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The increase in cytosolic Ca2+ can be a consequence of external Ca2+ influx via the Cch1p⁄ Mid1p Ca2+ channel on the plasma membrane [1,3,6] or release of vacuolar Ca2+ into the cytosol t

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yeast Saccharomyces cerevisiae

Claudia-Valentina Popa, Ioana Dumitru, Lavinia L Ruta, Andrei F Danet and Ileana C Farcasanu Faculty of Chemistry, University of Bucharest, Romania

Introduction

Eukaryotic cells, from yeast to mammals, respond and

adapt to environmental stress by evolutionarily

con-served multicomponent endogenous systems that utilize

a network of signal transduction pathways to regulate

the adaptive and protective phenotype Changes in the

chemical or physical conditions of the cell that impose

a negative effect on growth demand rapid cellular

responses, which are essential for survival Molecular

mechanisms induced upon exposure of cells to such

adverse conditions are commonly designated as stress

responses

Ca2+-mediated signaling of stress conditions is used

by virtually every eukaryotic cell to regulate a wide

variety of cellular processes through transient increases

in cytosolic Ca2+ Budding yeast (Saccharomyces

cere-visiae) cells use Ca2+as a second messenger when they

are exposed to various environmental stress conditions, such as hypotonic and cold stress [1,2], hyperosmotic and salt stress [3], b-phenylethylamine-induced intracel-lular H2O2generation [4], or high pH [5] The increase

in cytosolic Ca2+ can be a consequence of external

Ca2+ influx via the Cch1p⁄ Mid1p Ca2+ channel on the plasma membrane [1,3,6] or release of vacuolar

Ca2+ into the cytosol through the vacuole-located

Ca2+ channel Yvc1p [7,8] After acting as a second messenger, cytosolic Ca2+ is restored to the normal very low levels through the action of Ca2+pumps and exchangers Thus, the Ca2+-ATPase Pmc1p [9,10] and the vacuolar Ca2+⁄ H+exchanger Vcx1p [11,12] inde-pendently transport cytosolic Ca2+ into the vacuole, whereas Pmr1p, the secretory Ca2+-ATPase, pumps cytosolic Ca2+ into the endoplasmic reticulum and

Keywords

aequorin; cytosolic calcium; oxidative stress;

Saccharomyces cerevisiae; yeast

Correspondence

I C Farcasanu, University of Bucharest,

Faculty of Chemistry, Sos Panduri 90-92,

Bucharest, Romania

Fax: +40 021 410 01 40

Tel: +40 721067169

E-mail: farcasanu.ileana@unibuc.ro

(Received 16 April 2010, revised 2 July

2010, accepted 28 July 2010)

doi:10.1111/j.1742-4658.2010.07794.x

The Ca2+-dependent response to oxidative stress caused by H2O2 or tert-butylhydroperoxide (tBOOH) was investigated in Saccharomyces cerevisiae cells expressing transgenic cytosolic aequorin, a Ca2+-dependent photopro-tein Both H2O2 and tBOOH induced an immediate and short-duration cytosolic Ca2+ increase that depended on the concentration of the stres-sors Sublethal doses of H2O2 induced Ca2+ entry into the cytosol from both extracellular and vacuolar sources, whereas lethal H2O2 shock mobi-lized predominantly the vacuolar Ca2+ Sublethal and lethal tBOOH shocks induced mainly the influx of external Ca2+, accompanied by a more modest vacuolar contribution Ca2+transport across the plasma membrane did not necessarily involve the activity of the Cch1p⁄ Mid1p channel, whereas the release of vacuolar Ca2+into the cytosol required the vacuolar channel Yvc1p In mutants lacking the Ca2+transporters, H2O2or tBOOH sensitivity correlated with cytosolic Ca2+ overload Thus, it appears that under H2O2-induced or tBOOH-induced oxidative stress, Ca2+ mediates the cytotoxic effect of the stressors and not the adaptation process

Abbreviations

BAPTA, 1,2-bis(2-aminophenoxy)ethane-N,N,N ¢,N ¢-tetraacetic acid; tBOOH, tert-butylhydroperoxide; WT, wild-type.

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Golgi, and is responsible for Ca2+ extrusion from the

cell [13,14] These responses are mediated by the

uni-versal Ca2+sensor protein calmodulin, which can bind

and activate calcineurin; this inhibits, at the

post-tran-scriptional level, the function of Vcx1p [11,15,16] and

induces the expression of PMC1 and PMR1 genes via

activation of the Crz1 transcription factor [15,16] The

release of Ca2+ from intracellular stores stimulates

extracellular Ca2+influx, a process known as

capacita-tive calcium entry [17] Conversely, the release of

vacu-olar Ca2+ via Yvc1p can be further stimulated by

Ca2+ from outside the cell as well as that released

from the vacuole by Yvc1p itself in a positive feedback

process called Ca2+-induced Ca2+release [8,18–20]

