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Tiêu đề Protein Transport In Organelles: The Composition, Function And Regulation Of The Tic Complex In Chloroplast Protein Import
Tác giả J. Philipp Benz, Jürgen Soll, Bettina Bölter
Trường học Ludwig-Maximilians-Universität München
Chuyên ngành Plant Biochemistry
Thể loại Minireview
Năm xuất bản 2009
Thành phố Munich
Định dạng
Số trang 11
Dung lượng 512,64 KB

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The majority of Keywords chloroplast; import motor; preprotein channel; redox regulation; Tic complex; translocon Correspondence J.. The so-called ‘general import pathway’ makes use of t

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Protein transport in organelles: The composition,

function and regulation of the Tic complex in

chloroplast protein import

J Philipp Benz1,2, Ju¨rgen Soll1,2and Bettina Bo¨lter1,2

1 Plant Biochemistry, Ludwig-Maximilians-Universita¨t Mu¨nchen, Munich, Germany

2 Munich Center for Integrated Protein Science CiPS M , Ludwig-Maximilians-Universita¨t Mu¨nchen, Munich, Germany

Introduction

To fulfil their functions correctly, plastids permanently

communicate with the surrounding cell This requires a

substantial traffic of substances such as nutrients,

metabolites and proteins into and out of the organelle,

which have to be funnelled across the two envelope

membranes surrounding all plastid types Among these

transport processes, the translocation of proteins is of particular significance Due to the loss of more than 90% of their genetic information to the host nucleus during evolution, plastids have become almost com-pletely dependent on the surrounding cell Of the approximately 3000 proteins present in chloroplasts, typically only 50–250 (dependent on the species) are still encoded for on the plastome [1] The majority of

Keywords

chloroplast; import motor; preprotein

channel; redox regulation; Tic complex;

translocon

Correspondence

J Soll, Plant Biochemistry,

Ludwig-Maximilians-Universita¨t Mu¨nchen,

Großhaderner Strasse 2-4, D-82152 Munich,

Germany

Fax: +49 89 2180 74752

Tel: +49 89 2180 74750

E-mail: soll@lmu.de

Website: http://www.chloroplasts.de

(Received 31 July 2008, accepted 11

December 2008)

doi:10.1111/j.1742-4658.2009.06874.x

It is widely accepted that chloroplasts derived from an endosymbiotic event

in which an early eukaryotic cell engulfed an ancient cyanobacterial pro-karyote During subsequent evolution, this new organelle lost its autonomy

by transferring most of its genetic information to the host cell nucleus and therefore became dependent on protein import from the cytoplasm The so-called ‘general import pathway’ makes use of two multisubunit protein translocases located in the two envelope membranes: the Toc and Tic com-plexes (translocon at the outer/inner envelope membrane of chloroplasts) The main function of both complexes, which are thought to work in para-llel, is to provide a protein-selective channel through the envelope mem-brane and to exert the necessary driving force for the translocation To achieve high efficiency of protein import, additional regulatory subunits have been developed that sense, and quickly react to, signals giving infor-mation about the status and demand of the organelle These include calcium-mediated signals, most likely through a potential plastidic calmod-ulin, as well as redox sensing (e.g via the stromal NADP+/NADPH pool)

In this minireview, we briefly summarize the present knowledge of how the Tic complex adapted to the tasks outlined above, focusing more on the recent advances in the field, which have brought substantial progress concerning the motor function as well as the regulatory potential of this protein translocation system

Abbreviations

CaM, calmodulin; ClpC, caseinolytic protease C; Cpn, chaperonin; FNR, ferredoxin-NADP + -oxidoreductase; Hip, Hsp70-interacting protein; Hop, Hsp70/Hsp90-organizing protein; Hsp, heat shock protein; IEM, inner envelope membrane; OEM, outer envelope membrane; SDR, short-chain dehydrogenase; SPP, stromal processing peptidase; Tic, translocon at the inner envelope membrane of chloroplasts; Toc, translocon at the outer envelope membrane of chloroplasts; TPR, tetratricopeptide repeat; Trx, thioredoxin.

