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PsCCaMK is tightly associated with its substrate, a 40-kDa protein p40 that binds to specific sequence elements in the promoter of the Arabidopsis CaM5 gene AtCaM5 gene in a phosphorylati

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A Ca2+/CaM-dependent kinase from pea is stress regulated

Sona Pandey*, Shiv B Tiwari†, Wricha Tyagi, Mali K Reddy, Kailash C Upadhyaya and Sudhir K Sopory

School of Life Sciences, Jawaharlal Nehru University, New Delhi, India and International Center for Genetic Engineering and Biotechnology, New Delhi, India

An immuno-homologue of maize Ca2+/calmodulin

(CaM)-dependent protein kinase with a molecular mass of 72 kDa

was identified in pea The pea kinase (PsCCaMK) was

upregulated in roots in response to low temperature and

increased salinity Exogenous Ca2+ application increased

the kinase level and the response was faster than that

obtained following stress application Low

temperature-mediated, but not salinity-mediated stress kinase increase

was inhibited by the application of EGTA and W7, a CaM

inhibitor The purification of PsCCaMK using

immuno-affinity chromatography resulted in coelution of the kinase

with another polypeptide of molecular mass 40 kDa (p40)

Western blot revealed the presence of PsCCaMK in nuclear protein extracts and was found to phosphorylate p40 in vitro Gel mobility shift and South-Western analysis showed that p40 is a DNA-binding protein and it interacted specifically with one of the cis acting elements of the Arabidopsis CaM5 gene (AtCaM5) promoter The binding of p40 to the specific elements in the AtCaM5 promoter was dependent of its dephosphorylated state Our results suggest that p40 could

be an upstream signal component of the stress responses Keywords: calmodulin; DNA–protein interaction; plant protein kinase; protein phosphorylation; stress signaling

Plants perceive a variety of signals from the external

environment as well as from the internal cellular milieu

generated during various developmental processes Signals,

such as light, nutrients and various environmental stresses,

etc are perceived by specific receptors Following

percep-tion, a number of second messengers are generated that

regulate the activity of other proteins such as kinases and

phosphatases to transduce the signal downstream Towards

the end of the signal transduction pathway, these second

messengers and/or other accessory protein(s) affected by

them modulate the activity of the transcription factors,

which regulate the expression of specific gene(s) leading to

the final response The events related to perception of a

signal and corresponding changes in the activity and

concentration of various second messengers have been

studied in great detail However, the downstream pathways

leading to the final control of gene expression have been

elucidated in few cases only [1–3]

Calcium ions are the most important second messengers, controlling a variety of cellular and physiological responses [4,5] Cytosolic concentration of calcium ([Ca2+]cyt) chan-ges in response to a number of external stimuli and internal physiological developments [6,7] Besides, a num-ber of other second messenger such as cyclic ADP-ribose, inositol-3-phosphate and various proteins such as calmo-dulin (CaM) and calcium-dependent protein kinases (CDPKs) are also affected by changes in ([Ca2+]cyt) [6,8] The information through ([Ca2+]cyt) is transduced by two main pathways, one involving CaM and CaM-related proteins, and the other involving CDPKs Both of these pathways cross-talk at various points in the signaling cascade [9] The presence of CaM has been detected in different plant cell compartments especially in the nuclei [10] In animal systems, it has been shown conclusively that nuclear CaM, in combination with nuclear Ca2+changes, regulates the expression of various genes either by inter-acting with the transcription factors directly [11] or via specific calmodulin kinases (CaMKs) [12–14] In plant systems too, recent studies have shown that CaM is involved in the regulation of gene expression Szymanski

et al [15] have shown that CaM affects the binding of TGA3 to the Arabidopsis CaM3 promoter A study by van der Luit et al [16] showed that distinct calcium signaling pathways that operate during cold (predominantly cyto-plasmic) and wind (predominantly nucleus) signaling are regulated via CaM gene expression They have identified two different CaM isoforms, having different nucleotide sequences, but coding for the same polypeptide, and only one of these (NpCaM-1) is affected by cold and wind signaling

CaMKs are important junctions in signal transduction where Ca2+-dependent and CaM-dependent signaling pathways converge and these kinases are potential candi-dates in regulating gene expression Reports on the existence

Correspondence to S Pandey, 208 Mueller Laboratory,

Biology Department, Pennsylvania State University,

University Park, PA 16802, USA.

Fax: + 1 814 865 9131, E-mail: sxp49@psu.edu

Abbreviations: CaM, calmodulin; CaMK, calmodulin kinase;

CDPK, calcium-dependent protein kinase; GMSA, gel mobility shift

analysis; W7, N-(6-aminohexyl)-5-chloro-1-napthalenesulphonamide

hydrochloride; HMG, high mobility group.

Note: S Pandey and S B Tiwari contributed equally to this work.

*Present address: 208 Mueller Laboratory, Biology Department, The

Pennsylvania State University, University Park, PA 16802, USA.

Present address: Biochemistry Department, 117 Schweitzer Hall,

University of Missouri, Columbia, MO 65211, USA.