S cerevisiaeis a very useful model and an attractive

alternative to mammalian cell lines for studying the

effect of oxidative stress on the eukaryotic cells and

also an interesting model for studying antioxidants

in vivo [21–28] Living in an oxidant-rich medium

under natural conditions, it is expected that yeast cells

will respond promptly to variations in the oxidative

state of the environment How fast the cells respond to

oxidative stress and whether this type of response

is Ca2+-mediated are issues that are not clearly

understood

In this study, evidence is presented that the cytotoxic

effect of the exogenous oxidative stress induced by

H2O2or by the less hydrophilic oxidant

tert-butylhydr-operoxide (tBOOH) is triggered by transient elevations

in cytosolic Ca2+ as a result of both rapid influx from

outside the cell and of release from vacuolar stores

Results

H2O2induces a transient increase in cytoplasmic

Ca2+

As a free radical generator, H2O2 is known to have deleterious effects on cell growth, and exposure to high concentrations requires an immediate response for cell survival To determine whether the cell response to high concentrations of H2O2 is mediated by Ca2+ in

S cerevisiae, the wild-type (WT) strain BY4741 was transformed with a plasmid expressing the luminescent

Ca2+ reporter apoaequorin from a constitutive pro-moter After reconstitution of functional aequorin by addition of its cofactor coelenterazine, cells were exposed to H2O2 shock directly in the luminometer tube The cells responded promptly, as H2O2 initiated immediate and transient luminescence peaks, indicating sudden elevations in the cytosolic Ca2+ Ca2+ pulses could be recorded for H2O2 concentrations as low as 0.5 mm, and a sharp rise followed by a rapid fall in the cytosolic Ca2+-caused luminescence was noted for concentrations of 2 mm and over (Fig 1A) The pulse amplitude increased with H2O2 concentration (Fig 1B)

H2O2 treatment of the cells transformed with the empty vector under the same conditions did not elicit any luminescence response (data not shown) The luminescence spectra were reproducible for the range

of H2O2 concentrations used (0.5–10 mm), which covered toxic but nonlethal concentrations (0.5–2 mm) and lethal concentrations (3–10 mm)

Fig 1 Changes in cytosolic Ca 2+ upon exposure to H2O2 (A) Effect of H2O2on the intensity of the Ca 2+ -dependent cell luminescence WT BY4147 cells were transformed with the plasmid pYX212–cytAEQ The cells expressing coelenterazine-reconstituted aequorin were exposed

to various H2O2concentrations directly in the luminometer tube, as described in Experimental procedures The arrow indicates the addition

of H2O2 (B) Maximal response of H2O2-treated cells The WT cells transformed with pYX212–cytAEQ were subjected to H2O2shocks as in (A) (closed circles) The data are presented as the ratio of the maximum relative light units (RLU) to the average RLU recorded before H 2 O 2

shock Closed diamonds correspond to the response of control cultures not expressing aequorin (transformed with the empty vector pYX212) Each determination was repeated at least three times on different days, with no significant variations being seen (P < 0.05).

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Under H2O2stress, Ca2+is mobilized from both

external and internal sources

To further characterize the Ca2+ response to

exoge-nous H2O2, we examined whether the Ca2+flux comes

from an external or an internal source In the WT

cells, H2O2exposure induced sharp and transient

lumi-nescence peaks caused by the increase in cytosolic

Ca2+ (Fig 2A) The peak intensity was attenuated by

the presence of the membrane-impermeable Ca2+

che-lator

1,2-bis(2-aminophenoxy)ethane-N,N,N¢,N¢-tetra-acetic acid (BAPTA) (Fig 2D), suggesting that, at

least in part, the Ca2+ flux comes from outside the

cells Following the addition of BAPTA, the pattern of

the luminescence spectrum recorded for the WT strain

changed from a short-duration Ca2+ pulse (Fig 2A)

to a prolonged elevation of cytosolic Ca2+, which

gradually diminished within 2–3 min (Fig 2D)

Never-theless, addition of BAPTA did not completely

sup-press the cytosolic Ca2+ elevation, suggesting that, on

exposure to H2O2, internal stores are also mobilized

To test this possibility, the cytosolic Ca2+ burst was

also monitored in cells lacking the genes encoding the components of the main plasma membrane Ca2+ channel, Cch1p⁄ Mid1p It was found that, upon expo-sure to H2O2, the cch1D and mid1D null mutants exhibited robust, albeit different, responses Thus, whereas the luminescence peak caused by the Ca2+

flux decreased to approximately half in the cch1D cells (Fig 2B), in the mid1D mutant it was (surprisingly) slightly higher than in the WT cells (Fig 2C) This observation suggested that, if involved, Cch1p alone, independently of Mid1p, may be partially responsible for the Ca2+ influx under H2O2 stress As the differ-ence between the WT and mid1D cells was small, the tests described above were repeated on seven different days, with no obvious variations being seen from day

to day Statistical analysis showed that mid1D cells exhibited luminescence maximum peaks that were con-stantly higher than that recorded for the WT cells, with an average that was 10 ± 1.6% higher than the normal luminescence maximum intensity (P < 0.05)

