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Two protein bands 82 and 86 kDa were immunologically detected after PAGE and Western blot of cytosol or membrane prepared from transfected cells.. melanogaster DPP III DPP III activity w

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Characterization of a functionally expressed dipeptidyl

Claire Mazzocco1,*, Kayoko M Fukasawa2, Patrick Auguste3and Jacques Puiroux1,†

1

Laboratoire des Re´gulations Neuroendocriniennes, Universite´ Bordeaux I, Talence, France;2Department of Oral Biochemistry, Matsumoto Dental College, Shioriji, Nagano, Japan;3Laboratoire des Facteurs de Croissance et de la Diffe´renciation Cellulaire, INSERM EPI-0113, Universite´ Bordeaux I, Talence, France

A Drosophila melanogaster cDNA clone (GH01916)

encoding a putative 723-residue long (82 kDa) protein

(CG 7415) and displaying 50% identity with mammalian

cytosolic dipeptidyl aminopeptidase (DPP) III was

func-tionally expressed in Schneider S2cells

Immunocytochemi-cal studies using anti-(rat liver DPP III) Ig indicated the

expression of this putative DPP III at the outer cell

mem-brane and into the cytosol of transfected cells Two protein

bands (82 and 86 kDa) were immunologically detected after

PAGE and Western blot of cytosol or membrane prepared

from transfected cells Western blot analysis of partially

purified D melanogaster DPP III confirmed the

over-expression of these two protein bands into the cytosol and on

the membranes of transfected cells Despite the identification

of six potential glycosylation sites, PAGE showed that these protein bands were not shifted after deglycosylation experi-ments The partially purified enzyme hydrolysed the insect myotropic neuropeptide proctolin (Arg-Tyr-Leu-Pro-Thr)

at the Tyr-Leu bond (Km 4 lM) In addition, low con-centration of the specific DPP III inhibitor tynorphin pre-vented proctolin degradation (IC50¼ 0.62 ± 0.15 lM) These results constitute the first characterization of an evo-lutionarily conserved insect DPP III that is expressed as a cytosolic and a membrane peptidase involved in proctolin degradation

Keywords: enkephalinase; genome sequencing; insects; neuropeptides; proctolin

Mammalian DPP III was first discovered in the bovine

anterior pituitary gland [1] and it has been recently cloned

from rat liver as a 738-residue (82 kDa) cytosolic protein

[2,3] This enzyme (EC 3.4.14.4) is a zinc metallopeptidase

containing a specific domain HELLGH-18X-E where a zinc

molecule is bound to both histidines [4] DPP III is mainly

identified as a cytosolic peptidase, but DPP III was also

detected on membranes prepared from the brain of

guinea-pig [5] and rat [6] Angiotensins and enkephalins constitute

the preferred substrates of the rat brain cytosolic DPP III

[7] The routes of degradation of the insect myotropic

neuropeptide proctolin (Arg-Tyr-Leu-Pro-Thr) have been

compared to those of enkephalins Indeed, a dipeptidyl

aminopeptidase activity appears as one major proctolin-degrading peptidase, liberating the N-terminal Arg-Tyr dipeptide [8–11] This dipeptidyl aminopeptidase activity was compared to the vertebrate DPP III [11] and is mainly recovered as a cytosolic enzyme [8] Interestingly, a proct-olin-degrading DPP activity is also measured on membranes [8,9] especially those obtained from insect proctolin-rich tissues such as hindgut [10] None of the presumed proctolinases has been fully characterized yet

We recently purified [12] from hindgut membranes of the cockroach, Blaberus craniifer, a proctolin-degrading protein (76 and 80 kDa) that removes the N-terminal dipeptide from proctolin (Km¼ 3.8 ± 1.1 lM) and enkephalins (Km¼ 4.2 ± 0.8 lM) The partial sequencing of this puri-fied protein revealed a significant homology with the rat liver cytosolic DPP III that was confirmed by the specific detection of this purified insect protein with anti-(rat liver DPP III) Ig in Western blot analysis In addition, this sequencing allowed the identification in Drosophila melano-gaster of a set of homologous cDNA sequences and a related genomic sequence (available at the Berkeley Droso-philaGenome Project) that encode a deduced 723-residue long protein (82 kDa) sharing 50% identity with mamma-lian DPP III This D melanogaster DPP III is annotated CG7415 [13] Western blot analysis of crude membrane and soluble material prepared from D melanogaster showed the presence of two protein bands (82 and 86 kDa) immuno-logically related to vertebrate DPP III [12] From these results, it could be speculated that an evolutionarily conserved DPP III is present in insects

In the present study, the functional expression of the put-ative D melanogaster DPP III was attempted in Schneider

Correspondence to J Puiroux, Laboratoire de Neurobiologie des

Re´seaux, CNRS-UMR 5816, Universite´ Bordeaux 1, Avenue des

Faculte´s, 33405 Talence Cedex, France.

Fax: + 33 557 962561, Tel.: + 33 557 962569,

E-mail: j.puiroux@lnr.u-bordeaux.fr

Abbreviations: BDGP, Berkeley Drosophila genome project;

DAB, diaminobenzidine; DPP, dipeptidyl aminopeptidase.

