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The plastid transcription kinase from mustard Sinapis alba L.A nuclear-encoded CK2-type chloroplast enzyme with redox-sensitive function Karsten Ogrzewalla1, Markus Piotrowski2, Steffen

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The plastid transcription kinase from mustard ( Sinapis alba L.)

A nuclear-encoded CK2-type chloroplast enzyme with redox-sensitive function

Karsten Ogrzewalla1, Markus Piotrowski2, Steffen Reinbothe2,* and Gerhard Link1

1

Plant Cell Physiology & Molecular Biology and2Plant Physiology, University of Bochum, Germany

The plastid transcription kinase (PTK), a component of the

major RNA polymerase complex from mustard

chloro-plasts, has been implicated in redox-mediated regulation of

plastid gene expression A cloning strategy to define the PTK

gene(s) resulted in the isolation of a full-length cDNA for a

protein with overall high homology with the a subunit of

cytosolic casein kinase (CK2) that contained an N-terminal

extension for a putative plastid transit peptide Using

in organellochloroplast import studies, immunodetection

and MS, we found that the corresponding protein, termed

cpCK2a, is targeted to the chloroplast and is associated with

the plastid RNA polymerase PEP-A The bacterially over-expressed protein shows CK2 kinase activity and is subject to glutathione inhibition in the same way as authentic chloro-plast PTK Furthermore, it readily phosphorylates compo-nents of the plastid transcription apparatus in vitro with a substrate specificity similar to that of PTK

Keywords: chloroplast transcription factor; phosphorylation control; plant nuclear gene; protein kinase CK2; redox regulation

Chloroplasts, the vital organelles of green plant cells,

contain the photosynthetic apparatus responsible for most

life on earth [1] In addition, and in close physical proximity

to the photosynthetic apparatus, they have a functional gene

expression machinery different from that of the

nucleo-cytosolic compartment [2]

It has become increasingly clear that signaling

mecha-nisms exist that connect photosynthetic electron flow with

gene expression responses [3–5] These mechanisms include

both phosphorylation/dephosphorylation and reversible

changes in redox state, and they operate at more than one

level of gene expression [6] For instance, SH-group redox

regulation has been shown to control initiation of

chloro-plast translation in the case of the green alga

Chlamydo-monas reinhardtii, in which a redox-responsive oligomeric

protein complex capable of binding to the 5¢-untranslated

region of chloroplast mRNA has been shown to be a critical

component in this process [7–9] In addition, several other

post-translational steps in chloroplast gene expression,

including translation elongation [10], RNA degradation

[11,12] and RNA splicing [13], have been shown to be subject to redox regulation as well

Several lines of evidence suggest that, in higher plant chloroplasts, processes at the transcriptional level can also

be controlled by photosynthetic electron transport via the reduced or oxidised state of signal-transmitting proteins The transcription rate of isolated chloroplasts has been shown to be affected by both the spectral quality [14,15] and intensity [16] of photosynthetic light, and this has further been substantianted by the use of electron-transfer inhibi-tors and redox-reactive reagents (for a recent review, see [17])

Chloroplasts, and possibly all plastid types, contain dual-transcription machinery consisting of two different RNA polymerases named nuclear-encoded phage-type plastid RNA polymerase and bacterial-type plastid RNA polym-erase (PEP) [18] The former is a single-subunit (phage-type) enzyme of nuclear origin, whereas the latter is a multisub-unit (bacterial-type) polymerase with chloroplast-encoded core subunits Depending on the plastid type, the PEP enzyme can have a variable number of accessory polypep-tides, most of which seem to have a regulatory role in transcription For instance, the major chloroplast RNA polymerase (PEP-A) from mustard (Sinapis alba L.) has at least 15 subunits, including polypeptides sequence-related to iron superoxide dismutase, RNA-binding proteins, and annexins [19]

One of the polymerase-associated components has been functionally identified on the basis of its in vitro activity as a serine-specific protein kinase [20] It was shown to affect

in vitrotranscription in a reversible manner depending on its own phosphorylation state Furthermore, its activity varies with its SH-group redox state, as operationally defined by the extent of thiol/disulfide exchange at vicinal cysteine residues [21] This protein kinase was named plastid transcription kinase (PTK) because of its association and functional interaction with the PEP-A RNA polymerase Biochemical characterization [20,21] revealed that PTK can

Correspondence to G Link, Plant Cell Physiology & Molecular

Biology, University of Bochum, Universitaetsstr 150,

D-44780 Bochum, Germany.

