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Báo cáo khoa học: De novo synthesis, uptake and proteolytic processing of lipocalin-type prostaglandin D synthase, b-trace, in the kidneys pptx

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In this study, we examined the localization of L-PGDS in monkey kidney by in situ hybridization and immunohistochemical analysis with two novel MAbs against L-PGDS, and found that L-PGDS

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lipocalin-type prostaglandin D synthase, b-trace, in the

kidneys

Nanae Nagata1, Ko Fujimori1,2, Issey Okazaki1, Hiroshi Oda3, Naomi Eguchi1, Yoshio Uehara4 and Yoshihiro Urade1

1 Department of Molecular Behavioral Biology, Osaka Bioscience Institute, Japan

2 Laboratory of Biodefense and Regulation, Osaka University of Pharmaceutical Sciences, Japan

3 Central Research Institute, Maruha Nichiro Holdings, Inc., Ibaraki, Japan

4 Health Service Center, The University of Tokyo, Japan

Introduction

Lipocalin-type prostaglandin D synthase (L-PGDS;

EC 5.3.99.2) catalyzes the isomerization of

prostaglan-din H2 (PGH2), a common precursor of various

pro-stanoids, to produce PGD2, an endogenous regulator

of sleep and pain [1–5] L-PGDS was originally puri-fied from rat brain [6] and found to be a monomeric

Keywords

kidney; monoclonal antibody; renal disease;

urine; b-trace

Correspondence

Y Urade, Department of Molecular

Behavioral Biology, Osaka Bioscience

Institute, 6-2-4 Furuedai, Suita, Osaka

565-0874, Japan

Fax: +81 6 6872 2841

Tel: +81 6 6872 4851

E-mail: uradey@obi.or.jp

(Received 12 August 2009, revised 29

September 2009, accepted 6 October 2009)

doi:10.1111/j.1742-4658.2009.07426.x

Lipocalin-type prostaglandin D synthase (L-PGDS) is a multifunctional protein that produces prostaglandin D2 and binds and transports various lipophilic substances after secretion into various body fluids as b-trace L-PGDS has been proposed to be a useful diagnostic marker for renal injury associated with diabetes or hypertension, because the urinary and plasma concentrations are increased in patients with these diseases How-ever, it remains unclear whether urinary L-PGDS is synthesized de novo in the kidney or taken up from the blood circulation In crude extracts of monkey kidney and human urine, we found L-PGDS with its original N-ter-minal sequence starting from Ala23 after the signal sequence, and also its N-terminal-truncated products starting from Gln31 and Phe34 In situ hybridization and immunohistochemical staining with monoclonal antibody 5C11, which recognized the amino-terminal Ala23–Val28 loop of L-PGDS, revealed that both the mRNA and the intact form of L-PGDS were local-ized in the cells of Henle’s loop and the glomeruli of the kidney, indicating that L-PGDS is synthesized de novo in these tissues However, truncated forms of L-PGDS were found in the lysosomes of tubular cells, as visualized

by immunostaining with 10A5, another monoclonal antibody, which recog-nized the three-turn a-helix between Arg156 and Thr173 These results suggest that L-PGDS is taken up by tubular cells and actively degraded within their lysosomes to produce the N-terminal-truncated form

Structured digital abstract

l MINT-7266187 : L-PGDS (uniprotkb: P41222 ) and Cathepsin D (uniprotkb: Q4R4P0 ) colocal-ize ( MI:0403 ) by fluorescence microscopy ( MI:0416 )

l MINT-7266176 : L-PGDS (uniprotkb: P41222 ) and Cathepsin B (uniprotkb: Q4R5M2 ) colocal-ize ( MI:0403 ) by fluorescence microscopy ( MI:0416 )

Abbreviations

CSF, cerebrospinal fluid; DIG, digoxigenin; GST, glutathione S-transferase; KO, knockout; L-PGDS, lipocalin-type prostaglandin D synthase; MAb, monoclonal antibody; PG, prostaglandin; SPR, surface plasmon resonance.

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protein with a molecular mass of approximately

26 000 [1], and was later demonstrated to be

N-gly-cosylated at two positions, Asn51 and Asn78 [7]

L-PGDS is known to be identical to b-trace [8,9], the

major protein in human cerebrospinal fluid (CSF) [10]

Moreover, L-PGDS is a member of the lipocalin gene

family, as judged from its amino acid homology with

several conserved motifs in this family [11] L-PGDS

binds various lipophilic substances, such as retinoids,

thyroid hormones [12], bilirubin, biliverdin [13],

gan-gliosides [14] and amyloid b-peptide [15], with high

affinities (Kd= 0.02–2 lm), similar to those of other

proteins in the lipocalin gene family L-PGDS is

domi-nantly expressed in the brain, heart and male genital

organs [1], is secreted into various body fluids, such as

CSF, plasma, seminal plasma and urine [5], and

func-tions as both a PGD2-producing enzyme and an

extra-cellular transporter of various lipophilic substances

Previously, we have generated several types of mouse

monoclonal antibody (MAb) against human L-PGDS

and developed a sandwich ELISA with MAb-1B7 and

MAb-7F5 [16] The L-PGDS level in various human

body fluids, measured by the ELISA system, revealed

that the urinary excretion of L-PGDS is increased in the

early stage of diabetes [16] and declines with the control

of the blood glucose level by hospitalization [17,18]