(Received 15 February 2002, revised 8 May 2002,

accepted 13 May 2002)

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of this class of kinase are limited in plants [17–21] The

Ca2+/CaM kinase isolated from maize roots has been

shown to be involved in gravitropism [19] and the Ca2+/

CaM kinase isolated from lily anthers binds with the

translational elongation factor II [22]

We reported previously the purification and

characteri-zation of a novel Ca2+/CaM-dependent protein kinase,

ZmCCaMK from etiolated maize coleoptiles [21,23] We

have now identified an immuno-homologue of this kinase in

pea (PsCCaMK) and in this study we show that PsCCaMK

is involved in Ca2+/CaM-regulated stress signaling in

plants PsCCaMK is tightly associated with its substrate,

a 40-kDa protein (p40) that binds to specific sequence

elements in the promoter of the Arabidopsis CaM5 gene

(AtCaM5) gene in a

phosphorylation/dephosphorylation-dependent manner

E X P E R I M E N T A L P R O C E D U R E S

Plant material, growth conditions and stress

treatments

Pea (Pisum sativum) plants were grown in moist vermiculite

(16-h light/8-h dark) at 25C for 5 days For salinity stress,

5-day-old plants were treated in 50, 100, 200, 300 or 500 mM

NaCl solution for specified time periods For osmotic stress,

plants were similarly treated with 300 mMmannitol for 24,

48 or 96 h For temperature stress, 5-day-old plants were

transferred either to 4C (cold stress) or 40 C (heat stress)

for specified time periods Calcium treatment (10, 25, 50 or

100 mM) was given to the 5-day-old plants for 3, 6, 12 or

24 h Plants grown under normal conditions for the same

time period served as controls

For pharmacological experiments, 5-day-old plants were

treated with EGTA (10 mM), lanthanum (10 mM) or W7

(60 lM) for 12 h These plants were further subjected to

different stresses as described earlier Plants treated with

these compounds but without stress conditions served as

control for these experiments After the treatments roots

and shoots of the treated as well as untreated (control)

plants were harvested separately, frozen in liquid N2 and

stored at)80 C until use

Protein extraction, SDS/PAGE and immunoblotting

Frozen tissue was ground to a fine powder in liquid N2and

extracted with 3 vols extraction buffer [20 mM Hepes

pH 7.5, 2 mM EDTA, 5 mM EGTA, 2 mM

phenyl-methanesulfonyl fluoride, 5 mM dithiothreitol and 10%

glycerol (v/v)] on ice The slurry obtained was centrifuged at

12 000 g for 30 min and the supernatant was used for SDS/

PAGE and immunoblotting studies Protein estimation was

carried out according to Bradford [24] and equal amounts

of proteins were resolved on SDS/PAGE according to

Laemmli [25] Gels were run in duplicate; one part was used

for staining with Coomassie brilliant blue R250 to ascertain

equal loading of proteins, and the second part was

electrophoretically transferred to nitrocellulose membrane

Equal amount of the proteins on blots was further

confirmed by staining with Ponceau S (Sigma Chemical

Co.) The blots were probed with antibodies raised in rabbit

against purified ZmCCaMK [21] at 1 : 25000 dilution Goat

anti-(rabbit IgG) Ig conjugated with alkaline phosphatase

(Sigma Chemical Co.) was used as secondary antibody and the antigen–antibody complex was visualized by the reac-tion of 5-bromo-4-chloro-3-indocyl phosphate/nitroblue tetrazolium (Sigma Chemical Co.) as described by Harlow

& Lane [26]

Protein purification using immuno-affinity chromatography

For purification of the pea immuno-homologue of ZmC-CaMK, 5-day-old pea plants were treated overnight with CaCl2 (100 mM); roots were harvested and washed exten-sively with water Further steps were performed at 4C unless stated otherwise Tissue was ground in presence of liquid N2, extracted with 3 vol extraction buffer as described earlier and centrifuged at 15000 g for 45 min The crude protein extract obtained was precipitated with 0–40%, 40–50% and 50–80% ammonium sulfate and dialyzed extensively against 50 vols extraction buffer To detect the presence of the ZmCCaMK homologue, all the three fractions were immunoblotted with anti-ZmCCaMK

Ig The 40–50% ammonium sulfate precipitated proteins containing the kinase homologue were utilized for immuno-affinity chromatography

Protein A sepharose purified anti-ZmCCaMK Ig were linked to CNBr-activated Sepharose 6B (Pharmacia Bio-tech) according to the manufacturer’s instructions and the matrix was packed in a 4-mL column The column was equilibrated with buffer containing 50 mM Tris pH 7.5,

10 mM MgSO4, 1 mM phenylmethanesulfonyl fluoride,

1 mMdithiothreitol, 0.1% Triton-X 100, 10% glycerol (v/v) The proteins were bound to the column by recirculating twice through it The bound proteins were washed exten-sively with the same buffer containing 50 mMNaCl until the

A280of the column flow-through reached zero Specifically bound proteins were eluted either with a salt gradient of 0.05–1M in the presence of 50 mM Tris pH 7.5, 10 mM

MgSO4, 1 mM phenylmethanesulfonyl fluoride, 1 mM

dithiothreitol, 10 mM 2-mercaptoethanol, 0.5% Triton-X

100 and 10% (v/v) glycerol or with 2.9 pH glycine buffer [26] When low pH glycine buffer was used for elution, the samples were neutralized immediately using a calibrated amount of Tris pH 7.5

In vitro phosphorylation assays

In vitrophosphorylation assays were performed as described earlier [21] Briefly, protein eluted from the affinity column (1 lg) was incubated in phosphorylation buffer (30 mM