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proteins therefore have to be imported

post-transla-tionally from the cytoplasm, which is most generally

performed via two translocation machineries present in

the outer (OEM) and inner envelope membrane

(IEM), called Toc (translocon at the outer envelope of

chloroplasts) and Tic (translocon at the inner envelope

of chloroplasts), respectively [2–5] In this pathway,

nuclear encoded preproteins are translated with an

N-terminal extension called transit peptide, which

allows targeting of the precursor to the organelle,

specific recognition by the receptor proteins on the

surface, and subsequent translocation through both

membranes After successful import, the transit peptide

is cleaved off by the stromal processing peptidase

(SPP), resulting in the mature form of the protein The

entire process is superficially reminiscent of that

medi-ated by the protein translocases at the outer and inner

mitochondrial membranes [6], but plastids have

devel-oped their own ways to solve the main three tasks of

protein translocation: (a) the formation of a

prepro-tein-specific pore in the membrane (the channel); (b)

exerting the necessary driving force (the motor); and

(c) installing components that allow regulation of the

translocation efficiency depending on developmental or

environmental conditions (the regulon)

Based on biochemical and genetic evidence, eight

proteins have been implicated with respect to

prepro-tein import at the IEM of chloroplasts: Tic110, Tic62,

Tic55, Tic40, Tic32, Tic22, Tic21 and Tic20 (Figs 1

and 2) For each component, either a direct contact

with imported precursor has been demonstrated or,

otherwise, a close interaction with one of the

estab-lished Tic core proteins (usually Tic110) Last but not

least, the chaperone heat shock protein (Hsp) 93/

caseinolytic protease C (ClpC) has been demonstrated

to be a central constituent of the Tic motor complex

(see below)

The present minireview provides a short description

of recent advances in the understanding of the

chan-nel-, motor- and regulatory components of the Tic

complex For reference, some of the available

know-ledge, including the proposed function of all Tic

components, is summarized in Table 1

The Tic channel

Tic110 is undoubtedly the central protein of the

tran-slocon It is not only the largest, most abundant and

best studied of all Tic proteins, but also probably the

only component involved in translocation steps

hap-pening on both sides of the IEM This includes the

assembly of Toc–Tic ‘supercomplexes’ [7–9], preprotein

recognition [10], translocation, and folding steps of

successfully imported precursor proteins in the stroma [11,12] However, the exact topology of Tic110 within the IEM is still not completely solved There is mutual consent about two transmembrane-helices at the extreme N-terminus, which anchor the protein in the membrane The position and function of the long C-terminal tail on the other hand remains a matter of controversy [10,11,13–15] According to one hypothe-sis, the hydrophilic Tic110-Ct faces the stroma, where

it functions as a scaffold for the organization of the stromal processes occurring during import [10,13,14] These include the recruitment of chaperones to the import apparatus (see below), as well as providing a transit peptide-docking site, which is localized next to the exit site of the translocon [10] Another study dem-onstrated that the function of Tic110 could extend well beyond this role Full-length protein as well as

Tic110-Ct was shown to insert into liposomes and form a cation-selective ion channel, which was sensitive to chloroplast transit peptides [11] Interestingly, using structural prediction software, at least two amphi-pathic a-helices with acidic faces could be located around the proposed transit peptide binding site [10] These structures have been implicated with channel function (e.g in ligand-gated and voltage-gated K+ channels) [16], and thus could provide an explanation for the observed channel activity of Tic110, as well as for the binding of transit peptides in this region (Fig 1)

Another putative channel protein is Tic20 Structural predictions place Tic20 within the large group of small hydrophobic proteins with four transmembrane-domains (e.g including the channel proteins Tim17 and Tim23) (Fig 1) Distant sequence similarity also exists between Tic20 and two prokaryotic branched-chain amino acid transporters [17] No data have been published demonstrating channel activity but, because Tic20 has prokaryotic ancestors, this suggests that it could have been one of the very early constituents

of an evolving protein import translocon [18] By contrast, only eukaryotic homologues have been found for Tic110