Moreover, urinary L-PGDS excretion is increased in

patients with hypertension with latent renal injury [19]

Thus, L-PGDS is thought to be a useful diagnostic

mar-ker for these diseases [1,20] Urinary L-PGDS is believed

to reflect the change in glomerular permeability because

of its small molecular mass and anionic property

How-ever, the origin of urinary L-PGDS remains unclear

Furthermore, only 10% of L-PGDS administered

intra-venously in canines is recovered in the urine [21],

sug-gesting that the permeability of L-PGDS may be low

and⁄ or urinary L-PGDS is reabsorbed or metabolized

after filtration through the glomerular membrane

In this study, we examined the localization of

L-PGDS in monkey kidney by in situ hybridization

and immunohistochemical analysis with two novel

MAbs against L-PGDS, and found that L-PGDS was

synthesized de novo in monkey kidney, and that

N-terminal-truncated forms of L-PGDS were present

in monkey kidney and human urine

Results

Production and characterization of novel

anti-human L-PGDS MAbs

We purified b-trace from human CSF or the human

D1)22Cys65,167Ala L-PGDS from Escherichia coli

trans-formants In SDS-PAGE, b-trace showed a broad band

at position Mr= 25 000–27 000 as a result of its gly-cosylation (Fig 1A, lane 1), whereas D1)22Cys65,167Ala L-PGDS showed a sharp band at position Mr= 19 000 because of a lack of glycosylation (Fig 1A, lane 2) We generated two novel anti-human L-PGDS MAbs, i.e 5C11 and 10A5, by immunizing L-PGDS knockout (KO) mice with b-trace and rats with D1)22Cys65,167Ala L-PGDS, respectively Western blot analysis showed that both MAb-5C11 (Fig 1A, lanes 3 and 4) and MAb-10A5 (Fig 1A, lanes 5 and 6) recognized b-trace and D1)22Cys65,167Ala L-PGDS, similar to the case of polyclonal antibody against human L-PGDS (Fig 1A, lanes 9 and 10) By contrast, previously generated MAb-1B7 (Fig 1A, lanes 7 and 8) bound to D1)22Cys65,167Ala L-PGDS efficiently but to b-trace only slightly These results indicate that novel MAb-5C11 and MAb-10A5 recognize both highly glycosylated b-trace and non-gly-cosylated recombinant L-PGDS with affinities greater than those of the previously obtained MAb-1B7 [16] Epitopes recognized by MAb-5C11 and MAb-10A5 were determined by western blot analysis using gluta-thione S-transferase (GST)-fusion proteins containing different lengths of human L-PGDS (Fig 1B) Each GST-fusion protein was purified, separated by SDS-PAGE and stained with silver (Fig 1C, top panel) MAb-5C11 bound only to the Ala23–Gln190 protein, whereas MAb-10A5 bound to all constructs, except for that carrying the Glu174–Gln190 region, indicating that epitopes for MAb-5C11 and MAb-10A5 were located in Ala23–Val28 and Arg156–Thr173, respec-tively In the tertiary structure of human L-PGDS (Fig 1D, E) modeled from the crystallographic (PDB codes: 2CZT and 2CZU [22]) and NMR (PDB code: 2E4J [23]) structures of mouse L-PGDS, the epitopes for MAb-5C11 and MAb-10A5 were localized to the amino-terminal loop and the three-turn a-helical region of human L-PGDS, respectively The previ-ously generated MAb-1B7 [16] bound to the EF-loop

on the side opposite the sites for MAb-5C11 and MAb-10A5

The immunoglobulin subclass and light chain type were determined to be IgG1 (j) for MAb-5C11 and IgG2a (j) for MAb-10A5 (Table 1) Surface plasmon resonance (SPR) analysis of the antigen–antibody interaction demonstrated that immobilized MAb-5C11 and MAb-10A5 bound to the soluble form of b-trace with Kdvalues of 91 and 2900 nm, respectively, and to the recombinant D1)22Cys65,167Ala L-PGDS with values of 167 and 57 nm, respectively The binding affinities of MAb-5C11 and MAb-10A5 were increased about 50–100-fold for the immobilized b-trace to 1.1 and 4.5 nm, respectively, and for the recombinant