Hepes pH 7.5, 5 mMMgCl2, 0.5 mMdithiothreitol, 25 mM

NaCl) in the absence (control) or presence of 100 lM

calcium and 110 nM CaM The reaction was started by the addition of 100 lM[c-32P]ATP (Amersham Biosciences Corp.) to the reaction mix in a total volume of 50 lL and incubated at 30C for 5 min An equal volume of SDS sample buffer was added to stop the reaction The reaction mix was boiled at 100C for 5 min and resolved by SDS/ PAGE The gel was dried and exposed for autoradiography

To test the effect of KN-62, 50 lMof the compound was also included in the reaction mix To determine if anti-ZmCCaMK Ig blocked the phosphorylation reaction, the protein fraction was first incubated with 1 lg of antibodies

at room temperature for 1 h with shaking The antigen–

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antibody complex was then precipitated out using protein A

sepharose beads and the resulting supernatant was used for

phosphorylation assay

RT-PCR

Approximately 0.5 g plant tissue (control and stress treated)

was ground in liquid nitrogen and total RNA was extracted

with TRIzol reagent (Life Technologies) according to the

manufacturer’s protocol Total RNA concentration was

determined by UV absorbance at 260 nm For each sample

5 lg total RNA was reverse transcribed with an oligo dT

primer and Superscript II (Life Technologies) according to

manufacturer’s instructions One ll of reaction product was

used as template in PCR reaction with AtCaM5 primers

(forward primer: 5¢-GATGTTGATGGTGATGGTCA-3¢;

reverse primer: 5¢-AAACCAGCCATGAATGAAAT-3¢)

and with actin primers (forward primer: 5¢-GTTGGGAT

GAACCAGAAGGA-3¢; reverse primer: 5¢-GAACCA

CCGATCCAGACACT-3¢) as a control Reactions with

no DNA added served as a negative control The PCR

cycling profile was: denaturation at 92C for 30 s, annealing

at 58C for 1 min and extension at 72 C for 1.5 min for 25

cycles PCR products were analyzed on 1% agarose gels

Preparation of nuclear protein extract, heparin–agarose

chromatography and gel mobility shift analysis

Pea nuclei were isolated as described previously [27] and

purified on a discontinuous percoll gradient For

prepar-ation of nuclear protein extract, the nuclei were washed with

buffer containing 50 mMTris pH 7.8, 5 mMMgCl2, 1 mM

dithiothreitol, 20% glycerol (v/v) and collected by gentle

centrifugation Nuclei were resuspended in washing buffer

containing 110 mM KCl, 10 mM phenylmethanesulfonyl

fluoride, and 5 lgÆmL)1each of antipain and leupeptin and

the suspension was brought to 40% ammonium sulfate

saturation The suspension was centrifuged at 100 000 g for

1 h in a Beckman Ti 75 rotor The supernatant obtained

was brought to 70% saturation and the nuclear proteins

were obtained by centrifugation at 100 000 g for 1 h The

proteins were finally resuspended in the same buffer without

MgCl2and stored frozen in small aliquots at)80 C

A pre-packed 2.5-mL heparin–agarose column (Sigma

Chemical Co.) was equilibrated with 10 column vols of

binding buffer (50 mMTris pH 7.2, 10 mMMgSO4, 1 mM

dithiothreitol, 1 mM phenylmethanesulfonyl fluoride and

10% glycerol, v/v) Ten to 20 mg proteins were loaded on to

the column and washed with binding buffer containing

50 mM NaCl until the A260 of the flow through reached

zero The proteins specifically bound to the column were

eluted with a 0.05 to 1MNaCl gradient in binding buffer

and eluted proteins were tested for binding with the

AtCaM5promoter fragment Active fractions were pooled,

dialyzed and stored in small aliquots at)80 C

Gel mobility shift analysis (GMSA) were performed

according to Ausubel et al [28] either with the labeled

AtCaM5promoter fragment ()588 to )339) or with specific

oligonucleotides designed from the same promoter

frag-ment The sequences of the oligonucleotides used for these

experiments are: Oligo I, 5¢-CAAGGACGTTCGATGCA

CTTCCAAAAAACATATAAT-3¢; Oligo II, 5¢-CAAT

GTAGTATTAAAAAGTAGTAGTTAAAAGC-3¢; Oligo

III, 5¢-GTTTTTATCCGATGCAAATTTTTGCTTTGT GATTG-3¢

The reaction was performed in 20 lL DNA-binding buffer containing (50 mMTris pH 7.4, 50 mMKCl, 1 mM

dithiothreitol, 6% glycerol, v/v) supplemented with

1 lg sonicated calf thymus DNA Labeled probe ( 10 000 c.p.m.) was incubated with the required amount

of protein at room temperature for 10 min DNA–protein complexes formed were fractionated by 5% nondenaturing PAGE and autoradiographed To abolish any protein– protein interaction, 0.5% deoxycholate (Sigma Chemical Co) was incubated in the reaction mixture For supershift analysis, the required dilution of anti-ZmCCaMK Ig was included in the reaction mixture with or without deoxy-cholate Competition analyses were performed by including

