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Tài liệu Báo cáo Y học: The RuvABC resolvasome Quantitative analysis of RuvA and RuvC assembly on junction DNA doc

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This process involves two key steps: branch migration, catalysed by the RuvB protein that is targeted to the Holliday junction by the structure specific RuvA protein, and resolution, whic

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The RuvABC resolvasome

Quantitative analysis of RuvA and RuvC assembly on junction DNA

Mark J Dickman1, Stuart M Ingleston2, Svetlana E Sedelnikova3, John B Rafferty3, Robert G Lloyd2, Jane A Grasby4and David P Hornby1

1

Transgenomic Research Laboratory, Krebs Institute, Department of Molecular Biology and Biotechnology, University of Sheffield, UK;2Institute of Genetics, University of Nottingham, Queens Medical Centre, UK;3Krebs Institute, Department of Molecular Biology and Biotechnology, University of Sheffield, UK;4Krebs Institute, Centre for Chemical Biology, University of Sheffield, UK

The RuvABC resolvasome of Escherichia coli catalyses the

resolution of Holliday junctions that arise during genetic

recombination and DNA repair This process involves two

key steps: branch migration, catalysed by the RuvB protein

that is targeted to the Holliday junction by the structure

specific RuvA protein, and resolution, which is catalysed by

the RuvC endonuclease We have quantified the interaction

of the RuvA protein with synthetic Holliday junctions and

have shown that the binding of the protein is highly

struc-ture-specific, and leads to the formation of a complex

con-taining two tetramers of RuvA per Holliday junction Our

data are consistent with two tetramers of RuvA binding to

the DNA recombination intermediate in a co-operative manner Once formed this complex prevents the binding of RuvC to the Holliday junction However, the formation of

a RuvAC complex can be observed following sequential addition of the RuvC and RuvA proteins Moreover, by examining the DNA recognition properties of a mutant RuvA protein (E55R, D56K) we show that the charge on the central pin is critical for directing the structure-specific binding by RuvA

Keywords: RuvABC resolvasome; Holliday junction; surface plasmon resonance

Genetic recombination is a fundamental cellular process

that serves both to protect and expand the coding potential

of all organisms Through recombination events the genes

within and between chromosomes may be rearranged,

segregation at cell division may be modulated and DNA

repair facilitated All organisms have evolved many different

ways to repair the damage to DNA and failure of these

mechanisms leads to chromosomal disorders that can result

in mutation, malignant transformation or death Studies in

Escherichia coliand other bacteria have provided

consider-able insights into the molecular pathways of DNA repair

Prominent amongst these pathways is recombination

Genetic recombination occurs via breakage and reunion

of DNA chains and generally conserves sequence [1] DNA

recombination has also been shown to play a role in

re-establishing stalled replication forks [2]

During the late stages of recombination in E coli,

Holliday junction intermediates made by RecA-mediated

homologous pairing and strand exchange are processed into

mature recombinants by the RuvA, RuvB and RuvC

proteins [3,4] RuvA has been shown to be a highly structure

specific DNA binding protein whose function is to target

RuvB to the Holliday junction [5,6] RuvB assembles

around the DNA as hexameric rings, which are thought to

move along the DNA using energy derived from the

hydrolysis of ATP RuvC is an endonuclease that cleaves the junction via a process involving a dual incision mechanism at base specific contacts in which nicks are introduced into two strands having the same polarity, around a defined target sequence with the consensus 5¢ (A/T)TT(G/C) [7,8] Genetic studies have indicated that RuvAB mediated branch migration is intrinsically linked to RuvC mediated Holliday junction resolution [9–11] Taking into account the sequence specificity of RuvC, different models have been proposed to reconcile the genetic and biochemical data on the resolution of Holliday junctions In one scenario RuvAB promotes branch migration until suitable sequences are encountered, at which point the complex dissociates to allow RuvC binding Alternatively RuvC may act as part of a RuvABC complex in which migration and resolution are coupled

RuvA is a 22-kDa protein which exists as a tetramer in solution [12] and binds to both ssDNA and dsDNA [13], but binds with the greatest affinity to Holliday junctions Binding is structure specific and completely independent

of DNA sequence When the RuvA protein is bound to the Holliday junction in solution and is subjected to nondenaturing gel electrophoresis, two different complexes are observed Their electrophoretic mobilities are consis-tent with the formation of protein–DNA complexes containing one and two tetramers of RuvA [14,15] Under conditions in which RuvB exhibits a low affinity for DNA, the presence of RuvA results in the formation of a RuvAB–Holliday junction complex, indicating that RuvA targets RuvB to the junction [16] The determination of the molecular structure of RuvA [17] has shown that the four monomers of RuvA are related by fourfold sym-metry (see Fig 1), similar to a four petal flower with concave and convex surfaces normal to the fourfold axis

Correspondence to D P Hornby, Transgenomic Research

Laboratory, Krebs Institute, Department of Molecular

Biology and Biotechnology, University of Sheffield, Western Bank,

Sheffield S10 2TN, UK.