Enzyme: rat liver DPP III (EC 3.4.14.4).

*Present address: Groupe de Recherche pour l’Etude du Foie,

INSERM E 9917, Universite´ Victor Segalen Bordeaux II,

146 rue Le´o Saignat, 33076 Bordeaux, France.

Present address: J Puiroux, Laboratoire de Neurobiologie des

Re´seaux, CNRS-UMR 5816, Universite´ Bordeaux 1, Avenue

des Faculte´s, 33405 Talence Cedex, France.

(Received 20 March 2003, revised 19 May 2003,

accepted 27 May 2003)

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S2cells to investigate its apparent dual cellular location and

to examine the characteristics of this enzyme

Immunocyto-chemical studies, Western blot analysis using anti-(rat liver

DPP III), partial purification and proctolin degradation

studies demonstrate the overexpression of the D

melano-gaster DPP III on membranes and into the cytosol of

transfected cells These results confirm that DPP III can be

attached to cell membranes, and they represent the first

identification and characterization of an insect DPP III that

plays a major role in proctolin degradation

Experimental procedures

Materials

Diaminobenzidine (DAB), Hepes, hydrogen peroxide,

enkephalins, the enkephalin N-terminal dipeptide Tyr-Gly

and proctolin were purchased from Sigma (France) All

chromatographic materials were from Pharmacia (Uppsala,

Sweden) The specific DPP III inhibitor tynorphin

(Val-Val-Tyr-Pro-Trp) was a gift from K Fukasawa

(Matsu-moto Dental University, Nagano, Japan) The anti-(rat liver

DPP III) was prepared as described by Fukasawa et al [2]

Goat anti-rabbit Ig with peroxidase labelling was from

Boehringer-Mannheim The proctolin fragments Arg-Tyr

and Leu-Pro-Thr were a gift from B G Loughton (York

University, Ontario, Canada) The expression system in

S2cells was from Invitrogen

Stable transfection of S2cells with aD melanogaster

cDNA encoding a putative DPP III

A 2.484 k b HpaI fragment of the D melanogaster cDNA

clone GH01916 (in pOT2 vector) coding a putative DPP III

was subcloned into the EcoRV site of pMTA/V5-His B

expression vector previously dephosphorylated with calf

intestinal alkaline phosphatase

control of the metallothionein promoter Schneider S2cells

were cultured at 24C in Schneider S2 cell medium

containing L-glutamine (1 mM), Penicillin-Streptomycin

(25 mgÆmL)1) and 10% (v/v) heat-inactivated fetal bovine

serum Cells (106 cellsÆmL)1) were placed in Petri dishes

(35 mm) and incubated overnight at 24C before

transfec-tion The mixture for cell transfection was prepared by

mixing 36 lL of 2MCaCl2with 19 lg of expression vector

pMTA/DPP III and 1 lg of selection vector pCoHYGRO

coding for hygromycin B and adjusted to a final volume of

300 lL with sterilized MilliQ water The mixture was added

dropwise to 300 lL Hepes sterile buffer (50 mM Hepes,

1.5 mMNaH2PO4, 280 mM NaCl, pH 7.1) and incubated

for 30 min at room temperature prior to transfection of S2

cells A control transfection was carried out using the

pMTA expression vector without the HpaI fragment of the

D melanogaster cDNA (mock transfection) After

over-night incubation at 24C, the transfected cells were rinsed

twice with 2 mL of complete S2 medium to remove the

precipitates and finally incubated at 24C with 2 mL of

complete S2medium Stable recombinant cells were selected

by adding hygromycin B (300 lgÆmL)1) 2 days

post-trans-fection The protein expression was induced by addition of

CuSO4(final concentration 0.5 mM) to hygromycin-selected

recombinant cells 48 h before measurements

Analysis of transfected S2cells The transfection of S2cells by the expression vector pMTA/ DPP III was verified by PCR using a Perkin Elmer GeneAmp PCR System 2400 thermocycler A sense primer designed against the sequence of the pMTA vector (5¢-GGGGATCTAGATCGGGGT-3¢) and an antisense primer specific for the HpaI fragment (5¢-AGCGGAAGT GTGATGCCG-3¢) were used with DNA from transfected,

mock transfected or untransfected S2 cells as template These primers and a second set of primers (sense primer 5¢-GAATTCGAGGGCTTCGTGGCC-3¢ and antisense primer 5¢-AACGAGTCCTTCGCCTGCCT-3¢) specific for the HpaI fragment were used for RT-PCR Total RNAs from transfected, mock transfected or untransfected

S2 cells were used after DNAse I treatment to prepare cDNA templates

Immunocytochemistry of stable transfected S2cells Immunocytochemical studies were performed on stable recombinant S2cells 48 h after induction Twenty milliliters

of cell culture were centrifuged (1000 g, 5 min) and the pelleted cells were rinsed twice with 1 mL NaCl/Pi(137 mM NaCl, 2.7 mM KCl, 10 mM Na2HPO4, 1.8 mM KH2PO4,

pH 7.4) Then, the unfixed cells were incubated with anti-(rat liver DPP III) Ig (1/2000) in NaCl/Piwith or without 0.1% (w/v) Tween 20 for 1 h at room temperature under slow constant agitation The cells were centrifuged (1000 g,