In the parallel study, cch1D cells exhibited lumines-cence maximum peaks that were constantly lower than

F

50 s

Fig 2 Effect of mutations affecting Ca 2+ fluxes in response to H2O2 Isogenic strains expressing coelenterazine-reconstituted cytAEQ were exposed to H 2 O 2 (2 m M ; a toxic but sublethal concentration) directly in the luminometer tube When used, the membrane-impermeant Ca 2+

chelator BAPTA was added (5 m M final concentration) 1 min before the H2O2shock The arrows indicate the addition of H2O2 Each determi-nation was repeated at least three times on different days, with no significant variations being seen (P < 0.05) One typical luminescence spectrum is presented for each strain (A) WT strain (B) Null mutant cch1D strain (C) Null mutant mid1D strain (D) WT strain pretreated with BAPTA (E) Null mutant cch1D strain pretreated with BAPTA (F) Null mutant mid1D strain pretreated with BAPTA (G) Null mutant yvc1D strain (H) Null mutant yvc1D strain pretreated with BAPTA.

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that recorded for the WT cells, with an average that

was 33.5 ± 2.2% smaller than the normal

lumines-cence maximum intensity (P < 0.05)

Interestingly, BAPTA treatment of both cch1D

(Fig 2E) and mid1D (Fig 2F) cells attenuated the

Ca2+ influx to levels comparable to those detected for

the BAPTA-treated WT cells (Fig 2D), indicating

that, under H2O2 stress, external Ca2+ may enter the

cytosol via a transporter other than the Cch1p⁄ Mid1p

channel Similar results were obtained when BAPTA

was replaced with another Ca2+chelator, EGTA (data

not shown)

The addition of BAPTA or other Ca2+ chelators to

the medium equalized the H2O2-induced cytosolic

Ca2+peak in WT, cch1D and mid1D cells (Fig 2D–F),

but it still allowed a robust Ca2+ burst, suggesting

that, on exposure to the oxidant, internal stores are

also mobilized In yeast, the vacuole is the main

stor-age location for intracellular Ca2+, so the H2O2

-induced Ca2+ flux was monitored in cells lacking

Yvc1p, the vacuolar membrane channel responsible for

release of Ca2+ from the vacuole to the cytosol The

YVC1 gene deletion drastically reduced the amplitude

of the Ca2+ burst, indicating that most of the Ca2+

released into the cytosol after H2O2 exposure comes

from the vacuole via the Yvc1p channel

(approxi-mately 93%) However, a luminescence peak was still

noticeable in the yvc1D cells, reaching approximately

1⁄ 15 of the normal value (Fig 2G) This residual peak

was practically abolished by the addition of BAPTA

(Fig 2H), suggesting that the small Ca2+burst seen in

yvc1D cells was the result of Ca2+ influx from outside

the cell As BAPTA addition removes  50% of the

signal in the case of WT cells (Fig 2A,D), it seems

probable that, in the presence of H2O2, the vacuolar

Yvc1p channel is activated by cytoplasmic Ca2+ that

may come from outside the cell or be released from

the vacuole by Yvc1p itself in a positive feedback

pro-cess, as previously reported [8,18–20] Thus, by

dele-tion of YVC1, both the H2O2-induced component and

the Ca2+-induced component are removed If this is

so, the signal that disappears in BAPTA-treated WT

cells (Fig 2D) may be interpreted as the signal

through Yvc1p secondarily induced by external Ca2+

Adaptation to H2O2-induced oxidative stress is

favored under low-Ca2+conditions

As the elevation of cytosolic Ca2+ in response to

oxidative stress was different in the mutant cells

used, growth in media supplemented with H2O2 was

investigated It was found that the cch1D and yvc1D

cells were more tolerant to H2O2 than the WT cells,

suggesting that the lower level of cytosolic Ca2+ burst achieved during oxidative shock may result in a pro-tective effect on cell growth In this regard, mid1D cells, which exhibited the highest Ca2+ burst when exposed to H2O2shock, were slightly more sensitive to

H2O2 than WT cells and considerably more sensitive than cch1D and yvc1D cells (Fig 3A, upper right) At the same time, supplementation of the medium with the Ca2+ chelator EGTA augmented cell tolerance to

H2O2 (Fig 3A, middle), whereas supplementary Ca2+ augmented sensitivity to H2O2(Fig 3A, bottom right) Paradoxically, yvc1D cells, which exhibited the lowest cytosolic Ca2+ burst, were the most tolerant to exoge-nous H2O2 (Fig 3B), suggesting that lower cytosolic

Ca2+ bursts during oxidative shocks may actually increase the chances of cell survival To check this pos-sibility, transgenic cells expressing the YVC1 gene from

a galactose-inducible promoter were monitored in terms of sensitivity to oxidative stress WT cells over-expressing YVC1 are known to release more Ca2+into the cytosol [7] and, indeed, such cells were more sensi-tive to H2O2 than cells expressing the control vector (Fig 3C) Moreover, sensitivity increased with induc-tion time, probably because of increasing gene expres-sion induced by activation of the GAL1 promoter by galactose In contrast, cells overexpressing the PMC1 gene from a galactose-inducible promoter became more tolerant to H2O2than cells expressing the control vector (Fig 3C) Pmc1p transports Ca2+ to the vacu-ole, and its overproduction probably results in faster restoration of cytosolic Ca2+