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D1)22Cys65,167Ala L-PGDS to 0.52 and 0.16 nm,

respectively Thus, MAb-5C11 bound to both b-trace

and the recombinant D1)22Cys65,167Ala L-PGDS with

almost the same affinity, in either the soluble or

immo-bilized state The binding affinity of MAb-5C11 for immobilized b-trace was approximately fivefold higher than the affinities of MAb-1B7 and MAb-10A5 In this model, the N-terminal and C-terminal regions of

1B7

5C11 10A5 PAb

MAb

A

B

C

19 26 kDa

1

SYPRO orange

Silver staining

MAb-10A5

MAb-5C11

(Amino acids)

Gln190

* * Ala23

1 Ser29 2 Gln35 3 Ser52 4

Asp74 5

Glu90 6

Tyr107 7

Val121 8

Gly140 9

Arg156 10

Glu174 11

1 2 3 4 5 6 7 8 9 10 11

1 40 80 120 160 190

10A5

5C11

1B7

Asn51

2

1 3

A

H B G F

D C

E

N

C

10A5

5C11

1B7 Asn51

Asn78

Fig 1 Detection of human CSF b-trace and recombinant L-PGDS by MAbs against human L-PGDS and characterization of their antigenic epitopes (A) b-trace (lanes 1, 3, 5, 7 and 9) and recombinant D1)22Cys65,167Ala human L-PGDS (lanes 2, 4, 6, 8 and 10) were separated by SDS-PAGE and stained with SYPRO Orange (lanes 1 and 2), followed by blotting onto a polyvinylidine difluoride membrane The blots were then reacted with human L-PGDS MAb-5C11 (lanes 3 and 4), MAb-10A5 (lanes 5 and 6), MAb-1B7 (lanes 7 and 8) or polyclonal antibody (PAb, lanes 9 and 10) for western blot analysis Molecular size markers are shown on the left (B) Schematic representation of GST-fusion proteins containing a series of amino-terminus-truncated human L-PGDS The amino-terminal amino acid residue of each mutant is indicated

on the left The signal sequence of the amino-terminal 22 amino acid residues of human L-PGDS was removed in the parent mutant,

D1)22Cys 65,167 Ala L-PGDS (line 1) Asterisks indicate the two N-glycosylation sites (C) The purified GST-fusion proteins containing the series

of amino-terminus-truncated L-PGDS were separated by SDS-PAGE, followed by silver staining (top panel) or used for western blot analysis with MAb-5C11 (middle panel) or MAb-10A5 (bottom panel) Lanes 1–11 correspond to the mutants 1–11 shown in (B) (D) Positions of the antigenic epitopes for MAbs on the ribbon model of human L-PGDS, which is composed of nine b-strands (strand A, Gly40–Ala49; strand B, Cys65–Ala72; strand C, Gly76–Arg85; strand D, Gln88–Pro98; strand E, Ser104–Arg108; strand F, Tyr116–Thr123; strand G, Val128–Gly135; strand H, Phe143–Ser150; strand I, Ile177–Phe179) and a three-turn a-helix (Ala157–Ala169) The epitopes of MAb-5C11, MAb-10A5 and MAb-1B7 are shown in blue, orange and dark gray, respectively Two N-glycosylation sites (Asn51 and Asn78) are shown in green and pink, respectively (E) Positions of the antigenic epitopes on the surface model of L-PGDS drawn using PYMOL software (DeLano Scientific LLC, Palo Alto, CA, USA) The epitopes for MAb-5C11, MAb-10A5 and MAb-1B7 are shown in blue, orange and dark gray, respectively The N-glycosylation sites (Asn51) is shown in green.

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L-PGDS are exposed on the surface of the molecule.

However, in the soluble form, the affinities of

MAb-10A5 for native L-PGDS were lower than those for

the recombinant protein, suggesting that the

C-termi-nal region may be partially covered by a sugar chain

in native L-PGDS, because the N-glycosylation site

(Asn51) is near the C-terminal region in the surface

model (Fig 1E)