However, Tic20 and Tic110 also display some simi-lar features For example, tissue analysis in Arabi-dopsis thaliana indicated that both proteins can be detected throughout the plant and that expression does not appear to be restricted to photosynthetic tissue, even though absolute expression levels appear to be much lower for Tic20 than for Tic110 [13,19] When expression was silenced by antisense or completely abolished using a T-DNA knockout, both mutants exhibit severe phenotypes in A thaliana [13,19,20] Tic110 was shown to be essential for chloroplast

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biogenesis and embryo development In addition, it

displays a rare semi-dominant phenotype because

plants with a heterozygous knockout are already

clearly affected [13] Antisense plants of the pea

ortho-log and main Arabidopsis isoform of Tic20, AtTic20-I,

similarly exhibit pronounced chloroplast defects, and

attic20-I knockouts were albino even in the youngest

parts of the seedling [19,20] The presence of at least one other Tic20 isoform (AtTic20-IV) may prevent attic20-I plants from lethality Two more isoforms have been detected in Arabidopsis, which, however, do not possess a predicted transit peptide (Table 1) [18] Furthermore, chloroplasts from attic20-I antisense plants, as well as from heterozygous attic110, were

Fig 1 Schematic overview showing the predicted functional domains and topology of all Tic components Transmembrane domains are depicted as columns Regions involved in membrane binding are coloured in red, motifs involved in protein–protein interaction are blue and the dehydrogenase domains of Tic32 and Tic62 are shown in green Tic110 contains two transmembrane domains at the proximal N-termi-nus The topology of the long C-terminus is still not completely solved In this model, we tentatively tried to combine several views by add-ing some transmembrane columns havadd-ing amphipathic character (indicated by red–white colour marked with a ‘?’) Tic20 and Tic21/PIC1 both belong to the big group of four-transmembrane domain proteins Topology-predictions indicate an Nin/Cinorientation Tic62 belongs to the extended family of SDRs and can be divided in two distinct modules The N-terminus contains the dehydrogenase domain (green) and might mediate membrane binding via a hydrophobic patch on the surface of the protein, whereas the C-terminus features a series of Pro/ Ser-rich repeats (blue) that allow specific binding of FNR Tic22 is a soluble protein located in the intermembrane space (IMS) with no func-tional domains known so far Tic55 is a Rieske [2Fe-2S]-centre containing oxidoreductase with an addifunc-tional mononuclear iron binding site (both in brown) and two transmembrane helices at the C-terminus The conserved cysteine pair (CXXC) possibly involved in regulation by thioredoxins is indicated The SDR Tic32 contains an NADPH binding site and the active site motifs characteristic for SDRs (green) A CaM binding site was located in the extreme C-terminus (blue) Tic40 consists of an N-terminal transmembrane domain and a soluble C-terminus protruding into the stroma Conserved regions of the C-terminus are the TPR domain, consisting of seven predicted a-helices (blue), and the Sti1-like Hip/Hop domain at the extreme C-terminus (yellow), involved in activation of Hsp93.

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demonstrated to be defective in preprotein import

across the IEM [13,20]

Based on these similarities, the hypothesis was

pro-posed that Tic20 and Tic110 could both dynamically

associate to co-operate in channel formation [10] The

only real biochemical indication for this suggestion

shows that a minor fraction of Tic110 (approximately

5%) could be coeluted with Tic20 (and Tic22) in a

Toc–Tic supercomplex [21] However, no coelution

was detected in the absence of the Toc complex,

making a direct or permanent interaction unlikely

In summary, both Tic20 and Tic110 are clearly

important for plant viability and preprotein

transloca-tion, but only for Tic110 do the electrophysiological

and biochemical data indicate direct channel activity

as well as involvement in the import motor complex (see below) Similar data for Tic20 are still missing, but it can be speculated that either various translocons exist, or that Tic20 exhibits a different kind of protein translocation activity, which is possibly analogous to the inner membrane of mitochondria, where the Tim23/Tim17 and Tim22 channels exist in parallel, each responsible for translocation of a different subset

of precursors [6]