1000· concentration of self or nonself oligonucleotides in the reaction mix To test the affect of phosphorylation on binding of p40 with DNA, p40 was phosphorylated using cold ATP as described above and used for assays An identical experiment performed with labeled ATP was run

on a gel to verify the phosphorylation and to confirm the integrity of protein (data not shown) For dephosphoryla-tion 10 lg of phosphorylated protein was incubated in buffer containing 50 mM Hepes pH 7.5, 1 mM MgCl2, 0.5 mMdithiothreitol and calf intestinal phosphatase (10 U)

in a total volume of 50 lL, at 30C for 10 min Reactions were stopped by the addition 5 lL 100 mM sodium pyrophosphate Protein was precipitated using ice-cold acetone and resuspended in DNA-binding buffer to study DNA–protein interaction

For South-Western analysis, proteins separated on 10% SDS/PAGE were electro-blotted on nitrocellulose mem-brane The membrane was blocked with the binding buffer (described above) containing 3% BSA at room temperature with gentle shaking The membrane was washed twice with same buffer containing 0.25% BSA Hybridization was carried out in the presence of 50 lgÆmL)1 sonicated calf thymus DNA and labeled probe at room temperature for

1 h The membrane was washed, dried and exposed for autoradiography

R E S U L T S Immuno-homologue of maize ZmCCaMK is upregulated

by low temperature and salinity stresses in pea roots Western blot analysis using anti-ZmCCaMK Ig of total protein extracts from pea shoots and roots showed the presence immuno-homologue of maize kinase in pea (PsCCaMK) PsCCaMK showed a development-depend-ent and tissue-specific expression (S Pandey & S K Sopory, unpublished data) The level of PsCCaMK was very low in roots as compared to the shoots (Fig 1, control lanes) As some protein kinases are involved in stress signaling pathways [29] and recent work points towards the involvement of Ca2+/CaM-dependent protein kinases in stress signaling [16], changes in the level of PsCCaMK was evaluated under various stress conditions Five-day-old pea seedlings were subjected to temperature, salinity and osmotic stress (as described in Experimental procedures) and the level of PsCCaMK was monitored by Western blotting in both roots and shoots using anti-ZmCCaMK Ig It was seen that PsCCaMK level remained

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unchanged under all the conditions tested in shoots

(Fig 1) However, a strong upregulation of the protein

level was observed in roots when salt (0.3MNaCl) or low

temperature (4C) treatment was given to the plants

Osmotic stress or heat shock had no effect on the level of

PsCCaMK suggesting that this kinase is not a general

stress-regulated kinase but may specifically be involved in a

signaling pathway associated with salinity and low

tem-perature stress

As both NaCl and low temperature upregulated the

kinase level, time-kinetics experiments were performed for

these stress treatments The optimum concentration of

NaCl required to upregulate the kinase level was also

determined As shown in Fig 2, the level of PsCCaMK

started increasing in response to 50 mM NaCl, reached

maxima at 300 mM and then remained constant up to

500 mMNaCl The kinase level started increasing after 6 h

of treatment of plants with NaCl as well as low temperature

and the maximum level was observed following 24 h of

treatment

Calcium upregulates the PsCCaMK level in a

time-and concentration-dependent manner

Because PsCCaMK showed a strong upregulation in

response to low temperature and salinity stress in pea roots

under in vivo conditions, and the signaling pathways for

both of these stresses are often mediated by Ca2+, the effect

of exogenous Ca2+ was analyzed on the protein level of

PsCCaMK As shown in Fig 3, the level of the kinase was

strongly upregulated by Ca2+ The kinase level started

increasing at 10–25 mMexogenous Ca2+and the maximum level was observed at 100 mM The time-kinetics data showed that the appearance of PsCCaMK after Ca2+

Fig 2 Western blots showing the kinetics of induction of PsCCaMK following NaCl and cold treatment Five-day-old pea plants were given NaCl or cold treatment for indicated time periods and concentrations Roots were harvested and immediately frozen Twenty-five lg total protein extracts were separated by SDS/PAGE, and Western blotting was performed using anti-ZmCCaMK Ig Equal loading of proteins per lane was confirmed by Ponceau S staining of the Western blot Lane C denotes protein isolated from control plants that were not given any stress treatment.

Fig 1 Western blot analysis of level of PsCCaMK in response to

dif-ferent stresses in roots and shoots of pea Five-day-old pea plants were

given heat stress (42 C), low temperature stress (4 C), salt stress

(0.3 M NaCl) and osmotic stress (0.3 M mannitol) for 24 h and roots

and shoots were harvested separately Extracted proteins were

separ-ated by SDS/PAGE (25 lg per lane) and probed with

anti-ZmC-CaMK Ig Roots and shoots from normal vermiculite-grown plants

served as controls Numbers on the left indicate molecular weight

markers in kDa.

Fig 3 Effect of exogenous calcium on the level of PsCCaMK Calcium treatment was given to the 5-day-old pea plants for the indicated time periods and concentration and roots were harvested Total protein extracted (25 lg per lane) was Western blotted and probed with anti-ZmCCaMK Ig Mg denotes plants treated with 50 m M MgCl 2 instead

of CaCl 2 Lane C denotes protein isolated from control plants not given any calcium treatment.