We used these MAbs against human L-PGDS for

immunochemical and immunohistochemical analyses

of monkey kidney, because the homology between

human and monkey L-PGDS is very high (only five

amino acid substitutions of a total of 190 amino acid

residues, giving 97.4% amino acid identity; GenBank

M61900 for human and DDBJ Accession No

AB032480 for monkey; Fig 2A) The comparison of

the amino acid sequences revealed that the sequences

of the antigenic regions recognized by MAb-5C11,

MAb-1B7 and MAb-10A5 were also highly conserved

in both species The sequence of the antigenic epitope

of MAb-5C11 (Ala23–Val28) was the same in both

species; that of MAb-1B7 contained only one

substitu-tion (R108 in human and G108 in monkey) of 14

amino acid residues; and that of MAb-10A5 (Arg156–

Thr173) also contained only one substitution (T164 in

human and S164 in monkey) of 18 amino acid

resi-dues As a result of the highly conserved sequences

between both species, all anti-human L-PGDS MAbs

bound to monkey L-PGDS

Western blot analysis of monkey kidney samples,

par-tially purified by immunoaffinity columns conjugated

with MAb-1B7, MAb-5C11 or MAb-10A5, revealed

that all of these MAbs showed a broad single

immuno-reactive band at the same position (Mr= 25 000–

27 000) as that of purified human L-PGDS⁄ b-trace from

human CSF (Fig 2B) These results indicate that these

MAbs selectively recognized L-PGDS and did not bind

other proteins in monkey kidney

Localization of L-PGDS in monkey kidney

The localization of L-PGDS in monkey kidney was

then determined by immunohistochemical staining with

MAb-5C11, MAb-10A5 and MAb-1B7 and by in situ hybridization with antisense RNA for L-PGDS mRNA (Fig 3) The staining profile by in situ hybrid-ization of mRNA for L-PGDS was similar to that obtained with MAb-5C11 (Fig 3A, B) By contrast, the staining profile with MAb-10A5 was similar to that with MAb-1B7 (Fig 3C, D)

In the cortex and outer medulla, the L-PGDS mRNA and L-PGDS protein detected with MAb-5C11 were localized in the distal tubules, including Henle’s loop (Fig 3E, F) MAb-10A5 showed generally much weaker staining in the tubules than that obtained with MAb-1B7 (Fig 3G, H)

In the glomeruli, the mRNA and L-PGDS protein detected with MAb-5C11 were localized in the epithelial cells of Bowman’s capsule and in occasional podocytes (arrowhead and arrow, respectively, in Fig 3I, J) Podocytes were identified by morphological criteria as cells located adjacent to the outer aspect of the glomeru-lar basement membrane By contrast, MAb-10A5 showed scarce, and MAb-1B7 weak, immunoreactivity

in the glomeruli (Fig 3K, L)

In higher magnification analysis, positive staining in the tubules was observed in perinuclear regions by

in situ hybridization and by immunostaining with MAb-5C11 (Fig 3M, N) Although punctuate struc-tures were seen by immunostaining with MAb-10A5 (Fig 3O), diffuse cytoplasmic staining was observed with MAb-1B7 (Fig 3P) No positive signals were observed when sense RNA probe, mouse IgG or rat IgG was applied (Fig 3Q–T)

Confocal laser scanning microscopy revealed that MAb-5C11-positive fluorescence was colocalized with L-PGDS mRNA in Henle’s loop (Fig 4A) and glome-ruli (not shown), suggesting that L-PGDS was synthe-sized de novo in these regions of the kidney However, MAb-10A5-positive fluorescence overlapped that of cathepsin B, a lysosomal marker, in the tubules (Fig 4B) In higher magnification analysis, a minor immunoreactivity of cathepsin B was not colocalized with MAb-10A5 immunoreactivity, but the majority of these two immunoreactivities was colocalized to the same organella (Fig 4C) Furthermore,

MAb-10A5-Table 1 Characterization of the three anti-human L-PGDS MAbs used in this study.

K d (n M ) b-trace protein D1)22Cys 65,167, Ala L-PGDS

Soluble form Immobilized Soluble form Immobilized

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positive fluorescence overlapped that of cathepsin D,

another lysosomal marker (Fig 4D), indicating that

the MAb-10A5-positive punctate fluorescence was

distributed to lysosomes These results, taken together,

suggest that L-PGDS is re-absorbed from the urine

into the tubules and proteolytically degraded within

lysosomes in the tubule cells

Identification of L-PGDS of various sizes in

monkey kidney and human urine

We applied crude extracts of monkey kidney to a

MAb-1B7-conjugated immunoaffinity column and

obtained purified L-PGDS Because of its

N-glycosyla-tion at posiN-glycosyla-tions Asn51 and Asn78 [7], purified

L-PGDS showed a broad band of two different sizes,

Mr= 19 000–22 000 and Mr= 25 000–27 000, the latter of which corresponded to the intact form of L-PGDS⁄ b-trace with N-glycosylation Western blot analysis showed that MAb-1B7 and MAb-10A5 were reactive with both sizes of L-PGDS, whereas MAb-5C11 selectively reacted with the intact form of L-PGDS with Mr= 25 000–27 000 (Fig 5A) After glycopeptidase F treatment, the two forms of monkey L-PGDS migrated to positions of Mr= 18 000 and

Mr= 19 000, the latter of which corresponds to the non-glycosylated form of L-PGDS [7], and both of which were recognized by MAb-1B7 and MAb-10A5

By contrast, MAb-5C11 bound to non-, mono- and di-glycosylated forms of L-PGDS with Mr= 19 000,

Mr= 22 000 and Mr= 27 000, respectively, but not

to the small band at Mr= 18 000 (Fig 5B)

