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Mammalian mitochondrial endonuclease GDigestion of R-loops and localization in intermembrane space Takashi Ohsato1, Naotada Ishihara2, Tsuyoshi Muta1, Shuyo Umeda1, Shogo Ikeda3, Katsuyo

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Mammalian mitochondrial endonuclease G

Digestion of R-loops and localization in intermembrane space

Takashi Ohsato1, Naotada Ishihara2, Tsuyoshi Muta1, Shuyo Umeda1, Shogo Ikeda3, Katsuyoshi Mihara2, Naotaka Hamasaki1and Dongchon Kang1

1

Department of Clinical Chemistry and Laboratory Medicine, Kyushu University Graduate School of Medical Sciences, Fukuoka, Japan;2Department of Molecular Biology, Graduate School of Medical Sciences, Kyushu University, Fukuoka, Japan;

3

Department of Biochemistry, Faculty of Science, Okayama University of Science, Japan

Mammalian mitochondria contain strong nuclease activity

Endonuclease G (endoG), which predominantly resides in

mitochondria, accounts for a large part of this nuclease

activity It has been proposed to act as an RNase H-like

nuclease on RNAÆDNA hybrids (R-loops) in the D-loop

region where the origins of mitochondrial replication are

mapped, providing RNA primers for mtDNA replication

However, in contrast with this proposed activity, endoG has

recently been shown to translocate to nuclei on apoptotic

stimulation and act as a nuclease without sequence

specif-icity To clarify the role of endoG in mtDNA replication, we

examined its submitochondrial localization and its ability to

cleave R-loops At low concentration, it preferentially

produces double-stranded breaks in R-loops, but does not act as an RNase H-like nuclease In addition, it exists in the mitochondrial intermembrane space, but not in the matrix where mtDNA replication occurs These results do not support the involvement of endoG in mtDNA replication Based on the fact that guanine tracts, which are preferential targets of endoG, tend to form triplex structures and that endoG produces double-stranded breaks in R-loops, we propose that three-stranded DNA may be the preferred substrate of endoG

Keywords: endonuclease G; mitochondria; mitochondrial DNA; R-loop; triplex DNA

Mammalian mitochondria contain strong nuclease activity

which becomes evident when the membranes are disrupted

by detergents Endonuclease G (endoG) accounts for a large

part of this mitochondrial nuclease activity It is essentially a

nonspecific nuclease for all nucleic acid species including

double-stranded DNA, single-stranded DNA,

single-stran-ded RNA, and RNAÆDNA duplexes [1,2] As endoG

predominantly resides in mitochondria [1], it has been

thought to be involved in the metabolism of mtDNA It is

considered that mitochondrial transcripts stably hybridize

with template strands around conserved sequence blocks

(CSBs) during transcription, forming R-loops consisting of

two DNA strands and one RNA strand, and serve as

primers for mtDNA replication (Fig 1A) EndoG cleaves

the RNA of a linear RNAÆDNA duplex preferentially in the

CSB region [3], raising the possibility that endoG can

generate RNA primers for mtDNA replication [3]

How-ever, endoG is not a specific RNase On the other hand,

RNase MRP

1 , which is also thought to provide RNA

primers by cleaving the RNA of R-loops, is a specific

RNase In addition, the endogenous RNAÆDNA hybrid

is formed in supercoiled mtDNA and should be a

triple-stranded R-loop [4] The cleavage of the RNA of triple-stranded R-loops by endoG has never been shown, while RNase MRP has been shown to cleave the RNA of triple-stranded R-loops preferentially at the CSBs [5] Furthermore, NUC1, which is a yeast homolog of endoG and is also found in mitochondria, is not essential for mtDNA replication in yeast, as disruption of the gene leads

to no obvious derangement of the metabolism of mtDNA [6] Thus the role of endoG in mtDNA replication is still ambiguous

EndoG has recently been reported to be an apoptotic nuclease [7] It translocates to the nucleus upon apoptotic stimulus and extensively degrades nuclear DNA, suggesting that, in mitochondria, it has the potential to fully digest mtDNA This raises another issue of how mtDNA escapes extensive digestion by endoG under steady-state conditions