5 min) and rinsed with 1 mL NaCl/Pifor 15 min under slow agitation Cells were then incubated for 1 h at room temperature with horseradish peroxidase labeled secondary antibody (1/1000) Cells were rinsed as described above, then incubated in Tris buffer (50 mM Tris/HCl, pH 8) containing DAB (1.39 mM) for 5 min and finally revealed

by addition of 0.01% (v/v) H2O2 Cells were rinsed twice and mounted on glass slide in 80% (w/v) glycerol and observed with a microscope (Reichert–Jung model Polyvar) and image analysis software (Spot RT, Diagnostic Instru-ments, USA)

Partial purification of a putativeD melanogaster DPP III expressed in S2cells

Typically, 50 mL of cell culture were centrifuged (1000 g,

5 min, room temperature) and the pelleted cells were rinsed twice with 1 mL NaCl/Pi (pH 7) The pellet was suspended in 0.5 mL ice-cold Hepes buffer (10 mMHepes, 5% (w/v) glycerol, 5 mM MgCl2, pH 7.2) and homogen-ized with a motor driven Teflon-glass homogenizer The homogenate was centrifuged (3000 g for 10 min at 4C in

a Beckman J2-MC centrifuge) The pellet was discarded and the supernatant was centrifuged (40 000 g for 20 min

at 4C) The final supernatant (cytosolic sample) was separated from the membrane pellet, filtered (0.45 lm pore size syringe filter) and stored at )80 C The membrane pellet was suspended in 1 mL Hepes buffer and recentrifuged (40 000 g for 20 min at 4C) The final membrane pellet was suspended in 200 lL Hepes buffer and stored at )20 C A total of 8 L of stable trans-fected S2 cells induced for 48 h were thus prepared for chromatography and the total cytosolic sample contained

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about 50 mg protein The pooled membrane preparations

contained approximately 45 mg proteins and this

mem-brane homogenate (1 mg proteinÆmL)1) was solubilized by

adding a concentrated Chaps solution (10% w/v in cold

Hepes buffer) dropwise to a final concentration of 1%

Solubilization was carried out for 1 h at 4C under

constant agitation and the sample was then

ultracentri-fuged (100 000 g for 1 h at 4C, Beckman L8-55

centrifuge) The supernatant (solubilized sample) was

filtered, added with 90 mL Hepes buffer (to reduce the

detergent concentration) and processed for purification

The partial purification of expressed D melanogaster

putative DPP III was performed according to the method

already described in [14] Briefly, cytosolic or solubilized

sample was first loaded on a 5-mL HiTrap Q Sepharose

cartridge connected to a Pharmacia AKTA FPLC system

(Pharmacia, Uppsala, Sweden) delivering 5 mLÆmin)1

The cartridge was then rinsed with Hepes buffer

(con-taining 0.1% w/v Chaps for the solubilized sample) and

proteins were eluted by a regular NaCl gradient (from 10

to 500 mM in 25 min) generated with buffer B (Hepes

buffer containing 1MNaCl) Fractions were collected every

minute and the presence of DPP III was identified by

degradation studies using proctolin as substrate and by

Western blot analysis with anti-(rat liver DPP III) Ig The

enzyme fractions were pooled and concentrated by

ultrafil-tration (Macrosep Pall Filtron cartridge, molecular mass cut

off

2 ¼ 10 000 spun at 4000 g for 90 min at 4 C) The protein

content and the DPP III activity were measured and the

concentrated sample was applied to two Superdex HR 200

10/30 columns (connected in line) The isocratic separation

of proteins was obtained with Hepes buffer delivered at

0.25 mLÆmin)1 The enzyme fractions were identified as

above Both separations were monitored at 280 nm

Degrading activity of the functionally expressed

putativeD melanogaster DPP III

DPP III activity was measured in homogenates of whole

transfected cells, in cytosolic or solubilized membrane

samples and in partially purified fractions with proctolin

(40 lM, 6 nmol) as substrate The incubation was carried

out in presence of bestatin (100 lM) in a final volume of

150 lL for 15 min at 25C under constant stirring The

reaction was stopped by the addition of 5 lL of 2MHCl

and centrifugation (Hettich EBA 12R, 16 500 g at 4C for

8 min) The degradation products were separated on a

Pharmacia PepRPC HR 5/5 reversed-phase column

con-nected to an FPLC system (pump A: 0.1% v/v

trifluoro-acetic acid in MilliQ water; pump B: 0.1% v/v

trifluoroacetic acid, 60% v/v CH3CN in MilliQ water)