Recently, another protein with four predicted trans-membrane-domains, similar to Tic20, was identified as

a third putative translocon component and named CIA5/Tic21 (Fig 1) [19] The phenotype of attic21 plants resembled that of attic20-I, but the affiliation with the Tic complex was questioned by a second

Fig 2 Schematic illustration of the Toc and Tic chloroplast import machineries with focus on the components involved in preprotein translo-cation at the IEM Individual Tic components are labelled with their respective names and some key functional domains are additionally indi-cated (Tic40 and Tic62); Toc components are not labelled The predicted transmembrane domains of Tic40 and Tic55 are shown as small columns protruding into the IEM Components of the channel/motor complex are depicted in yellow (Tic110, Tic40 and Hsp93), redox-regula-tory subunits in blue (Tic62 with associated FNR, Tic55 and Tic32), the proposed alternative import channel Tic20 and the intermembrane space (IMS) component Tic22 in red and the second involved chaperone Cpn60 in green A cytoplasmically translated preprotein with an N-terminal transit peptide is shown during its translocation through the Toc and Tic complexes Tic22 may be involved in the stabilization of the Toc/Tic/preprotein supercomplex In this model, Tic110 forms the channel protein and also acts in the recruitment of Hsp93 in concert with the co-chaperone Tic40 The TPR domain of Tic40 is considered to mediate the interaction with Tic110, whereas the Sti1-like Hip/Hop domain was shown to enhance the ATPase activity of the chaperone Hsp93 The motor activity of this AAA+ ATPase probably accounts for most of the ATP requirement of the import reaction, exerting the pulling force on the incoming precursor The SPP is thought to act very early after the preprotein emerges from the Tic channel, and Cpn60 (a GroEL-homologue) is probably involved in folding of the processed precursor The association of the redox-sensing regulatory subunits Tic62 (with the FNR bound to the C-terminus) and Tic32 appears to be quite dynamic (double arrows) It is not known whether this is also true for the Rieske protein Tic55, but a similar behaviour is assumed in this model.

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study demonstrating that the same gene locus does not

encode a protein conducting channel, but instead an

iron permease (PIC1) [22]

Tic motor function

Early chloroplast import studies demonstrated that

cytoplasmically synthesized preproteins are imported

into the organelle in an ATP-dependent process [23]

By contrast to mitochondria, the energy is not used to

generate a membrane potential for driving the import

reaction, but exerts its effect on a stromal ATPase with

a different function [24] Chaperones subsequently

have been the main candidates for this ATPase activity

and, indeed, members of the Hsp60 [chaperonin

(Cpn)60] and Hsp100 (Hsp93) families have been

found to interact with the Tic translocon [7,8,12] To

date, no involvement of Hsp70s or Hsp90s with

pre-protein import has been reported, although both have

homologues present in the chloroplast stroma This is

somewhat surprising, given that the analogous motor

of mitochondria relies solely on the activity of an

Hsp70 [6,25,26]

Cpn60 (60 kDa), a homologue to bacterial GroEL,

was the first chaperone demonstrated to specifically

co-immunoprecipitate with Tic110 in an

ATP-depen-dent manner [12] However, analysis of the interaction

between Tic110, Cpn60 and imported preprotein

revealed that only the interaction with the mature form

is ATP-dependent and thus mediated by Cpn60 This

suggests that Tic110 serves in the recruitment of the

chaperonin, which then acts in the folding of the pro-cessed protein

All subsequent studies indicated that it is actually the ternary complex of Tic110, Tic40 and Hsp93/ClpC that comprises the import motor at the IEM of chlo-roplasts (Fig 2) All three proteins function at approx-imately the same (late) stage of the import process [27] Genetic characterization of double mutants in Arabidopsis revealed non-additive interactions (epista-sis) amongst the respective knockout mutations, providing additional support for this functional co-operation [28]

