Tris Ruthenium Research Articles

A fluorescent chemosensor for cobalt ions based on a multi-substituted phenol-ruthenium(II) tris(bipyridine) complex

An amide-linked 2,6-bis{[(2-hydroxy-5- tert-butylbenzyl)(pyridyl-2-methyl)-amino]-methyl}-4-methylphenol-ruthenium(II) tris(bipyridine) 2PF 6 − complex, 1, was first used to recognize Co(II) in EtOH/H 2O (1:1, v/v) solution, with the ruthenium(II) tris(bipyridine) moiety selected as a fluorophore and the multi-substituted phenol unit chosen as a receptor. The fluorescence quenching of 1 was attributed to the formation of an inclusion complex between multi-substituted phenol unit and Co(II) by 1:1 complex ratio ( K = 2.5 × 10 5), which has been utilized as the basis of the fabrication of the Co(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Co(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Co(II) with a linear range covering from 1.0 × 10 −7 to 5.0 × 10 −5 M and a detection limit of 5 × 10 −8 M. The experiment results show that the response behavior of 1 to Co(II) is pH-independent in medium condition (pH 4.5–9.5) and show excellent selectivity for Co(II) over transition metal cations except Cu(II). The chemosensor has been used for determination of Co(II) in water samples.

Solar water disinfection by photocatalytic singlet oxygen production in heterogeneous medium

Water disinfection in isolated rural areas of less-developed countries poses specific problems since operational expenses must be low, chemicals are not easily deployable and qualification of operators is scarce. Therefore, alternative technologies to the widespread chlorination have been considered for household use. We have evaluated the viability of a photocatalytic process for bacteria inactivation with sunlight, affordable 0.8m2 compound parabolic collectors (CPC) and an UV–vis absorbing ruthenium (II) tris–chelate complex immobilised (2gm−2) onto porous silicone as singlet molecular oxygen generator. We have tested the efficiency of two CPC prototypes with different configuration of the photosensitising material, namely, a coaxial- and a fin-type one. Mineral water flowing at 2Lmin−1 and spiked with Escherichia coli or Enterococcus faecalis was subject to the photocatalytic treatment for 5h (a 0.6–0.8MJm−2L−1 dose of 360–700nm sunlight radiation at 40°N latitude). Using the fin-type reactor under these conditions, the bacterial survival for 104 to 102CFUmL−1 initial concentrations drop to ca. 1% and 0.1% for E. coli and E. faecalis, respectively. The average disinfection rates are similar with both photoreactor designs, regardless the bacteria used (ca. 2×104 and 2×106CFUL−1h−1 for the low and the high initial levels of bacteria, respectively). The novel systems are comparable to or better than solid-supported TiO2 photocatalysts at inactivating waterborne bacteria.

Luminescence lifetime-based carbon dioxide optical sensor for clinical applications

The development of both an optical planar and capillary based carbon dioxide sensor, which final aim is pCO 2 monitoring in adipose tissue of critically ill patients, is reported. The sensor is based on the measuring principle of phase fluorometry using a dual luminophore referencing scheme (DLR) to convert the CO 2 dependent intensity signal into phase domain. The CO 2 sensors have been prepared by incorporating two appropriate luminophores and a phase transfer agent in a same hydrophobic polymer as matrix. The short-lifetime luminophore used as pH indicator is 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS). The second inert luminophore is the long-lifetime dye Ruthenium(II) tris(4,7-diphenyl-1,10-phenanthroline) (Ru(dpp) 3 2+), which has been made insensitive to oxygen by immobilising in a suitable oxygen impermeable polymer. As phase transfer agent, tetraoctylammonium hydroxide (TOA-OH) has been chosen. Both sensor types have been characterised with respect to optimise sensitivity and mechanical stability. For this purpose, several polymers, such as ethylcellulose, eudragit RL100 (EG), copolymer eudragit/poly(ethylene glycol) (PEG) and silicone have been examined as appropriate matrix for incorporation of two indicators. The largest phase shift up to 13° and 15° has been observed in the case of silicone and copolymer EG/PEG, respectively, and they have been in detail examined in terms of sensitivity and stability. The presented sensors enable the measurement of pCO 2 in the range from 0 to 150 mmHg, with a resolution of 0.5 mmHg and an accuracy of ±1 mmHg absolute or less than 7% of the read-out value. All measurements have been carried out only in aqueous solutions before clinical measurements.