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treatment was earlier (at 3 h) than that obtained following

NaCl and low temperature stress treatment (at 6 h) To

exclude the possibility of this upregulation being mediated

via a divalent cation in general, the effect of Mg2+was also

tested Plants treated with 50 mM Mg2+for 24 h did not

show any upregulation of the PsCCaMK level

Low temperature, but not salinity-stimulated kinase

level is mediated via a Ca2+/CaM pathway

To further confirm that the upregulation of PsCCaMK by

NaCl and low temperature is mediated via a Ca2+/CaM

signaling pathway, the plants were pretreated with EGTA

(10 mM), lanthanum (10 mM) or W7 (60 lM), before

exposure to low temperature, NaCl or Ca2+ Plants

treated with these compounds but not given any further

stress treatments served as controls along with normal

vermiculite-grown plants The Western blot analysis

showed that EGTA as well as W7 almost completely

blocked low temperature- and Ca2+-induced upregulation

of the kinase but that the NaCl-stimulated kinase level

was unaffected by these treatments (Fig 4) These results

suggest that the low temperature-induced response may be

mediated by Ca2+/CaM whereas the salt-induced

upreg-ulation might be mediated via some other pathway

Lanthanum had no effect on the expression level of the

kinase

Purification of PsCCaMK by immuno-affinity chromatography: a 40-kDa protein always coelutes

To purify PsCCaMK, 5-day-old pea plants were treated overnight with 100 mMCa2+and then roots were excised for purification of protein The total soluble protein extract was fractionated with 40–50% ammonium sulfate and loaded on to an immuno-affinity column prepared using anti-ZmCCaMK Ig The protein was bound in the presence of 50 mM NaCl and eluted either using a salt gradient of 0.05–1M containing 0.5% TritonX-100 and

10 mM 2-mercaptoethanol or with low pH glycine buffer (pH 2.9) Under both of these sets of conditions a 40-kDa protein eluted first from the column followed by elution of the 72-kDa protein corresponding to the PsCCaMK (Fig 5) Under all elution conditions tested, the 72-kDa protein could not be eluted independently of the 40-kDa protein Western blot analysis of the eluted fractions with the same antibodies that were used for making the immuno-affinity column showed cross-reactivity with the 72-kDa PsCCaMK protein only This suggests that the 40-kDa protein does not bind to the antibodies on the column directly but possibly it is very tightly associated with PsCCaMK

PsCCaMK is present in nuclear protein extracts and possibly interacts with DNA

A number of CaM kinases from animal systems have been reported to be present in nuclei and to regulate gene expression [30] Our studies with the AtCaM5 promoter, which is induced under different stress conditions (S B Tiwari & K C Upadhyaya, unpublished data), gave indications that the anti-ZmCCaMK Ig affected binding of the AtCaM5 promoter with specific proteins eluted from

Fig 4 Effect of various pharmacological compounds on the expression

level of PsCCaMK Five-day-old pea plants were pretreated with

EGTA (10 m M ), lanthanum (La, 10 m M ) or W7 (60 l M ) Pre-treated

plants were given low temperature (4 C), NaCl (0.3 M ) or calcium

(100 m M ) treatment for 24 h Pre-treated plants, not given further

treatment, as well as normal vermiculite-grown plants (C) served as

different controls Twenty-five lg total proteins extracted from roots

were separated by SDS/PAGE, Western blotted and probed with

anti-ZmCCaMK Ig.

Fig 5 Purification of PsCCaMK from immuno-affinitycolumns Roots of 5-day-old plants treated with calcium (100 m M ) for 24 h were used for the purification of kinase using the immuno-affinity column prepared using anti-ZmCCaMK Ig Elution was with a 0.05–1 M NaCl gradient The left panel shows the SDS/PAGE profile of proteins from fractions 7, 9 and 11 after silver staining The right panel shows the Western blot of the same fractions using anti-ZmCCaMK Ig.

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the heparin–agarose column Moreover, expression of

AtCaM5 gene is strongly upregulated in response to

identical conditions of low temperature and salinity stress

as analyzed by RT-PCR (Fig 6A) Taking clues from these

observations we tested for the presence of PsCCaMK in

nuclear protein fractions as well as in the proteins

fractionated on the heparin–agarose column As shown in

Fig 6B, the antibodies cross-reacted with a 72-kDa protein

in the total nuclear protein fractions indicating its possible

nuclear localization The antibodies also cross-reacted with

the nuclear proteins fractionated on the heparin–agarose

column The 72-kDa kinase band could be detected

specifically in the 0.2–0.4M salt-eluted protein fractions

The same fractions also showed binding to the AtCaM5

promoter under different physiological conditions

(unpub-lished data) As the salt concentration used was high

enough not to let nonspecific proteins interact with the

heparin column, it was predicted that this protein might be

interacting with DNA directly To confirm this

observa-tion, we performed GMSA of total pea nuclear protein

extract with a 249-bp labeled AtCaM5 promoter region

()588 to )339) in the presence and absence of

anti-ZmCCaMK Ig This particular region was selected as it

showed maximum protection and structural changes when

foot-printing analysis was performed (S B Tiwari & K C

Upadhyaya, unpublished data) As shown in Fig 6B, a

strong DNA–protein complex was formed with the

AtCaM5promoter fragment and total pea nuclear protein

extract, which showed a supershift with the anti-ZmC-CaMK Ig Addition of 0.5% deoxycholate to abolish any ionic protein–protein interactions showed the presence of two loose complexes Addition of antibodies along with deoxycholate also showed a supershift, giving further indications that the kinase interacts with DNA either directly or it is strongly associated with some DNA binding protein Antibodies alone showed no interaction with DNA We could not determine the direct binding of the purified kinase with DNA as we could not obtain the kinase preparation without p40 under any conditions and attempts to purify the kinase by gel elution gave a very low yield and the eluted protein was highly labile