To further elucidate the function of endoG, we examined its submitochondrial localization and its ability to cleave reconstituted R-loops Here we show that it preferentially produces double-stranded breaks in the R-loops and that it

is localized in the mitochondrial intermembrane space We discuss the possibility that noncanonical DNA structures are preferential substrates for endoG

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

Cloning and expression of human mature endoG

A human cDNA library (Human HeLa S3 MATCHMA-KER cDNA Library; Clontec Laboratories, Palo Alto, CA, USA) was used for amplification of human mature endoG cDNA by PCR A plasmid for mature human endoG with

an N-terminal histidine tag was constructed by inserting the

Correspondence to D Kang, Department of Clinical Chemistry and

Laboratory Medicine, Kyushu University Graduate School

of Medical Sciences, Fukuoka 812-8582, Japan.

Fax: + 81 92 642 5772, Tel.: + 81 92 642 5749,

E-mail: kang@biochem2.med.kyushu-u.ac.jp

Abbreviations: endoG, endonuclease G; CSB, conserved sequence

blocks; mHSP70, mitochondrial heat shock protein 70.

(Received 24 June 2002, revised 2 September 2002,

accepted 6 September 2002)

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cDNA coding for mature endoG (A49-K297) into

pProEX-HTb(Clontec) and named pHis-hmEG Recombinant

histidine-tagged endoG (His-endoG) was expressed in

Escherichia coli BL21 cells The expressed recombinant

protein formed inclusion bodies The aggregated His-endoG

was denatured and solubilized with buffer containing 6M

guanidine, 0.5MNaCl, 50 mMTris/HCl, pH 8.0, and 1 mM

dithiothreitol The solubilized protein was bound to Ni2+

-chelating Sepharose resin (Amersham Pharmacia Biotech)

The resin was washed with buffer consisting of 20 mMTris/

HCl, pH 7.5, 0.5M NaCl, 5 mM imidazole, 0.1% Triton

X-100, 2 mM 2-mercaptoethanol, 10% glycerol, and 6M

urea The denatured His-endoG was renatured on the resin

by sequentially reducing the urea in the buffer from 6Mto

0M, in 10 steps The renatured His-endoG was finally eluted

with buffer consisting of 20 mM Tris/HCl, pH 7.5, 0.5M

NaCl, 300 mM imidazole, 0.1% Triton X-100, 2 mM

2-mercaptoethanol, and 10% glycerol The eluted sample

was dialyzed against 20 mMTris/HCl, pH 7.5, 0.5MNaCl,

0.1% Triton X-100, 2 mM 2-mercaptoethanol, and 50%

glycerol The recombinant His-endoG was purified to

apparent homogeneity as judged by SDS/PAGE (results not shown) After separation by SDS/PAGE, we deter-mined protein concentrations by Coomassie Brilliant Blue staining using a LAS-1000 CCD camera and IMAGE GAUGETMimage analysis software (Fuji Photo Film) BSA was used as a standard

Cleavage of R-loops by endoG The plasmid pGEMhmD was used for in vitro R-loop formation (Fig 3A) [8] Because we used SP6 RNA polymerase instead of mtRNA polymerase, the human mitochondrial D-loop region lacking authentic promoters for the light and heavy strands was inserted downstream of the SP6 promoter in pGEMhmD R-loops were reconsti-tuted as described previously [8] Briefly, a reaction mixture containing 5 nM pGEMhmD, 50 mM KCl, 20 mM Tris/ HCl, pH 8.0, 10 mMMgCl2, 1 mM dithiothreitol, 0.1 mM NTPs, and 0.2 UÆlL)1SP6 RNA polymerase was incubated for 30 min at 37C essentially as described by Lee & Clayton [9] To remove NTPs, the reaction mixture was applied to a gel-filtration spin column The R-loops in the eluate were ethanol-precipitated, dried, and resolubilzed in distilled water R-loop resolution with RNase H was performed in 20 lL buffer containing 0.1 pmol R-loops,

20 mMTris/HCl, pH 8.0, 50 mMKCl, 4 mMMgCl2, 1 mM dithiothreitol, RNase H (6 U), and 0.05% BSA at 37C for

10 min The reaction was stopped by the addition of

1 lgÆmL)1proteinase K and 0.5% SDS, and then incubated for another 10 min The cleavage reaction was performed in