Fax: + 44 114276 2687, Tel.: + 44 114222 4236,

E-mail: d.hornby@shef.ac.uk

(Received 4 July 2002, accepted 11 September 2002)

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The two faces of the RuvA tetramer are different; one

face is convex and is mainly negatively charged whereas

the opposite face is concave and positively charged The

negatively charged central pin containing the conserved

Glu55 and Asp56 residues is shown in Fig 2

Three crystal structures have been determined for a

RuvA–synthetic Holliday junction complex [18–20] The

crystal structures of the E coli RuvA–DNA complex

consist of a single RuvA tetramer with a nearly square

planar DNA molecule bound to its concave surface

[18–20] This is in agreement with a predicted model

derived from the RuvA crystal structure [17] The DNA

duplex arms in the junction are located in the grooves on

the surface of the RuvA as predicted, and a central pin

region of the concave surface, which includes the

conserved Glu55 and Asp56 residues, perfectly matches

a hole of approximately 20 A˚ diameter at the centre of

the junction The crystal structure of the Mycobacterium

lepraeRuvA–junction complex contains a RuvA tetramer

on both faces of the junction, such that the DNA is

sandwiched between two tetramers [19] In the latter

structure RuvA forms an octameric shell through which

the DNA must pass during branch migration Recently it

has been shown that the acidic pin of E coli RuvA

modulates Holliday junction resolution by preventing

binding to duplex DNA and constraining the role of

branch migration in the RuvAB complex [21]

One of the enduring questions relating to the molecular

recognition of the Holliday junction–resolvasome is the

molecular nature of the components involved in the

catalytic complex In this paper we have carried out a

detailed quantitative analysis of the binding of E coli

RuvA to synthetic Holliday junctions using a variety of

biochemical procedures Specifically we investigated protein–DNA interactions involving the RuvA and RuvC proteins, and have analysed both quantitative and qualitative differences between wild-type RuvA and a mutant which lacks the wild-type acidic pin We show that two RuvA tetramers bind to Holliday junctions possibly via a co-operative mechanism with an overall Kd

of approximately 0.2 nM and also demonstrate the formation of a RuvA/C complex on the Holliday junction

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

Synthesis and purification of oligodeoxynucleotides used in the binding studies

Oligonucleotide synthesis was performed on an Applied Biosystems 394 DNA synthesiser using cyanoethyl phos-phoramidite chemistry The biotin phosphos-phoramidite was obtained from Glen Research Oligodeoxynucleotides were provided in solution after deprotection in 30% ammonia The oligonucleotides were purified using dena-turing PAGE and subsequently evaporated to dryness and desalted using a Pharmacia NAP 10 column according to the manufacturer’s instructions Synthetic Holliday junc-tions, HJ24 and HJ50, each comprised four 24-mer and four 50-mer oligonucleotides DNA annealing and puri-fication were essentially as described previously [33] HJ50 contained HJ5, 6, 7 and 8 HJ 25 contained HJ1, 2, 3 and

4 Three way junctions were prepared using HJ5, 6 and 7 and duplex DNA annealed using D1 and D2, ASP1 and ASP2 All oligonucleotides used in the binding studies are shown in Table 3

Fig 2 Molecular surface of the pin region of the RuvA tetramer showing its electrostatic surface potential The view is along the fourfold axis of the tetramer into the concave face with electrostatic surface potential displayed (blue, positive; red, negative) The conserved Glu55 and Asp56 residues in each monomer are highlighted.

Fig 1 Molecular representation of an Escherichia coli RuvA tetramer

illustrating its fourfold symmetry The helices (barrels) and strands

(arrows) are coloured red and blue, respectively The view is along the

fourfold symmetry axis into the concave face of the tetramer Domains

A, B, C and D are indicated for one monomer and the dashed lines

depict the flexible linkers.

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Synthesis and purification of proteins used

in the binding studies

RuvA was purified as described [31] RuvC was

overex-pressed to about 10% of total cell protein in BL21 plysS

(Cmr) harbouring pGS775 (RuvC+cloned in pT7-7) (Apr)

