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Here we show that human pFGE, but not FGE, is retained in the ER through its C-terminal tetrapeptide PGEL, a noncanonical variant of the classic KDEL ER-retention signal.. Here we show t

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retention in the endoplasmic reticulum by canonical and noncanonical signals

Santosh Lakshmi Gande1, Malaiyalam Mariappan1, Bernhard Schmidt1, Thomas H Pringle2,

Kurt von Figura1and Thomas Dierks3

1 Zentrum fu¨r Biochemie und Molekulare Zellbiologie, Abteilung Biochemie II, Universita¨t Go¨ttingen, Germany

2 Sperling Foundation, Eugene, OR, USA

3 Fakulta¨t fu¨r Chemie, Biochemie I, Universita¨t Bielefeld, Germany

In the catalytic center of eukaryotic and prokaryotic

sulfatases, a unique amino acid, Ca-formylglycine

(FGly), can be found that is essential for enzymatic

activity [1–5] The FGly participates as an aldehyde

hydrate in the hydrolysis of sulfate esters according to

a novel trans-sulfation⁄ elimination mechanism [5–9]

The FGly in all eukaryotic and in most prokaryotic

sulfatases is post-translationally generated by oxidation

of a specific cysteine residue and, in most cases, this oxidation is catalyzed by the recently discovered form-ylglycine-generating enzyme (FGE), a novel oxygenase with unusual structural and catalytic properties [10–15] The genetic defect of FGE in human leads to multiple sulfatase deficiency, a rare inherited disorder

Keywords

endoplasmic reticulum;

formylglycine-generating enzyme; KDEL receptor; protein

retention; SUMF2

Correspondence

T Dierks, Fakulta¨t fu¨r Chemie, Biochemie I,

Universita¨t Bielefeld, Universita¨tsstr 25,

33615 Bielefeld, Germany

Fax: +49 521 106 6014

Tel: +49 521 106 2092

E-mail: thomas.dierks@uni-bielefeld.de

Website: http://www.uni-bielefeld.de/

chemie/bc1/bc1.htm

(Received 28 October 2007, revised 17

December 2007, accepted 4 January 2008)

doi:10.1111/j.1742-4658.2008.06271.x

Formylglycine-generating enzyme (FGE) catalyzes in newly synthesized sul-fatases the oxidation of a specific cysteine residue to formylglycine, which

is the catalytic residue required for sulfate ester hydrolysis This post-trans-lational modification occurs in the endoplasmic reticulum (ER), and is an essential step in the biogenesis of this enzyme family A paralog of FGE (pFGE) also localizes to the ER It shares many properties with FGE, but lacks formylglycine-generating activity There is evidence that FGE and pFGE act in concert, possibly by forming complexes with sulfatases and one another Here we show that human pFGE, but not FGE, is retained in the ER through its C-terminal tetrapeptide PGEL, a noncanonical variant

of the classic KDEL ER-retention signal Surprisingly, PGEL, although having two nonconsensus residues (PG), confers efficient ER retention when fused to a secretory protein Inducible coexpression of pFGE at dif-ferent levels in FGE-expressing cells did not significantly influence the kinetics of FGE secretion, suggesting that pFGE is not a retention factor for FGE in vivo PGEL is accessible at the surface of the pFGE structure

It is found in 21 mammalian species with available pFGE sequences Other species carry either canonical signals (eight mammals and 26 nonmammals)

or different noncanonical variants (six mammals and six nonmammals) Among the latter, SGEL was tested and found to also confer ER retention Although evolutionarily conserved for mammalian pFGE, the PGEL signal

is found only in one further human protein entering the ER Its conse-quences for KDEL receptor-mediated ER retrieval and benefit for pFGE functionality remain to be fully resolved

Abbreviations

ER, endoplasmic reticulum; FGE, C a -formylglycine-generating enzyme; FGly, C a -formylglycine; PDI, protein disulfide isomerase;

pFGE, paralog of Ca-formylglycine-generating enzyme.

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of a fatal nature that is characterized by the synthesis

of catalytically inactive sulfatases lacking FGly

[12,13,16,17] All multiple sulfatase deficiency patients

analyzed so far carried mutations in the FGE-encoding

SUMF1gene [12,13,18–20]

In eukaryotes, a paralog gene (SUMF2) encoding a

paralog of FGE (pFGE) can be traced back reliably

via conserved sequence signatures to early

deuterosto-mes [12,13,21–23], and indeed to lophotrochozoans,

prebilaterans and even unicellular eukaryotes, although

it appears to have been lost throughout certain large

clades, such as arthropods (this work; see Results)