The involvement of the AAA+ family ATPase Hsp93/ClpC in preprotein translocation is interesting because it also acts in intracellular degradation and substrate turnover, which it performs in association with its proteolytic counterpart ClpP [29,30] Neverthe-less, Hsp93/ClpC was also shown to display intrinsic chaperone activity [31] and thus appears to be capable

of performing several tasks in the chloroplast, which are probably dependent on the suborganellar compart-ment (stromal versus membrane-tethered) and the respective interaction partners

Subsequent to the initial demonstration of a specific, ATP-dependent association of Hsp93 with Tic110 and incoming precursor [7,8], considerable progress has been made, especially concerning the role of Tic40 and Hsp93 in the motor complex [27,28,32–34] and the possible order of events [35]

Tic40 is an integral membrane protein containing

a single transmembrane span within its extreme

Table 1 Components implicated with the Tic complex, their Arabidopsis isoforms, and the proposed function.

Tic component

Isoforms in

Tic110 AtTic110 (At1g06950) Channel protein; chaperone recruitment in motor complex [10–15,28,33,57]

Tic55 AtTic55 (At2g24820) Redox regulation; possibly regulated by thioredoxins [48,49,58]

Tic40 AtTic40 (At5g16620) Co-chaperone in motor complex; Hsp93 activator; timing

device

[27,28,32,34,35,59,60]

AtTic32-IVb (At4g23420) AtTic32-IVc (At4g11410)

Redox regulation: sensing of NADP+/NADPH ratio; site of

Ca 2+ /CaM regulation

[46,61]

AtTic22-III (At3g23710)

Intermembrane space complex (with Toc12, imsHsp70 and Toc64)

[21,62–64]

Tic21/PIC1 AtTic21/AtPIC1

(At2g15290)

AtTic20-IV (At4g03320) AtTic20-V (At5g55710) AtTic20-II (At2g47840)

Hsp93 (ClpC) AtHsp93-V (At5g50920)

AtHsp93-III (At3g48870)

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N-terminus, anchoring it in the IEM, whereas the

C-terminus of the protein projects into the stroma

(Fig 1) [34] Two motifs can be located in the

C-termi-nal half of the stromal domain: (a) the last

approxi-mately 60 amino acids are weakly similar to a

conserved motif of the mammalian co-chaperones

Hsp70-interacting protein (Hip) and

Hsp70/Hsp90-organizing protein (Hop) and (b) the region

immedi-ately preceding this domain is predicted to form a

structure similar to a tetratricopeptide repeat (TRP)

motif Hip and Hop play regulatory roles in Hsp70

and Hsp90 cycles [36–39] and, interestingly, the yeast

Hop homologue Sti1p was also shown to associate

with Hsp104, which is a member of the Hsp100 family

[40] TPR domains are degenerate 34-amino acid

repeats forming anti-parallel a-helices known to be

involved in an array of protein–protein interactions

(generally with non-TPR proteins) [41] Both domains

are very characteristic for co-chaperones

Using various Tic40-deletion constructs in an

attempt to complement the pale green and slow

growing tic40 knockout phenotype, it could be

shown that the C-terminal Hip/Hop (Sti1-like)