The 40-kDa protein is phosphorylated by PsCCaMK and binds directly with theAtCaM5 promoter

As p40 remains tightly bound to the PsCCaMK during the purification process, the possibility of it being a substrate for PsCCaMK was tested Further it was also examined if p40 binds with the specific regions of AtCaM5 promoter To ascertain these facts, proteins eluted from the immuno-affinity column were pooled in two different fractions, one containing pure p40 (fraction A) and other containing both the p72 and p40 (fraction B) Both of these fractions were used for in vitro phosphorylation experiments As shown in Fig 7A, no phosphorylation could be detected in fraction A under any of the

Fig 6 RT-PCR, Western blot and supershift analyses (A) RT-PCR of AtCaM5 gene RNA isolated from roots of control, low temperature (4 C) and salinity (0.3 M NaCl) stressed plants was reverse transcribed and amplified with AtCaM5 gene-specific primers PCR with actin primers is included as control (B) Western blot analysis of pea nuclear extracts Five lg pea nuclear proteins (NP) and 2 lg pea nuclear proteins fractionated

on heparin–agarose column (HAFr) were separated by SDS/PAGE in duplicate One set was silver stained while the other set was Western blotted and probed with anti-ZmCCaMK Ig (C) Interaction of pea nuclear proteins with AtCaM5 promoter and supershift analysis The nuclear proteins were used in GMSAs to analyze their interaction with AtCaM5 promoter fragment Analysis was also performed in the presence or absence of 0.5% deoxycholate and anti-ZmCCaMK Ig to determine supershift Antibodies (Abs) alone were included as control.

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conditions tested, but a Ca2+-dependent, CaM-stimulated

phosphorylation of p40 could be seen in fraction B This

phosphorylation could be specifically blocked by KN-62, a

Ca2+/CaM kinase inhibitor as well as with

anti-ZmC-CaMK Ig Addition of 50 ng fraction B proteins into

fraction A led to phosphorylation of p40 in fraction A

also On longer exposure of the blots a faint signal could

be detected at the 72-kDa position, corresponding to the

autophosphorylated PsCCaMK in fraction B, but no such

signal was observed with fraction A (data not shown),

confirming that p40 has no phosphorylation activity of its

own These results clearly established that the PsCCaMK

has Ca2+/CaM kinase activity and uses p40 as its in vitro

substrate

To ensure the DNA-binding property of p40, both

fractions A and B were used for South-Western analysis

with the AtCaM5 promoter fragment ()588 to )339) that

was used earlier for GMSA A strong signal was

observed at the 40-kDa position with both the fractions,

showing that p40 binds to this promoter fragment

(Fig 7B) To confirm this observation GMSA was

performed with the AtCaM5 promoter fragment and

fraction B, in the presence of excess of calf thymus DNA

As shown in Fig 7C two specific DNA–protein

com-plexes were formed These data showed that p40 binds

directly to the AtCaM5 promoter, but whether

PsC-CaMK binds with DNA directly or through p40 remains

inconclusive

p40 binds to the specificcis-elements in the AtCaM5 promoter region and the binding is affected

by phosphorylation

To further analyze the specific binding of p40 to DNA, GMSAs were performed with fraction A (pure p40) and three specific oligonucleotides (see Experimental proce-dures) These oligonucleotides were designed based on the protected regions of the AtCaM5 promoter fragment ()588

to)339) in the foot-printing experiments (data not shown) p40 showed binding with two of the sequences, Oligo I and Oligo III but not with Oligo II (data for Oligos I and II are shown in Fig 8) The specificity of the binding was further confirmed by competition assays where excess concentra-tions (1000·) of the self-oligonucleotides as well as nonself oligonucleotides were used As shown in the autoradiogram (Fig 8), the DNA–protein complex could not be detected when the self-oligonucleotides were used at higher concen-tration, whereas no such effect could be seen with the nonself oligonucletides

As p40 was found to be an in vitro substrate for the PsCCaMK, the effect of phosphorylation on its DNA-binding property was tested The protein was in vitro phosphorylated using cold ATP and used for DNA binding studies No binding was detected when prephosphorylated protein was used for the DNA binding reaction To confirm the reversibility of the phosphorylation reaction and the associated DNA-binding activity, phosphorylated p40 was

Fig 7 In vitro protein phosphorylation, South-Western and DNA GMSA with pea nuclear proteins fractionated byimmuno-affinitychromatography (A) Protein fractions eluted from kinase antibody affinity column containing 1 lg purified p40 (fraction A) and those containing 1 lg of both p40 and p72 PsCCaMK kinase (fraction B) were used for in vitro phosphorylation in the absence or presence of Ca2+, CaM, kinase antibodies and

KN-62 In one set 50 ng fraction B was added to fraction A (B) Proteins from fraction A and B were separated by PAGE and probed with labeled AtCaM5 promoter fragment in South-Western analysis (C) GMSA was performed in the absence (control) or presence of fraction B proteins with labeled AtCaM5 promoter fragment.