Like FGE, pFGE localizes to the endoplasmic

reticu-lum (ER), where FGly formation occurs in newly

syn-thesized sulfatases [23,24] FGE and pFGE show

highly similar tissue-specific expression levels and share

many structural properties [23–25] However, pFGE

lacks the enzymatic FGly-generating activity of FGE,

as it lacks the two catalytic cysteines, Cys336 and

Cys341, in the active site of FGE [23–25] pFGE has a

substrate-binding groove similar to FGE, and shows

weak binding of sulfatase-derived synthetic peptides

in vitro [23–25] Also in vivo, pFGE seems to contact

nascent sulfatases in the ER Moreover, pFGE

over-expression interferes with FGly formation, thereby

counteracting FGE function [23,24] The exact role of

pFGE in this process and how this regulatory effect is

brought about is presently under investigation

Several observations, including yeast two-hybrid and

biochemical data, are in agreement with heterodimer

formation of FGE and pFGE [23,24], and indeed, Zito

et al [24] have found multimeric complexes with and

without sulfatases by coimmunoprecipitation The

structural pFGE dimer found in pFGE crystals and

superposition with the FGE monomer suggests that

heterodimer formation is feasible in a face-to-face

manner with regard to the substrate-binding cleft [25]

Heterodimer formation could be stabilized by an

unfolded sulfatase polypeptide, which might explain

the regulatory function of pFGE Alternatively, the

inhibitory effect of pFGE observed on FGE function

could be indirect, namely by competing for a common

ER retention mechanism, thereby dislocating FGE

from the ER In fact, a small fraction of endogenous

pFGE was found to be secreted, and upon

overexpres-sion, pFGE could be detected in other cellular

com-partments of the secretory pathway [23]

Therefore, the question arises of how pFGE and

FGE are retained in the ER Here we show that pFGE

is retained via its C-terminal PGEL tetrapeptide

sequence, which, like the classic KDEL signal, can act

as an autonomous retrieval signal, most likely

engag-ing a KDEL receptor (vertebrates have three

paralo-gous KDELR genes), for retrieving pFGE from the cis-Golgi back to the ER FGE lacks a signal even remotely resembling KDEL in mammals However, pFGE overexpression shows no effect on FGE reten-tion

Results

pFGE retention is mediated by a saturable mechanism

A small fraction of endogenous pFGE can be detected extracellularly, whereas upon overexpression the recombinant pFGE is efficiently secreted [23] To determine whether secretion of human pFGE is due to saturation of the retention⁄ retrieval system, an induc-ible, human-derived expression system was established consisting of a Tet-On HT1080 fibrosarcoma cell line stably expressing the reverse tetracycline-controlled transactivator These cells, upon transient transfection and doxycycline addition, allowed us to trigger pFGE expression at defined levels from a Tet-responsive pro-moter (see Experimental procedures) The transfected HT1080 cells were analyzed for intracellular and extra-cellular pFGE by western blotting using a polyclonal pFGE-specific antibody [23] Extracellular pFGE is detected as a 32.5⁄ 31.5 kDa double band, due to heter-ogeneous processing of its N-glycan in the secretory pathway [23] Treatment with up to 8 ngÆmL)1 doxycy-cline for 28 h led to expression of pFGE ranging from 0.34 to 6.1 lg of pFGE per mg of cell protein (Fig 1) Analysis of cells and medium revealed that retention

of pFGE was decreasing with increasing expression levels, with about 50% retention at the lowest and 12% retention at the highest expression level This lat-ter value (about 10% of ‘retained’ protein) is likely to largely represent newly synthesized material on its way

to the cell surface, because typically no more than 90% of total protein is found in the medium, even in the case of a native secretory protein (see below) This indicated that the mechanism used for pFGE retention

is saturable

The C-terminus is involved in ER retention of pFGE

In initial experiments, we had expressed human pFGE carrying a His6-tag at the C-terminus to facilitate detection and purification of pFGE In these experi-ments, we noted that about 90% of the tagged pFGE was secreted [23] To analyze a possible effect of the C-terminal His6-tag on retention⁄ secretion of pFGE, tagged and untagged (wild-type) pFGE were

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transiently expressed in HT1080 cells When analyzed

24 h after transfection, His6-tagged pFGE was nearly

quantitatively secreted (96% of total), whereas

untag-ged pFGE was significantly retained inside the cells

(26% retention) (Fig 2) This cannot be explained by

different expression levels, because the expression of

intracellularly retained pFGE was two-fold higher than

that of pFGE-His6 Thus, the C-terminal His6-tag

impaired retention of pFGE, indicating that the

C-ter-minus of pFGE might be involved in the ER retention

mechanism

pFGE carries canonical or noncanonical ER

retention signals in different species

Inspection of the available pFGE protein sequences

from 67 species (Fig 3) revealed that 34 of these

sequences contain a canonical ER retention signal of

the KDEL type (basic-X-acidic-leucine) at the

C-termi-nus, with the basic residue being lysine (21 species),

arginine (nine) or histidine (four), and the acidic

residue being glutamate (30) or aspartate (four) Mur-ine and rat pFGE carry the canonical KEDL motif, and the prototype KDEL can be found in orthologs from platypus, the snail Biomphalaria glabrata, the pla-narian Schmidtea mediterranea, and the sea anemone Nematostella vectensis However, human pFGE and also pFGE from 20 further mammalian species (from various primates to squirrel, bat, dolphin, sloth and wallaby) carry a C-terminal PGEL tetrapeptide, i.e lacking the critical basic residue in position 1 but with