Fax: + 49 234 3214 188, Tel.: + 49 234 322 5495,

E-mail: gerhard.link@ruhr-uni-bochum.de

Abbreviations: CK, casein kinase; PEP, bacterial-type plastid RNA

polymerase with core subunits encoded by organellar genes; pSSU,

small subunit precursor; PTK, plastid transcription kinase; Rubisco,

ribulose-1,5-bisphosphate carboxylase/oxygenase.

Enzymes: DNA-dependent RNA polymerase (EC 2.7.7.6); protein

kinase (EC 2.7.1.37); ribulose-1,5-bisphosphate carboxylase/oxygenase

(EC 4.1.1.39); superoxide dismutase (EC 1.15.1.1).

*Present address: Plant Molecular Genetics, University of Grenoble,

38041 Grenoble, France.

(Received 26 March 2002, revised 17 May 2002,

accepted 23 May 2002)

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be best classified into the so-called CMGC group of protein

kinases [22] This group includes mostly nucleo-cytosolic

members that often represent terminal components of

signaling chains acting on, for example, (nuclear)

transcrip-tion factors [23] This is particularly true for casein kinase II

(CK2), which is a well-known transcriptional regulator both

in animal and yeast [24] as well as in plant systems [25]

CK2-type kinase activity has also been reported in

chloroplasts [26], and among the known substrates are

photosynthetic proteins such as CP29 [27] and the b subunit

of the ATP synthase [28] Considering the biochemical

similarity of PTK to (nucleo-cytosolic) CK2 kinases noted

in our previous studies [20,21], we set out to clone the gene

for the catalytic PTK component, and to study the

recombinant protein in relation to the authentic chloroplast

transcription kinase

M A T E R I A L S A N D M E T H O D S

PCR cloning and library screening

Primer 1 (5¢-CCATTGAACAGCAAGGGACTCG-3¢) was

derived from Arabidopsis thaliana EST sequence 11926,

GenBank accession number T88230 (now assigned to

gi17065109 for a putative Ck2a gene) It was used in

combination with a vector primer (5¢-AGGGATGTTTA

ATACCACTAC-3¢) for PCR amplification from a mustard

cDNA library This HybriZAP (Stratagene) library had

previously been generated using RNA from 5-day-old

light-grown mustard seedlings [29] Resulting PCR fragments

were purified using the QIAquick kit (Qiagen), cloned into

the EcoRV site of pBluescript (Stratagene), and then

sequenced A positive clone, pBS/CK2A-0.3 containing an

 300-bp insert with Ck2a homology, was used as a probe for

rescreening of the cDNA library by plaque-filter

hybridiza-tion Sequencing identified clone pAD/CK2A-1.5, which

contains the full-length Cpck2a cDNA sequence This clone

served as a template for further PCR amplification Primers 2

(5¢-TCATTGGGCACGCGGGGTGGA-3¢) and 3 (5¢-GC

ACAGAAGATCGGTAAATCC-3¢) resulted in

amplifica-tion of an 1-kb fragment containing the coding region

without the transit peptide region This PCR product was

purified as described above and cloned into the SmaI site of

pBluescript The insert was subsequently excised with

BamHI and KpnI and cloned into the expression vector

pQE30 (Qiagen) Primers 2 and 4 (5¢-ATGGCCTTTAG

GCCTATCGGA-3¢) were used for amplification of the

1.2-kb full-length coding region of Cpck2a After purification

(see above) the fragment was cloned into the EcoRV site of

pBluescript vector, resulting in clone pBS/CK2A-1.2

Protein kinase assays

Kinase activity was assayed in a reaction mixture containing

20 mMTris/HCl, pH 7.5, 50 mMKCl, 10 mMMgCl2and

40 lM[c-32P]GTP or [c-32P]ATP (10 lCiÆmmol)1) Where

indicated, 2 lg hydrolyzed and partially dephosphorylated

casein (Sigma, C4765) was added to the reaction mixture as

substrate for phosphorylation After incubation at 30C for

30 min, reactions were stopped by the addition of SDS

sample buffer, and the polypeptides were then separated by

SDS/PAGE (10% or 12% gels) [30] The gels were

subsequently dried and exposed to a phosphoimaging plate

(Fuji BAS 2040) or autoradiographed using Kodak X-Omat films and Dupont Quanta-II screens