delivering 1 mLÆmin)1under the following gradient

condi-tions: from 1 to 15% CH3CN for the first 5 min, then from

15 to 30% CH3CN for the next 15 min The detection of

neuropeptide fragments was monitored at 206 and 280 nm

The proctolin fragments Arg-Tyr and Leu-Pro-Thr were

identified by coelution with standard solutions of di- and

tripeptide The effect of proctolin concentrations (from 1 to

250 lM) and the effect of tynorphin concentrations (from

100 lMto 0.1 nM) on the degradation of proctolin (40 lM)

were examined with the putative DPP III partially purified

from cytosol or solubilized membrane sample The effect of

the divalent metal ions Zn2+ and Co2+was checked on DPP III activity contained in whole cell homogenates A curve-fitting computer program (CRICKET GRAPH)

to determine the Kmvalue for proctolin and the IC50for tynorphin

Cell surface degradation and internalization

of proctolin by stable transfected S2cells Transfected S2cells were previously induced for 48 h with CuSO4 (final concentration in culture medium 0.5 mM) Then, transfected cells were rinsed twice in NaCl/Pi and incubated (50 000 cells per tube) in Hepes degradation buffer (100 lL) with proctolin (25 nmol) as substrate At the end of incubation, the supernatant (incubation medium) was separated from the cells by centrifugation (1000 g for 8 min at room temperature)

5 lL HCl (2M) Then, the cell pellet was rinsed twice before cell disruption and centrifugation (13 000 g for

15 min) to isolate the cytosolic sample also added with

5 lL HCl (2M)

5 Proctolin degradation was analyzed by reversed-phase separation of the incubation medium in order to estimate the metabolism of proctolin at the cell surface The reversed-phase separation of cytosolic samples indicated the rate of neuropeptide degradation after internalization These results were compared to those obtained with transfected S2cells not previously induced SDS/PAGE and Western blot analysis

The samples consisting of transfected, mock transfected or untransfected cells, cytosol or membrane preparations (30 lg per lane) or partially purified expressed enzyme (1

or 2 lg) were prepared in sample buffer (62.5 mMTris/HCl,

pH 6.8, 0.025% bromophenol blue, 10% w/v glycerol and 1% w/v SDS) and electrophoresed [15] on a 7.5% acryl-amide 1 mm-thickmini gel at 20 mA for 150 min Then the gel was stained with Coomassie Brillant Blue R-250, silver stained (Silver Stain Plus Kit, Bio-Rad), or transferred to a nitrocellulose membrane (Hybond C extra, pore size 0.45 lm, Amersham) for 1 h using a mini-trans-blot apparatus (Bio-Rad) for Western blot analysis The mem-brane was soaked in Tris buffered saline with Tween-20 (TBS Tween, 20 mM Tris/HCl, 137 mM NaCl, 0.1% v/v Tween-20, pH 7.3) with 5% (w/v) dry low fat milk(used as blocking agent) for 30 min at 37C under constant stirring Then, the membrane was incubated overnight at 4C with rabbit polyclonal anti-(rat liver DPP III) Ig (1/2000 in TBS Tween under constant slow agitation) and then with goat anti-rabbit Ig (Boehringer-Mannheim) conjugated with horseradish peroxidase (1/2000 in TBS Tween, 30 min at

37C) Staining was obtained by incubation with a fresh solution of 1.39 mMDAB (in 50 mMTris/HCl, pH 7.3 for

5 min at room temperature) added with H2O2(0.1 lLÆmL)1 Tris buffer) Deglycosylation experiments were carried out

on partially purified D melanogaster DPP III using an enzymatic deglycosylation kit (Bio-Rad, including NANase

II, O-glycosidase DS and PNGase F) according to the manufacturer’s instructions Samples were checked before and after deglycosylation by SDS/PAGE, followed by staining with Coomassie Blue, using fetuin as a glycosylated protein standard

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Sequence comparisons

The coding sequences of D melanogaster and rat liver

DPP III were aligned with homologous coding sequences

from the worm Caenorhabditis elegans and the protozoan

Leishmania major using CLUSTALW 1.8 In addition, the

corresponding protein sequences were analyzed for the

presence of a signal peptide and transmembrane regions

usingSIGNALPfrom the Expasy proteomic tools andTMat

the EMBNET [16]

Measurement of protein content

Membrane, cytosolic and purified proteins were measured

using a commercial protein assay reagent kit (Bio-Rad) with

BSA as a standard [17] Proteins in solubilized samples were

measured according to the instructions of a commercial

detergent-compatible reagent kit (Bio-Rad), again with

BSA as the standard

Results

Stable transfection of S2cells expressing a putative

D melanogaster DPP III

S2 cells were double transfected with the pMTA/DPP III

and pCoHygro vectors and then selected for their resistance

to hygromycin The transfection of hygromycin-resistant S2

cells with the pMTA/DPP III vector was first verified by

PCR, using a sense primer specific for pMTA and an

antisense primer designed against the putative D

melano-gaster DPP III HpaI fragment (Fig 1A) to amplify a

1017 bp fragment (Fig 1B) The transcription of specific

mRNAs was deduced from the amplification of the 1017 bp

fragment after RT-PCR with cDNA templates prepared

from total RNA of transfected S2cells previously induced

for 48 h (Fig 1C, lane 5) When RT-PCR was carried out

with these cDNA templates and a second set of primers

specific to the core D melanogaster DPP III sequence

(Fig 1A), a 783 bp fragment was also amplified (Fig 1C,

lane 5) By contrast, the results of RT-PCR experiments

with the second set of primers clearly indicated no

significant transcription of endogenous DPP III in

untrans-fected and mock transuntrans-fected S2cells, and also in transfected

S2cells that have not been previously induced (Fig 1C)