Photophysical Properties and Excitation Polarization offac/mer-Ruthenium Complexes with 5‘-Amino-2,2‘-bipyridine-5-carboxylic Acid Derivatives

Novel ruthenium(II) complexes, fac/mer-[Ru(MeCO-5Bpy-R)3]2+ (H-5Bpy-OH = 5'-amino-2,2'-bipyridine-5-carboxylic acid; R = -NHtBu, -NH(cHex), -N(cHex)2), have been synthesized. The fac and mer isomers have been successfully separated using HPLC techniques, and their photophysical/electrochemical properties have been investigated. In the absorption and emission spectra of fac/mer-[Ru(MeCO-5Bpy-R)3]2+ with secondary amines (R = -N(cHex)2) in acetonitrile at room temperature, the maximum wavelengths based on the MLCT are longer than those for the amide derivatives with primary amines (R = -NHtBu, -NH(cHex)). A small solvent effect on the photophysical properties between fac- and mer-[Ru(MeCO-5Bpy-NHtBu)3]2+ has been observed. The excitation polarization spectra, giving P values reflecting the relation between the absorption and the emission oscillators, for the fac- and mer-ruthenium(II) complexes (C3 and C1 symmetry, respectively) have been measured for the first time. Almost no difference in the excitation polarization spectra between the fac and mer complexes is found, and these spectra are similar to that for [Ru(bpy)3]2+ with D3 symmetry. This finding suggests that the orientations of the absorption and emission oscillators, in the case of the ruthenium(II) tris(2,2'-bipyridine) derivatives, would not be affected by the symmetries of the complexes and that the P values for any derivatives would be similar to that for [Ru(bpy)3]2+.

A novel ruthenium(II) tris(bipyridine)–zinc porphyrin–rhenium carbonyl triad: synthesis and optical properties

A novel ruthenium(II) tris(bipyridine)–zinc porphyrin–rhenium carbonyl triads and its free base porphyrin derivative were synthesized and characterized by 1H, 13C NMR, UV–vis, mass-spectrometry and elemental analysis. The redox potentials of the two compounds were measured and compared to their corresponding reference complexes. The fluorescence and transient absorption spectra of the two complexes revealed the features of two different pathways for possible photoinduced intramolecular electron transfer or energy transfer in the triads.

Competing through-space and through-bond, intramolecular triplet-energy transfer in a supposedly rigid ruthenium(ii) tris(2,2′-bipyridine)–fullerene molecular dyad

A ditopic ruthenium(II) tris(2,2'-bipyridyl)-based fullerene conjugate has been synthesized so as to separate the photoactive terminals by way of a short ethynylene spacer group that is expected to act as a rigid rod. Intramolecular triplet-energy transfer from the metal complex to the fullerene is quantitative at all temperatures and there is no indication for competing electron transfer. Temperature dependence studies indicate two pathways for triplet-energy transfer. An activationless route dominates at low temperature and is attributed to through-bond electron exchange that takes place via super-exchange interactions. The triplet energy of the bridging unit lies well above that of the metal complex. An activated process is switched-on at high temperatures and is believed to involve through-space electron exchange within closed conformations. Molecular dynamics simulations predict that, in addition to an extended conformation, the linker can distort in such a way that the terminals come into orbital contact. In fact, the resultant closed conformation possesses an idealised geometry for fast electron exchange.