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treated with calf intestinal phosphatase A DNA–protein

complex could be detected using the dephosphorylated

protein, confirming that p40 could bind to the AtCaM5

promoter only in the dephosphorylated form

D I S C U S S I O N

Role of PsCCaMK in stress signaling

Protein kinases and phosphatases are important

compo-nents of signaling cascades, which by changing the

phosphorylation status of the target proteins transduce

the signal to elicit the final response [31] A number of

studies in recent years have linked the stress signaling with

changes in the calcium level and the upregulation of

various protein kinase transcripts [1–3,32–36] A receptor

protein kinase RPK1 is regulated in response to multiple

stresses and probably has a role at the very beginning of

multiple stress signaling pathways [37] Involvement

of CDPKs in stress signaling has also been shown by

using chimeric gene constructs containing

abscisic-acid-responsive elements and the GFP reporter gene [29] In this

system, transient expression of CDPKs could be observed

in response to various stresses as well as exogenous

calcium A number of kinases of the mitogen activated

protein signaling cascade have also been reported to be

involved in stress signaling pathways [38]

Upregulation of protein kinase transcripts is a complex process, as multiple signals (stress, light as well as phyto-hormones) affect the level of same kinase and in turn different kinases are modulated by the same signal, depending on the specificity of calcium signal and position

of the kinase in the signaling cascade Though the role of some protein kinases is established in the stress signaling pathways, the exact sequence of events that leads to the final gene expression in response to a particular signal is not very well elucidated

We have reported earlier the purification and character-ization of ZmCCaMK and the presence of its immuno-homologues in a variety of other plants [21] including Arabidopsis(data not shown) We now show that the kinase homologue from pea is involved in stress signaling Con-ditions such as 0.3MNaCl and 4C are widely reported to cause severe stress to plants Under these conditions, pea plants showed visible effect of stress in both roots and shoots However, the upregulation of kinase level was observed in roots only Shoots had higher kinase levels compared to roots to begin with, and it was not altered by stress treatment This is similar to the Nicotiana tobacum CDPKl transcript that could not be detected in leaves of the normal plants, but shows a strong upregulation in response

to different stresses [39]

The kinase level also increases in response to exogenous

Ca2+and even though a maximum increase in the kinase

Fig 8 GMSA with p40 with specific cis elements (oligonucleotides) of AtCaM5 promoter Oligonucleotides I and II representing specific cis-regions

of the AtCaM5 promoter were used to study the specific interaction of p40 Proteins from fraction A (see Fig 7) interacted specifically with Oligo I (A) but not with Oligo II (B) For competition a 1000 · excess of self or nonself oligonucleotides were included in the reaction mix Addition of ATP abolished the DNA–protein complex formation with Oligo I The binding with Oligo I was also studied following phosphorylation/dephospho-rylation of p40 (C).

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level was obtained with 100 mMCa2+, stimulatory effects

are seen at much lower concentrations (10–25 mM) as well

As these treatments were given to whole plants (not to

isolated protoplasts or proteins) for very short duration, the

actual Ca2+uptake would be much lower Moreover, the

low temperature- and Ca2+-induced increase in kinase level

could be blocked by EGTA and W7 (a CaM inhibitor) and

the high Mg2+treatment given for 24 h has no effect on the

kinase level; it is therefore very likely that Ca2+is acting as a

signal molecule However, the possibility that at such high

concentrations Ca2+ might be causing some pleiotropic

effects to cell physiology cannot be ruled out totally

It has been shown earlier that both salt- and low

temperature stress-mediated signaling pathways are

modu-lated via Ca2+[2,40–42] In most of the cases the same

protein is affected in response to both of these stresses, but

proteins affected by low temperature but not by salt or

dehydration and vice versa are also known [34,43,44]

Recently, the role of a novel kinase SOS2 in salt tolerance

has been suggested [36,45] Specific sequence elements have

been identified (e.g DRE) that are important for cold and/

or dehydration responses [46] In some cases different

proteins bind to the same sequence under different

physio-logical conditions to give specific responses [43,47,48]

PsCCaMK does not appear to be a general

stress-responsive kinase, as its expression does not change in

response to mannitol or heat shock As dehydration or

osmotic shock are known to affect the level of proteins

regulated by salt stress, this kinase falls into a different

category The response of PsCCaMK to NaCl is similar to

that of the SOS3 gene [42] and Ca2+appears to be involved

in its regulation by upregulating the protein level; also the

response is faster than that to either NaCl or to low

temperature treatment The differential effects of EGTA

and W7 on low temperature- and salinity-mediated

expres-sion of PsCCaMK indicate that their responses are

medi-ated by different signaling pathways and that Ca2+/CaM

signaling is involved only in the upregulation of PsCCaMK

in response to low temperature To ascertain whether this

kinase acts as a junction point of two different signaling

pathways needs further work

Purification of PsCCaMK and its substrate protein

and their functional characterization

PsCCaMK is present in the nuclear protein fractions as well

as in the protein fractions eluted from the heparin–agarose

column and possibly interacts with the AtCaM5 promoter

In animal systems, a number of CaM kinases have been

identified in the nuclei that are shown to affect the

expression of specific genes by changing the

phosphoryla-tion status of transcripphosphoryla-tion factors [30,49] It has been shown

that plant nuclear extracts could be phosphorylated [50],

showing the presence of kinase(s) in the nuclei In addition,

different signaling pathways point towards the possibility of

Ca2+and CaM acting through the nucleus via specific CaM

kinases [16] However, our study provides strong evidence

of the presence of a CaM kinase and its possible function in

plant nuclei

It has been observed that during purification of

PsC-CaMK using an immuno-affinity column, p40 always

coelutes with the PsCCaMK, even under very stringent

conditions Moreover, p40 does not cross-react with the

kinase antibodies used to make the column, showing that it

is not interacting directly with the antibodies linked with the column but is possibly very tightly associated with the PsCCaMK There are other examples where substrate or interacting protein has been eluted from the affinity column along with the relevant protein [45] In vitro phosphoryla-tion experiments show that p40 could not be phosphoryl-ated on its own, but only in the presence of PsCCaMK, in a