an acidic residue and a leucine in positions 3 and 4, typical for the KDEL retention signal (Fig 3) More-over, there are further variants of the PGEL motif in pFGEs, such as FGEL (guinea pig), MGEL (hyrax), SGEL (opossum), PEEL (tree shrew, lemur), PREL (kangaroo rat), and PDEL (lamprey) With the excep-tion of the latter, these species, like all PGEL species, are mammals It should be noted that both proline (or methionine and phenylalanine) in the first position and glycine in the second position do not fit with the gen-eral KDEL-like signal consensus [KRHQSA]-[DENQ]-E-L deposited in the PROSITE database [26]

The C-terminal PGEL and SGEL tetrapeptides function as retention signals for pFGE

To look for a potential ER retention function of the C-terminal PGEL tetrapeptide of human pFGE, three mutant pFGE proteins were constructed with differ-ent C-termini The PGEL tetrapeptide was either deleted (truncated pFGE) or substituted either by the canonical KDEL or by SGEL, one of the other non-canonical tetrapeptide sequences (see above) In sev-eral independent experiments, one of which is shown

in Fig 4A, truncated pFGE was mostly secreted, whereas the wild-type and the KDEL form were mostly retained Also, the SGEL form showed

Fig 1 Retention of pFGE is mediated by a saturable mechanism HT1080 cells stably expressing the reverse tetracycline-controlled trans-activator (Tet-On cells) were transiently transfected to express pFGE under control of a doxycycline-responsive promoter (see Experimental procedures) Six hours after transfection, pFGE expression was induced with 0.5–8 ngÆmL)1doxycycline, as indicated Twenty-eight hours after induction, pFGE was determined in cell lysates (C) and media (M) by western blotting Note that the aliquots of cells and medium were loaded at a ratio of 10 : 1 The amount of total pFGE in cells and medium and the percentage of intracellular pFGE are given below the lanes Two differentially glycosylated forms of pFGE (arrows) were detected in the medium (see text).

Fig 2 ER retention of pFGE is impaired by a C-terminal tag pFGE

and pFGE-His were transiently expressed in HT1080 cells

Twenty-four hours after transfection, aliquots of cells and medium (at a

ratio of 10 : 1) were analyzed for pFGE by western blotting, using

an antiserum against pFGE The total expression level and the

per-centage of intracellular pFGE are given.

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Fig 3 Canonical and noncanonical ER

retention signals in SUMF-encoded proteins.

SUMF2-encoded pFGE and SUMF1-encoded

FGE sequences were recovered from

bases (see Experimental procedures;

data-base mining freeze date August 2007) for

67 and 69 species, respectively Species are

given with their systematic and common

names, and ordered according to the

mod-ern phylogenetic tree (relative to human,

subtrees not uniquely orderable) Sequences

were aligned at their C-terminal regions to

locate conserved pspecific and

FGE-specific anchors, respectively (see

supple-mentary Figs S1 and S2) The last four

encoded residues preceding the stop are

indicated for all 67 pFGE C-termini Species

with canonical pFGE retention signals are

colored in blue, and those with noncanonical

pFGE signals in red (PGEL only) or green

(other noncanonical) For species in black,

no SUMF2 could be recovered; this may be

explained (in some species but not all) by

incomplete coverage of the genome FGE

C-termini are given for those 11 species

having a KDEL-type signal; non-KDEL-like

C-termini are indicated by four periods ( ).

A dash (–) indicates that either no SUMF1

or no SUMF2 sequence could be recovered,

as indicated The presence of the three

KDEL receptor genes is indicated by

num-bers (123) KDELR1 is present in tetrapods

from frog onwards, and KDELR3 in all

tele-ost fish and tetrapods, but apparently not in

chondrichthyans (skates, elephantfish,

shark), agnathans (hagfish, lamprey),

urochordates, or earlier KDELR2 is the only

receptor available to interact with

SUMF-encoded KDEL signals in all species The

given occurrence of KDELR genes is based

on species for which full-length sequences

could be recovered (those indicated by an

asterisk and other species, not shown).