domain, as well as the N-terminal

transmembrane-helix and a central region including the putative

TPR motifs, is essential for correct protein activity

Only the full-length cDNA clone was able to reverse

the phenotype to wild-type growth [32] A more

detailed characterization of the single domains

pro-vided valuable insight into the possible functional

role of Tic40: the Sti1-like region of Tic40 was

shown to be functionally equivalent to the Sti1

domain of human Hip, corroborating the role of

Tic40 as a bona fide co-chaperone [32] Additionally,

in in vitro assays using overexpressed Hsp93 and

var-ious Tic40 deletion constructs, the same domain was

found to stimulate the ATPase activity of the

chap-erone [35] Because this stimulating effect was only

visible with the Hip/Hop-domain alone and not with

the entire stromal domain including the TPR motifs,

it was hypothesized that the protein exists in a

closed conformation, in which the TPR domain

shields the Hip/Hop-domain from the chaperone

Surprisingly, the TPR motifs themselves appear to

mediate the interaction with Tic110 and not with the

chaperone partner (Hsp93), which is in contrast to

the function of these motifs in Hop and Hip

[40,42,43] Interestingly, binding of Tic40 to Tic110 is

favoured when the transit peptide-binding site of

Tic110 is occupied by incoming preprotein, but

inter-action with Tic40 appears to decrease the affinity of

Tic110 for the transit peptide, which is subsequently

released and therefore accessible for processing by

the SPP and interaction with Hsp93 [35] Conforma-tional changes occurring upon binding of Tic40 to Tic110 presumably also open the Hip/Hop-domain of Tic40, allowing it to stimulate the motor activity of Hsp93

Obviously, the import motor is still functional in the absence of Tic40 because tic40 knockout plants are viable, even though the plants are very pale [27] In addition, dominant-negative phenotypes could be observed in some Tic40 complementation lines, indi-cating that the overexpressed deletion-constructs inter-fered with some residual motor activity [32] Thus, Tic40 clearly enhances the operational efficiency of the complex and was proposed to function as a timing device, co-ordinating the sequential steps of transloca-tion (Fig 2) [32,35]

The function of the ATPase Hsp93 in protein import was further analyzed using the characterization of Arabidopsis knockout mutants [28,33] In Arabidopsis, two homologues of Hsp93 exist (III and Hsp93-V), sharing high (approximately 91%) sequence iden-tity Hsp93-V is thought to be the main isoform with a several-fold higher expression rate than Hsp93-III Nevertheless, some degree of redundancy appears to exist among both proteins because the mildly chlorotic hsp93-Vknockout phenotype can be complemented by overexpression of the other isoform However, analysis

of double knockouts of both Hsp93 homologues did not result in the identification of double homozygotes, establishing that Hsp93 function is essential for viabil-ity, just as is the case for Tic110 [28,33] This observa-tion indicates that Hsp93 and Tic110 are of similar importance for the organelle

Another finding concerns the significance of the Hsp93-related motor activity on the overall import of preproteins through both envelope membranes It is known that Tic110 and Hsp93 are constituents of Toc–Tic supercomplexes that are associated with pre-cursor protein [7,8] Therefore, it could be possible that the ATPase activity of Hsp93 exerts a pulling effect also at the level of the OEM, similar to the situation

in mitochondria When performing import experiments with tightly folded as well as unfolded preprotein in viable hsp93-III/-V double-mutant (knockdown) chloroplasts, the use of an unfolded preprotein did not alleviate the decreased import efficiency in hsp93-III/-V (and tic40) plants This implies that the rate-limiting step for protein import in the mutant chloroplasts is not precursor unfolding [33,44] and could be interpreted as an indication for separate unfolding forces (and thus motor activities) in the outer and inner membranes of the chloroplast envelope during preprotein import

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Possible ways of regulation

As outlined above, a great amount of protein traffic

has to take place at the envelope membranes of

chlo-roplasts, which has to be tightly regulated to ensure

that the supply correlates with the demand of the

orga-nelle at any given time Logically, translocation across

the envelope is surely a bottleneck in the path of

trans-ported proteins from the cytosol to their final

destina-tion in the chloroplast The Tic and Toc translocons

are therefore perfectly situated to impose a regulatory

control over incoming preproteins Additionally,

because the demand of the chloroplast is ‘sensed’

inside the organelle, the IEM is closest to the origin of

the signal, and thus regulation at the Tic complex

could be one of the fastest ways to react efficiently

To our current knowledge, at least two types of

sig-nals convene at the Tic complex: (a) the stromal

NADP+/NADPH ratio sensed via Tic62 and Tic32,

giving information about the metabolic state of the

chloroplast and (b) a calcium signal, which is mediated

by a still elusive chloroplast calmodulin (CaM),

associ-ated with Tic32 (Fig 3)