These results were corroborated by SDS/PAGE

(Fig 2A) and Western blot analysis (Fig 2B) with

anti-(rat liver DPP III) Ig, revealing two protein bands in the

expected range of 82 and 86 kDa only in transfected S2cells

after 48 h induction By contrast, soluble DPP III related

protein could not be detected by Western blot analysis (data

not shown) in transfected S2cell culture medium after 48 h

induction When immunocytochemical studies were

per-formed with anti-(rat liver DPP III) Ig on unfixed

trans-fected and induced S2 cells in the absence of detergent, a

significant and presumably surface labeling was observed

(Fig 3A,B) When cells were treated with 0.1% Tween 20,

approximately twice as many transfected and induced S2

cells were stained than in the absence of detergent (data not

shown) By comparison, no labeling could be observed after

immunocytochemical treatment of untransfected S2cells or

transfected S cells not previously induced (data not shown)

After a 5-min incubation of proctolin (25 nmol) with stably transfected and induced S2cells in NaCl/Picontaining the aminopeptidase inhibitor bestatine (100 lM), 6.25 nmol

of proctolin and 1.75 nmol Arg-Tyr (and Leu-Pro-Thr, not shown) were recovered into the incubation medium as determined after reversed-phase separation (Fig 3C) When incubation was carried out for 10 min, only 5 nmol proctolin and 2.75 nmol Arg-Tyr (and Leu-Pro-Thr, not shown) were measured After 20 min incubation, 2.7 nmol proctolin and 4.55 nmol Arg-Tyr (and Leu-Pro-Thr, not shown) were quantified, indicating a correlated degradation

of extracellular proctolin via DPP activity over the 20 min incubation By comparison, cytosolic contents of induced

Fig 1 Schematic model of the pMTA/DPP III construction vector and verification of the transfection of S 2 cells with this vector (A) Hatched area indicates the 2.484 kb HpaI fragment of D melanogaster cDNA clone GH 01916 coding for a putative DPP III This fragment was inserted in the pMTA/V5-His B expression vector Arrows represent the primer pairs (1 and 2; 3 and 4) used in the PCR and RT-PCR experiments, and the approximative sequence area expected to be amplified (1 kb and 0.8 kb, respectively) (B) Transfection of S 2 cells with pMTA/DPP III vector was verified by PCR with DNA from

mock transfected and from stable transfected S 2 cells amplified using

a set of primers specific for the pMTA/DPP III construction vector (primers 1 and 2) A 1.0 kb fragment (expected size 1.02 kb) was observed after separation on a 0.8% (w/v) agarose gel of PCR prod-ucts obtained with DNA of stable transfected and induced S 2 cells (lane 2) No amplification product could be detected from control PCR with DNA from mock transfected S 2 cells (lane 1) (C) Transcription

of putative D melanogaster DPP III mRNA in transfected S 2 cells was verified by RT-PCR experiments carried out on RNAs extracted from

mock transfected and stable transfected S 2 cells using a second set of primers (3 and 4) specific for the HpaI fragment encoding a putative DPP III Control amplification of a 0.8 kb product (expected size 0.78 kb) was obtained with DNA of the D melanogaster clone

GH 01916 as observed after separation on a 0.8% (w/v) agarose gel (lane 1) No amplification product was observed after RT-PCR using RNA from mock transfected S 2 cells (lane 2) A 0.8 kb fragment was visualized after separation of RT-PCR products performed with RNAs from stably transfected and induced S 2 cells (lane 3) When RT was omitted (control for contaminant DNA extracted from stable transfected S 2 cells) the 0.8 kb PCR product was not detected (lane 4) When using the first set of primers (1 and 2), the 1.0 kb fragment was amplified after RT-PCR using RNA from transfected S 2 cells after induction (lane 5).

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S2cells contained only traces of proctolin and Arg-Tyr after