Bacterial expression of cpCK2a Recombinant cpCK2a lacking the transit peptide and containing an N-terminal hexahistidine tag was expressed

in Escherichia coli strain M15 using the pQE system (Qiagen) After isopropyl thio-b-D-galactoside induction at

1 mM and 25C for 2 h, cells were lysed and soluble cpCK2a protein was purified on a Ni-nitrilotriacetatic acid– agarose (Qiagen) column according to the manufacturer’s instructions Inclusion bodies were isolated from cultures after incubation at 37C for 4 h, and recombinant protein was solubilized with SDS [31]

Antibodies and immunoblot analysis Rabbit antisera directed against the recombinant cpCK2a protein after solubilization from bacterial inclusion bodies were generated at Eurogentech using their standard immunization protocol Antibodies were purified from whole sera using antigen-affinity chromatography after coupling of cpCK2a to CNBr-activated Sepharose 4B (Amersham Biosciences) For immunodetection, protein samples were separated by SDS/PAGE and transferred to nitrocellulose membranes They were then probed with purified cpCK2a primary antibody at 4C for 12 h, followed by incubation with anti-(rabbit IgG) Ig (whole molecule) as an alkaline phosphatase conjugate (Sigma) for

1 h at 25C Signals were detected using nitroblue tetrazo-lium/5-bromo-4-chloro-3-indolyl phosphate

Purification of PTK and PEP-A RNA polymerase The chloroplast transcriptional complex (PEP-A and PTK) was purified from 5-day-old light-grown mustard seedlings

as described [21] Fractions were assayed for protein kinase activity as outlined above, and for RNA polymerase activity [32] In brief, chloroplast lysates were chromatographed on heparin–Sepharose CL6B (Amersham Biosciences) Frac-tions containing both the RNA polymerase and PTK activity were pooled and either used directly or further purified by centrifugation on linear 15–30% (v/v) glycerol gradients

In-gel protein digestion and MS Coomassie-stained protein bands were in-gel digested with sequencing-grade modified trypsin (Promega) [33] After extraction from the gel, peptides were desalted using ZipTips C18 (Millipore) MS measurements were carried out in a Q-TOF2 (Micromass) The nanospray sample was introduced in positive ion mode and spectra were recorded

at m/z 400–1600 and 2.4 s integration time Doubly or triply charged molecules were selected for fragmentation in MS/

MS mode, and spectra were analysed using theMAXENT3 algorithm andBIOLYNXsoftware (Micromass)

In organello chloroplast import

35S-Labeled translation products were synthesized in vitro using the wheat germ TNT quick coupled transcription/

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translation system (Promega) Chloroplast isolation from

rosette leaves of 3-week-old Arabidopsis plants by

differen-tial centrifugation, followed by Percoll (Amersham

Bio-sciences) density gradient centrifugation, and subsequent

import assays were carried out as described previously [34]

In brief, the translation reaction mixture was incubated with

intact chloroplasts, which were then treated with

thermo-lysin to remove adhering proteins Membrane and stroma

fractions were prepared by differential centrifugation and

polypeptides were analysed by SDS/PAGE and subsequent

autoradiography The mRNA-directed translation products

representing the precursor of the small subunit of

ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco pSSU)

from barley served as a control [34]

Southern and Northern blot analysis

Total DNA was isolated from 5-day-old light-grown

mustard seedlings using the CTAB method as described

[35] After restriction enzyme digestion of the DNA, 20-lg

samples were separated on 1% (w/v) agarose gels and

blotted on to positively charged nylon membrane (Roche)

The 300-bp cDNA insert of pBS/CK2A-0.3 was transcribed

in vitrousing digoxigenin (DIG) labeling (Roche) Blotted

DNA fragments were probed with the DIG-labeled RNA in

50% (v/v) formamide and 5· NaCl/Cit at 50 C for 12 h

Washing was in 0.1% (w/v) SDS in either 0.5· NaCl/Cit

or, at higher stringency, in 0.1· NaCl/Cit, and

chemilumi-nescent bands were then detected using CDP-StarTM

(Roche)