20 lL buffer containing 0.1 pmol R-loops, 20 mM Tris/ HCl, pH 8.0, 50 mMKCl, 4 mMMgCl2, 1 mM dithiothre-itol, 2 mM ATP, and 0.05% BSA in the presence of the indicated concentration of endoG for 10 min at 37C The reaction was stopped by the addition of 1 lgÆmL)1 prote-inase K and 0.5% SDS, and then incubated for another

10 min R-loops were analyzed by 0.7% agarose gel electrophoresis in buffer consisting of 89 mM Tris base,

89 mMboric acid, and 2 mMEDTA

Determination of cleavage sites After 1 lg R-loops or pGEMhmD had been treated with

50 ng endoG for 10 min, DNA was ethanol-precipitated, washed with 70% ethanol, dried, and solubilized in distilled water To determine the 5¢ ends of cleavage sites, one cycle

of primer extension reactions was performed using 5¢-fluorescein isothiocyanate (FITC)-labeled primers [FD7 (FITC-ctacgttcaatattacaggcg) and FpGEM (FITC-ctttatgcttccggctcgtatg) for the heavy and light strands, respectively] DNA was denatured for 5 min at 95C, the primer was annealed for 0.5 min at 55C, and then an extension reaction was performed for 1 min at 72C using

LA Taq polymerase (Takara, Seta, Japan) For sequence ladders, 25 cycles of primer extension reactions were similarly performed, but using a Thermo Sequence Core Sequencing kit (Amersham Pharmacia Biotech) and 0.5 lg pGEMhmD as a template in the presence of one of the dideoxy dNTPs according to the manufacturer’s instruc-tions The products were resolved on a 7Murea/5% Long RangerTM sequencing gel (FMC Bioproducts, Rockland,

ME, USA) and analyzed with FluorImager 595 (Amersham Pharmacia Biotech)

Fig 1 Cleavage of R-loops (A) The scheme for R-loop formation

in vivo For in vitro R-loop formation, we used SP6 RNA polymerase

instead of mitochondrial RNA polymerase Therefore, in pGEMhmD,

the human mitochondrial D-loop region lacking authentic promoters

for the light and heavy strands is inserted downstream of the SP6

pro-moter (see Fig 3A) LSP, light strand propro-moter; TFAM, mitochondrial

transcription factor A; CSBs, conserved sequence blocks; TAS,

ter-mination associated sequence (B) Supercoiled pGEMhmD plasmids

(upper) or R-loops (lower) were treated with various concentrations of

recombinant human endoG for 10 min at 37 C and then resolved on a

0.7% agarose gel rEG, recombinant human endonuclease G; OC, open

circular form; L, linear form; SC, supercoiled form.

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Submitochondrial localization of endoG

Anti-endoG sera were obtained by immunizing rabbits with

the recombinant human His-endoG The resulting antisera

also reacted with human, bovine, mouse, and rat endoG

Mouse monoclonal antibodies against cytochrome c and

mitochondrial heat shock protein 70 (mtHSP70) were

purchased from Becton Dickinson and StressGen,

respect-ively Antisera against rat Tim23, Tim43, and Tom20 were

as previously described [10,11]

Rat liver mitochondria were prepared as previously

described [10] For preparation of soluble and particulate

fractions, intact rat mitochondria (1 mg proteinÆmL)1)