Ca2+-dependent, CaM-stimulated manner The phos-phorylation of p40 could be blocked by KN-62 (a specific CaM kinase inhibitor) as well as the anti-ZmCCaMK Ig (Fig 7) This shows that PsCCaMK properties are similar

to those of ZmCCaMK and p40 is one of its in vitro substrates

To check the interaction of these proteins with DNA, we selected the promoter of the Arabidopsis CaM5 gene (AtCaM5) The reason to use this promoter was that the AtCaM5 gene was strongly upregulated in response to identical conditions of salinity and low temperature stress Besides, PsCCaMK was specifically present in the same fractions of heparin–agarose eluted proteins that show binding with the AtCaM5 gene promoter We also had preliminary data for this promoter, using GMSA and DNase I foot-printing, about the regions of the promoter showing structural changes under different physiological conditions Based on these studies we used the)588 to )399 fragment of this promoter (that showed maximum protec-tion and changes in footprinting analysis) for our studies Detection of DNA–protein complexes by South-Western analysis, using the labeled fragment and the affinity purified protein fraction, shows the binding of the promoter with the p40 protein and not with PsCCaMK (Fig 7) The absence

of binding with PsCCaMK could be due either to the fact that it does not bind to DNA at all, to a weak interaction, or

to a very much lower amount of protein that could not be detected However, GMSAs with the nuclear protein extract and anti-ZmCCaMK Ig showed a supershift though weak, even in presence of high concentration of deoxycholate, indicating the possible interaction of this kinase directly with the DNA (Fig 6B) On the other hand, pure p40 protein showed direct binding with the AtCaM5 gene promoter fragment by GMSA Binding experiments with specific oligonucleotides confirm that the p40 interacts with defined sequence elements of the promoter, and that the binding is highly specific The same oligonucleotides, which do not show binding with p40 when tested for binding with total pea nuclear extract, show a strong binding (data not shown) which further confirms that p40 binds to some specific cis sequences only The question of whether PsCCaMK binds directly or via its association with p40 has not been fully resolved During purification of the protein the association

of the protein kinase and its substrate was not affected even though stringent conditions were used It is possible therefore, that these two proteins physically interact and even in the presence of 0.5% deoxycholate this interaction remains intact In this case the supershift could be a result of antibody interacting with the PsCCaMK bound to p40, which in turn interacts directly with DNA

Of the several strategies that modulate the binding of a protein with its target DNA, to effect transcription, phosphorylation is regarded as one of the major mecha-nisms [51,52] In plants too, a number of studies have shown that phosphorylating the transcription factors affects their

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binding with DNA [27,53–55] We have found that the

binding of p40 is dependent on the dephosphorylation

status of the protein and the binding is fully abolished once

the protein is phosphorylated

Analysis of the specific sequence elements, with which

the p40 interacts, shows that these elements are not yet

reported in any of the stress responsive genes On

computational analysis, both of the sequences with which

p40 interacts show the presence of a binding site for high

mobility group proteins (HMG boxes) HMG box

proteins have been identified from many plant species

and it has been shown that their binding with DNA is

affected by the phosphorylation status of the proteins [56–

58] In animal systems it has been shown conclusively that

these proteins usually interact with the AT-rich sequences

that show high structural changes [59–62], which is the

case with the oligonucleotides that we used It could

therefore be speculated that p40 is a protein similar to

HMG box proteins; this, however, requires further

char-acterization

Proposed mechanism of action

Based on all these results we propose that p40 is a negative

regulator of the CaM5 gene promoter that may act in a

similar way to the DREAM protein, a negative

transcrip-tional regulator that acts in a calcium-dependent manner

[63] During normal growth and development, p40 is

bound to the promoter When the plant is under salinity or

low temperature stress, the calcium level inside the cell

increases This elevated calcium could then affect the level

and activity of the Ca2+/CaM-dependent protein kinase

homologue, which is either always present in the nuclei or

it gets translocated to the nuclei [55,64] Once activated,

the kinase phosphorylates p40 and as a result its binding

to DNA is abolished and the protein is released from the

DNA We also have preliminary data (not shown) which

show that some other protein of unknown identity binds

to the same sequence elements, after p40 dissociates from

it following phosphorylation There are earlier reports

which show that different proteins, though unrelated, bind

to the same sequence elements, as in case of DREB1A and

DREB2A [48] The present study thus proposes that

protein kinases that are upregulated in response to specific

stress function in the nuclei, might use DNA binding

proteins as substrate(s) and affect their binding property

thereby regulating the expression of stress-induced genes

To be able to apply this statement in a broader

perspec-tive, it would be essential to look for genes for both

CCaMK and p40 to be able to functionally dissect the

underlying mechanistic pathways It would also be

important to look for true functional orthologues of the

kinase and p40 in other plant species, especially in

Arabidopsis where powerful genetic tools are available

for further studies

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

This work was supported partly by internal grants from the

International Center for Genetic Engineering and Biotechnology and

funds from Department of Science and Technology, Government of

India We thank Prof S Assmann for critical reading of the manuscript

and constructive suggestions and B Yadav for technical help.

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