RuvC was then purified to 90% using two stages of

chromatography The first step involved pseudo-affinity

chromatography using heparin-Sepharose The second step

was gel filtration on a Hi-Load Superdex-200 column

(Pharmacia) in buffer A (0.5M NaCl, 50 mM Tris/HCl,

pH 7.5) Protein was then concentrated by precipitation

with ammonium sulphate (0.55 gÆmL)1) to approximately

10 mgÆmL)1and dialysed against buffer A to remove the

ammonium sulphate The RuvA and RuvC proteins were

diluted in the appropriate running buffer to give final

concentrations between 2000 and 1 nM

Binding assays using surface plasmon resonance

The SPR analysis was performed using a BIAcore 2000TM

(BIAcore, Uppsala, Sweden) The oligonucleotides were

diluted in HBS [0.01MHepes (pH 7.4), 0.15MNaCl, 3 mM

EDTA, 0.05% (v/v) surfactant P20] buffer to final

concen-tration of 1 ngÆmL)1and passed over a streptavidin sensor

chip (SA) at a flow rate of 10 lLÆmin)1until approximately

100–200 response units of the oligonucleotide was bound to

the sensor chip surface The protein was diluted in HBS A

range of protein concentrations (1–2000 nM) were injected

over the DNA attached to the sensor chip at a flow rate of

20 lL minute)1for 3 min and were allowed to dissociate

for 5 min The bound protein was then removed by injecting

10 lL of 1M NaCl This regeneration procedure did not

alter to any measurable extent the ability of the Holliday

junction to bind to RuvA Analysis of the data was

performed using the BIAevaluation software supplied with

the BIAcore To remove the effects of the bulk refractive

index change at the beginning and end of the injections

(which occur as a result of a difference in the composition of

the running buffer and the injected protein), a control

sensorgram obtained over the streptavidin surface was

substracted from each protein injection

Stoichiometry analysis

The biotinylated Holliday junctions were injected over the

surface of the streptavidin coated sensor chip and the

changes in response recorded RuvA (1 lM) diluted in HBS

buffer was then injected over the Holliday junction attached

to the sensor chip surface The change in response of RuvA

binding to the junction was recorded, the stoichiometry was

calculated using Eqn (1):

S ¼ RmaxRuvA

R junc M r RuvA

M r junc

where Rmax RuvA is the maximum response of RuvA

binding, Rjunc is the response of the binding of the

biotinylated Holliday junction, MrRuvA is the molecular

mass of RuvA and Mr junc is the molecular mass of the

Holliday junction The following values were used: Mr RuvA

88 000, Mr junc (HJ50) 63 200, Mr junc (HJ24) 32 000,

Kinetic analysis The dissociation rate constants were calculated using linear regression analysis assuming a zero order dissociation using Eqn 2:

dR=dt¼ kdR0ekd ðtt 0 Þ ð2Þ where dR/dt is the rate of change of the SPR signal, R and

R0, is the response at time t and t0 kdis the dissociation rate constant

Nonlinear regression analysis was used to determine the equilibrium dissociation constant from the sensorgrams and allows the calculation of both association and dissociation rate constants from a single sensorgram using the following equation Using a 1 : 1 homogenous single site binding model:

R¼ ½ðkaCRmaxÞ=ðkaCþ kdÞ ð1  eðk a C þ k d ÞtÞ ð3Þ where C is the concentration of analyte, Rmax is the maximum analyte binding capacity in RU and R is the SPR signal in RU at time t, kathe association rate constant and

kdthe dissociation rate constant

Using a heterogenous model (where the component interactions are independent of each other, the response curve is the sum of the separate binding events), the following equation can be used:

R¼Xn n1½ðka;nCnRmax;nÞ=ðka;nCnkd;nÞ

 ð1  eðka;n Cnþ k d;n ÞtÞ ð4Þ This equation assumes the analyte species bind independ-ently to separate ligand sites (BIA evaluation software) Equilibrium binding analysis

BIAcore equilibrium binding experiments were performed

as described by Myszka et al [28] with minor modifications The instrument was equilibrated at 25C with HBS buffer (0.01MHepes (pH 7.4), 0.15MNaCl, 3 mMEDTA, 0.05% (v/v) surfactant P20) at a flow rate of 100 lLÆmin)1 Baseline data were collected for 45 min at the start of the experiment, before the incorporation of the protein into the running buffer After equilibrium binding profiles had been generated, the responses from the four flow cells were baseline corrected during the initial washing phase The response from the reference flow cell was subtracted from the other three flow cells to correct for refractive index changes, nonspecific binding and instrument drift

R E S U L T S

Stoichiometry and kinetics of the RuvA–Holliday junction interaction

The stoichiometry and kinetics of the RuvA–Holliday junction interaction was analysed using surface plasmon resonance (SPR) on a BIAcore 2000 The biotinylated synthetic Holliday junctions (HJ50/HJ24, see Materials and methods) were immobilized on a streptavidin coated sensor chip (SA) and the protein injected over the surface of the immobilized Holliday junction The sensorgram can be used

to derive kinetic and equilibrium constants and also allows

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the calculation of the stoichiometry of the interaction This

method has been used previously to study protein–DNA

interactions [22,23]