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effective ER retention In conclusion, the

noncanoni-cal PGEL and SGEL sequences serve as retention

signals for pFGE

The data shown above reflect the levels of pFGE

inside and outside the cells 24 h after induction of pFGE

expression To kinetically analyze retention and

secre-tion of newly synthesized pFGE protein,

doxycycline-induced cells were metabolically labeled for 90 min with

[35S]methionine⁄ cysteine and analyzed by

immuno-precipitation of pFGE from cell lysates and medium

immediately or after 3 and 6 h of chase in unlabeled

growth medium The data obtained clearly show that

truncated pFGE was significantly secreted already

dur-ing pulse labeldur-ing After 3 h of chase, only 25% of

trun-cated pFGE were retained within the cells (Fig 4B) On

the contrary, very little of the wild-type and the KDEL

form of pFGE was secreted during the pulse, and most

of these forms were retained intracellularly after 3 h of chase (88% and 66%, respectively)

The C-terminal PGEL tetrapeptide is

an autonomous ER retention signal The canonical KDEL signal is known to confer ER retention to any soluble passenger protein that normally traverses this compartment on its way to the cell surface

To test whether this holds true also for the noncanonical PGEL signal, we equipped lysozyme, a typical secretory protein, with either a C-terminal KDEL or PGEL tetra-peptide A c-Myc-tag, also located at the C-terminus, but upstream of the KDEL⁄ PGEL extension, allowed detection through western blotting Upon doxycycline-induced expression, 90% of lysozyme was found in the medium, whereas the form extended with KDEL was quantitatively retained inside the cells (Fig 5) The PGEL-extended form of lysozyme was likewise effec-tively retained (76%)

Using indirect immunofluorescence, we could detect lysozyme–c-Myc intracellularly in Golgi-like structures (Fig 6B), suggesting that this compartment is the bot-tleneck for secretion of overexpressed lysozyme–c-Myc When equipped with a C-terminal KDEL or PGEL extension, lysozyme colocalized with the ER marker protein disulfide isomerase (PDI) (Fig 6C,D) Whereas pFGE and lysozyme–c-Myc-KDEL fully colocalized with PDI (Fig 6A,C), a fraction of lysozyme–c-Myc-PGEL was also detected in the Golgi-like structures (Fig 6D) This became particularly obvious under con-ditions of maximum doxycycline-induced expression,

as chosen in Fig 6 In conclusion, the noncanonical PGEL, like the KDEL tetrapeptide, is a transferable signal conferring ER retention per se Although less efficient than KDEL, PGEL: (a) massively increases

A

B

Fig 4 Retention of pFGE with and without a C-terminal KDEL,

PGEL or SGEL tetrapeptide pFGE and C-terminal variants of pFGE

(see text), as indicated, were transiently expressed in stable

HT1080 Tet-On cells (cf Fig 1) (A) Six hours after transfection, the

cells were induced with 2 ngÆmL)1doxycycline After induction for

24 h, cells and medium (at a ratio of 10 : 1) were analyzed for

pFGE by western blotting (B) Twelve hours after induction with

0.5 ngÆmL)1doxycycline, cells were starved for 1 h and then

meta-bolically labeled for 90 min with [ 35 S]methionine ⁄ cysteine pFGE

was immunoprecipitated from cell lysates and medium, harvested

after 0, 3 and 6 h of chase Equal aliquots of precipitates from cells

and medium were analyzed by SDS ⁄ PAGE and phosphorimaging.

Bands were quantified; intracellularly retained pFGE is given as

per-centage of total.

Fig 5 The PGEL tetrapeptide confers ER retention to lysozyme Myc-tagged lysozyme and its C-terminally extended variants (see text) were transiently expressed in stable HT1080 Tet-On cells Six hours after transfection, the cells were induced with 1 lgÆmL)1 doxycycline Equal aliquots of cells and medium were analyzed by western blotting, using c-Myc-specific antibodies The intracellularly retained lysozyme is given below the lanes as percentage of total.

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intracellular lysozyme retention (Fig 5); and (b) clearly

shifts this intracellular material from a mainly non-ER

to a mainly ER localization [Fig 6; compare

lyso-zyme–c-Myc staining in (B) and (D)]

Effect of pFGE on FGE retention

Formylglycine-generating enzyme and its paralog

pFGE are both soluble ER-resident proteins [12,13,27]

In contrast to pFGE, FGE lacks a C-terminal

reten-tion signal in vertebrates and most other species

(Fig 3; see Discussion) As there are several

indica-tions that pFGE and FGE interact with each other

(see Introduction), we analyzed whether pFGE confers

ER retention to FGE We constructed a Tet-On

HT1080 cell line stably expressing pFGE under control

of a doxycycline-responsive promoter When the

expression of pFGE was induced by addition of

6 ngÆmL)1 doxycycline, secretion was very low for the first 8 h after induction (not shown) In control

Tet-On HT1080 cells, expressing no pFGE, we studied the expression and secretion kinetics for FGE after transient transfection with a noninducible expression vector FGE is secreted in two forms (37 and 42 kDa) The

