Diamagnetic Metal Ions Research Articles

Dynamic nuclear polarization of (1)H, (13)C, and (59)Co in a tris(ethylenediamine)cobalt(III) crystalline lattice doped with Cr(III).

The study of inorganic crystalline materials by solid-state NMR spectroscopy is often complicated by the low sensitivity of heavy nuclei. However, these materials often contain or can be prepared with paramagnetic dopants without significantly affecting the structure of the crystalline host. Dynamic nuclear polarization (DNP) is generally capable of enhancing NMR signals by transferring the magnetization of unpaired electrons to the nuclei. Therefore, the NMR sensitivity in these paramagnetically doped crystals might be increased by DNP. In this paper we demonstrate the possibility of efficient DNP transfer in polycrystalline samples of [Co(en)3Cl3]2·NaCl·6H2O (en = ethylenediamine, C2H8N2) doped with Cr(III) in varying concentrations between 0.1 and 3 mol %. We demonstrate that 1H, 13C, and 59Co can be polarized by irradiation of Cr(III) with 140 GHz microwaves at a magnetic field of 5 T. We further explain our findings on the basis of electron paramagnetic resonance spectroscopy of the Cr(III) site and analysis of its temperature-dependent zero-field splitting, as well as the dependence of the DNP enhancement factor on the external magnetic field and microwave power. This first demonstration of DNP transfer from one paramagnetic metal ion to its diamagnetic host metal ion will pave the way for future applications of DNP in paramagnetically doped materials or metalloproteins.

Dinuclear, star-shaped tetranuclear and trinuclear-based two-dimensional metal complexes derived from a less investigated Schiff base ligand: Syntheses, crystal structures and spectroscopic correlation

The work in this paper deals with five new complexes of composition [CuII(MeCN)L(UVIO2)(NO3)2]⋅MeCN (1), [(CuIIL)3CdII](ClO4)2 (2) and [(CuIIL)2MII(μ1,5-dicyanamide)2]n (M=Co (3), M=Ni (4) and M=Zn (5)) derived from a single-compartment Schiff base ligand H2L, which is the [2+1] condensation product of salicylaldehyde and 1,4-diaminobutane. Single crystal X-ray structures of all the five complexes have been determined. Compound 1 is a diphenoxo-bridged CuII(UVIO2) system, compound 2 is a star-shaped tetranuclear system where the cadmium(II) center is encapsulated in between three [CuIIL] moieties and the three isomorphous compounds 3–5 are trinuclear CuIIMIICuII-based (M=Co, Ni, Zn) two-dimensional, square-grid systems where the trinuclear units are bridged by μ1,5-dicyanamide ligands. In addition to the exploration of much less investigated Schiff base ligand family having four carbon atoms between the two imine nitrogen atoms, the types of structures presented here either have some novelties or are new examples and therefore deserves importance. The d–d spectra of copper(II)-diamagnetic metal ion complexes (1, 2 and 5) and the corresponding mononuclear copper(II) compound have been recorded with the aim to shed light on the correlation of d–d band position with the displacement of copper(II) from the least-squares basal plane, revealing excellent correlation.

Enhancing the effective energy barrier of a Dy(III) SMM using a bridged diamagnetic Zn(II) ion.

Field induced single-molecule-magnet behaviour is observed for both a heterodinuclear [ZnDy(L(-))2](3+) complex (1) and a mononuclear [Dy(HL)2](3+) complex (2), with effective energy barriers of 83 cm(-1) and 16 cm(-1), respectively. Insights into the relaxation mechanism(s) and barrier heights are provided via ab initio and DFT calculations. Our findings reveal an interesting observation that the U(eff) of SMMs can be enhanced by incorporating diamagnetic metal ions.

The first tyrosyl radical intermediate formed in the S2-S3 transition of photosystem II.