Other mutations that alter cytosolic Ca2+were also investigated For example, whereas pmc1D and vcx1D null mutants were both more tolerant than the wild type, the double mutant pmc1D vcx1D was found to be hyper-sensitive to H2O2 (Fig 3B) This double mutant lacks

Ca2+in the vacuole, and therefore cannot release Ca2+ via Yvc1p Nevertheless, this strain is deficient in restor-ing cytosolic Ca2+levels after a stress burst [12], and is consequently less tolerant to exogenous oxidants Cytosolic Ca2+was reported to upregulate the calci-neurin-dependent degradation of Yap1p [29], the main transcription factor inducing gene expression in response to oxidative stress [19,20,30] If the high cyto-solic Ca2+achieved by cells when they are exposed to

H2O2 can result in calcineurin-dependent Yap1p degradation and hence sensitivity to oxidants, cells lacking functional calcineurin should gain a certain tolerance to H2O2 To check this possibility, the growth of cnb1D cells (which lack the gene encoding the regulatory subunit of calcineurin) under oxidative stress was tested It was noted that CNB1 deletion resulted in an increase of tolerance to H2O2 (Fig 3B),

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suggesting that the Ca2+-mediated toxicity of H2O2

may be also the result of Ca2+-mediated degradation

of Yap1p

Exposure to lethal H2O2concentrations results in

Ca2+mobilization predominantly from the

vacuole

In the experiments described above, Ca2+ appearance

in the cytosol was monitored in cells exposed to toxic,

but nonlethal, concentrations (as seen from the cell

viability following exposure; data not shown) of H2O2

To determine whether cells behaved differently when

subjected to stronger oxidative insults, WT cells were

exposed to a lethal concentration of H2O2(10 mm) In

this case, it was found that BAPTA pretreatment of

cells did not attenuate the Ca2+ burst (Fig 4A,B), indicating that, under lethal oxidative conditions, cells rely mainly on internal Ca2+ stores Under the same stress conditions, yvc1D cells exhibited only faint

Ca2+-mediated luminescence (Fig 4A,B), suggesting that when cells are confronted with higher, lethal con-centrations of H2O2, they utilize the vacuole as the main source for Ca2+to be directed to the cytosol

Alkylhydroperoxide also induces a transient increase in cytosolic Ca2+

To determine whether the Ca2+-mediated response to exogenous H2O2 is part of a more general oxidative stress response mechanism, a less hydrophilic oxidant, tBOOH, was considered This substance is largely used

A

B

C

Fig 3 Effect of H 2 O 2 -induced oxidative

stress on the cell growth of Ca 2+ channel

mutants (A) Growth properties of Ca 2+

channel mutants Isogenic strains

(WT, cch1D, mid1 and yvc1D) were spotted

(approximately 4 lL) in 10-fold serial

dilutions (from 10 7 cellsÆmL)1, left, to

103cellsÆmL)1, right) onto YPD plates

supplemented with the indicated chemicals

(4 m M H2O2, 20 m M EGTA, 10 m M CaCl2).

Early exponential growth phase cultures

were used to prepare the diluted cultures,

which were spotted on plates by means of

a replicator Cells were photographed after

3 days of incubation at 28 C The

concen-trations used were 4 m M H2O2, 20 m M

EGTA and 10 m M CaCl 2 (B) Effect of YVC1

and PMC1 overexpression on sensitivity to

oxidative stress WT cells transformed with

plasmids pGREG506DSalI (empty vector,

with fragment SalI–SalI excised),

pGAL11–YVC1 and pGAL11–PMC1 were

shifted from a fresh preculture to SG-Ura for

galactose induction of the genes, 6 or 16 h

before being stamped [approximately 4 lL,

in 10-fold serial dilutions from 10 7 cellsÆmL)1

(left) to 103cellsÆmL)1(right)] onto SG-Ura

agar plates containing H2O2 Time variation

was not observed in the case of the PMC1

galactose-induced phenotype Similar results

were obtained for tBOOH (1.5 and 2 m M ,

data not shown) (C) H2O2effect on growth

of mutants with altered Ca 2+ -related

phenotype The strains were spotted

(approximately 4 lL, 10 6 cellsÆmL)1) onto

YPD plates containing the indicated

concentrations of H 2 O 2

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to mimic the oxidative stress that causes formation of

alkyl hydroperoxides (e.g oxidation of unsaturated

lipid chains) As the minimal inhibitory concentration

for the WT strain is approximately 1 mm, Ca2+pulses

were recorded in aequorin-expressing WT cells exposed

to 0.25–1.5 mm tBOOH (Fig 5A) The pulse

ampli-tude increased with tBOOH concentration (Fig 5B)