42 kDa form represents the full-length FGE, whereas the major 37 kDa form results from N-terminal pro-cessing within the secretory pathway [27] Secretion of FGE by these cells started about 12 h after transfec-tion, and was linear with time for another 10–12 h (Fig 7A) To find out whether FGE secretion

is reduced by coexpression of pFGE, FGE was transiently expressed in Tet-On HT1080 cells stably expressing pFGE (Fig 7B) Twelve hours after trans-fection with the FGE plasmid (the starting point of

A

B

C

D

Fig 6 PGEL-mediated retention of

lyso-zyme in the ER HT1080 Tet-On cells

tran-siently expressing (at 2 lgÆmL)1doxycycline

induction) pFGE (A) or lysozyme–c-Myc

without (B) or with C-terminal KDEL (C) or

PGEL extension (D) were analyzed by

indi-rect immunofluorescence microscopy (see

Experimental procedures) The merge

reveals colocalization of pFGE and

lyso-zyme–c-Myc with the ER marker PDI

medi-ated by the C-terminal KDEL ⁄ PGEL

extensions A fraction of

lysozyme–c-Myc-PGEL is detected in Golgi-like structures, as

indicated by the arrows (D).

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linear FGE secretion), pFGE expression was induced

by addition of doxycycline Measuring intracellular

and extracellular FGE and pFGE every 2 h, we

observed that pFGE did not interfere with FGE

secre-tion (Fig 7B,C), even though the expression of pFGE

clearly exceeded that of FGE (Fig 7B) In addition,

the data shown in Fig 7A,B may suggest that pFGE

coexpression promotes N-terminal processing of FGE

However, careful quantification of many experiments

(under various conditions) did not provide significant

evidence for this interpretation

Discussion

Human pFGE is retained in the ER through its C-terminal PGEL signal

In an earlier study, we localized pFGE mainly in the

ER, but found smaller amounts also in the Golgi and even in the secretions (13% of endogenous pFGE 16 h after synthesis) [23] In this work, we found that pFGE retention is mediated by a saturable mechanism involv-ing KDEL-like signals at the C-terminus of pFGE In fact, the canonical prototype KDEL can only be found

in pFGE of four species (platypus, planorbid snail, planarian flatworm, and sea anemone; Fig 3) Here we studied retention of human pFGE as a representative

of the most common PGEL-containing pFGEs found

in 21 different species Notably, the first two positions

of the PGEL do not match with any of the deposited consensus KDEL patterns (see below)

We found that deletion of PGEL or positioning a tag C-terminal of PGEL more or less fully impaired retention On the other hand, when added to the C-ter-minus of a secretory protein such as lysozyme, PGEL conferred ER retention Thus, PGEL is an autono-mous retention signal It conferred ER retention with similar (pFGE) or almost (76%) similar (lysozyme) efficiency as KDEL itself (Figs 4 and 5) On the one hand, this is surprising, as Pelham et al [28] found that even the canonical HDEL, i.e the yeast prototype retention signal with a rather conservative exchange in the first position, cannot substitute for KDEL in medi-ating lysozyme retention in COS cells On the other hand, in vitro experiments have shown quite efficient binding of an HDEL tetrapeptide and even weak bind-ing of a DDEL tetrapeptide [29] The latter acts as a low-efficiency retrieval signal when present at the C-terminus of lysozyme in COS cells coexpressing either the hERD2.1 or hERD2.2 KDEL receptor [30] Here, we also studied another noncanonical variant, SGEL, as a representative of six further PGEL-like signals found in pFGE, and observed that it also con-ferred ER retention (Fig 4A)

The PGEL tetrapeptide is accessible at the surface of the pFGE molecule

The PGEL C-terminus of pFGE is located on the sur-face of the molecule as part of an eight amino acid extension (AGRPPGEL) of a three-stranded b-sheet opposite to the monomer–monomer interface (Fig 8) [25] The last seven residues including the PGEL could not be resolved in the crystal structure, suggesting that they show a high degree of flexibility As the directly

A

B

C

Fig 7 Influence of pFGE coexpression on FGE retention A

Tet-On cell line stably expressing, from a doxycycline-responsive

pro-moter, pFGE (B) or not (A) was transiently transfected with the

noninducible FGE expression plasmid pSB-FGE at time 0 Twelve

hours later, 6 ngÆmL)1doxycycline was added to induce (B)

coex-pression of pFGE at the indicated levels Then, every 2 h, i.e 14–

22 h after transfection, FGE expression and intracellular retention

were quantified, as given below the lanes The relative retention

of FGE as observed in the absence (A) or presence (B) of pFGE is

plotted in (C).

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preceding three residues (ADA) stick out at the protein

periphery (Fig 8), the PGEL should be easily

accessi-ble for binding by one of the KDEL receptors It

should be noted, however, that both PGEL and

KDEL are obviously more efficiently bound when

present at the C-terminus of lysozyme, as concluded

from its high retention efficiency

pFGE as a retention factor for FGE?