5 min incubation A significant peakof tyrosine (about

15 nmol) was detected and suggested a complete and rapid

degradation of the 65–70% internalized neuropeptide

despite the utilization of bestatine (data not shown) In

addition, no DPP activity could be measured into

concen-trated (ultrafiltration) culture medium (data not shown)

using proctolin as a substrate

Although no trace of putative D melanogaster DPP III

could be noticed after Western blot analysis of transfected

S2cells not previously induced, homogenates of uninduced

S2 cells contained proctolin-degrading activities including

a weakdipeptidyl aminopeptidase activity of 0.07 ± 0.45

nmol proctolinÆmg protein)1Æmin)1 By contrast, a

signifi-cant DPP activity was measured in homogenates of

trans-fected and Cu2+-induced S2 cells using met-enkephalin

(data not shown) or the insect neuropeptide proctolin

as substrate (1.66 ± 0.35 nmol proctolinÆmg protein)1Æ

min)1) When divalent metal ions (Zn2+) were added to

the incubation medium, the rate of met-enkephalin (data

not shown) or proctolin degradation was similar (1.59 ±

0.45 nmol proctolinÆmg protein)1Æmin)1) By contrast, the

expressed dipeptidyl aminopeptidase activity contained in

S2cell homogenates was strongly increased by the presence

of Co2+(13.6 ± 1.4 nmol proctolinÆmg protein)1Æmin)1)

Given these results, cytosol and membranes were prepared

separately from stably transfected and induced S2 cells,

electrophoresed and analyzed with anti-(rat liver DPP III) Ig

after Western blotting Two protein bands at 82 and 86 kDa,

already visualized from whole transfected and induced S2

cells, were clearly detected in cytosolic samples (Fig 4A,B)

Both protein bands were also observed in membrane samples

(data not shown) Although an equivalent amount of

cytosolic or membrane protein was initially loaded, the

cytosolic 82 and 86 kDa protein bands were approximately

twice as intense as those observed from membrane samples,

indicating that a proportionally larger amount of

over-expressed D melanogaster DPP III is present into the

cytosol than on the membranes of transfected cells

Partial purification and characterization of the putative

D melanogaster DPP III expressed in S2cells

Cytosolic and membrane DPP activities expressed after

48 h induction in stable transfected S cells were partially

purified, first using a 5-mL Hitrap Q cartridge then two size exclusion columns (Table 1) The DPP fractions were identified by degradation studies using proctolin (40 lM)

as the substrate SDS/PAGE analysis of fractions contain-ing partially purified DPP activitiy revealed two major bands in the range of 82 and 86 kDa in both cytosolic and membrane samples (Fig 5) Western blot analysis of both partially purified samples confirmed the presence of two protein bands with similar molecular masses (82 and

86 kDa) that were immunologically related to rat liver DPP III (Fig 5) Both partially purified D melanogaster DPP III removed Arg-Tyr from the N terminus of proctolin (data not shown) with Kmvalues of 4.1 ± 0.7 lMfor the cytosolic enzyme and 3.0 ± 0.6 lM for the membrane enzyme They both hydrolysed met-enkephalin at the Gly-Gly bond (data not shown) An IC50of 0.62 ± 0.15 lM was obtained with the DPP III inhibitor tynorphin (40 lM)

of proctolin degradation induced with D melanogaster DPP III partially purified from the cytosol of transfected cells (data not shown)

The contamination of transfected S2 cell membranes was investigated by the addition of partially purified cytosolic DPP III to membranes prepared from trans-fected S2 cells not previously induced After a routine twice washing of the membrane pellet, Western blot analysis of this membrane sample revealed only traces of DPP III proteins that are not proportionally related to the amount of partially purified DPP III added to this sample Furthermore, DPP III activity was measured on these contaminated membranes when no DPP III acti-vity could be detected on control membranes (transfected cells not previously induced), but this contamination accounted for only a third of the total DPP activity recovered on membranes prepared from transfected S2 cells after induction

Sequence analysis The comparison of protein sequences identified in animals

as putative or fully characterized DPP III showed variable regions at both extremities and consensus regions in the core sequence (Fig 6) An ancestral molecule of 679 amino acids, found in the protozoan Leishmania major, includes a potential signal peptide with a possible cleavage site between residues 23 and 24 that is not recovered in the studied

Fig 2 Expression of a putative D melanogaster DPP III protein in stably transfected S 2 cells (A) Whole cell homogenates (30 lg per lane) prepared from stably transfected cells (cell lines 1a and 1b) after 48 h induction (lanes 1 and 3) or not previously induced (lanes 2 and 4) for the synthesis of

D melanogaster DPP III were separated by SDS/PAGE on a 7.5% acrylamide gel and stained with Coomassie Brillant Blue The arrow indicates the region where two protein bands at 82–86 kDa are specifically detected in induced cells (B) Western blot analysis of cell line 1a was performed with anti-(rat liver DPP III) Ig Transfected S 2 cells were induced for 48 h (lane 2) or not previously induced (lane 1).