When exposed to toxic, but nonlethal,

concentra-tions of tBOOH, WT cells promptly responded with a

transient elevation in cytosolic Ca2+, as seen by the

luminescence spectrum of the aequorin-expressing cells

(Fig 6A) This observation suggested that, as in the

response to H2O2, cells utilize Ca2+-mediated signaling

to initiate the defense mechanisms CCH1 deletion lowered the amplitude of the Ca2+ burst to approxi-mately 75% of the normal peak (Fig 6B), but MID1 deletion resulted in a Ca2+ cytosolic burst that was slightly higher than in the WT cells (Fig 6C); this was paralleled by an increased sensitivity of the mid1D mutant to tBOOH (Fig 7A,C) As the difference between WT and mid1D cells was small, the tests described above were repeated on seven different days, with no major variations being seen from day to day Statistical analysis showed that mid1D cells exhibited luminescence maximum peaks that were consistently greater than that recorded for WT cells, with an aver-age that was 12.14 ± 0.8% higher than the normal luminescence maximum intensity (P < 0.05) In the parallel study, cch1D cells exhibited luminescence maxi-mum peaks that were consistently lower than that recorded for WT cells, with an average that was 25.56 ± 1.2% lower than the normal luminescence maximum intensity (P < 0.05)

Surprisingly, BAPTA addition prior to exposure to tBOOH strongly attenuated the Ca2+ burst to less than one-quarter of the normal level, both in WT and mutant cch1D and mid1D cells (Fig 6D–F) This obser-vation suggested that, under tBOOH stress, external

Ca2+ may be predominantly responsible for the cyto-solic bursts, but that the major route of entry into the cell may, again, not be through the Cch1p⁄ Mid1p channel The contribution of vacuolar stores could not, however, be ruled out, because although the

Ca2+-dependent luminescence was drastically reduced

by the presence of BAPTA, it still peaked at approxi-mately one-fifth to one-quarter of the normal

Fig 4 Ca 2+ mobilization under lethal H2O2 conditions Isogenic

strains (WT and yvc1D) expressing coelenterazine-reconstituted

cytAEQ were exposed to 10 m M H2O2(lethal) in the absence (A) or

presence (B) of 5 m M BAPTA directly in the luminometer tube The

arrow indicates the addition of H 2 O 2 Each determination was

repeated at least three times on different days, with no significant

variations (P < 0.05) being seen One typical luminescence

spectrum is presented for each type of experiment RLU, relative

light units.

Fig 5 Changes in cytosolic Ca 2+ concentration upon exposure to tBOOH (A) Effect of tBOOH on the intensity of the Ca 2+ -dependent cell luminescence WT cells expressing coelenterazine-reconstituted cytAEQ were exposed to various tBOOH concentrations directly in the lumi-nometer tube The arrow indicates the addition of tBOOH (B) Maximal response of tBOOH-treated cells The WT cells transformed with pYX212–cytAEQ were subjected to tBOOH shocks as in (A) (closed squares) The data are presented as ratio of the maximum relative light units (RLU) to the average RLU recorded before tBOOH shock Closed diamonds correspond to the response of control cultures not expressing aequorin (transformed with the empty vector pYX212) Each determination was repeated at least three times on different days, with no significant variations being seen (P < 0.05).

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maximum, and this was followed by a steady state,

which was observed throughout the recording time To

determine whether the Ca2+also comes from the

vacu-ole, the cytosolic Ca2+ release under tBOOH stress

was monitored in yvc1D cells It was seen that, as

com-pared with WT cells, the Ca2+burst was attenuated in

yvc1D cells (towards approximately one-quarter of the

normal peak; Fig 6G), suggesting that the vacuolar

stores may also contribute to the total cytosolic pool

The burst was completely abolished when yvc1D cells

were preincubated with BAPTA (Fig 6H), indicating

that, under tBOOH shock also, the transient elevation

in cytosolic Ca2+ is the result of cooperative influx

from both outside the cell and from the vacuole, even

though, in this case, the vacuolar contribution seems

to be lower In terms of growth, cch1D and yvc1D cells

were more tolerant to tBOOH than WT cells, whereas

mid1D cells were more sensitive to tBOOH than WT

cells (Fig 7A,C) Supplementation of the medium with

the Ca2+chelator EGTA slightly augmented cell

toler-ance to tBOOH (Fig 7A, right), but external Ca2+

had no obvious effect on cell growth (data not shown)

It was found that the Ca2+-mediated cytosol lumi-nescence increased when the tBOOH concentration was varied from 0.75 mm (toxic, but nonlethal) to 1.5 mm (lethal) (Fig 7B, dotted lines), but did not change when the same conditions were applied to BAPTA-pretreated cells (Fig 7B, solid line) This observation indicated that, unlike the case with H2O2, the extent of vacuolar Ca2+ mobilization may not be dependent on tBOOH concentration