To calculate the stoichiometry of the interaction of RuvA

with the Holliday junction, the biotinylated Holliday

junc-tions were injected over the surface of the streptavidin coated

sensor chip and the change in response recorded 1 RU

corresponds to 1 pgÆmm)2protein [24] For DNA, a value of

1 RU corresponding to 0.73 pgÆmm)2was used, as

deter-mined by Speck et al [23] The change in response for the

binding of the RuvA to the junction was recorded and using

Eqn (1) (see Materials and methods), the stoichiometry at a

given RuvA concentration was calculated and the results are

summarized in Table 1 From these results it can be

concluded that two RuvA tetramers bind to the Holliday

junction, this occurs in both the 24-mer strand and 50-mer

strand junctions This experiment was repeated using

differ-ent amounts of junction bound to the sensor chip surface

The results were consistent with two RuvA tetramers bound

per Holliday junction These results support the evidence

from both gel shift assays [15], electron microscopy studies

[25] and neutron scattering data [26], which demonstrate

that two RuvA tetramers can bind to synthetic Holliday

junctions Crystallographic studies of the RuvA–synthetic

Holliday junction show either one [18,20] or two [19] RuvA

tetramers bound to the Holliday junction The results

from the SPR experiments described here support the latter

model in solution These experiments also show that

complete removal of RuvA from DNA can be affected by

addition of 1M salt, highlighting the role of electrostatic

interactions in the binding of RuvA to the junction (data not

shown)

The binding of RuvA was studied using the BIAcore to

obtain kinetic parameters for the interaction of RuvA with

the synthetic Holliday junctions attached to a streptavidin

sensor chip The interaction of RuvA with both the 24-mer

and the 50-mer Holliday junctions was then investigated

From the sensorgrams obtained (see Fig 3) the data were

fitted to a mathematical model which describes the

inter-action of two analyte molecules (two RuvA tetramers)

binding to a single ligand (Holliday junction) at different

sites The model used was a heterogeneous parallel model

(BIAevaluation software) which describes the interaction:

A+B ¡ ABþ B ¡ AB2

This mathematical model was used to obtain association

and dissociation rate constants for the above reaction (see

Eqn 4) However, the results clearly show that this model

produces an unsatisfactory fit to the data The residuals

shown in Fig 3B indicate how well the mathematical model fits the data High residual values, indicating a poor fit to the data, are obtained for the association phase However, by contrast, low residuals were obtained for the dissociation phase indicating a very acceptable fit to the data Several other mathematical models were used to fit the data, including a 1 : 1 Langmuir binding model All yielded poor correlation with the association phase of the RuvA– Holliday junction interaction The mathematical models employed, appeared to be unable to support the very fast association kinetics observed experimentally Such a kinetic mechanism obtained for the interaction of two RuvA tetramers with the Holliday junction could be explained by a co-operative effect during the association phase Two analyte molecules interacting with a single ligand at different sites may introduce a co-operative function not described by the mathematical models This co-operativity may lead to the fast association kinetics observed in the binding of RuvA to the Holliday junction Whilst there are other possible explanations for the binding data, the experiments carried out below seem to be consistent with a co-operative component to the RuvA–DNA interaction

Equilibrium binding profile of the RuvA–Holliday junction interaction

To further evaluate the interaction of RuvA with the Holliday junction, equilibrium binding analysis was

Table 1 Stoichiometry of RuvA and RuvC bound to Holliday junctions

as determined by SPR analysis using Eqn (1) (see Materials and

meth-ods).

Holliday Junction

RuvAa

RuvCb

1 l M 2 l M 0.75 l M

a Tetramers bound per Holliday junction b Dimers bound per

Holliday junction.

Fig 3 Kinetic analysis of the RuvA–Holliday junction interaction (A) Binding of RuvA at various concentrations (10–2000 n M ) to the syn-thetic Holliday junction (HJ50) The experimental binding curve is shown as a continuous line and the fitted data is shown as a broken line The data were fitted to a mathematical model describing the interaction of two analyte molecules binding a ligand at two separate sites (a homogenous parallel model) The residuals, the difference of the experimental data and the fitted values for the association and dissociation phase, are shown in (B).

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performed The protein was placed directly in the running

buffer, which was then passed over the sensor chip surface

continuously The chip contained duplex DNA and the

Holliday junction attached to the different flow cells

Figure 4 shows the equilibrium binding profile for the

E coliRuvA interacting with the Holliday junction (HJ50)