The EPR "split signals" represent key intermediates of the S-state cycle where the redox active D1-Tyr161 (YZ) has been oxidized by the reaction center of the photosystem II enzyme to its tyrosyl radical form, but the successive oxidation of the Mn4CaO5 cluster has not yet occurred (SiYZ˙). Here we focus on the S2YZ˙ state, which is formed en route to the final metastable state of the catalyst, the S3 state, the state which immediately precedes O-O bond formation. Quantum chemical calculations demonstrate that both isomeric forms of the S2 state, the open and closed cubane isomers, can form states with an oxidized YZ˙ residue without prior deprotonation of the Mn4CaO5 cluster. The two forms are expected to lie close in energy and retain the electronic structure and magnetic topology of the corresponding S2 state of the inorganic core. As expected, tyrosine oxidation results in a proton shift towards His190. Analysis of the electronic rearrangements that occur upon formation of the tyrosyl radical suggests that a likely next step in the catalytic cycle is the deprotonation of a terminal water ligand (W1) of the Mn4CaO5 cluster. Diamagnetic metal ion substitution is used in our calculations to obtain the molecular g-tensor of YZ˙. It is known that the gx value is a sensitive probe not only of the extent of the proton shift between the tyrosine-histidine pair, but also of the polarization environment of the tyrosine, especially about the phenolic oxygen. It is shown for PSII that this environment is determined by the Ca(2+) ion, which locates two water molecules about the phenoxyl oxygen, indirectly modulating the oxidation potential of YZ.

DNA as sensors and imaging agents for metal ions.

Increasing interest in detecting metal ions in many chemical and biomedical fields has created demands for developing sensors and imaging agents for metal ions with high sensitivity and selectivity. This review covers recent progress in DNA-based sensors and imaging agents for metal ions. Through both combinatorial selection and rational design, a number of metal-ion-dependent DNAzymes and metal-ion-binding DNA structures that can selectively recognize specific metal ions have been obtained. By attachment of these DNA molecules with signal reporters such as fluorophores, chromophores, electrochemical tags, and Raman tags, a number of DNA-based sensors for both diamagnetic and paramagnetic metal ions have been developed for fluorescent, colorimetric, electrochemical, and surface Raman detection. These sensors are highly sensitive (with a detection limit down to 11 ppt) and selective (with selectivity up to millions-fold) toward specific metal ions. In addition, through further development to simplify the operation, such as the use of "dipstick tests", portable fluorometers, computer-readable disks, and widely available glucose meters, these sensors have been applied for on-site and real-time environmental monitoring and point-of-care medical diagnostics. The use of these sensors for in situ cellular imaging has also been reported. The generality of the combinatorial selection to obtain DNAzymes for almost any metal ion in any oxidation state and the ease of modification of the DNA with different signal reporters make DNA an emerging and promising class of molecules for metal-ion sensing and imaging in many fields of applications.

Magnetic Interactions Mediated by Diamagnetic Cations in [Mn18M] (M = Sr2+, Y3+, Cd2+, and Lu3+) Coordination Clusters

We previously reported how the synthesis of [Mn(III)12Mn(II)7(μ4-O)8(μ3-η(1)-N3)8(HL(1))12(MeCN)6]Cl2·10MeOH·MeCN (1), which has a Mn19 core corresponding to two supertetrahedral {Mn(II)4Mn(III)6} units sharing a common Mn(II) vertex, can be modified such that the central octacoordinate Mn(II) ion can be replaced by metal ions more likely to favor this coordination geometry such as Dy(III) as exemplified in the compound [Mn(III)12Mn(II)6Dy(III)(μ4-O)8(μ3-Cl)6.5(μ3-N3)1.5(HL)12(MeOH)6]Cl3·25MeOH (2). Here, we report a systematic survey of the effects of incorporating various diamagnetic metal ions M(n+) into this central position. We chose diamagnetic ions with electron configurations with fully occupied or completely empty frontier orbitals in order to gauge the effect on the overall magnetic behavior. The syntheses, structures, and magnetic properties of the heterometallic aggregates [Mn(III)12Mn(II)6Sr(II)(μ4-O)8(μ3-η(1)-N3)7.5(μ3-η(1)-Cl)0.5(HL(1))12(MeCN)6]Cl2·15MeOH (3), [Mn(III)12Mn(II)6Y(III)(μ4-O)8(μ3-η(1)-N3)8(HL(1))12(MeCN)6](NO3)3·11MeOH (4), [Mn(III)12Mn(II)6Cd(II)(μ4-O)8(μ3-η(1)-N3)6.8(μ3-η(1)-Cl)1.2(HL(1))12(MeCN)6](CdCl4)0.25Cl1.5·14.5MeOH (5), and [Mn(III)12Mn(II)6Lu(III)(μ4-O)8(μ3-η(1)-N3)6.5(μ3-η(1)-Cl)1.5(HL(2))12(MeCN)6]Cl3·3H2O·7MeOH·MeCN (6) (H3L(1) = 2,6-bis(hydroxymethyl)-4-methylphenol, H3L(2) = 2,6-bis(hydroxymethyl)-4-fluorophenol) are reported. The aggregates were prepared in one-pot self-assembly reactions of H3L(1) (or H3L(2)), MnCl2·4H2O or Mn(NO3)2·4H2O, NaOAc·3H2O or Et3N, and NaN3 in the presence of the appropriate diamagnetic metal salt in MeCN/MeOH mixtures. Compounds 3-6 crystallize isotypically to 1 in the trigonal space group R3 with Z = 3. The effects on the magnetic properties were investigated, paying attention to the presence of any weak coupling mediated by the diamagnetic cations between the two {Mn(II)3Mn(III)6} S = 39/2 subunits. In the Cd(2+) compound 5, the two {Mn(II)3Mn(III)6} units are magnetically isolated. In 3, 4, and 6, the diamagnetic Sr(2+), Y(3+), and Lu(3+) cations mediate weak antiferromagnetic interactions between the two {Mn(II)3Mn(III)6} subunits. DFT calculations show that the inter-{Mn(II)3Mn(III)6} interactions in the Mn18M systems are attributable to the electronic structure of the central diamagnetic cation, with systems containing trivalent central cations showing stronger antiferromagnetic interactions than those with isoelectronic divalent cations.