The susceptibility to tBOOH of other transgenic strains with altered Ca2+homeostasis was tested Simi-lar to what was seen with H2O2, YAP1 overexpression reduced, whereas PMC1 overexpression augmented, the tolerance of WT cells to tBOOH (data not shown) Other mutations that alter cytosolic Ca2+ were also investigated, and the response to tBOOH paralleled the response to H2O2 For example, whereas pmc1D and vcx1D null mutants were both more tolerant than the wild type, the double mutant pmc1D vcx1D was found to be hypersensitive to tBOOH (Fig 7C) Also, CNB1 deletion resulted in an increase in tolerance to tBOOH (Fig 7C) Thus, it seems that Ca2+ mediates

Fig 6 Effect of mutations affecting Ca 2+ fluxes in response to tBOOH Isogenic strains expressing coelenterazin-reconstituted cytAEQ were exposed to tBOOH (0.5 m M , a toxic but sublethal concentration) directly in the luminometer tube When used, the membrane-imper-meant Ca 2+ chelator BAPTA was added (5 m M final concentration) 1 min before the tBOOH shock The arrows indicate the addition of tBOOH Each determination was repeated at least three times on different days, with no significant variations being seen (P < 0.05) One typical luminescence spectrum is presented for each strain (A) WT strain (B) Null mutant cch1D strain (C) Null mutant mid1D strain (D)

WT strain pretreated with BAPTA (E) Null mutant cch1D strain pretreated with BAPTA (F) Null mutant mid1D strain pretreated with BAPTA (G) Null mutant yvc1D strain (H) Null mutant yvc1D strain pretreated with BAPTA RLU, relative light units.

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the cytotoxic effect of exogenous oxidants rather than

the adaptative process

Discussion

Aerobic cells are continuously exposed to oxidative

insults that have to be perceived and scavenged rapidly

to allow normal growth and development Studies

con-cerning the antioxidant arsenal of the cell are

numer-ous, and many defense mechanisms have been

elucidated, but how exactly the cell senses the threat of

oxidative species that are above the non-noxious thresholds is still not clearly understood Ca2+ is an important second messenger in the eukaryotic cell, and there is increasing evidence that cytosolic Ca2+ entry

in yeast is critical for survival under a variety of stress conditions, including hypo-osmotic or hyperosmotic shock [1,3,5,7], protein-unfolding agents [30], or anti-fungal drugs [31,32] The results presented in this study provide evidence that exogenous oxidative stress induces a transient increase in cytosolic Ca2+ that originates from both outside the cell and from the

A

B

C

Fig 7 (A) Effect of tBOOH-induced oxida-tive stress on cell growth Isogenic strains (WT, cch1D, mid1D and yvc1D) were spotted (approximately 4 lL) in 10-fold serial dilutions [from 10 7 cellsÆmL)1(left) to

10 3 cellsÆmL)1(right)] onto YPD plates supplemented with the indicated chemicals (0.75 m M tBOOH, 20 m M EGTA) Early exponential growth phase cultures were used to prepare the diluted cultures, which were spotted on plates by means of a repli-cator Cells were photographed after 3 days

of incubation at 28 C (B) Ca 2+

mobilization under lethal tBOOH concentrations WT cells expressing coelenterazine-reconstituted cytAEQ were exposed to toxic but nonlethal (0.75 m M , left) or lethal (1.5 m M , right) concentrations of tBOOH directly in the luminometer tube The arrow indicates the addition of tBOOH When used, BAPTA was added to a final concentration of 5 m M Each determination was repeated at least three times on different days, with no significant variations being seen (P < 0.05) One typical luminescence spectrum is pre-sented for each type of experiment (C) The effect of tBOOH on growth of mutants with altered Ca 2+ -related phenotype The strains were spotted (approximately 4 lL,

10 6 cellsÆmL)1) onto YPD plates containing the indicated concentrations of tBOOH.

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vacuole Toxic, but sublethal, concentrations of

exoge-nous H2O2 (1–2 mm) induced very rapid and transient

Ca2+ bursts Cytosolic Ca2+ elevations dropped to

roughly half the normal value when cells were

pretreat-ed with Ca2+ chelators (BAPTA or EGTA) shortly

before the oxidative shock, so part of the Ca2+ must

come from outside the cell However, the external

Ca2+ seems to be taken up through a system that is

different from the Cch1p⁄ Mid1p channel, as Ca2+

bursts were still clearly detectable in cch1D cells and

were higher than normal in mid1D mutants At the

same time, the process seems to be assisted by the

Yvc1 vacuolar channel, as the H2O2-triggered cytosolic

Ca2+ elevation was rather modest in the yvc1D

mutant The residual Ca2+ increase observed in the

yvc1D mutant could be explained by the existence of a

low-affinity Ca2+ system of unknown identity [30,33]