were disrupted by sonication in low-salt isotonic buffer

(10 mMHepes/KOH, pH 7.4, 0.22Msucrose, and 0.07M

mannitol), with 0.1MNa2CO3added before sonication in

some experiments Next, 2.0M NaCl and 1.0% Triton

X-100 were added, and the samples were centrifuged at

100 000 g for 30 min and separated into pellets and

supernatants The pellets were suspended in the same

volume of buffer, and each fraction was solubilized with an

equal volume of SDS sample buffer The outer membranes

were disrupted by hypotonic treatment (10 mM Hepes/

KOH, pH 7.4), and the resulting mitoplasts were incubated

with or without proteinase K (100 lgÆmL)1) in the low-salt

isotonic buffer for 1 h at 4C Outer memb ranes were also

disrupted by treatment of intact mitochondria (1 mg

proteinÆmL)1) with digitonin for 10 min in the low-salt

isotonic buffer at 4C Protein concentrations of

mito-chondria were determined by the Lowry method using

BSA as a standard

R E S U L T S

Cleavage of R-loops by endoG

When supercoiled pGEMhmD plasmid was treated with

recombinant human endoG, it was first converted into an

open circular form (Fig 1B, upper panel) With increasing

endoG concentration, a linear form appeared accompanied

by further degraded products It is likely that endoG

introduced nicks into the plasmids, and, in due course, the

accumulation of nicks resulted in double-stranded breaks

We reconstituted R-loops using supercoiled pGEMhmD

plasmids containing the human mitochondrial D-loop

region [8] The R-loops generated showed retarded mobility

on a gel (Fig 2, lane 1 in lower panel) R-loop formation

was confirmed by the restoration of electrophoretic mobility

after treatment with RNase H, which digests the RNA in an

RNAÆDNA duplex (Fig 2, lane 2 in lower panel) The

R-loop mimics the endogenous RNAÆDNA hybrid better

than does a linear RNAÆDNA duplex R-loops were

linearized at concentrations at which endoG converted

ordinary supercoiled plasmids into open circular forms

(Fig 1B, lanes 2 and 3 in upper and lower panels) At higher

concentrations, R-loops were eventually degraded into

small pieces These results suggest that endoG directly

produced double-stranded breaks in the R-loop, instead of

introducing nicks Subsequently, the linearized DNA was

further digested Consistent with this, the linear form

appeared as early as 1 min after the addition of endoG

(Fig 2, lower panel) At this time point, the ordinary

supercoiled plasmid was hardly converted into a relaxed

form at all (Fig 2, upper panel) It is noteworthy that a closed circular form was never observed during endoG treatment of R-loops over the time course of the study (Fig 2 lower panel) If RNA was first cleaved with RNase H activity of endoG, the R-loops would have reverted to closed circular plasmids as they were with RNase H (Fig 2, lane 2 in lower panel) This suggests that cleavage of DNA is a primary event

Fig 2 Time course of endoG digestion Supercoiled pGEMhmD plasmids (upper) or R-loops (lower) were incubated with 50 ng endoG for the indicated periods (lanes 4–10) Supercoiled pGEMhmD plas-mids were incubated without endoG (lanes 2 and 3 in upper panel) R-loops (lane 1 in lower panel) were treated with RNase H (lane 2 in lower panel).

Fig 3 Cleavage sites of R-loops (A) Diagram of pGEMhmD (B) R-loops after cleavage by 50 ng endoG (lane 2), and after further cleavage with ScaI (lane 3) or NaeI (lane 4).

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We mapped the cleavage sites of the R-loops The

R-loops were treated with endoG and then cleaved with a

restriction enzyme (ScaI or NaeI) that cuts at a unique site

on the plasmid pGEMhmD (Fig 3A) ScaI created two

bands of about 2.1 and 1.9 kbp (Fig 3B, lane 3) NaeI

similarly produced two bands corresponding to about 2.8

and 1.2 kbp (Fig 3B, lane 4) From these results, the

cleavage site by endoG was mapped to the CSB region

(Fig 3A) The positions were further localized by primer

extension The cleavage signals were mapped to the

guanine-rich region in CSB II of the mitochondrial heavy

strand in the ordinary supercoiled plasmids (Fig 4A, lanes

3 and 4) The signals were hardly observed at all at the opposite side, i.e the cytosine-rich region of the light strand (Fig 4B, lane 4), which is consistent with endoG having a preference for a G-tract over an opposite C-tract [12] These observations also explain how endoG produced

an open circular form in the case of ordinary supercoiled plasmids (Figs 1 and 2) In contrast, the cleavage sites in R-loops were clustered between the CSB II and SP6 promoter region in both the heavy (Fig 4A, lanes 7 and 8) and light (Fig 4B, lane 5) strands, and there seemed to be

no sequence specificity We observed nonspecific signals for the heavy strands (Fig 4A, lanes 1–8, asterisk)

Fig 4 Precise mapping of cleavage sites The

2 supercoiled pGEMhmD plasmids and R-loops were incubated with or without EcoRI or endoG (A) Heavy strand The cleavage sites were determined by primer extension using the primer FD7 Lanes T, G, C, and A indicate sequence ladders (lanes 9–12) Except for the sequence lanes, each sample was duplicated; the two lanes correspond to 0.5 lg (lanes 1, 3, 5, and 7) and 1.0 lg (lanes 2, 4, 6, and 8) of template DNA, respectively Signals marked with * may be nonspecific artifacts caused by stalling of the extension reaction (B) Light strand The reactions were performed as in (A), except the primer FpGEM was used Except for the sequence lanes (lanes 6–9), each sample corresponds to 1.0 lg template DNA (lanes 1–5).