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metazoan enzymes In addition, a C-terminal extension of

about 20 amino acid residues is found in metazoan DPP III

but no specific function could be attributed to this region

Among metazoa, the analysis of D melanogaster DPP III

revealed the presence of six potential glycosylation sites

compared with two sites on rat DPP III However, no

significant shift of the partially purified 86 kDa D

melano-gaster DPP III could be observed on SDS/PAGE after

deglycosylation experiments (data not shown)

In addition, the analysis of D melanogaster DPP III

indicated four strong putative transmembrane fragments,

including two adjacent hydrophobic regions, located near

the N terminus (Fig 6), that could be involved in membrane

anchorage of D melanogaster DPP III By comparison, the analysis of mammalian DPP III resulted in the identifica-tion of two distant transmembrane regions with lower significance (data not shown)

Discussion

A D melanogaster cDNA clone coding for a putative DPP III of 82 kDa (CG 7415) was stably transfected in S2 cells After 48 h induction, transfected S2 cells specifically synthesized two protein bands detected at 82 and 86 kDa after SDS/PAGE Western blot analysis using anti-(rat liver DPP III) Ig confirmed that these protein bands were immunologically related to rat liver DPP III This putative

D melanogasterDPP III expressed in transfected cells after induction was partially purified by chromatography accord-ing to the measurement of dipeptidyl aminopeptidase activity and the detection of immunologically related DPP III material in the enzyme fractions The partially purified enzyme is similar to mammalian DPP III in that it hydrolyses small neuropeptides such as met-enkephalin and the insect myotropin proctolin, from which it removes the N-terminal dipeptide, and because it is inhibited by the specific DPP III inhibitor tynorphin [18] The Kmvalues of the recombinant D melanogaster DPP III for proctolin (4 lMand 3 lM) are very similar to the Kmvalue (also 4 lM)

of the presumed DPP III purified in cockroach [12] The potency of tynorphin against recombinant DPP III (IC50¼ 0.62 lM) and that purified in cockroach (0.68 lM) are also very close In addition, D melanogaster DPP III is sensitive to divalent metal ions in a similar manner to vertebrate DPP III [19–21] The deduced amino acid sequence of the putative D melanogaster DPP III predicted

a strong sequence identity ( 50%) with mammalian DPP III [12] The functional expression of the D melano-gasterDPP III cDNA in S2cells does, indeed, confirm that the translated protein product is a genuine DPP III

Fig 3 Immunocytochemistry of transfected S 2 cells and

proctolin-degrading activity of transfected S 2 cells (A,B) Anti-(rat liver DPP III)

Ig was used to probe transfected S 2 cells (see Experimental

proce-dures) After 48 h induction, transfected S 2 cells were stained without a

treatment with detergent Arrows indicate the positively stained cells.

(C) Proctolin (25 nmol) was incubated in NaCl/P i with stably

trans-fected S 2 cells After different time intervals, proctolin and its

N-ter-minal dipeptide Arg-Tyr were measured in the incubation medium by

reversed-phase chromatography The results are the mean of three

experiments ± SEM Two thirds of this proctolin (approximately

16–17 nmol) were rapidly internalized into S 2 cells and recovered as

tyrosine (not shown).

Fig 4 SDS/PAGE and Western blot analysis of transfected S 2 cells Cytosolic samples were prepared from transfected S 2 cells after induction and electrophoresed (A) Cytosolic sample (30 lg protein per lane) was separated on a 7.5% (w/v) acrylamide gel and stained with Coomassie Brillant Blue Arrows indicate both bands corres-ponding to overexpressed D melanogaster DPP III proteins visualized

at 82 and 86 kDa (B) Western blot analysis of cytosolic sample probed with anti-(rat liver DPP III) that allowed the detection of both bands

at 82 and 86 kDa.

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However, a number of features of the D melanogaster

DPP III are different from the mammalian DPP III For

instance, cytosolic rat liver DPP III is expressed in E coli as

a single 82 kDa protein [2,22] that is in agreement with the

expected size and coincides with the molecular mass of the

DPP III protein deduced after purification from rat [3]

Although the transfection of S2 cells was also carried out

with a single D melanogaster DPP III cDNA sequence, two

major protein bands at 82 and 86 kDa are expressed and detected in transfected S2 cells Both bands are also identified after partial purification from transfected S2cells The expected molecular mass of the D melanogaster DPP III is 81 937, which coincides with the lower protein band revealed at about 82 kDa after Western blot analysis using anti-(rat liver DPP III) The presence of six predicted putative glycosylation sites on the insect DPP III compared with only two sites on rat liver DPP III suggested that the heavier D melanogaster DPP III protein may result from post-transductional processing of the 82 kDa DPP III to raise the molecular mass of the D melanogaster DPP III up

to 86 kDa Deglycosylation experiments performed on partially purified D melanogaster DPP III and verified by SDS/PAGE were inconclusive in demonstrating conven-tional glycosylation of the 86 kDa expressed protein The structure of the 86 kDa expressed DPP III is not yet elucidated but it cannot be inferred from the expression in S2 cells because similar bands at 82 and 86 kDa have been already detected in soluble samples and membranes pre-pared from fruit flies [12] In addition, control SDS/PAGE and Western blot experiments were performed with rat liver samples that resulted in the detection of a single protein band at 82 kDa as previously reported [2,3,23]

The expression of the insect DPP III as a membrane protein represents the second major difference with mam-malian DPP III, typically recovered as a cytosolic peptidase Immunocytochemical studies of transfected S2cells with or without detergent indicated that D melanogaster DPP III is possibly expressed at the cell surface Even though the contamination of transfected S2cell membrane preparations from transfected S2 cell cytosol containing overexpressed