Total RNA was prepared from 5-day-old mustard

seedlings grown in the light or in the dark as described

[36] Samples of 10 lg were separated in 1.5% (w/v) agarose

gels containing 6.7% (v/v) formaldehyde and transferred to

positively charged nylon membranes The blots were probed

with the DIG-labeled 300-bp cpCK2a transcript in

5· NaCl/Cit at 68 C for 12 h They were then washed

and treated with CDP-Star following the Roche users’

guide

R E S U L T S

Cloning of the cDNA for a putative chloroplast

CK2 kinase

A nuclear gene for a plastid-localized CK2-type protein

kinase would be expected to give rise to a precursor protein

that reveals both an N-terminal transit peptide and

conserved CK2 elements Database searches identified an

Arabidopsis EST (11926; GenBank accession number

T88230) that could potentially specify a protein that fulfils

these criteria By using a primer derived from the 5¢ end of

this sequence (primer 1) in combination with a vector

primer, we were able to amplify a 300-bp PCR product from

a mustard cDNA library The derived amino-acid sequence

showed a conserved stretch of residues reminiscent of

(nucleo-cytosolic) CK2a subunits, which was preceded by a

region assigned both by PSORT [37] and ChloroP [38] as a

potential plastid transit peptide (data not shown)

We next used the 300-bp fragment as a probe to screen

the mustard cDNA library by plaque-filter hybridization,

which led to the isolation of an  1.5-kb cDNA insert

with an ORF coding for 414 amino acids (clone pAD/

CK2A-1.5).BLAST[39] searches (not shown) and multiple alignments [40] with amino-acid sequences from A thaliana (gi585349), maize (gi3318993), rice (gi12697577), human (gi11421546) and mouse (gi3413816) (Fig 1) suggested that this mustard cDNA clone contained the complete coding region for a mature CK2a protein In addition, the derived mustard protein was found to have an N-terminal exten-sion, which was subsequently analysed for features consis-tent with a possible role as a transit peptide

Chloroplast import

As shown in Fig 2A, the N-terminal extension of the putative CK2a precursor is rich in serine and threonine residues and contains many positively charged amino acids but only a few acidic amino acids, which are considered

Fig 1 Alignment of the putative chloroplast trancription kinase with nucleo-cytosolic CK2a proteins The derived protein of the mustard cDNA clone (Sin; EMBL accession number AJ420786) is shown on top, followed by CK2a from Arabidopsis (Ara; gi585349), rice (Ory; gi12697577), maize (Mai; gi3318993), human (Hom; gi11421546), and mouse (Mus; gi3413816) Marked residues in this ClustalW alignment [40] include identical positions (*) as well as conservative (:) and semiconservative substitutions (.) Also indicated are the four cysteines mentioned in the Discussion as well as the putative cleavage site of the predicted transit peptide (Fig 2).

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typical features of chloroplast transit peptides [41] ChloroP

[38], PSORT [37] and PCLR [42] all predicted a significant

(at least 60%) probability of chloroplast import As a

conserved cleavage-site motif according to [43] could not be

detected within the N-terminal extension, we tentatively

assigned the potential site to the location predicted by

ChloroP, i.e between residues 66 (leucine) and 67 (alanine)

To demonstrate the chloroplast targeting of the

CK2a-like mustard protein, we carried out in organello import

experiments (Fig 2B) As a control, an in vitro-synthesized

small subunit precursor of ribulose-1,5-bisphosphate

carboxylase/oxygenase (Rubisco pSSU; not shown) was used

[34], which is a prototype nuclear-encoded protein localized

to the chloroplast stroma [41] After coupled

transcription-translation of clone pBS/CK2A-1.2 in the wheat germ TNT

system (Promega), SDS/PAGE of the35S-labeled reaction

products revealed the presence of a major 48-kDa

polypep-tide corresponding to the expected full-length size (Fig 2B,

lane 1) This 48-kDa product was found to be largely absent

after incubation with chloroplasts and instead a smaller band of 38–40-kDa appeared (lane 2) which was resistant to thermolysin treatment of the chloroplasts (lane 3) After fractionation of the organelles into membrane (lane 4) and stroma (lane 5) fractions, the putative processed polypep-tide was predominantly found in the stroma This directly reflects the situation observed for the 20-kDa Rubisco pSSU polypeptide, which likewise was converted into a smaller ( 15 kDa) thermolysin-resistant product and was localized to the stroma (not shown) These results streng-thened the conclusions from the sequence analyses (Fig 2A) that the mustard CK2a-like protein is synthesized as a precursor (Fig 2B), which is imported post-translationally into the chloroplast and processed to mature size To indicate the plastid localization, the protein represented by cDNA clone pAD/CK2A-1.5 hence was named cpCK2a and the corresponding cDNA sequence Cpck2a

Bacterial expression and functional analysis of cpCK2a

To study functional properties of the gene product in vitro,

we constructed a truncated version of cpCK2a lacking the 66-amino-acid putative transit peptide It was expressed in