Ion-induced diversity in structure and magnetic properties of hexacyanometalate–lanthanide bimetallic assemblies

The reaction of trivalent DyIII/HoIII, 2,2′:6′,2′′-terpyridine (terpy), and hexacyanometallate [MIII(CN)6]3− (M = FeIII and CoIII) leads to the formation of a series of cyano-bridged complexes (1–4). In the case of DyIII, one-dimensional (1-D) alternating chains [DyIII(terpy)(DMF)2(H2O)2][MIII(CN)6]·3H2O (M = FeIII for 1 and CoIII for 2) were obtained, where each [MIII(CN)6]3− entity acts as a bis-monodentate bridging ligand towards two DyIII ions through two of its six cyanide groups in cis positions, respectively. Contrarily, in the case of HoIII, a molecular rectangle {[HoIII(terpy)(DMF)(H2O)2][MIII(CN)6]}2·nH2O·2CH3OH {(M = FeIII (3) and CoIII (4); and n = 6 or 7} has been formed although the synthesis method is same as for 1 and 2. Interestingly, solid-state direct-current magnetic susceptibility analyses demonstrate competing ferromagnetic interactions for 1 while complex 3 shows antiferromagnetic interactions. The variable-temperature magnetic behaviours observed for 2 and 4 only originate from isolated Dy and Ho ions, since a diamagnetic CoIII metal ion links the magnetic LnIII ions.

Insight into the Dynamics of Lanthanide-DTPA Complexes As Revealed by Oxygen-17 NMR

DTPA chelates of various diamagnetic and paramagnetic lanthanide(III) metal ions, as well as the chemically similar DTPA chelate of Y(3+), were studied in aqueous solution by variable temperature (17)O NMR with the aim of characterizing their internal dynamics. As a consequence of poor chemical shift dispersion and fast quadrupole relaxation, no dynamic exchange process could be detected for the diamagnetic complexes nor for the Sm-DTPA complex. In contrast, the spectra recorded for the Eu-DTPA complex show chemical exchange due to the well-known racemization process and, at high temperature, feature signal broadening that reveals a fluxional process involving the interchange of the coordinated and noncoordinated oxygen atoms of the carboxylate groups. The spectra recorded for the Pr-DTPA complex feature coalescence events due to such a fluxional process, which is ascribable to the rotation of the carboxylate groups. The activation free energy barriers determined experimentally are remarkably lower than the calculated activation barriers recently reported for the rotation of the carboxylate groups of various Ln-DOTA complexes. Furthermore, the smallest activation free energy measured for the Pr-DTPA complex, about 45 kJ mol(-1), is significantly lower than the activation free energy characterizing the racemization process. The fluxional behavior of the carboxylate groups is, however, not expected to significantly affect the residence time of the water molecule coordinated to the metal ion.