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Because these signals were observed even in nondigested

plasmids (Fig 4A, lanes 1 and 2), the DNA polymerase

used in the primer extension reaction may tend to pause

around the sites, and the signals may be technical artifacts

We also saw several signals for the light strand when

nondigested R-loops were used (Fig 4B, lane 3) Because

such signals were not observed when normal pGEMhmD

was used (Fig 4B, lane 2), primer extension reactions

would frequently and artificially terminate only when using

R-loops Although the exact reason for the termination is

not clear, considering that R-loops are fairly stable to heat

[9] and the template light strand was originally hybridized

with RNA, one possibility is that RNAÆDNA hybrids that

remain even after denaturation by heat may block the

extension reaction

Submitochondrial localization of endoG

Next we examined the submitochondrial localization of

endoG When rat liver mitochondria were disrupted by

sonication in low-salt isotonic buffer, endoG was mainly

recovered from a particulate fraction (Fig 5A, lanes 7 and

8) On the other hand, it was released into the soluble

fraction in the presence of 2.0MNaCl, 0.1MNa2CO3, or

0.5% nonionic detergent Triton X-100 (Fig 5A, lanes

1–6), indicating that it is peripherally associated with the

mitochondrial membranes Cytochrome c, a protein

loosely associated with inner membranes on the

inter-membrane-space side, showed the same behavior as

endoG (results not shown) EndoG in intact mitochondria

was resistant to proteinase K (Fig 5B, lanes 1 and 2), but

when the outer membranes were disrupted by hypotonic treatment, it was digested by proteinase K (Fig 5B, lanes

3 and 4) This indicates that it is localized in the intermembrane space, because the inner membranes remained intact, protecting mHSP70 (a mitochondrial matrix protein) from digestion (Fig 5B, lane 4) Although

a trace of endoG remained even after the proteinase K treatment (Fig 5B, lane 4), cytochrome c also remained to

a similar extent (Fig 5B, lane 4), suggesting that the residual endoG is due to incomplete disruption of the outer membranes To confirm this localization, the outer membranes were disrupted with digitonin and then digested with proteinase K At 500 lgÆmL)1 digitonin (Fig 5C, lane 3), Tim23, an inner membrane protein facing the intermembrane space, was completely digested with proteinase K, whereas neither mHSP70 nor Tim44,

an inner membrane protein facing the matrix side, was digested This indicates that the protease has access to the outside of the inner membranes but not the matrix side Under these conditions, both cytochrome c and endoG were digested (Fig 5C, lane 3) Both mHSP70 and Tim44 were completely digested with proteinase K when mito-chondria were solubilized with 0.5% Triton X-100 (results not shown) Thus, endoG and mtDNA are localized to different compartments, which may protect mtDNA from extensive digestion by endoG

D I S C U S S I O N

EndoG is essentially a nonspecific nuclease [1,2], which is evident in vivo after apoptotic stimulation, when endoG

Fig 5 Submitochondrial localization of endoG (A) Intact rat mitochondria (lane 9) were disrupted by sonication in low-salt isotonic buffer (lanes 7 and 8) Then 2.0 M NaCl (lanes 5 and 6) and 1.0% Triton X-100 (lanes 1 and 2) were added In some preparations, 0.1 M Na 2 CO 3 was added before sonication and there was no further treatment (lanes 3 and 4) The samples were centrifuged and separated into pellets (P) and supernatants (S) Samples corresponding to 20 lg mitochondrial protein were applied to each lane EndoG was detected by Western blotting (B) Intact mito-chondria were incubated without proteinase K (lane 1) or with proteinase K (lane 2) for 1 h at 4 C Outer membranes were disrupted by hypotonic treatment The mitoplasts were then incubated without proteinase K (lane 3) or with proteinase K (lane 4) in the low-salt isotonic buffer for 1 h at

4 C Tom20, endoG, cytochrome c, Tim44, and mHSP70 were detected by Western blotting (C) Intact mitochondria were treated with digitonin for 10 min in the low-salt isotonic buffer at 4 C followed by proteinase K digestion (lanes 1–3) mHSP70, Tim44, Tim23, endoG, and cytochrome c were detected by Western blotting.