E colias a fusion protein with an N-terminal hexahistidine tag and, after nickel-chelate affinity purification, the recombinant protein was tested for protein kinase activity (Fig 3) The His-tagged cpCK2a protein phosphorylates casein in the presence of either [c-32P]ATP (lane 1) or [c-32P]GTP (lane 2), and it is inhibited by the polyanion heparin (lane 3) The same enzymatic characteristics, which are typical CK2 features [23], were also observed with the authentic PTK from mustard chloroplasts As is shown in Fig 3B for a partially purified preparation (heparin– Sepharose stage), and in Fig 3C for the more highly purified enzyme (glycerol gradient stage), both PTK prep-arations shared the ability to phosphorylate casein using ATP (lanes 1) or GTP (lanes 2) as phosphate donor, and in both cases this activity was inhibited in the presence of heparin (lanes 3)

Another approach to test the biochemical similarity between recombinant cpCK2a and authentic PTK was based on findings that the latter is selectively inhibited by GSH, but not by either the oxidized form (GSSG) or other reductants such as dithiothreitol and 2-mercaptoethanol [21] As shown in Fig 3, lower panel, the recombinant cpCK2a protein was inhibited by GSH (Fig 3D) but not by GSSG (Fig 3E), and neither dithiothreitol nor 2-mercapto-ethanol had any effect on its kinase activity (not shown) Hence, these data suggest an essentially similar in vitro behaviour of cpCK2a and PTK activity in response to SH-group redox state

We next asked whether both the authentic chloroplast PTK and the recombinant cpCK2a protein were capable of using the same set of transcription-associated proteins as phosphorylation targets As chloroplast PTK had previ-ously been shown to phosphorylate sigma-like transcription factors [20], the same may be true also for cpCK2a With recombinant sigma factor 1 (SIG1) from mustard [29] as a substrate (Fig 4A), neither cpCK2a (lane 2) nor SIG1 (lane 4) alone showed any phosphorylated polypeptides in the kinase assay Mixing the two recombinant proteins, however, resulted in a single phosphorylation signal at

43 kDa (lane 3), i.e the size of the sigma factor [29]

Fig 2 Transit peptide and in organello chloroplast import of cpCK2a.

(A) The 66-amino acid N-terminal region of the cloned full-length

protein shows features of plastid transit peptides, i.e high contents of

serine and threonine residues (shaded) and positively charged amino

acids (+) (B) In organello chloroplast import assays Left panel: The

48-kDa cpCK2a translation product (lane 1) was incubated with

Arabidopsis chloroplasts, resulting in a processed 38-to 40- kDa

polypeptide detectable before (lane 2) and after (lane 3) thermolysin

treatment After import, the organelles were lysed and separated into

membrane (lane 4) and stroma fractions (lane 5) Reactions were

analysed by SDS/PAGE, followed by autoradiography Numbers in

margins: sizes of precursor and processed polypeptides (kDa).

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To test further the possible relation of the recombinant

cpCK2a polypeptide to the plastid transcription apparatus

from mustard, we took advantage of the known

phos-phorylation pattern of a partially purified PEP-A RNA

polymerase that contains associated PTK activity (kinase–

polymerase complex; heparin–Sepharose stage) [20] As

shown in Fig 4B, lane 1, incubation of this fraction in the

presence of [c-32P]GTP resulted in a number of labeled

polypeptides None of these signals were detected when

cpCK2a was incubated alone in the absence of the

chloroplast protein substrates; neither did we observe any

qualitative changes in the phosphorylation pattern when the

recombinant protein was added to the latter (data not

shown) However, when the endogenous chloroplast kinase

was first heat-inactivated at 50C for 10 min (preventing

phosphorylation; Fig 4B, lane 3), subsequent addition of

cpCK2a restored the phosphorylation signals (lane 2) in a

pattern very similar to that with active PTK (lane 1) To substantiate this, we used highly purified PEP-A RNA polymerase that had retained only weak endogenous PTK activity (see Fig 3C) [20] Incubation of neither PEP-A alone (Fig 4B, lane 5) nor cpCK2a alone (see Fig 4A, lane 2) gave any significant phosphorylation signals As shown in Fig 4B lane 4, however, the full reaction mixture containing both the polymerase and recombinant kinase produced a pattern of labeled PEP-A polypeptides similar

to that previously observed after phosphorylation by chloroplast PTK, i.e major bands at 72–76 kDa and

30 kDa [19,20]

