mutant forms of CD38 are not preferentially retained in

the intracellular compartments (Fig 3C–E) Furthermore,

intracellular expression analysis of CD38 on Ba/F3 trans-fectants and normal B cells using confocal microscopy or subcellular fractionation and immunobloting revealed that neither CD38 nor any of the CD38 mutant proteins analyzed in this study were detected in intracellular mem-branes (data not shown)

CD38 homodimers have been proposed to play a number

of different functional roles including formation of a transmembrane pore, allowing for transport of cADPR into the cytosol [37] However, it is clear that stable homodimers are not obligate for enzyme activity as the unstable CD38 homodimer mutant, CD38-lATG, had perfectly normal enzyme activity when the activity was adjusted to reflect CD38 expression levels on the membrane (Table 2) In agreement with this, we also observed NADase activity from the p42 monomeric form of CD38 (data not shown), suggesting that CD38 monomers are enzymatically active This is in agreement with the results of Bruzzone et al [18] Interestingly, although mutations in the active site do not decrease the formation or stability of CD38 homodimers (Table 2), the cells expressing the unstable CD38 homodimer, CD38-G68E, had significantly decreased CD38 dependent enzyme activity (Table 2) Thus, while CD38 enzyme activity is not critically dependent on the presence of stable CD38 homodimers, it

is clear that mutating a single residue in the a1-helix interface can decrease both homodimer stability and enzyme activity In conclusion, we have shown that CD38

is normally expressed as a noncovalently associated homodimer on the plasma membrane of B cells Mutations that affect the stability of the CD38 homodimer do not necessarily alter CD38-dependent enzyme activity; however, these mutations do result in reduced plasma membrane stability and decreased expression of CD38 on the plasma membrane

Acknowledgements The authors would like to thank Troy Randall for discussions and critical reading of this manuscript The authors also thank Dr Jose´ Manuel Herna´ndez-Herna´ndez for technical advice and Q F B He´ctor Romero Ramı´rez for technical assistance M E M.-G., A S.-T and L S.-A are supported by CONACyT Me´xico grants, # 28093N, 33497N and 40218Q J P., S P-S., and F E L are supported by NIH grant AI-43629 and the Trudeau Institute.

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