and duplex DNA (D1/2) The binding profiles clearly

demonstrate the higher affinity of RuvA for Holliday

junctions in comparison to duplex DNA This is illustrated

by the binding of RuvA to the Holliday junction at lower

concentrations (0.022 and 0.22 nM) No binding to duplex

DNA is seen until a concentration of 22.6 nMis used, where

it is also seen to bind to the duplex arms of the Holliday

junction These results demonstrate that the E coli RuvA

has the ability to target Holliday junctions over duplex

DNA with approximately 1000-fold greater efficiency Also,

E coliRuvA has the ability to bind to the duplex arms of

the Holliday junctions after specifically binding to the

Holliday junction at the crossover point

From the analysis of the equilibrium binding profile it can

also be shown that at low concentrations of RuvA (0.0026

and 0.026 nM) only very small amounts of protein bind to

the Holliday junction even after 2.5 h of incubation Only

after the concentration of RuvA is increased to 0.22 nM, is

significant binding to the Holliday junction observed

However, at this concentration, equilibrium is soon reached

with only small amounts of additional binding to the

junction at concentrations above this value Therefore over

only a 10-fold increase in protein concentration, nearly

100% of the binding sites are occupied by RuvA The

concentration at which approximately 50% of the DNA

binding sites are bound by RuvA is 0.2 nM Previous

analysis of the high affinity Ets1 protein–DNA interaction

[27] showed that binding occurs over three to four orders of

magnitude of protein concentration until 100% of the

binding sites are occupied However, the RuvA–Holliday

junction binding occurs over two orders of magnitude of

RuvA concentration until 100% of the binding sites are

occupied These results provide further evidence to support

a co-operative mode of binding in the RuvA–Holliday

junction interaction; an idea supported by the RuvA

tetramer–tetramer interactions observed in the M leprae

RuvA–Holliday junction complex [19] Whilst complex

modes of interaction could account for the data, a

co-operative mode of binding seems to be the most plausible explanation

SPR analysis of the RuvAC–Holliday junction ternary complex

To further examine the hypothesis that a tetramer of RuvA can bind to each face of a Holliday junction, the effect of the addition of RuvC to the RuvA–Holliday junction complex was investigated Analysis of the interaction of RuvA and RuvC with the Holliday junction was performed by sequential addition of the RuvA and RuvC proteins to the Holliday junction The resulting sensorgram is shown in Fig 5A and shows that after the addition of RuvA (1 lM)

to the Holliday junction, RuvC (1 lM) does not bind to the junction This would be expected, if RuvA occupies the site for this interaction

A series of concentrations of RuvC (10–2000 nM) were injected over the immobilized Holliday junctions attached

to the sensor chip surface and the stoichiometry calculated

as previously A summary of the values obtained are shown in Table 1 From the results it can be seen that at high concentrations (2 lM), RuvC forms a complex in which more than one dimer interacts with the junction, suggesting that RuvC possibly binds to both faces of the junction in a similar manner to RuvA It had been thought previously that only one RuvC dimer binds to the junction, which is the active form of the complex [7] However,

at lower concentrations of RuvC, the complex only con-tains on average one RuvC dimer per DNA junction as expected These experiments also show that complete removal of RuvC from DNA can be effected by addition

of 1M salt (data not shown), highlighting the role of electrostatic interactions in the binding of RuvC to the junction

A further experiment was performed by first binding RuvC (2 lM) to the junction followed by the addition of RuvA (1 lM) The resulting sensorgram is shown in Fig 5B

No significant RuvA binding was observed, which indicates that two RuvC dimers may bind to the junction in a similar manner to the two RuvA tetramers, and that the two bound RuvC dimers prevent the binding of RuvA under the conditions used in the experiment A small amount of RuvA binding is observed, possibly due to RuvC dissociation from the Holliday junction before the injection of RuvA A final experiment was carried out in which RuvC was added to the Holliday junction under conditions where the mean stoichio-metric calculation shows one RuvC dimer was bound per junction After adding RuvC (0.75 lM) to the junction, RuvA (1 lM) was then added and the resulting sensorgram is shown in Fig 5C These results show that under these conditions RuvA can bind to a RuvC–Holliday junction complex, allowing the formation of a RuvAC complex on the Holliday junction The effect of addition of antibodies raised against RuvA (anti-RuvA) to the proposed RuvAC complex is shown in Fig 5D The sensorgram shows the binding of RuvA after the addition of RuvC, followed by the binding of the anti-RuvA A large response is seen due to the large molecular mass of the anti-RuvA complex These results demonstrate that after the addition of RuvC, RuvA can bind to the complex as confirmed by the binding of the anti-RuvA No binding of the anti-RuvA is seen on the RuvC complex (data not shown)

Fig 4 Equilibrium binding of the E coil RuvA protein to linear duplex

and Holliday junction substrates The profiles shown were obtained by

incorporating the E coli RuvA in the running buffer at concentrations

of 0.00226 n M (a), 0.0226 n M (b), 0.226 n M (c), 2.6 n M (d) and 22.6 n M

(e) The arrows indicate the time points that the concentration of

RuvA was altered.