Together, the data presented in Fig 4A,B therefore support the notion that recombinant cpCK2a has a substrate specificity similar to that of PTK with regard to phosphorylation of chloroplast proteins

Detection of cpCK2a in mustard chloroplast preparations

If recombinant cpCK2a was equivalent to the catalytic subunit of PTK, it should be possible to demonstrate the direct physical existence of a CK2a-type subunit as a functional constituent of the chloroplast transcription apparatus in vivo This was addressed by immunodetection (Fig 5) and MS (Table 1)

Both partially (heparin–Sepharose stage; Fig 5A) and highly purified (glycerol gradient stage; Fig 5B) PEP-A preparations were probed using an antibody to recombinant cpCK2a In either experiment, after SDS/PAGE and Western blotting, subsequent immunodetection revealed a signal at 38–40 kDa (Fig 5A,B, lane 2), i.e the estimated size of cpCK2a polypeptide lacking the transit peptide (Fig 2) That this signal appears as a double band in Fig 5A, lane 2 (and less so in Fig 5B, lane 2) is probably the result of limited proteolysis, as has been observed for nucleo-cytosolic CK2a from animal sources [23]

To confirm the presence of a PEP-A constituent that is immunochemically related to cpCK2a by an independent technique, PEP-A fractions were also analysed by electro-spray ionization-MS Initial attempts using highly purified preparations after glycerol gradient centrifugation (Fig 5B) did not give consistent results, because of limited amounts of material and variations from one preparation to another (data not shown; see Discussion) Using partially purified PEP-A after heparin–Sepharose chromatography (Fig 5A), the prominent stained band at 38–40 kDa was found to contain three similar-sized but different polypeptides (Table 1): cpCK2a; the a core subunit (rpoA gene product)

of the plastid RNA polymerase; an RNA-binding protein that had been previously identified as part of the polymerase complex [19] The cpCK2a polypeptide in this triple band was present in substochiometric amounts, which explains why it was previously difficult to detect this minor component in the more highly purified PEP-A preparation

by electrospray ionization-MS

Southern and Northern blot analyses Mustard total genomic DNA was digested and hybridized

to a DIG-labeled RNA probe generated by transcription of the 300-bp insert of pBS/CK2A-0.3 Washing under stand-ard conditions (see Materials and methods) resulted in

Fig 3 Phosphorylation andred ox characteristics of recombinant

cpCK2a andauthentic PTK Upper panel: the bacterially expressed

cpCK2a protein (A) and chloroplast PTK after heparin–Sepharose

chromatography (B) or after additional gycerol gradient centrifugation

(C) were assayed for kinase activity Reaction mixtures containing

casein as substrate were carried out with [c- 32 P]ATP (lane 1) or

[c- 32 P]GTP in the absence (lane 2) or presence (lane 3) of heparin.

Samples were subjected to SDS/PAGE, followed by autoradiography.

Lower panel: recombinant cpCK2a was incubated with increasing

concentrations of reduced (D) or oxidized glutathione (E) (lanes 1–4),

followed by activity assays using [c-32P]GTP as in (A)–(C).

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multiple signals, the majority of which were thought to be

due to detection of nucleo-cytosolic CK2A-type sequences

by this probe (data not shown) At higher stringency,

however, only a few signals per lane were visible (Fig 6A),

suggesting the possible existence of a single-copy gene or a

small gene family for cpCK2a in mustard

For Northern blot transcript analysis, total RNA was

isolated from 5-day-old mustard seedlings grown in either

the light or dark, and gel blot hybridizations were carried

out at equal loading per lane (Fig 6B, lower panel) using

the same probe as described above As shown in Fig 6B,

upper panel, this revealed a single RNA signal at 1.5 kb,

i.e matching the size of the full-length cpCK2a cDNA (Fig 2) The labeled hybridization band was visible with RNA from either dark-grown or light-grown seedlings Unlike for the b-tubulin transcript [44] used as a constitutive control (not shown), the signal intensity was higher under light growth conditions, suggesting that cpCK2a gene expression at RNA level is not completely constitutive but may be under moderate light control