Nevertheless, as the H2O2 concentration increased

from very toxic to lethal doses (3–10 mm), the cells

gradually turned to internal vacuolar stores rather

than external Ca2+

The tolerance to high H2O2correlated inversely with

the amount of cytosolic Ca2+ achieved during

oxida-tive shock Thus, the mid1D mutant, which exhibited

the highest cytosolic Ca2+burst, was the least tolerant,

and the yvc1D mutant, with the lowest Ca2+load, was

the most tolerant Excessive or unregulated levels of

Ca2+ in the cytosol can lead to cell death [34] and,

indeed, there was a good correlation between

hyper-sensitivity to H2O2 or tBOOH and excessive cytosolic

Ca2+ elevation The triad Ca2+⁄ oxidative stress ⁄ cell

death has already been reported for other systems In

mammals, for instance, Ca2+ overload apparently

leads to mitochondrial dysfunction, reactive oxygen

species production and cell death [35] However, Ca2+

has also been reported to upregulate the

calcineurin-dependent degradation of Yap1p [29], the transcription

factor that regulates gene expression in response to

oxidative stress in yeast [24,25,36] In this respect, the

high cytosolic Ca2+ achieved by the cells when

exposed to lethal concentrations may result in Yap1p

degradation, a situation in which the cells become

hypersensitive to oxidative stress

The cell response to high H2O2 was paralleled by

the response to the less hydrophilic oxidant tBOOH

Here also, the cytosolic Ca2+ transients could be

detected upon exposure, with both external and

vacuo-lar contributions Again, the mid1D mutant exhibited

the highest Ca2+ load and the lowest tolerance,

whereas the yvc1D mutant exhibited the lowest Ca2+

burst, correlating with the highest tolerance to

tBOOH The only difference seemed to reside in the

prevalence of the external Ca2+ contribution to the

cytosolic pool, as seen by the low Ca2+burst in BAP-TA-pretreated cells Release of vacuolar Ca2+through Yvc1p requires activation by Ca2+ on the cytosolic side of the vacuolar membrane [8], and the low level of cytosolic Ca2+ achieved in BAPTA-pretreated cells might be accounted for by the inactive Yvc1p One can also speculate that tBOOH, being less hydrophilic than H2O2, diffuses more slowly in the yeast aqueous environment, exerting a milder signaling effect On the other hand, being unable to synthesize polyunsaturated fatty acids, the yeast has not evolved special protective mechanisms against lipid peroxidation, and is less pre-pared to respond to a stressor that mimics lipid hydro-peroxides

Special attention deserves to be paid to the discrep-ancy between the mid1D and cch1D mutants Although Mid1p and Cch1p cooperate to form a high-affinity influx system, differences between mid1D and cch1D mutants have already been reported [4,37] Among other things, Mid1p is known to localize not only in the plasma membrane, but also in the endoplasmic reticulum membrane [38] Recently, MID1 mutations have been reported to cause a defect in the cell wall structure [39] that might render mid1D cells more per-meable to Ca2+ or more susceptible to stressors such

as H2O2or tBOOH

The data above suggest that Ca2+ pulses serve fre-quently, but not invariably, to transduce an oxidative burst signal However, Ca2+ seems unlikely to be involved in the adaptation to oxidative stress Yap1p, the major yeast transcription factor responsible for the transcriptional regulation of many genes involved in the response to oxidative stress, is upregulated directly

by the presence of oxidants [40–43], whereas Ca2+ mediates its calcineurin-dependent degradation [29] Thus, it is probable that, under strong oxidative condi-tions, the cytosolic Ca2+ elevations actually signal the ultimate possible way out, which is cell death This would explain why, under extreme H2O2stress, the cell blocks the import of external Ca2+ and turns in a last effort to internal stores

Experimental procedures

Strains and culture conditions The S cerevisiae strains used in this study were isogenic with the WT parental strain BY4741 (MATa; his3D1; leu2D0; met15D0; ura3D0) [44] The deletion mutant strains used were Y04847 (BY4741, cch1::kanMX4), Y01153 (BY4741, mid1::kanMX4), Y01863 (BY4741, yvc1::kan-MX4), Y04374 (BY4741, pmc1::kanMX4), Y03825 (BY4741, vcx1::kanMX4), Y13825 (MATa; his3D1; leu2D0;

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lysD0; ura3D0 vcx1::kanMX4) and Y05040 (BY4741,

cnb1::kanMX4) All strains were obtained from

EURO-SCARF (European S cerevisiae Archive for Functional

Analysis, Institute of Molecular Biosciences Johann

Wolf-gang Goethe-University Frankfurt, Germany) Strain

VP012 (BY4741, pmc1::kanMX4 vcx1::kanMX4) was

obtained by crossing of strains Y04374 and Y13825

fol-lowed by diploid sporulation and random spore analysis

The absence of PMC1 and VCX1 from VP102 cells was

checked by colony PCR with primers specific for PMC1

(forward primer, 5¢-ATGTCTAGACAAGACGAAAAT-3¢;

reverse primer, 5¢-GAAATGACATCACCGACTAA-3¢)