Redox regulation

Redox regulation is long known to play a prominent

role in the chloroplast metabolism, and also at least

two preproteins (the nonphotosynthetic ferredoxin

FdIII and the ferredoxin-NADP+-oxidoreductase iso-form II of maize) were demonstrated to be differen-tially imported in the light compared to the dark [45] Diurnal changes in the thylakoids or, more generally, the stromal redox system (e.g the NADP+/NADPH pool) thus appear to have an impact on the import characteristics of the organelle It is therefore not sur-prising to find proteins with redox-active domains as Tic constituents Up to now, the ‘regulon’ of the Tic complex comprises three proteins: Tic62, Tic32 and Tic55 The former two proteins belong to the (extended) family of short-chain dehydrogenases/reduc-tases (SDRs) and have already been demonstrated to possess dehydrogenase activity in vitro [46,47] Less is known about the redox properties of Tic55 Sequence analysis revealed the presence of a Rieske-type [2Fe-2S] cluster and a mononuclear iron-binding site [48] Database research classifies Tic55 as a member of the chlorophyll a oxygenase/pheophorbide a oxygenase-like oxygenases, which act for example in chlorophyll biogenesis or oxygen-dependent degradation pathways Rieske proteins generally play important roles in elec-tron transfer (e.g in the cytochromes present in the respiratory chain of mitochondria or in the thylakoids

of chloroplasts) Whether Tic55 acts as an oxygenase

in vitro or in vivo has not been studied to date, but the close proximity of the Rieske protein Tic55 and the two bona fide dehydrogenases Tic32 and Tic62 at the Tic complex holds the intriguing possibility of a

Fig 3 Schematic model of the proposed regulatory signals sensed by the Tic complex and their effect on the involved subunits Three sig-nals are thought to convene at the Tic complex: (1) information about the chloroplast metabolic redox state, represented by the stromal NADP+/NADPH ratio and sensed by the two dehydrogenases Tic62 and Tic32; (2) a calcium signal, mediated by a still unknown plastidic CaM or CaM-like protein binding to Tic32; and (3) a second redox-related signal, in which a stromal thioredoxin interacts with a conserved cysteine pair (CXXC) of the Rieske protein Tic55 The redox state of the NADP + /NADPH pool was demonstrated to have a drastic effect on the association of Tic62 and Tic32 with the Tic complex Both components dissociate from the complex at high NADPH concentrations Tic62 was shown to reversibly shuttle between the stroma the IEM dependent on the NADP+/NADPH ratio For Tic32, a similar relocaliza-tion as for Tic62 is assumed in this model.

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small electron transfer chain being present at the Tic