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Comparison of DNA recognition by RuvA and a mutant

RuvA (E55R D56K)

SPR analysis demonstrated that two tetramers of E coli

RuvA bind to Holliday junctions in a structure specific

manner, with a significantly greater affinity than for duplex

DNA A further experiment was performed to compare the binding of RuvA and a mutant RuvA The mutant E coli RuvA has the negatively charged central pin residues Glu55 and Asp56 mutated to Arg55 and Lys56, which results in a positively charged central pin

A biotinylated Holliday junction (HJ50), a three-way junction and a duplex DNA (D1/2, see Materials and methods) were immobilized on different flow cells on a streptavidin sensor chip The binding of 2 lME coliRuvA with the different complexes is shown in Fig 6A The difference in stability of the duplex and three-strand-RuvA complex compared to the four-strand-RuvA–protein com-plex can clearly be seen in the sensorgram (note the gradient

of the dissociation phase) The dissociation rate constants were calculated using Eqn (2) (see Materials and methods) and shows a three- to fourfold difference between the duplex/three-strand junctions, compared to the four-strand-RuvA complexes (see Table 2), indicating that the formation

of the Holliday junction-protein complex is more stable than the duplex/three-way junction complex Using small duplex DNA (< 25 bp) no significant binding of the E coli RuvA was seen using SPR (data not shown) These experiments present further evidence that the E coli RuvA is highly structure specific in its binding to Holliday junctions The effect of the charge on the central pin with respect to the specificity of the interaction was further investigated by SPR analysis of the mutant E coli RuvA (RuvA E55R D56K) The protein was passed over the streptavidin sensor chip containing the duplex and the three/four-strand junctions The resulting sensorgram is shown in Fig 6B The dissociation rate constants were calculated for the dissociation of the protein from the different complexes and are shown in Table 2 These results demonstrate that all the protein-DNA complexes have very slow dissociation rates, indicating the formation of very stable protein–DNA complexes The calculated rate constants are lower than

Fig 5 Binding of RuvA and RuvC to Holliday junctions (A) SPR

sensorgram showing the binding of RuvA to the Holliday junction

followed by the addition of RuvC 1 shows the binding of RuvA

(1 l M ) to the Holliday junction to form a proposed complex

con-taining two RuvA tetramers bound to the Holliday junction 2 shows

the subsequent addition of RuvC (1 l M ) to the RuvA–Holliday

junction complex, the sensorgram indicates no binding of RuvC (B)

Sensorgram showing the binding of RuvC to the Holliday junction

followed by the addition of RuvA 1 shows the binding of RuvC

(2 l M ) to the Holliday junction to form a proposed complex

con-taining two RuvC dimers bound to the junction 2 shows the

subse-quent addition of RuvA (1 l M ) and indicates no significant binding to

the RuvC–junction complex (C) Sensorgram showing the formation

of a RuvAC-junction complex 1 shows the binding of RuvC (0.75 l M )

to the Holliday junction to form a proposed complex which contains

one RuvC dimer bound to the junction 2 shows the subsequent

addition of RuvA (1 l M ) to the RuvC–junction complex The

sen-sorgram indicates after RuvC has bound to the junction RuvA can

bind to the RuvC–junction complex to form a RuvAC complex (D)

Sensorgram showing the binding of anti-RuvA to the RuvAC-junction

complex 1 shows the binding of RuvA to form the RuvAC complex 2

shows the binding of the RuvA antibody to the RuvAC complex The

sensorgram demonstrates that the antibody can bind to the complex,

indicating further evidence of the formation of the RuvAC-complex.

Fig 6 SPR sensorgram showing the DNA binding specificity of RuvA (A) Binding of wild-type RuvA (2 l M ) and (B) binding of the mutant RuvA (E55R D56K) (1.2 l M ) to Holliday junction, linear duplex and 3-strand junction substrates.

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previous values obtained for the binding of the wild-type