Fig 2 Alignment of the amino acid sequences of monkey and human L-PGDS (A) Amino acid sequence of human L-PGDS was compared with that of monkey L-PGDS Grey tinted boxes indicate substituted amino acid residues Open boxes indicate the epitopes of MAb-5C11, MAb-1B7 and MAb-10A5 Conserved residues (*) are indicated below the sequences (B) Crude extracts of monkey kidney (1 lg protein, lane 1) and purified human CSF L-PGDS ⁄ b-trace (0.1 lg protein, lane 2) were applied for SDS-PAGE and stained with SYPRO Orange The purified human CSF L-PGDS ⁄ b-trace (0.1 lg protein, lane 3) and the partially purified samples from the crude extracts of monkey kidney (2 mg protein, lanes 4–6), obtained by immunoaffinity chromatography with MAb-1B7, MAb-5C11 or MAb-10A5, were separated by SDS-PAGE and analyzed by western blot analysis with each MAb (lanes 4, 5 and 6, respectively) Positions of molecular size markers are shown on the left.

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* *

*

*

G

K

L

E

C B

A

J I

1B7

1 mm

50 m

20 m 5 m

5 m

20 m

50 m

T

5 m

20 m

D

Fig 3 Localization of L-PGDS-immunoreactive protein and mRNA in monkey kidney Sections of monkey kidney were used for in situ hybridization (ISH) and immunoperoxidase staining with MAb-5C11, MAb-10A5 and MAb-1B7 (A–D) Low-magnification views At high magnification, L-PGDS signals were detected in the tubules in the cortex and outer medulla (E–H) The signals were also detected in the glomeruli (I–L) Asterisks, arrowheads and arrows indicate Bowman’s space, Bowman’s capsule and cytoplasm of podocytes, respectively (M–P) High-magnification micrographs of L-PGDS signals in tubule cells (Q–S) Staining profile by in situ hybridization with sense RNA probe (Q) and immunostaining with mouse IgG (R) or rat IgG (S and T) Scale bars: (A–D) 1 mm; (E–H, Q–S) 50 lm; (I–P, T) 20 lm; insets, 5 lm.

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N-terminal amino acid sequence analysis revealed

that L-PGDS of the intact form in monkey kidney

started from Ala23, which is the same as the

amino-terminal end of human b-trace (GenBank: M61900),

and that the smaller sized proteins of Mr= 18 000

began from Gln31 and Phe34, which were 8 and 11

amino acids shorter, respectively, than the intact

protein (Fig 5C) These results indicate that the kidney

contained both intact L-PGDS and the

N-terminal-truncated form MAb-5C11 recognized solely the intact

form of L-PGDS, whereas MAb-10A5 detected both

forms Furthermore, immunohistochemical staining

with MAb-5C11 indicated that the intact forms of

L-PGDS were localized to cells of Henle’s loop and the

glomeruli of the kidney By contrast, immunostaining

with MAb-10A5 indicated that the truncated forms of

L-PGDS were taken up by tubular cells and degraded

within their lysosomes

We then analyzed human and monkey urine by

wes-tern blotting with MAb-5C11 and MAb-10A5 before

and after incubation with glycopeptidase F Without glycopeptidase F treatment, both MAbs showed a single immunoreactive band corresponding to the intact form of L-PGDS (Mr= 27 000, Fig 5D) By contrast, after treatment of the urine samples with glycopeptidase F, MAb-10A5, but not MAb-5C11, detected the presence of low-molecular-mass forms

of L-PGDS in human urine (filled arrow) These results suggest that the N-terminal-truncated form of L-PGDS is also excreted in human urine

Discussion

L-PGDS (Mr= 27 000) is much smaller than serum albumin (Mr= 66 000), although these proteins share similar chemical properties to secretory proteins, such

as having anionic charges at pH 7.4 Renal filtration is considered to be a major clearance pathway for low-molecular-mass proteins (Mr< 30 000 [24]) Thus, L-PGDS passes through the glomerular capillary walls

A

B

D

C

*

*

*

*

DAPI

DAPI

Nomarski

*

*

Nomarski

Nomarski Nomarski

10 µm

10 µm

DAPI

10 µm

10 µm

Fig 4 Confocal laser scanning micrographs of monkey kidney (A) In situ hybridization (ISH) combined with immunohistochemistry Anti-sense cRNA probe for L-PGDS (DIG, red) was used in combination with anti-L-PGDS MAb-5C11 (green) Cells in Henle’s loop positive for MAb-5C11 fluorescence were also positive for L-PGDS mRNA (B) Double immunofluorescence for L-PGDS with MAb-10A5 (green) and lyso-somal marker cathepsin B (red) (C, D) High-magnification micrographs of double immunofluorescence for L-PGDS with MAb-10A5 (green) and two lysosomal markers (red) cathepsin B (C) and cathepsin D (D) Asterisks indicate lumen of a tubule Scale bar, 10 lm for (A)–(D).

Trang 8

of the kidney more easily than does serum albumin.