SUMFgene duplication was a rather ancient event, as

in early unicellular eukaryotes such as Emiliana

hux-leyi, both SUMF1 and SUMF2 genes can be found

(Fig 3) Later, SUMF2 was lost in several clades

Fig-ure 3 shows that KDEL-type signals can also be found

in SUMF1-encoded FGE of several invertebrate

spe-cies In total, 11 of 69 available FGE sequences show

a KDEL-type extension at the highly conserved

C-ter-minal region constituting the catalytic site of FGE

Eight of those 11 species lack pFGE, because – despite

generally high sequencing coverage – the SUMF2 gene

is undetectable (Fig 3) The presence of a retention

signal on either FGE or pFGE lends support to the

idea that in those species pFGE and FGE mutually

act as retention factors, involving heterodimer

forma-tion On the other hand, pFGE⁄ SUMF2 is

systemati-cally absent from the Insecta, whereas all 18 of the

insect species have FGE⁄ SUMF1, which, however,

lack a KDEL signal (Fig 3) Thus, there are species in

which a retrieval signal is provided by no, one or both SUMF-encoded proteins Importantly, for all species expressing both FGE and pFGE, heterodimer forma-tion as a prerequisite for ER retenforma-tion could apply, as pFGE always carries a KDEL-related signal

In fact, there are examples of a retention mechanism through hetero-oligomer formation with [KRH]-D-E-L-containing proteins, such as PDI⁄ prolyl hydroxylase [31–33] and b-glucuronidase⁄ egasyn [34] Similarly, Ero1 retention occurs through disulfide bridge forma-tion with RDEL containing ERp44 [35] pFGE⁄ FGE heterodimerization and ternary complex formation with sulfatases was reported by Zito et al [24] to serve

as a regulatory mechanism for FGE activity We have

to point out that, although we have several indications for binding of pFGE to sulfatases as well as to FGE,

we have failed so far to biochemically prove the exis-tence of pFGE⁄ FGE heterocomplexes Our experimen-tal data, showing no influence of coexpressed pFGE

on the secretion of FGE (Fig 7), clearly argue against pFGE as a stand-alone retention factor for FGE Ongoing experiments suggest that regulation of retention versus secretion of FGE employs several mechanisms, one of which involves the noncatalytic N-terminal extension of FGE The possibility that pFGE contributes to this regulation cannot be excluded, as the FGE⁄ pFGE coexpression experiments reported here may have missed ternary complex forma-tion with unfolded sulfatase substrates or other inter-acting components in the ER

Bioinformatic and evolutionary considerations

on pFGE and KDEL signals The well-known KDEL ER retrieval signal, discovered

by Munro & Pelham [36], was found to be widely used In fact, many variants have been described, and the pattern [KRHQSA]-[DENQ]-E-L was deposited as

a general consensus in the PROSITE database [26] Informatic inspection of ER proteins deposited in the human ER Aperc¸u (HERA) database led to the suggestion that this pattern should be extended to [KRHQSADEN]-[DENQTFIV]-E-[LF] [37] Even more extensive bioinformatic studies compiled further variations leading to the pattern [KHRDENQAS]-[DENQIYCV]-[DENQ]-L, which shows more flexibil-ity in the penultimate position [38] Of the C-terminal sequences of pFGE from 67 species (Fig 3), only 17

fit with the latter consensus patterns, most of them nearly ideally (KDEL, KEDL, RDEL, RQEL, RNEL, RTEL, KTEL, HQEL) The remaining 50 sequences differ in either the first position [proline (25 sequences), methionine (one), phenylalanine (one), or threonine

Fig 8 The C-termini of the pFGE dimer are exposed at the surface

of the molecule The ribbon model of the pFGE dimer 3D structure

is shown, as determined through X-ray crystallography [25] The

three N-terminal residues (27-ATS-29, in red) and C-terminal

resi-dues (292-ADA-294, in yellow) of the resolved structure are shown

in stick representation Ala27 represents the N-terminus of the

mature form of pFGE The C-terminal residues 295–301 including

PGEL are not visible in the crystal The two calcium ions in each of

the monomers are shown as gray spheres.

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(one)], in the second position [glycine (28), alanine