E coli RuvA protein, and show similar values for the

binding to the duplex, three-strand and four-strand

junc-tions; demonstrating that the mutant RuvA protein forms a

complex with duplex DNA which is of equal stability as the

Holliday junction–protein complex The sensorgram in

Fig 6B also illustrates that increased amounts of the protein

interact with the DNA, as shown by the larger response

observed on the sensorgram compared to the wild-type

E coliRuvA These results give stoichiometry values of five

RuvA tetramers bound per DNA

From the SPR analysis it shows that the effective

charge of the central pin region dramatically influences the

binding of duplex DNA to the protein: changing the

charge on the central pin from negative to positive,

increases the stability of the duplex DNA-protein

com-plexes These results are consistent with those obtained by

Ingleston et al [21] using gel retardation assays and

indicate that the charge on the central pin of the RuvA

has a substantial effect on the ability of the protein to

bind to duplex DNA, and therefore to direct the structure

specificity involved in binding a Holliday junction The

mutant E coli RuvA forms a stable complex with duplex

DNA, there is no additional stability of the Holliday

junction–protein interaction over the duplex DNA–protein

interaction These data suggest that the protein may now

be binding to the duplex arms of the junction, as opposed

to only the crossover points of the junction, suggesting

that the protein may no longer be binding in a structure

specific manner to the junction, but in a nonspecific

fashion to duplex DNA

Equilibrium binding profile of the mutantE coli

RuvA (E55R D56K) protein

To further analyse the interaction of the mutant E coli

RuvA protein, equilibrium binding analysis was performed

similar to that performed with wild-type E coli RuvA The equilibrium binding profiles were generated to obtain further information on the specificity of binding Figure 7A shows the binding profile of the mutant E coli RuvA protein to the DNA complexes From this profile it can clearly be seen that the protein binds to both the Holliday junction and the duplex DNA at the same concentration (2.6 nM), indicating that the protein has a similar affinity for the duplex DNA and the Holliday junction These results demonstrate that the mutant E coli protein is binding to the duplex arms of the Holliday junction and is no longer binding in a structure specific manner to the Holliday junction

Table 2 Dissociation rate constants (k d ) for RuvA–DNA complexes as determined by SPR analysis.

DNA RuvA wild-type (1/s) ± SD RuvA E55R,D56K (1/s) ± SD

Duplex 19 · 10)4± 2.2 · 10)4 8 · 10)5± 4.2 · 10)6 3-strand junction 17 · 10)4± 1.9 · 10)4 2.7 · 10)5± 6.2 · 10)6 4-strand junction 5.5 · 10)4± 4.2 · 10)5 4.7 · 10)5± 6.4 · 10)6

Fig 7 Equilibrium binding of the mutant RuvA (E55R D56K) protein to linear duplex and Holliday junction substrates The profiles shown were obtained by incorporating the mutant RuvA in the running buffer at concentrations of 0.064 n M (A), 0.64 n M (B), 6.4 n M (C) and 37 n M

(D) The arrows indicate the time at which the concentration of the protein was altered.

Table 3 Oligodeoxynucleotides.

Name Sequence (5¢-3¢)

ASP1 Bio-AATGCTACAGTATCGTCCGGTCACGTACAACATCCAG

ASP2 CTGGATGTTGTACGTGACCGGACGATACTGTAGCATT

DU1 Bio-GTACGAGCAGCTCCCGGGTCAGTCTGCCTA

DU2 TAGGCAGACTGACCCGGGAGCTGCTCGTAC

HJ5 Bio-AAAAATGGGTCAACGTGGGCAAAGATGTCCTAGCAATGTAATCGTCTATGACGTT HJ6 GTCGGATCCTCTAGACAGCTCCATGTTCACTGGCACTGGTAGAATTCGGC

HJ7 TGCCGAATTCTACCAGTGCCAGTGAAGGACATCTTTGCCCACGTTGACCC

HJ8 CAACGTCATAGACGATTACATTGCTACATGGAGCTGTCTAGAGGATCCGA

HJ4 Bio-AAAAAACCTACAACAGATCATGGAGCTTCT

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D I S C U S S I O N

Co-operative binding of RuvA tetramers to Holliday

junctions

The stoichiometry analysis presented here (see Table 1),

clearly shows that two RuvA tetramers bind to synthetic

Holliday junctions, which is in agreement with the crystal

structure obtained for the M leprae RuvA–Holliday

junc-tion complex [19] In this structure the two RuvA tetramers

make direct protein–protein contacts at four equivalent

points The protein–protein contacts involve side chain

interactions between the helix from residues 117–129 of an

A chain in one tetramer, with the same helix in a B chain on

the other tetramer A total of six ion-pair interactions are

formed at the helix–helix interface (see Fig 8) The residues

involved in protein–protein interactions are also conserved

in the E coli RuvA protein These protein–protein

interac-tions may be the source of the co-operativity proposed from

the binding profiles observed for E coli RuvA and synthetic

Holliday junctions presented here The two binding surfaces

of the Holliday junction are expected to bind to the RuvA

tetramers with different affinities: the binding surface of the

Holliday junction in the crystal structure obtained by

Hargreaves et al [18] is predicted to be the optimal binding

site The second RuvA tetramer that binds to the opposite

surface of the Holliday junction may bind with lower

affinity The results obtained from the equilibrium binding

profile of the interaction of RuvA with the Holliday

junction demonstrate that only a 10-fold increase in protein

concentration is required for the formation of a complex

with two RuvA tetramers bound to the Holliday junction

No intermediate is seen where equilibration is reached with

one RuvA tetramer bound to the Holliday junction This

suggests co-operativity in the binding of the tetramers,

which may involve protein-protein contacts between the

two tetramers, leading to a possible stabilization of the weaker binding RuvA tetramer