D melanogaster DPP III was established, this accounted for only 30% of the total membrane DPP III activity recovered from transfected S2cell membranes These results are in line with the detection of native DPP III after Western blot analysis of soluble and membrane samples prepared from D melanogaster [12] and with the purifica-tion of a presumed DPP III from gut membranes in cockroach [12,14] Our results also agree with the dual localization of DPP III previously reported in rat [6] and guinea-pig [5] brain cytosol and membranes The partial purification of D melanogaster DPP III expressed in transfected S2 cells was achieved from both cytosol and solubilized membranes after thorough washing, and the characterization of both D melanogaster DPP III partially purified from cytosol and membrane of transfected cells showed similar Km values to met-enkephalin and proctolin

Fig 5 SDS/PAGE and Western blot analysis of overexpressed

D melanogaster DPP III (A) D melanogaster DPP III partially

purified from cytosol of transfected S 2 cells (1 lg) was electrophoresed

on a 7.5% (w/v) acrylamide gel and silver stained (lane 1) revealing the

presence of two protein bands at 82 and 86 kDa After Western blot

analysis using anti-(rat liver DPP III) Ig, both bands were specifically

detected (lane 2) (B) An aliquot from the different steps of separation

of solubilized membranes from transfected S 2 cells was electrophored

on a 7.5% (w/v) acrylamide gel and silver stained Solubilized

mem-branes of transfected S 2 cells (18 lg, lane 1), positive fractions resulting

from anion exchange separation (5 lg, lane 2) and from size exclusion

separation (2 lg, lane 3) were electrophoresed to confirm the isolation

of two protein bands at 82 and 86 kDa during the process of

separ-ation (C) Western blot analysis of overexpressed D melanogaster

DPP III partially purified from membranes (2 lg, lane 1) probed with

anti-(rat liver DPP III) Ig Both bands at 82 and 86 kDa were thus

detected.

Table 1.

6 Purification of D melanogaster cytosolic DPP III overexpressed in S 2 cells.

DPP III loaction Purification steps Proteins (mg)

Total activity (nmolÆmin)1)

Specific activity (nmolÆmg)1min)1) Purification factor

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The examination of several DPP III sequences indicated

that this enzyme was highly conserved during the

evolution process from protozoa to mammals and that

the extremities of the sequences are mostly variable No

signal peptide could be identified in the D melanogaster

DPP III and this was supported by the absence of

detection of recombinant DPP III in transfected S2 cell

culture media as verified by Western blot analysis

Furthermore, no trace of DPP activity could be measured

in ultrafiltered culture media of transfected S2 cells The

D melanogaster DPP III is not secreted and is not a

circulating DPP The fact that D melanogaster DPP III

contains a putative N-terminal membrane anchor

seq-uence with a significantly higher probability than that

calculated for mammalian DPP III corroborates our

results that argue for a membrane DPP III in insects

when it is mainly identified as a cytosolic peptidase in

mammals Furthermore, the analysis of the orientation of

the two putative transmembrane helices identified in

D melanogasterDPP III (amino acid residues 44–62 and

81–106) indicates that the resulting loop between 63 and

80 is presumably on the inner side of the membrane,

whereas the other protein regions of D melanogaster

DPP III are on the outer side In these conditions and

considering the anchorage of the D melanogaster DPP III

on the plasma membrane, the six potential glycosylation

sites and the HELLGH active site of the protein would be

exposed on the outer surface of the cell Thus, one can

expect a significant cell surface-located DPP III activity in transfected S2 cells This was confirmed by the detection

of a substantial amount of the proctolin N-terminal dipeptide Arg-Tyr in the incubation medium (degradation buffer) following incubation of the neuropeptide proctolin with whole transfected and induced S2 cells (Fig 3C) These results provide evidence that D melanogaster DPP III is expressed in S2 cells as a cytosolic enzyme and also as a membrane peptidase

In terms of proctolin degrading activity, a dipeptidyl aminopeptidase activity was shown to hydrolyse proctolin

in insects and was referred as to mammalian DPP III [11] but this was not further investigated In another study, a dipeptidyl aminopeptidase activity was identified

in locust synaptosomes as a major proctolin-degrading enzyme [8] In this example, two thirds of DPP activity was measured in the mitochondrial (cytosolic) fraction and one third was recovered in the synaptosome (membrane) fraction In transfected S2 cells, D melano-gaster DPP III is roughly expressed in these proportions

in the cytosol and on membranes as an efficient proctolin-degrading enzyme

In conclusion, our results confirm that the putative

D melanogasterDPP III is a genuine DPP III, expressed in the cytosol and on the membranes of transfected S2 cells The D melanogaster DPP III herein identified represents the first fully characterized peptidase involved in proctolin degradation

Fig 6 Alignment of D melanogaster and rat DPP III with putative homologous proteins identified in the worm C elegans and the protozoan

L major Blackframes correspond to the identity of residues in at least three sequences, grey frames indicate similarity between residues and dots represent gaps inserted for optimal alignment with CLUSTAL W Both squares correspond to potential transmembrane segments in D melanogaster DPP III as determined with TM software at the EMBNET.

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