The mechanism of long-range electron exchange in molecular-scale photonic wires

Several disparate systems have been examined as putative molecular-scale wires able to conduct charge over relatively long distances under illumination. The key feature of such systems concerns the level of electronic coupling between the terminals, which are themselves formed from photoactive metal poly(pyridine) complexes. In particular, a series of linear polynuclear ruthenium(II) tris(2,2'-bipyridine) complexes has been synthesized whereby individual chromophores are separated by 1,4-diethynylenebenzene subunits bearing dialkoxy groups for improved solubility. These arrays contain two, three, four five metal centres. The compounds are reasonably soluble in polar organic solvents and possess optical absorption spectral properties that are dominated by transitions associated with the polytopic ligand. Weak luminescence is observed for each complex in deoxygenated acetonitrile at room temperature that appears to be characteristic of emission from a metal-to-ligand, charge-transfer triplet state. The emission lifetime is essentially independent of temperature, at least over a modest range. There is no indication for interaction between close-lying triplet states and no obvious sign of a low-energy pi,pi* triplet associated with the polytopic ligand. The photophysical properties suggest, however, that the longer arrays are segmented due to intramolecular charge-transfer interactions. The ligands bind zinc(II) cations in solution and thereby affect the absorption and emission spectra.

Luminescence temperature sensing using poly(vinyl alcohol)-encapsulated Ru(bpy)32+ films

The ruthenium(II) diimine complexes, such as ruthenium(II) tris(bipyridyl), Ru(bpy)3 2+, possess highly luminescent excited states that are not only readily quenched by oxygen but also by an increase in temperature. The former effect can be rendered insignificant by encapsulating the complex in an oxygen impermeable polymer, although encapsulation often leads also to a loss of temperature sensitivity. The luminescence properties of Ru(bpy)3 2+ encapsulated in PVA were studied as a function of oxygen concentration and temperature and found to be independent of the former, but still very sensitive towards the latter. The results were fitted to an established Arrhenius-type equation, based on thermal quenching of the emitting state by a slightly higher (DeltaE= 3100 cm(-1))3d-d state that deactivates very rapidly (10(-13) s)via a non-radiative process.

Optical imaging in microfluidic bioreactors enables oxygen monitoring for continuous cell culture

For the first time, a fluorescence lifetime calibration method for an oxygen-sensitive dye ruthenium tris(2,2'-dipyridyl) dichloride hexahydrate (RTDP) is applied to image oxygen levels in poly(dimethyl siloxane) (PDMS) bioreactors containing living C2C12 mouse myoblasts. PDMS microsystems are broadly used in bioengineering applications due to their biocompatibility and ease of handling. For these systems, oxygen concentrations are of significance and are likely to play an important role in cell behavior and gene expression. Fluorescence lifetime imaging microscopy (FLIM) bases image contrast on fluorophore excited state lifetimes, which reflect local biochemistry. Unique attributes of the widefield, time-domain FLIM system include tunable excitation (337.1 to 960 nm), large temporal dynamic range (> or =600 ps), high spatial resolution (1.4 microm), calibrated detection (0 to 300+/-8 microM of oxygen), and rapid data acquisition and processing times (10 s). Oxygen levels decrease with increasing cell densities and are consistent with model outcomes obtained by simulating bioreactor oxygen diffusion and cell proliferation. In single bioreactor loops, FLIM detects spatial heterogeneity in oxygen levels with variations as high as 20%. The fluorescence lifetime-based imaging approach we describe avoids intensity-based artifacts (including photobleaching and concentration variations) and provides a technique with high spatial discrimination for oxygen monitoring in continuous cell culture systems.

A star-shaped ruthenium complex with five ferrocenyl-terminated arms bridged by trans-platinum fragments

We present the synthesis of the new heteropolytopic penta(4-ethynylphenyl)cyclopentadiene ligand, its complexation through the Cp ring to ruthenium tris(indazolyl)borate and through the terminal alkyne groups to five ferrocenyl ethynyl platinum units, yielding an undecanuclear heterotrimetallic complex.