Previously, we established a sandwich ELISA system

using anti-human L-PGDS MAb-1B7 and MAb-7F5

to estimate the L-PGDS level in urine [16] Urinary

L-PGDS reflects even slight changes in glomerular

permeability because of its low molecular mass and

anionic property Thus, urinary L-PGDS is a useful

diagnostic marker for renal diseases [1,20] However,

our recent study [21] demonstrated that only 10% of

the intravenously administered L-PGDS in canines was

recovered in urine, suggesting that the urinary

L-PGDS concentration is not determined by leakage

through the glomeruli only, and that a large part of

the urinary L-PGDS filtered through the membranes is

reabsorbed or metabolized To clarify the precise

local-ization and metabolism of L-PGDS in the kidney, we

attempted to generate novel MAbs against the epitopes

distinct from those of previously obtained MAbs

However, as the orthology of the amino acid sequence

of L-PGDS is high (70.4%) between human and mouse [25], the generation of MAbs with a variety of epitopes is difficult in wild-type mice Therefore, in this study, we used rats and L-PGDS KO mice for immu-nization and obtained two novel anti-human L-PGDS MAbs recognizing distinct epitopes: Ala23–Val28 for MAb-5C11 and Arg156–Thr173 for MAb-10A5 (Fig 1); both antigenic epitopes were distinct from that for the previously generated MAb-1B7, which is Tyr107–Val120 [16] These novel MAbs recognized efficiently both native and recombinant human L-PGDS proteins in western blot (Fig 1) and SPR analyses (Table 1), and detected immunohistochemi-cally the L-PGDS immunoreactive protein in kidney tissue with high sensitivity and specificity (Figs 3 and 4) Therefore, these novel MAbs are useful for further diagnostic analysis to clarify the localization of L-PGDS in tissues and various body fluids, such as CSF, plasma and urine

MAb

Glycopeptidase F (–)

Monkey kidney L-PGDS

Human urine Monkey urine

Glycopeptidase F(+)

1B7 5C11 10A5

APEAQVSVQPNF

34 31

FQPDKFLGRWFS

MATHHTLWMGLVLLGLLGGLQAAPEAQVSVQPNFQPDKFLGRWFSAGLAS

Human L–PGDS

L-PGDS

27 kDa 22

19.3 kDa

30

28

16.2

19.3

kDa 28

16.2

C B

A

MAb 1B7 5C11 10A5

L–PGDS

27 kDa 22 19 18

{

Truncated form Intact form

Truncated form

Truncated form

Intact form

Intact form

Truncated form

D

Intact form

10A5 5C11

19.3 28

16.2

kDa

19.3 28

16.2

kDa

Intact form

10A5 5C11

Fig 5 Identification of novel forms of

L-PGDS in monkey kidney and human urine.

(A) L-PGDS was purified from the

homo-genates of monkey kidney by

MAb-1B7-con-jugated affinity chromatography The purified

L-PGDS proteins were separated by

SDS-PAGE and analyzed by western blot analysis

with MAb-1B7, MAb-5C11 and MAb-10A5.

Positions of molecular size markers are

shown on the right (B) Purified L-PGDS was

treated with glycopeptidase F and used for

western blot analysis with MAb-1B7,

MAb-5C11 and MAb-10A5 Truncated forms

of L-PGDS were detected by MAb-1B7 and

MAb-10A5, but not by MAb-5C11 Positions

of molecular size marker proteins are shown

on the right (C) N-terminal amino acid

sequences of the three different forms of

L-PGDS (D) Human and monkey urine were

treated or not with glycopeptidase F (GPF),

and used for western blot analysis with

MAb-5C11 and MAb-10A5

N-terminal-trun-cated forms of L-PGDS were detected with

MAb-10A5 (filled arrow) Molecular size

markers are shown on the left.

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In this study, we demonstrated that monkey kidney

contained at least three different forms of L-PGDS,

i.e an intact form (Mr= 19 000 after removing

N-gly-cosylated groups) and two truncated forms lacking 8

or 11 N-terminal amino acid residues (Mr= 18 000

for the non-glycosylated form; Fig 5B, C) Moreover,

the L-PGDS immunoreactivity of the C-terminal

epitope of MAb-10A5 was detected in lysosomes in the

tubules of monkey kidney (Fig 4), suggesting that

truncated L-PGDS was proteolytically degraded in the

kidney We also found that the truncated forms of

L-PGDS were excreted in human urine (Fig 5D)

These data, taken together, suggest that a major part

of urinary L-PGDS is processed by proteolytic

degra-dation after leakage through the glomeruli As the

L-PGDS level is altered in clinical samples, such as the

serum, CSF and urine of patients with hypertension

[19], arteriosclerosis [26], hemorrhage [27] and diabetes

[17,18,28–30], L-PGDS has been proposed to be a

use-ful diagnostic marker for these diseases [1,20]