A model for the active RuvAB branch migration complex bound to the Holliday junction has been proposed [5,24] The complex comprises a central RuvA oligomer with RuvB hexameric rings bound to the duplex arms on opposite sides of the Holliday junction Roe et al [19] propose that the RuvB ATPase is anchored to the complex

to achieve maximum efficiency of branch migration, and this can only be achieved by the presence of two RuvA tetramers Our data suggest that two RuvA tetramers bind

to the Holliday junction in the absence of RuvB in a co-operative manner, with no observable intermediate con-taining one RuvA tetramer These data provide further evidence to support the formation of a RuvAB complex containing two RuvA tetramers which subsequently under-goes branch migration

Observation of a RuvAC–Holliday junction complex The formation of the RuvAC–Holliday junction complex,

in which one RuvA tetramer and one RuvC dimer are bound on opposite faces of the junction, is significant Its formation may represent an important stage in the trans-ition between RuvAB mediated branch migration and RuvC mediated cleavage Alternatively this structure could

be part of a larger RuvABC–junction complex The assembly of a RuvABC complex has been supported through various experiments [15,28,29] RuvBC promoted branch migration has been observed [29] providing addi-tional support for a RuvABC active complex However, formation of a RuvABC complex by displacement of a RuvA tetramer from the octameric RuvAB complex is not supported by our results Figure 5A demonstrates that there was no displacement of RuvA when RuvC was added to the octameric RuvA complex However the formation of a RuvABC complex after the formation of a RuvBC complex containing a single RuvC dimer is supported by the binding

of RuvA after the addition of RuvC to form a RuvAC complex (see Fig 5C) Eggleston et al [28] proposed that an equilibrium may exist between two types of complex: a RuvAB branch migration complex and a RuvABC branch migration/resolution complex

The charge on the central pin modulates DNA recognition

The SPR profiles reveal that E coli RuvA is a structure specific protein that binds with a much greater affinity to Holliday junctions compared to duplex DNA The E coli RuvA was demonstrated to target Holliday junctions 1000 times more efficiently than duplex DNA The mutant E coli RuvA (E55R D56K), which contains a positively charged pin region, binds to duplex DNA with high affinity These results are consistent with those obtained using gel retarda-tion assays, which demonstrated that the protein binds Holliday junctions with approximately the same affinity as

it binds duplex DNA [21] The SPR analysis shows that the mutant protein no longer binds to Holliday junctions in a structure specific manner but binds to the duplex arms of the junction (see Fig 7) The data also show that the pro-tein binds with a greater stoichiometry (five tetramers) compared to the binding of the wild-type E coli RuvA

Fig 8 Protein–protein interface in the structure of the M leprae RuvA

Holliday junction complex The side chains along the helices from 117

to 129 are shown with the A chain and B chain coloured gold and

purple, respectively The basic side chains are shown in blue, acidic in

red and hydrophobic in grey.

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(two tetramers) to Holliday junctions, indicating that more

than one tetramer or octamer binds to the DNA molecule

This suggests that the protein does not simply bind at the

ends of the duplex DNA arms but binds along the linear

duplex DNA across the central pin The formation of a

positive charge on the pin region also leads to a further

increase in affinity for duplex DNA There remains the

caveat that alteration of these amino acids may have

affected the conformation of this pin However, the mutant

protein was purified using the same procedure designed for

wild-type RuvA, indicating that the mutation caused little

effect on the overall structure of the protein [21] The overall

structure of the pin region, which exquisitely matches a

cavity of approximately 20 A˚ diameter at the center of the

junction, was expected to direct the structure specific

binding of the protein to the Holliday junction The

observed structural specificity seems to originate both from

the charge and the structure of the pin region However, the

charge carried by the pin region appears to have an equally

important role

Ingleston et al [21] demonstrated that the E55R D56K

mutant E coli protein was unable to block the activity of

RusA resolvase in vivo and inhibited junction resolution

and branch migration with respect to the wild-type RuvA

These data are consistent with the SPR analysis, which

indicates that the protein does not target Holliday

junctions, and multiple tetramers or octamers bind along

linear duplex DNA However, Ingleston et al [21] also

demonstrated that the E coli RuvA mutants with a more

positively charged pin were unable to promote repair

more efficiently than those with a more negative pin

Excluding the E55R D56K protein their results

demon-strated that the mutant proteins increased the rate of

branch migration in the RuvAB complex compared to the

wild-type RuvA The changes also reduced the ability to

stimulate RuvC in the RuvABC resolvasome It still

remains to be seen if the increased rate of branch

migration directly inhibits the ability of RuvC to perform

junction cleavage in the resolvasome complex Ingleston

et al had previously shown the RuvA mutants have an

increased rate of branch migration of the RuvAB complex

and in conjunction with the reduced ability to target

Holliday junctions this may explain the inability of the

mutant proteins to promote DNA repair

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

We thank the Wellcome Trust for the Prize Wellcome Studentship

awarded to Mark J Dickman and the Medical Research Council for

the programme Grant awarded to Robert G Lloyd and Gary J.

Sharples.

R E F E R E N C E S

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