(Strept)avidin as Host for Biotinylated Coordination Complexes: Stability, Chiral Discrimination, and Cooperativity

Incorporation of a biotinylated ruthenium tris(bipyridine) [Ru(bpy)(2)(Biot-bpy)](2+) (1) in either avidin or streptavidin-(strept)avidin-can be conveniently followed by circular dichroism spectroscopy. To determine the stepwise association constants, cooperativity, and chiral discrimination properties, diastereopure (Lambda and Delta)-1 species were synthesized and incorporated in tetrameric (strept)avidin to afford (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin, and (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin (x = 1-4) For these four systems, the overall stability constants are log beta(4) = 28.6, 30.3, 36.2, and 36.4, respectively. Critical analysis of the CD titrations data suggests a strong cooperativity between the first and the second binding event (x = 1, 2) and a pronounced difference in affinity between avidin and streptavidin for the dicationic guest 1 as well as modest enantiodiscrimination properties with avidin as host.

Photoelectrochemical Oxidation of DNA by Ruthenium Tris(bipyridine) on a Tin Oxide Nanoparticle Electrode

Selective photoelectrochemical oxidation of DNA was achieved by ruthenium tris(bipyridine) immobilized on a tin oxide nanoparticle electrode. The metal complex was covalently attached to a protein, avidin, which adsorbed strongly on the tin oxide electrode by electrostatic interaction. Upon irradiation with 473-nm light, anodic photocurrent was generated in a blank electrolyte and was enhanced significantly after addition of poly(guanadylic acid) (poly-G) into the electrolyte. The current increased progressively with the nucleotide concentration, suggesting the enhancement effect was related to poly-G. The action spectrum indicates that the photocurrent was initiated by light absorption of the ruthenium compound immobilized on the electrode. Among the various polynucleotides examined, poly-G produced the largest photocurrent increase, followed by poly-A, single-stranded DNA, chemically damaged DNA, and double-stranded DNA, whereas poly-C and poly-U showed little effect. The combined experimental data support the hypothesis that the photoexcited Ru2+ species injects an electron into the semiconductor and produces Ru3+, which is then reduced back to Ru2+ by guanine and adenine bases in DNA, resulting in the recycling of the metal complex and enhanced photocurrent. The photoelectrochemical reaction can be employed as a new method for the detection of DNA damage.

Tailored amphiphilic star‐shaped light‐harvesting copolymers

AbstractAmphiphilic star‐shaped light‐harvesting copolymers comprising six diblock arms of styryl coumarin (St‐Coumarin) and N‐isopropylacrylamide (NIPAM) surrounding a ruthenium(II) tris(bipyridyl) energy‐trap core have been synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The mechanism of excitation energy transfer (EET) from initially excited St‐Coumarin chromophores to the Ru(II) trap has been investigated and is concluded to occur mainly through a single‐step induced dipole–dipole process. Incorporation of the NIPAM sequences results in enhanced EET efficiencies and confers water solubility to the polymers. The photophysical behavior of the copolymers is reported; marked differences are exhibited in aqueous solution when compared to organic solutions. Copyright © 2005 Society of Chemical Industry

Effects of thermal oxidation conditions of silicon electrodes on cathodic electrochemiluminescence of Ru(bpy) 32+ chelate

Hot electrons emitted from thin oxide film-coated heavily doped silicon electrodes by cathodic pulse polarization can induce electrochemiluminescence from luminophores. The intensity of electrochemiluminescence produced at the electrode surface is dependent on the features of thin oxide films formed by thermal oxidation. As a preliminary study, we investigated the effect of thermal oxide growth conditions on the intensity of electrochemiluminescence produced at these electrodes, such as oxidation atmospheres, oxidation temperature, oxidation time and pre-treatment of wafers, using ruthenium(II) tris-(2,2′-bipyridine) chelate as a model luminophore. Optimal oxidation conditions of heavily doped silicon electrodes were obtained for the generation of intense electrochemiluminescence at this kind of silicon electrodes.