Fig 4 Substrate recognition of cpCK2a (A) Phosphorylation of recombinant sigma factor 1 (SIG1) from mustard by cpCK2a Purified SIG1 (lane 1, silver-stained) was incubated in the presence (lane 3) or absence (lane 4) of cpCK2a under phosphorylation conditions A control reaction mixture contained only cpCK2a (lane 2) (B) Phos-phorylation of chloroplast polypeptides A partially (heparin– Sepharose) purified RNA polymerase preparation with associated PTK activity [20] showed phosphorylation of endogenous substrates (lane 1) The same fraction did not show any kinase activity after heat treatment at 50 C for 10 min (lane 3) When the heat-treated fraction was supplemented with recombinant cpCK2a and again tested for kinase activity (lane 2), a phosphorylation pattern comparable to that

in lane 1 was observed A highly purified PEP-A polymerase prepar-ation after glycerol gradient centrifugprepar-ation showed little, if any, phosphorylation activity in the absence of cpCK2a (lane 5) In its presence, effective labeling of the endogenous substrates was noticeable (lane 4), with a pattern that closely resembled that for PEP-A phoshorylation by PTK [20] All phosphorylation assays were performed using [c- 32 P]GTP.

Fig 5 Immunodetection of cpCK2a in transcriptionally active fractions from mustardchloroplasts PEP-A RNA polymerase preparations were analysed by silver-staining (lane 1) and by immunoblotting using antibodies raised against the recombinant cpCK2a polypeptide (lane 2) (A) Partially purified fraction after heparin–Sepharose chro-matography; (B) highly purified PEP-A after subsequent glycerol gradient centrifugation.

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D I S C U S S I O N

In this study we have obtained evidence for the existence of

a nuclear-encoded chloroplast protein from mustard

(S alba L.) which can be assigned as a CK2a-type protein

kinase on the basis of the following criteria (a) The cloned

protein shows overall high homology with nucleo-cytosolic

CK2a sequences from other organisms (b) In addition, it

has an N-terminal extension typical of chloroplast transit

sequences (c) The gene product synthesized in vitro by

coupled transcription–translation was found to be imported

into isolated chloroplasts as a precursor, followed by

processing to a size expected for the mature protein (d)

The bacterially overexpressed and purified recombinant

protein had biochemical characteristics typical of the

catalytic subunit of protein kinase CK2 [23] (e) The

authentic plastid protein was detected as a component of

the chloroplast transcription apparatus by both antibodies

raised against the recombinant protein and MS

The existence of a plastid CK2 activity was initially

demonstrated by Kanekatsu and coworkers [26], who were

able to biochemically characterize such an enzyme from

spinach chloroplasts In addition, chloroplast proteins were

identified that could serve as potential substrates for

CK2-type kinases, including the chlorophyll a/b-binding PSII

protein CP29 [27] and the b subunit of chloroplast ATP

synthase [28]

That a protein kinase with biochemical properties similar

to nucleo-cytosolic CK2 could be a component of the

chloroplast transcription apparatus was initially borne out

by in vitro studies on purified plastid RNA polymerase PEP-A

[20,21] It was shown that this polymerase contains an

associated serine/threonine kinase activity named PTK The

cloned recombinant cpCK2a protein described in the

present work resembles the authentic PTK by several

criteria (a) Both enzyme preparations are capable of using

ATP as well as GTP as a phospho donor (b) They both are

inhibited by heparin (this work) and 5,6-dichloro-1-b-D

-ribofuranosylbenzimidazole [20], and the latter was found

also to severely affect run-on transcription in isolated

chloroplasts (T Pfannschmidt, K Ogrzewalla & G Link,

unpublished data) (c) Both PTK and recombinant cpCK2a

seem to act independently of second-messenger molecules

[20] (data not shown), and both are capable of using plastid

sigma factor(s) and other RNA polymerase-associated

proteins as phosphorylation substrates (Fig 4) (d) Finally,

both PTK and cpCK2a activity is negatively affected in vitro

by the presence of GSH, whereas other reducing reagents such as 2-mercaptoethanol and dithiothreitol seem to have little effect [21] (Fig 3, this work) Together, these data

Table 1 MS assignment of polypeptides within the 38-kDa bandof mustardPEP-A RNA polymerase Chloroplast RNA polymerase preparations after heparin–Sepharose chromatography [20] were subjected to SDS/PAGE, followed by electrospray ionization-QTOF MS and database peptide analyses as described in Materials and methods Each component was identified by two peptides L, note that leucine and isoleucine cannot be distinguished by Q-TOF MS M*, oxidized methionine.