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translocates en masse from mitochondria to nuclei and

extensively digests nuclear DNA [7] Under these

condi-tions, endoG at high concentration appears to act as a

nonspecific nuclease However, at low concentration, it

appears to be quite specific for kinked DNA, such as that in

R-loops (Fig 1) We have shown that endoG preferentially

introduced double-stranded breaks in a specific region of

R-loops

RNA consistently forms a hybrid in CSB II [9], and

transcription for R-loop formation starts from the SP6

region in our in vitro transcription system Therefore, the

starting point of the RNAÆDNA hybrid formation must

be located between these two regions Considering that

there was no sequence specificity, endoG may recognize a

three-stranded junction structure formed at the starting

point of the RNAÆDNA hybrid Alternatively, it may

recognize the looping-out single-stranded DNA and an

A-form helix that an RNAÆDNA duplex is likely to take

on As reported elsewhere, endoG preferentially cleaves

damaged DNA [13] Many kinds of DNA damage cause

distortion of the DNA helix Guanine-rich DNA, which

is a preferential target of endoG [12], tends to form

irregular structures such as triplexes and quadruplexes

[14] Taken together with our observations of the activity

of endoG on R-loops, it is evident that noncanonical

structures of DNA, e.g damaged DNA, triplex DNA,

and R-loops, may generally be preferential substrates for

endoG

Triplex or quadruplex DNA strands can be formed

intramolecularly or intermolecularly in vivo in purine-rich

regions [14] These structures block transcription and

replication For instance, it has been reported that

expansion of the GAA triplet repeat of the frataxin

gene results in triplex structures, thereby causing

tran-scription to be paused [15] R-loop formation can occur

in a nonspecific manner during transcription [16] and can

serve as a primer for DNA synthesis [17], although the

nascent RNA molecule is normally displaced from the

DNA template strand shortly after synthesis

Accumula-tion of R-loops is hazardous to cells, because of

induction of unregulated replication [18] In addition,

guanine-rich RNA can participate in very stable

three-stranded structures by establishing both Watson–Crick

and Hoogsteen-type hydrogen bonds [19], the formation

of which inhibits transcription Given that endoG is

normally regulated to exist in nuclei at a very low level,

it may have a role in survival in normal states

by eliminating kinked DNA formed in guanine-rich

regions

EndoG has been proposed to provide primers for

mtDNA replication by cleaving the RNA moiety of

RNAÆDNA hybrids formed at the origin of replication [3]

However, based on our observations, endoG would not

act as an RNase in these conditions, but would instead

preferentially degrade mtDNA in an R-loop

Further-more, we have shown that endoG exists in the

intermem-brane space (Fig 5B,C), whereas mtDNA replication

should take place in the matrix On the other hand,

RNase MRP has been shown to cleave RNA of

triple-stranded R-loops preferentially at the CSBs [5], and is

another RNase proposed to create RNA primers The role

of endoG in mtDNA replication may require careful

re-evaluation

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

This work was supported in part by Grants-in Aid for Scientific Research from the Ministry of Education, Science, Technology, Sports, and Culture of Japan.

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7 Li, L.Y., Luo, X & Wang, X (2001) Endonuclease G is an apoptotic DNase when released from mitochondria Nature (London) 412, 95–99.

8 Ohsato, T., Muta, T., Fukuoh, A., Shinagawa, H., Hamasaki, H.

& Kang, D (1999) R-loop in the replication origin of human mitochondrial DNA is resolved by RecG, a Holliday junction-specific helicase Biochem Biophys Res Commun 255, 1–5.

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10 Ishihara, N & Mihara, K (1998) Identification of the protein import components of the rat mitochondrial inner membrane, rTIM17, rTIM23, and rTIM44 J Biochem (Tokyo) 123, 722– 732.

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18 Hong, X., Cadwell, G.W & Kogoma, T (1995) Escherichia coli RecG and RecA proteins in R-loop formation EMBO J 14, 2385–2392.

19 Praseuth, D., Guieysse, A.L & Helene, C (1999) Triple helix formation and the antigene strategy for sequence-specific control

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