Photophysical Properties of Ruthenium(II) Tris(2,2‘-Bipyridine) and Europium(III) Hexahydrate Salts Assembled into Sol−Gel Materials

A series of luminescent sol−gel-encapsulated Ru(bpy)3Cl2·6H2O and EuCl3·6H2O mixtures with Zn(NO3)2·6H2O were assembled and characterized in terms of their steady-state and time-dependent photophysical properties. UV−vis absorption, steady-state emission, and FT-IR spectra were measured for the materials both in rigid and fluid media. Time-resolved luminescence measurements were also performed in order to determine radiative decay times. The samples described in this study were prepared without the addition of excess water. This was achieved by allowing the hydrolysis and condensation reactions to only consume hydration water, thus utilizing the metal salts as reactants rather than passive dopants in the system. By using this approach, the amount of hydroxyl quenchers is minimized, which can be expected to yield luminescent materials with higher luminescence quantum yields than a conventional sol−gel entrapment procedure. The emission bands of both chromophores studied here, Ru(bpy)32+ and Eu3+, were found to exhibit higher emission intensities, hypsochromic shifts in the emission bands, and increased decay times upon sol-to-gel conversion, which can be attributed to rigidochromism. In the case of sol−gel-encapsulated Ru(bpy)32+, the complexes are thought to be surrounded by solvent molecules that interact with the silanol groups of the gel network. Thus, the Franck−Condon excited state of the complex is relaxed to a lesser extent, giving rise to the observed hypsochromic shift of the luminescence associated with the materials upon sol-to-gel conversion. A similar mechanism is proposed to be in effect for the Eu3+-functionalized materials.

Platinum Chromophore-Based Systems for Photoinduced Charge Separation: A Molecular Design Approach for Artificial Photosynthesis

Photoinduced charge separation is a fundamental step in photochemical energy conversion. In the design of molecularly based systems for light-to-chemical energy conversion, this step is studied through the construction of two- and three-component systems (dyads and triads) having suitable electron donor and acceptor moieties placed at specific positions on a charge-transfer chromophore. The most extensively studied chromophores in this regard are ruthenium(II) tris(diimine) systems with a common 3MLCT excited state, as well as related ruthenium(II) bis(terpyridyl) systems. This Forum contribution focuses on dyads and triads of an alternative chromophore, namely, platinum(II) di- and triimine systems having acetylide ligands. These d8 chromophores all possess a 3MLCT excited state in which the lowest unoccupied molecular orbital is a pi orbital on the heterocyclic aromatic ligand. The excited-state energies of these Pt(II) chromophores are generally higher than those found for the ruthenium(II) tris(diimine) systems, and the directionality of the charge transfer is more certain. The first platinum diimine bis(arylacetylide) triad, constructed by attaching phenothiazene donors to the arylacetylide ligands and a nitrophenyl acceptor to 5-ethynylphenanthroline of the chromophore, exhibited a charge-separated state of 75-ns duration. The first Pt(tpy)(arylacetylide)+-based triad contains a trimethoxybenzamide donor and a pyridinium acceptor and has been structurally characterized. The triad has an edge-to-edge separation between donor and acceptor fragments of 27.95 Angstroms. However, while quenching of the emission is complete for this system, transient absorption (TA) studies reveal that charge transfer does not move onto the pyridinium acceptor. A new set of triads described in detail here and having the formula [Pt(NO2phtpy)(p-C triple-bond C-C6H4CH2(PTZ-R)](PF6), where NO2phtpy = 4'-{4-[2-(4-nitrophenyl)vinyl]phenyl}-2,2';6',2''-terpyridine and PTZ = phenothiazine with R = H, OMe, possess an unsaturated linkage between the chromophore and a nitrophenyl acceptor. While the parent chromophore [Pt(ttpy)(C triple-bond CC6H5)]PF6 is brightly luminescent in a fluid solution at 298 K, the triads exhibit complete quenching of the emission, as do the related donor-chromophore (D-C) dyads. Electrochemically, the triads and D-C dyads exhibit a quasi-reversible oxidation wave corresponding to the PTZ ligand, while the R = H triad and related C-A dyad display a facile quasi-reversible reduction assignable to the acceptor. TA spectroscopy shows that one of the triads possesses a long-lived charge-separated state of approximately 230 ns.