translocon [47] In addition, a very recent study

identi-fied Tic55 as a target of stromal thioredoxins (Trx) in

barley chloroplasts [49] Trxs are small ubiquitous

pro-teins with redox-active disulfide bridges that regulate

enzyme activities (e.g in the Calvin cycle or the

oxida-tive pentose phosphate cycle) by dithiol oxidoreduction

of their target proteins [50] Necessary for this reaction

is a conserved pair of cysteines, which can be detected

in Tic55 (CXXC motif; Fig 1) However, no further

conclusion about how the oxidoreduction affects Tic55

function in the Tic complex could be drawn from this

analysis

Investigation of the Tic complex under changing

redox conditions revealed a high degree of dynamics

For example, addition of NADPH leads to

dissocia-tion of the two dehydrogenases Tic32 and Tic62 from

the complex, indicating that the metabolic state of the

organelle appears to have a profound influence on Tic

composition [46] Further studies with Tic62

corrobo-rated this finding and revealed that this protein

shut-tles between the chloroplast membrane compartment

and the stroma dependent on the stromal NADP+/

NADPH ratio [47] (Fig 3) Oxidizing conditions lead

to fast membrane binding and integration into the Tic

complex Reducing conditions on the other hand lead

to solubilization into the stroma and increased

interac-tion with its other known interacinterac-tion partner

ferre-doxin-NADP+-oxidoreductase (FNR) Interestingly,

this membrane binding was found to be reversible, and

is assumed to be mediated by a hydrophobic patch on

the protein surface, located in the N-terminal half of

the protein, including the dehydrogenase domain

Spe-cific binding of the FNR is mediated by a unique series

of proline/serine-rich repeat motifs located in the

C-terminus For the integration into the Tic complex

finally, a central region of the protein was shown to be

sufficient, which contains parts of both, the

N-termi-nus and C-termiN-termi-nus (Fig 1) These results demonstrate

that Tic62 is able to react very sensitively to redox

changes in the chloroplast stroma and that it adjusts

its localization accordingly These features would allow

it to fulfil its proposed role as a redox-sensor protein

in the chloroplast [47,51] How exactly changes in the

redox state of the chloroplast affect the translocation

is not yet known, but it has been suggested that the

dynamic Tic composition could influence the import

characteristics of a certain subset of preproteins, which

might also act in redox-dependent pathways [47]

The reason for the strong association of Tic62 with

the FNR still remains one of many open questions

Because flavin-containing proteins have already been

described to be present in redox chains in chloroplast

envelope membranes [52], one possibility is the recruit-ment of FNR from the stroma or even thylakoids to the Tic complex in order to become part of the hypo-thetical electron transfer chain mentioned above How-ever, the involvement of the FNR appears to be an evolutionary young mode of regulation This notion derives from an extensive database analysis of the Tic62 protein looking for homologues in other sequenced organisms [53] It was found that the N-ter-minal half of the protein, comprising the dehydro-genase domain, is highly conserved in all oxyphototrophs, and homologues can be found even

in green sulfur bacteria The C-terminus, containing the FNR binding repeats, on the other hand, is present only in higher plants This C-terminal extension there-fore appears to have been added only recently in evo-lution, which could make Tic62 one of the youngest Tic constituents

Ca2+/CaM regulation Calcium is a common secondary messenger that regu-lates many biochemical processes (e.g relaying envi-ronmental signals to various cellular response pathways) This is generally achieved through binding

to calcium sensing proteins such as CaM, which subse-quently change their affinities to downstream target proteins, leading to further responses [54,55] Even though regulation by calcium/CaM is considered to be

a eukaryotic trait, import analyses into chloroplasts could demonstrate that organellar processes have been integrated into the calcium signalling network of the cell [56] Calcium ionophores as well as the CaM-inhibitor ophiobolin A affected the translocation of preproteins containing a cleavable N-terminal transit peptide This indicates that: (a) the general Toc/Tic pathway is involved in calcium regulation and (b) a CaM or CaM-like protein is the most likely mediator

of this regulation In an attempt to isolate CaM-bind-ing proteins, Tic32 was identified as the only IEM protein specifically interacting with CaM in a calcium-dependent manner, corroborating the idea that the Tic complex is the site of calcium regulation (Fig 3) Fur-ther binding assays employing several Tic32-deletion constructs allowed the localization of the CaM-binding site to the 26 most C-proximal amino acids (Fig 1) This region was predicted to form a basic amphipathic helical structure characteristic for CaM-binding domains, and contains at least one conserved potential CaM-binding motif [46] Additionally, the binding of CaM at the C-terminus and the binding of NADPH at the extreme N-terminus appear to be mutually exclu-sive, suggesting that two different signalling pathways

Trang 9

convene at Tic32 and are integrated at the Tic

complex

Conclusions

Increasing evidence is accumulating to suggest that we

experience not only the one Tic complex, but also that

the composition and activity of the Tic machinery can

be adapted (regulated) Distinct regulatory circuits

might sense distinct organellar requirements via: (a) a

Ca2+/CaM; (b) a metabolic NADP+/NADPH; or (c)

an environmental Trx mediated signal These signals,

either alone or in combination, could influence the

import of preproteins A prominent and difficult task

for future studies will therefore be to determine how

organelle metabolism and physiology influences protein

import by the Tic complex and by the Toc–Tic

trans-locon as a whole

Acknowledgements

We would like to thank our colleagues from the

labo-ratory for helpful discussions, and especially Anna

Stengel for critical reading of the manuscript

Finan-cial support was provided by the Deutsche

Fors-chungsgemeinschaft Grant SFB594 and the Elite

Network of Bavaria (to J P Benz)

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