However, the previous ELISA system with anti-human

L-PGDS MAb-1B7 and MAb-7F5 [16] did not detect

N-terminal-truncated L-PGDS Therefore, a new

ELISA system with MAb-10A5, recognizing the

C-ter-minal a-helical region of L-PGDS, will be useful for

further clinical analysis

Although the localization of L-PGDS in the kidney

remains controversial [19,28,29], we have clearly

demonstrated by immunohistochemistry with

MAb-5C11 and by in situ hybridization that the L-PGDS

protein is synthesized de novo in Henle’s loop,

Bow-man’s capsule and podocytes of the glomeruli in the

kidney (Fig 3) The cellular distribution of L-PGDS in

the kidney is in good agreement with the results of a

previous report indicating that a substantial amount of

PGH2, a substrate of L-PGDS, is released from rat

glomeruli and glomerular mesangial cells [31]

Although the physiological role of L-PGDS in the

kid-ney has not yet been clarified, Shirahase et al [32] have

demonstrated previously that pretreatment of rat

mes-enteric artery with PGD2 attenuates organ damage

induced by endotoxin shock with lipopolysaccharide

In addition, PGD2 and its metabolites reduce the

expression of mRNA for inducible nitric oxide synthase

stimulated by interleukin-1b [33] NO generation

induced by the overexpression of inducible nitric oxide

synthase seems to play a pathogenic role in diabetic

nephropathy [34] The inhibition of cytokine-mediated

NO production following an increase in PGD2⁄

L-PGDS in the kidney possibly attenuates the

progres-sion of kidney damage In some renal diseases, the

increase in the biosynthesis of L-PGDS in the kidney

may be a type of adaptation mechanism against kidney

injury An L-PGDS inhibitor, AT-56, found recently [35], is useful for clarifying the pathophysiological sig-nificance of L-PGDS in Henle’s loop and the glomeruli

in the kidney

Materials and methods

Animals

Sprague–Dawley rats were purchased from Shizuoka Labo-ratory Animal Center (Hamamatsu, Japan) L-PGDS KO mice were generated as described previously [36] Mice and rats were maintained under specific pathogen-free condi-tions in isolated cages with a 12 h light⁄ 12 h dark photo-period in a humidity- and temperature-controlled room (55% at 24C) Water and food were available ad libitum The protocols used for all animal experiments in this study were approved by the Animal Research Committee of Osaka Bioscience Institute

Purification of recombinant D1)22Cys65,167Ala L-PGDS and b-trace

We cloned the coding region of human L-PGDS without the signal sequence at the amino-terminal portion (amino acid residues 1–22, defined translation initiation codon Met

as 1) [37] into the pGEX-2T vector (GE Healthcare, Amer-sham, Buckinghamshire, UK) to produce a fusion protein with GST The Cys residues at positions 65 and 167 were substituted for Ala residues using a QuikChange Site-Direc-ted Mutagenesis Kit (Stratagene, La Jolla, CA, USA) to minimize misfolding of the recombinant protein as a result

of incorrect S–S bridging in E coli [37] The plasmid was designated as GST-D1)22Cys65,167Ala and used to transform

E coli BL21 (DE3) The recombinant GST-fusion protein was produced by the addition of isopropyl-b-d-thioga-lactopyranoside (final concentration, 0.6 mm) The cells were further cultured for 6 h at 37C, and then harvested and disrupted by sonication The resultant cell lysates were incubated with glutathione-Sepharose 4B resin (GE Healthcare), followed by digestion of the purified

Cys65,167Ala L-PGDS was further purified by gel filtra-tion chromatography with HiLoad Superdex 75 (GE Healthcare)

b-Trace was purified by MAb-1B7-conjugated immunoaf-finity column chromatography [38], followed by gel filtra-tion chromatography with a HiLoad Superdex 75 column (GE Healthcare), from the culture medium of Chinese ham-ster ovary cells stably expressing human L-PGDS [39], or from human CSF provided by Dr M Mase (Department of Neurosurgery, Nagoya City University Hospital, Nagoya, Japan) Proteins were analyzed by SDS-PAGE and stained with SYPRO Orange (Invitrogen, Carlsbad, CA, USA)

Trang 10

Protein concentrations were measured using a BCA Protein

Assay Kit (Pierce Biotechnology, Rockford, IL, USA)