(six), proline (one), methionine (one), arginine (one),

or lysine (one)], or in both positions (24) The PGEL

motif accounts for 21 of the 24 sequences with

non-consensus residues in both positions

In Fig 3, the pFGE C-termini of all 67 species are

ordered according to the modern taxonomic tree It

becomes obvious that pFGEs with canonical retention

signals (colored in blue) originated first, and that the

PGEL signal (red) developed with the mammalian

line-age PGEL can be found in many different

phyloge-netic groups, from marsupials (wallaby) to primates

However, within these groups, there is fluctuation

between canonical KDEL-like, PGEL and other

non-canonical retrieval signals (green) in the end leaves of

various subclades We thus conclude that the invention

of noncanonical retrieval signals is not coherent with

specific evolutionary developments Nevertheless, it is

interesting to note that the other noncanonical signals

(Fig 3, green) found in mammalian pFGEs are rather

similar to PGEL

Unfortunately, without supporting experimental

data for the many pFGE species listed in Fig 3, we

cannot say whether all the variations of the retention

tetrapeptide are accepted by the in-species KDEL

receptor(s) and the underlying retrieval system, as this

also varies over the vast phylogenetic timescale In the

mammalian system, where experimental data are

avail-able, PGEL is functional as an autonomous retention

signal (Fig 5) Surprisingly, it is commonly found in

mammalian pFGEs and evolutionarily conserved over

a lot of branch lengths; but at the same time, it is

highly specific for this protein, as becomes evident

from the databases, where only very few PGEL ER

proteins can be found In fact, not a single human

PGEL ER protein, apart from pFGE, and only one

human protein with an N-terminal signal peptide and

an SGEL C-terminus (endonuclease domain-containing

protein ENDOD1), could be retrieved from Swissprot

or Ensembl The UCSC browser retrieved in addition

a GDNF receptor-like protein with a PGEL

C-termi-nus, which, even as a membrane protein, may be

sub-jected to KDEL receptor-mediated ER retention The

specific advantage conferred to pFGE by its PGEL

ter-minus needs to be determined

Relevance for KDEL receptor-mediated ER

retention

The topology of the KDEL receptor-binding pocket

has been probed and found to involve four hydrophilic

residues (Arg5, Asp50, Tyr162 and Asn165 in

KDELR1) located in three different transmembrane

helices, which are highly conserved and found in all three human KDEL receptor isoforms [29] These and other data led to a model in which the KDEL peptide inserts into a charge-lined pocket formed by the trans-membrane helices [39] Asp50 has been suggested to form an ion pair with the normally positively charged first residue of the KDEL-type signal Such ion pairs are supposed to contribute to the very pH-sensitive association–dissociation equilibrium, with association being favored in the slightly acidic environment of the Golgi, and quantitative dissociation in the neutral ER, which has a higher pH by roughly 0.5 units [40] This view seems to contrast with the finding reported here that even the nonpolar proline in the PGEL motif con-fers ER retention However, in vitro peptide-binding experiments suggest that this ion pair is not obligatory,

at least not for the association step, and that the sequence directly upstream of the KDEL-type tetra-peptide contributes to the interaction with the receptor [29] Moreover, mutagenesis of Asp50 did not affect binding of DDEL-containing ligands in vitro and

in vivo, which suggests that different retrieval signals make different contacts in the binding pocket

The variability in the retrieval signature could also

be related to the existence of three paralogous verte-brate KDEL receptor genes All three are found in tet-rapods (mammals, birds, reptiles, amphibians) (Fig 3) KDELR2 is present in all eukaryotes, KDELR3 in all teleost fish and tetrapods, and KDELR1 only in tetra-pods from the frog onwards Human KDEL receptors (ERD2) 1 and 2 are obviously ubiquitously expressed,

as suggested by cDNA libraries from different tissues, but human ERD2.2 is inducible through the ER stress response [30] Both are functionally identical with regard to lysozyme-KDEL and lysozyme-DDEL retrie-val [30] Residues 50–56 of KDEL receptor 1 were sug-gested to determine ligand specificity [29,41] Of these, only positions 54⁄ 55 show minor variations among the three KDEL receptor isoforms (50-DLFTNYI-56⁄ DLFTSFI⁄ DLFTNFI) Unfortunately, no 3D model

of the binding pocket is available Coexpressing the individual receptors with pFGE might show that, indeed, a particular receptor isoform is well adapted for pFGE retrieval

Conclusions

This study on the mechanism of pFGE retention in the ER has uncovered a novel retrieval signal that autonomously confers ER retention to passenger pro-teins Surprisingly, this noncanonical PGEL variant of the classic KDEL signal, although evolutionarily con-served for most mammalian pFGEs, is not being

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widely used by other mammalian ER proteins Why