Protein

(plant species)

GenBank identifier

Identified by peptide:

Fig 6 Genomic andtranscript analyses (A) Southern blot hybridiza-tion of mustard total DNA digested with EcoRI (E, lane 1), BamHI (B, lane 2) and HindIII (H, lane 3) and probed with DIG-labeled cpCK2A-RNA (B) RNA gel blot hybridization using total RNA from dark-grown (lane 1) and light-grown (lane 2) mustard seedlings Upper panel: autoradiograph Lower panel: ethidium bromide-stained samples (10 lg each) The heavily stained bands contain 25S rRNA (top; 3.7 kb), 18S rRNA (second; 2.0 kb), and large chloroplast rRNAs, including the 23S hidden break fragments [1,2].

Trang 8

suggest that the cloned recombinant protein representing

cpCK2a closely mimics the catalytic component of PTK

that is associated with the PEP-A polymerase

These findings raise a number of intriguing questions

about the role of a CK2-type chloroplast kinase as a

potential mediator of both phosphorylation and redox

signaling, its own regulation, and the identity of its

interaction partners In this context, it seems appropriate

to compare the chloroplast enzyme with plant

nucleo-cytosolic CK2, which has long been characterized

and cloned (for a recent review, see [45]), and in the case

of CK2a from Zea mays even the crystal structure is

available [46] These studies have provided detailed

insights into the domain structure of the a subunit [46],

but the role of reversible disulfide bond formation was

not addressed Furthermore, available evidence in animal

cells does not support a role for nucleo-cytosolic CK2 in

redox signaling [47] It is interesting to note, however,

that the mustard cpCK2a sequence in Fig 1 has four

cysteine residues (C139, C163, C221, and C294), the

C-terminal pair of which is conserved in all aligned

species (both animal and plant), whereas the N-terminal

pair seems to be plant-specific Considering the known

differences between plant and animal CK2a (such as

different length, stability and interaction properties) [45],

it is conceivable that redox regulation may be another

distinguishing feature

In addition, other polypeptides that interact with the

a subunit could be expected to modulate the catalytic

properties of the kinase In the case of nucleo-cytosolic

CK2a, a prototype interaction protein is the regulatory

a subunit [23], although it is interesting to note that plant

CK2 preparations lacking the a polypeptide have been

described [45] Our preliminary evidence from

immunose-lection studies suggests that several proteins of the

organ-ellar transcription machinery specifically interact with

cpCK2a (K Ogrzewalla, D Scharlau & G Link,

unpub-lished data) This is consistent with our previous findings

that the (PTK) kinase activity can be biochemically purified

as a more than 100-kDa subcomplex of the chloroplast PEP

transcription apparatus containing several polypeptides

[20] Work is in progress to investigate the contribution of

these additional components to the activity and specificity of

the complex

Part of the work reported here was directed towards the

question of whether cpCK2a sequences can be detected in

chloroplasts, and more specifically, in purified PEP-A

preparations Both the immunodetection experiments

(Fig 4) and the results of MS (Fig 5) support this notion,

although the latter technique detected CK2-related peptides

in partially purified PEP-A preparations, but not the most

highly purified preparations after glycerol gradient

centrif-ugation This apparent failure is most likely related to the

presence of the cpCK2a polypeptide in a band that contains

two additional polypeptides, i.e the a core subunit of the

RNA polymerase (rpoA gene product) and an

RNA-binding protein previously described [19] (Table 1) We note

that the PTK activity was found to be loosely associated

with the chloroplast polymerase activity, with a major free

and a minor bound form of the kinase detected throughout

the purification [20] This is reminiscent of the situation

reported for mammalian (nucleo-cytosolic) CK2 in

prepa-rations of nuclear RNA polymerase I [48], where the kinase

is also loosely associated and present in lower than expected amounts The reason for this behaviour is not clear, but could reflect different conformational states of the tran-scription kinase, which in turn might affect both the activity and interaction with other components of the transcription complex

In view of the close physical and functional similarity between the cloned cpCK2a polypeptide and the authentic PTK kinase moiety of chloroplast RNA polymerase

PEP-A, it seems reasonable to suggest that it is this CK2a-type activity that is directly involved in the phosphorylation and redox control of the PEP-A transcription system [20,21] Available in cloned and overexpressed form, this gene product now provides an opportunity to investigate its role in protein–protein interaction studies as well as a target for mutagenesis and functional analysis of chloroplast transcription

A C K N O W L E D G E M E N T S

We thank Professor E W Weiler for guidance and support during mass spectrometry, and Anke Homann for critical reading of the manuscript and discussion This work was funded by the Deutsche Forschungsgemeinschaft (Li 261/18-1; FOR 387/1-1).

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