Preparation of MAbs for human L-PGDS

Sprague–Dawley rats were subcutaneously immunized with

the recombinant D1)22Cys65,167Ala human L-PGDS protein

expressed in E coli Alternatively, purified b-trace from the

culture medium of Chinese hamster ovary cells was used to

immunize L-PGDS KO mice Splenocytes from the

immu-nized rats or mice were fused with myeloma cells (P3U1)

under standard protocols [40] Positive hybridomas were

cloned by the limiting dilution method For MAb-10A5

obtained in rats, ascites was produced in male BALB⁄

cA-nu mice by the intraperitoneal injection of hybridoma

cells For MAb-5C11 generated in L-PGDS KO mice, IgG

antibody was purified from the serum-free medium of

hybridoma cultures The immunoglobulin isotype of MAbs

was determined using a Rat Monoclonal Antibody

Isotyp-ing Kit (Serotec, Oxford, UK) or IsoStrip Mouse

Monoclo-nal Antibody Isotyping Kit (Roche Diagnostics, Mannheim,

Germany), according to the manufacturer’s instructions

SPR analysis

The kinetics of binding of MAbs to human L-PGDS were

determined by SPR analysis using a Biacore 2000 system

(GE Healthcare) D1)22Cys65,167Ala L-PGDS, b-trace or

MAbs for human L-PGDS were coupled to a CM5 sensor

chip (GE Healthcare) by the amine-coupling method,

according to the manufacturer’s protocol The Kd values

were calculated from the sensorgrams using biaevaluation

3.1 software (GE Healthcare)

Western blot analysis

Protein samples were dissolved in 62.5 mm Tris⁄ Cl (pH 6.8)

containing 2% (w⁄ v) SDS, 15% (v ⁄ v) glycerol and 5%

(v⁄ v) b-mercaptoethanol, and electrophoresed in 10–20%

(w⁄ v) polyacrylamide gels, followed by silver staining with

Silver Stain Reagent (Daiichi Pure Chemicals, Tokyo,

Japan) or blotted onto a polyvinylidine difluoride

mem-brane (Immobilon P; Millipore, Bedford, MA, USA) The

blots were incubated with human L-PGDS MAbs After

washing, the blots were incubated with anti-mouse IgG

conjugated with horseradish peroxidase Immunoreactive

signals were detected using the ECL Western Blotting

Detection System (GE Healthcare)

Mapping of antigenic epitopes recognized by

MAbs

The coding region of human L-PGDS was sequentially

truncated from the 5¢-terminus of the coding strand by

PCR Each amplified fragment was cloned downstream of GST in the pGEX-2T vector Expression, purification and analyses of recombinant proteins were carried out as described above

N-terminal amino acid sequence analysis of L-PGDS

Monkey (Macaca fascicularis) tissues were provided by Drs

Y Eguchi and R Torii (Shiga University of Medical Science, Otsu, Japan) L-PGDS was purified by MAb-1B7-conjugated immunoaffinity column chromatography from monkey kidney [38] The affinity-purified L-PGDS protein was separated by SDS-PAGE and transferred onto a poly-vinylidine difluoride membrane The blots were stained with Coomassie brilliant blue The protein bands were excised and utilized for sequencing analysis by Edman degradation employing the HP G1005A Protein Sequencing System (Hewlett-Packard, Palo Alto, CA, USA) The blots were also used for western blot analysis as described above

Immunohistochemical analysis

Monkey kidney was fixed in Bouin’s fixative and embedded

in paraffin The paraffin sections (thickness, 5 lm) were mounted on glass slides, deparaffinized in xylene and rehy-drated in ethanol with increasing concentrations of water The rehydrated sections were pretreated with 0.3% (v⁄ v)

H2O2 in methanol for 30 min at room temperature, and then incubated with 0.3% (w⁄ v) pepsin (Sigma, St Louis,

MO, USA) in 0.01 N HCl for 5 min at room temperature Next, the sections were incubated for 1 h at room tempera-ture with 10% (v⁄ v) normal goat serum, 0.1% (v ⁄ v) Triton X-100 and 0.1% (w⁄ v) sodium azide in NaCl ⁄ Pi, for 16 h

at 4C with anti-human L-PGDS MAbs in NaCl ⁄ Pi con-taining 1% (v⁄ v) normal goat serum and 0.1% (v ⁄ v) Triton X-100, and for 1 h at room temperature with biotinylated antibody against mouse or rat IgG (Vector Laboratories, Burlingame, CA, USA) The immunoreactive signals were visualized as the avidin-biotinylated enzyme complex (Vectastain Elite ABC Kit; Vector Laboratories) after incu-bation in 50 mm Tris⁄ Cl (pH 7.6) containing 0.001% (v ⁄ v)

H2O2 and 0.02% (w⁄ v) 3,3¢-diaminobenzidine tetrahydro-chloride The sections were then counterstained with hema-toxylin and observed under an ECLIPSE E600 microscope (Nikon, Tokyo, Japan)

For double staining with rabbit polyclonal anti-cathepsin

D IgG (Assay Designs, Ann Arbor, MI, USA) and MAb-10A5, after the primary antibodies had been applied, the sections were sequentially incubated with Alexa Fluor 594-conjugated antibody against rabbit IgG (Invitrogen) and biotinylated antibody against rat IgG (5 lgÆmL)1; Jackson ImmunoResearch, West Grove, PA, USA) followed by Alexa Fluor 488-conjugated streptavidin (5 lgÆmL)1;

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