the PGEL signal or its other noncanonical variants are

specific for pFGE remains elusive at present As long

as the role of pFGE in sulfatase activation through

FGE remains speculative, one can only suppose that

FGE function and possibly trafficking is regulated via

pFGE If it is true that FGE trafficking out of the cell

eventually reaches even the ER of other cells [42],

anterograde and retrograde transport of this essential

activator of sulfatases definitely need complex

regula-tion

Experimental procedures

Construction of expression plasmids

C-terminal tetrapeptide variants of pFGE and lysozyme were

constructed by cloning corresponding cDNAs into

multiclon-ing site I of the pBI Tet vector (BD Biosciences, Heidelberg,

Germany), which allows the simultaneous expression of two

genes of interest from one bidirectional tet-responsive

pro-moter For cloning wild-type pFGE, pFGEDPGEL

(‘trun-cated pFGE’) and pFGE with KDEL or SGEL instead of

PGEL, pFGE cDNA [23] served as a template for an add-on

PCR using 5¢-CTAGCTAGCCACCATGGCCCGGCAT

GGGTTAC-3¢ as a forward primer, and reverse primers

5¢-TCTAGAGATATCTACAGCTCCCCTGGCG-3¢ (for

wild-type pFGE), 5¢-TCTAGAGATATCTACGGCCGGC

CTGCGTC-3¢ (pFGEDPGEL), 5¢-TCTAGAGATATCTA

CAGCTCGTCTTTCGGCCGGCCTG-3¢ (pFGE-KDEL),

or 5¢-TCTAGAGATATCTACAGCTCCCCGGACGGCC-3¢

(pFGE-SGEL) An NheI site was added at the 5¢-end and an

EcoRV site at the 3¢-end, which facilitated directional cloning

of the PCR product into multicloning site I

For cloning wild-type lysozyme–c-Myc and lysozyme–

c-Myc with PGEL or KDEL at the C-terminus, plasmid

pCMV2-Lys-cmyc-KDEL [43] served as a template for

add-on PCR, using GTCAGCTAGCCGGCCCGCCAT

GAGGTCTTTGCTAATC as a forward primer, and

reverse primers 5¢-CCGGATATCGATTCACTCACTATC

GATGTTGAGGTC-3¢ (for wild-type lysozyme), 5¢-CC

GGATATCGATTCATAGCTCCCCTGGCTCACTATC-3¢

(lysozyme-PGEL) or 5¢-CCGGATATCGATTCATAGCTC

GTCCTTCTCACT-3¢ (lysozyme-KDEL) Also here, 5¢-end

NheI sites and 3¢-end EcoRV sites facilitated directional

cloning of the PCR product into the pBI Tet vector

Cell culture and transfections

Human HT1080 fibrosarcoma cells were grown in normal

growth medium, i.e in DMEM supplemented with 10%

fetal bovine serum and 1% penicillin⁄ streptomycin

(Invitro-gen, Karlsruhe, Germany) under 5% CO2at 37C HT1080

cells stably expressing the reverse tetracycline-controlled

transactivator rtTA (Tet-On cells) and Tet-On cells stably expressing pFGE were grown in normal growth medium with neomycin or neomycin and puromycin, respectively The stable Tet-On cell line was established by cotransfect-ing HT1080 cells with pUHrT62 (kindly provided by

N Jung, Institute of Chemistry and Biochemistry, Freie Universitaet, Germany), encoding the reverse tetracycline-controlled transactivator [44], and the neomycin-resistant vector pSB4.7pA at a ratio of 10 : 1 Transfectants were selected with increasing concentrations of neomycin from 0.2 to 0.8 mgÆmL)1 Stable clones were screened first for doxycycline-dependent fluorescence after transient trans-fection with a pBI-EGFP plasmid The best clones were then rescreened through western blotting for doxycycline-dependent pFGE production after transient transfection with pBI-pFGE

A Tet-On cell-line stably expressing pFGE under control

of a doxycycline-responsive promoter was established by cotransfecting Tet-On cells with pBI-pFGE and the puro-mycin resistance vector pSV.pac (10 : 1 ratio) Transfec-tants were selected as mentioned above and screened for pFGE expression

Transient transfections of HT1080 Tet-On cells were per-formed using Lipofectamine 2000, following the protocol from Invitrogen Typically, 2 lg of expression plasmid DNA (see above) was used for a 3 cm dish After 6 h of transfection, medium was replaced by DMEM with various concentrations of doxycycline ranging between 0 and

1000 ngÆmL)1, as indicated for each experiment (see Results and legends to Figs 1, 4, 5, 6 and 7) Cells and medium were harvested after 24 h of induction, unless otherwise specified (see figure legends), and analyzed by western blot-ting

Western blotting For western blot detection of pFGE, FGE and lysozyme– c-Myc, polyclonal antibodies to pFGE [23], FGE [27] and c-Myc (Sigma, Taufkirchen, Germany) were used as primary antibodies Horseradish peroxidase-conjugated goat anti-(rabbit IgG1) sera were used as secondary antibodies ECL signals were quantified using the aida 2.1 software package (Raytest, Straubenhardt, Germany)

Pulse-chase experiments and immunoprecipitation

HT1080 Tet-On cells, grown to 50–60% confluency, were transiently transfected with pBI-pFGE, pBI-pFGEDPGEL

or pBI-pFGE-KDEL plasmids After 6 h, the medium was replaced by medium with 0.5 lgÆmL)1 doxycycline After

12 h of induction, cells were starved in 2 mL of methio-nine⁄ cysteine-free DMEM for 1 h, and pulsed for 90 min with 1 mL of medium containing 100 lCi of 35S-labeled

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