Reversible Colorimetric Probes for Mercury Sensing

The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions.

Hydroxyl radical-related electrogenerated chemiluminescence reaction for a ruthenium tris(2,2′)bipyridyl/co-reactants system at boron-doped diamond electrodes

An electrogenerated chemiluminescence (ECL) reaction of the Ru(bpy) 3 2+ (2,2′-bipyridyl, bpy)/co-reactant system in the extremely high-potential region (over 2.6 V versus Ag/AgCl) was probed using a boron-doped diamond (BDD) electrode. At the BDD electrode, three ECL waves (1.25, 2.30 and 3.72 V) were observed in cyclic voltammograms for 20 mM ascorbic acid (AA). For the ECL peaks observed at 1.25 V corresponding to the oxidation potential for Ru(bpy) 3 2+ (1.15 V), the light intensities and current densities were found to depend on the square root of the AA concentration. This suggests that AA oxidation, followed by the formation of the reducing radical that is necessary for generating the excited state of Ru(bpy) 3 2+* occurred through homogeneous electron-transfer between Ru(bpy) 3 3+ and the AA species. However, for the ECL peaks at 2.30 V, the current densities and light intensities linearly increased with increasing AA concentration, suggesting that the reducing radical was formed through the direct oxidation at the electrode surface. The ECL reaction at 3.72 V was observed only at the BDD electrode and not at other electrodes. The onset potentials for the light intensity were approximately 2.6 V, independently of the type of the co-reactants (e.g. 2-propanol and AA). The peak potentials exhibited linear relation with the co-reactant concentration. In the analysis of the ECL intensity for various co-reactants (alcohols) that show different reactivity for the hydrogen abstraction reaction, the order of the light intensities at the peaks for alcohols was found to be consistent with that for the rate constants of the hydrogen abstraction reaction. These results indicate that the co-reactant radical was formed through the hydrogen abstraction reaction with the hydroxyl radical (HO ) generated during the oxygen evolution reaction.

A composite thin film optical sensor for dissolved oxygen in contaminated aqueous environments

A robust optical composite thin film dissolved oxygen sensor was fabricated by ionically trapping the dye ruthenium(II) tris(4,7-diphenyl-1,10-phenanthroline) dichloride in a blended fluoropolymer matrix consisting of Nafion ® and Aflas ®. Strong phosphorescence, which was strongly quenched by dissolved oxygen (DO), was observed when the sensor was immersed in water. The sensor was robust, optically transparent, with good mechanical properties. Fast response, of a few seconds, coupled with sensitivity of about 0.1 mg L −1 (DO) over the range 0–30 mg L −1 and resistance to leaching, were also exhibited by this system. The Stern–Volmer (SV) plot exhibited slight downward turning at all oxygen concentrations. A linear plot was obtained when the SV equation was modified to account for the varying sensitivity of dye molecules in the matrix to the quencher. Good long term stability was observed.

DNA Mismatch Detection by Resonance Energy Transfer between Ruthenium(II) and Osmium(II) Tris(2,2‘-bipyridyl) Chromophores

Octahedral tris-chelate complexes [M(II)(bpy)(3)](2+) (M = Ru or Os, bpy = 2,2'-bipyridyl), covalently attached to the 3'- and 5'-phosphates of two oligonucleotides, are juxtaposed when hybridized contiguously to a fully complementary DNA target. Visible metal-to-ligand charge-transfer (MLCT) excitation of the [Ru(II)(bpy)(3)](2+) unit leads to resonance energy transfer to the MLCT state of the [Os(II)(bpy)(3)](2+) moiety, with the energy transfer efficiency depending on the degree of hybridization. The extent of attenuation of the intense red luminescence from the Ru(II) chromophore hence allows highly sensitive structural probing of the assembly and constitutes a novel approach to DNA sensing which is capable of detecting mutations.