and for VCX1 (forward primer,

5¢-ATGGATGCAACTA-CCCCACT-3¢; reverse primer,

5¢-GGATAACTCCAATAT-TTTTC-3¢) Internal control primers for ACT1 (forward

primer, 5¢-GAGGTTGCTGCTTTGGTTAT-3¢; reverse

primer, 5¢-GCGGTTTGCATTTCTTGT-3¢) were included

in all PCR reactions Cell growth and manipulation were

performed as previously described [45] Strains were grown

in standard YPD, SD or SG supplemented with the

neces-sary amino acids For solid media, 2% agar was used

Plasmid construction

The expression vectors harboring PMC1 or YVC1 were

obtained as follows The corresponding ORFs were

ampli-fied from the yeast genome by PCR, and were subsequently

cloned into vector pGREG506 [46], which allows for

galac-tose-inducible expression via the GAL1 promoter Plasmid

pGREG506 was purchased from EUROSCARF The

fol-lowing primers were used: for PMC1, 5¢-CATTGGAT

CCATGTCTAGACAAGACGAAAAT-3¢ (forward primer,

introducing the BamHI site, underlined) and 5¢-TACTGTC

GACTTAATAAAAGGCGGTGGACT-3¢ (reverse primer,

introducing the SalI site, underlined); and for YVC1, 5¢-TA

CTGTCGACATGGTATCAGCCAACGGCGA-3¢ (forward

primer, introducing the SalI site, underlined) and 5¢-GAG

ACTCGAGTTACTCTTTCTTATCCTTTA-3¢ (reverse

pri-mer, introducing the XhoI site, underlined) The PMC1 and

YVC1ORFs obtained by PCR were purified with a Wizard

SV gel and PCR Clean-up System (Promega), cut with

the appropriate restriction enzymes, and cloned into the

BamHI–SalI and SalI–XhoI sites of pGREG506,

respec-tively, to generate pGAL1–PMC1 and pGAL1–YVC1 As

control vector, pGREG506 with the SalI–SalI fragment

deleted was constructed (pGREG506DSalI) This deletion

removes the HIS3 gene used as a counterselective marker

of pGREG vectors for the in vivo plasmid recombination

[46]

Growth assessment

Overnight precultures were inoculated in fresh media at a

density of 105cellsÆmL)1, and cells were then incubated

with shaking (200 r.p.m.) at 28C for 2 h before H2O2,

tBOOH, BAPTA or EGTA was added from sterile stocks prepared in 0.1 m Mes⁄ Tris (pH 6.5) The influence of stressors on cell growth was monitored at time intervals

by determining the attenuance (D) of a cell suspension at

600 nm (Shimadzu UV–visible spectrophotometer, UV mini 1240) For spot assays, fresh cell cultures of

D600 nm 1 were diluted 10-fold, 100-fold, 1000-fold and 10 000-fold, and stamped on agar plates with a replicator

In vivo monitoring of oxidative stress-induced

Ca2+pulse Monitoring of cytosolic Ca2+was performed with an apo-aequorin cDNA expression system [47] Yeast strains were transformed with the plasmid pYX212–cytAEQ, containing the apoaequorin gene under the control of the TPI pro-moter, generously provided by E Martegani (Department

of Biotechnology and Biosciences, University of Milano-Bicocca, Milan, Italy) [48] Yeast transformation was per-formed with a modified lithium acetate method [49], and Ura+transformants were selected for growth on SD med-ium lacking uracil For luminescence assays, overnight pre-cultures of cells expressing the apoaequorin gene were diluted in fresh SD-Ura medium to a density of

5· 106 cellsÆmL)1 The cells were incubated with shaking for another 2 h at 28C, before being harvested by centri-fugation The cells were washed three times (by centrifuga-tion at 9167 g, 1 min) and resuspended at a density of approximately 109cellsÆmL)1 in 0.1 m Mes⁄ Tris buffer (pH 6.5) To reconstitute functional aequorin, 50 lm native coelenterazine (Sigma; stock solution of 1 lgÆlL)1in meth-anol) was added to the cell suspension, and the cells were incubated for 2 h at 28C in the dark Aliquots containing approximately 107cells were harvested, and excess coelen-terazine was removed by centrifuging three times (9167 g,

30 seconds) The cells were resuspended in 0.1 m Mes⁄ Tris buffer (pH 6.5) and transferred to the luminometer tube A cellular luminescence baseline was determined by 1 min of recording at 1 s intervals The exogenous oxidants H2O2 and tBOOH were added from sterile stocks to give the final concentrations indicated, and light emission was monitored with a single-tube luminometer (Turner Biosystems,

20n⁄ 20) The light emission was monitored for at least

5 min after the stimulus at 1 s intervals, and reported as relative luminescence units⁄ s When used, the calcium che-lator BAPTA was added to the cell suspension to the final concentration of 5 mm 1 min before application of the stress To ensure that total reconstituted aequorin was not limiting in our assay, at the end of each experiment aequorin expression and activity were checked by lysing cells with 10% Triton X-100, and only the cells with con-siderable residual luminescence were considered Multiple tests, on different days (a minimum of three for large differ-ences between transgenic lines; a maximum of seven for

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