Photodegradation of selected β-blockers in aqueous fulvic acid solutions: Kinetics, mechanism, and product analysis

The photodegradation of the widely used β-blockers atenolol and metoprolol were investigated in the presence of fulvic acid (FA) under simulated sunlight. Both atenolol and metoprolol undergo indirect photodegradation in the FA solutions. The triplet excited state of FA (3FA∗) was verified to be main reactive species responsible for the photosensitized degradation of β-blockers. An electron transfer mechanism for the interaction between β-blockers and 3FA∗ was proposed on the basis of a series of experiments. Magnetic property of metal ions exhibited significant impact on photosensitized degradation. Diamagnetic metal ions such as Mg2+, Ca2+, Zn2+, and Al3+ negligibly affected the degradation. In contrast, paramagnetic metal ions including Mn2+, Cu2+, Fe3+, and Cr3+ markedly inhibited the reactions in the order of Cr3+ < Fe3+ < Cu2+ < Mn2+. The inhibition was related to the complexation ability with FA. By LC-ESI-MS/MS analysis, deisopropyl-atenolol (metoprolol) was identified as the main photosensitized product. The degradation pathways of β-blockers involving electron transfer processes were proposed. This finding strongly suggests that 3FA∗ was important reactive species for the degradation of β-blockers in natural waters.

Metal Complexes of Bridging Neutral Radical Ligands: pymDTDA and pymDSDA

Metal complexes of the 4-(2'-pyrimidyl)-1,2,3,5-dithiadiazolyl (pymDTDA) neutral radical ligand and its selenium analogue (pymDSDA) are presented. The following series of metal ions has been studied using M(hfac)(2) as the coordination fragment of choice (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato): Mn(II), Co(II), Ni(II), and Zn(II). The binuclear cobalt and nickel complexes of pymDTDA both exhibit ferromagnetic (FM) coupling between the unpaired electrons on the ligand and the metal ion, while the binuclear zinc complex of pymDTDA is presented as a comparative example incorporating a diamagnetic metal ion. The binuclear manganese complex of pymDTDA, reported in a preliminary communication, is compared to the pymDSDA analogue, and new insight into the magnetic behavior reveals that intermolecular magnetic coupling, mediated by chalcogen-oxygen contacts, gives rise to a significant increase in the χT product at low temperature. Surprisingly, the binuclear nickel complex of pymDSDA forms dimers in the solid state, as do the mononuclear complexes of cobalt and nickel with pymDTDA. In addition, mixed mononuclear/binuclear complexes of Mn- and Zn(pymDTDA) have been identified.

Spin Transition and Exchange Interaction: Janus Visions of Supramolecular Spin Coupling between Face‐to‐Face Verdazyl Radicals

Look both ways: Coordination bonding of verdazyl radicals to diamagnetic metal ions dramatically modifies the crystal packing of the electronic spin bearers. The face-to-face positioning of two radicals leads to a magnetic behavior that is more relevant to a S=0 to S=1 spin-transition phenomenon than to the usual exchange-interaction view.

Radical Stabilization in Dissolved Humates

Quinoid entities, in which quinone and hydroquinone groups equilibrate via a semiquinone radical intermediate, are a common structural feature in humic materials. The electron paramagnetic resonance (EPR) signals of these radicals are significantly enhanced in the presence of diamagnetic divalent metal ions such as Mg2+, while monovalent ions do not show the effect. The addition of trivalent ions leads to rapid precipitation, leaving little room for observation. It was noted that the metal ions producing EPR signal enhancement were also underwent effective bridging interactions with humic subunits, forming pseudomicellar structures. Particle growth determined through dynamic light scattering measurements coincided with the onset of EPR signal enhancement, and surface tension measurements further corroborated the coincidence of aggregation. The addition of a chaotrope (urea), which broke up the humic structures, eliminated the EPR signal increases. These observations strongly suggested that bridging interactions by divalent metal ions, and the intramo- lecular aggregation that accompanied it, led to significant stabilization of semiquinone radicals within the humic structure.

Metallation of pentaphyrin with Lu(III) dramatically increases reactive-oxygen species production and cell phototoxicity

Photodynamic therapy (PDT) is an emerging cancer treatment modality based on the excitation of a nontoxic photosensitizer with harmless visible light to produce reactive-oxygen species (ROS) that induce apoptosis and/or necrosis in cancer cells. As the efficacy of this therapy strongly depends of the nature of the photosensitizer, there is a great interest to develop new photoactive molecules. Here we report for the first time the synthesis, characterization and bioactivity of metal complexes between the non-aromatic expanded porphyrin, namely 20-[[4′-(Trimethylsilyl)ethoxycarbonyl]phenyl-2,13-dimethyl-3,12-diethyl-[24] iso-pentaphyrin (PCRed) and Zn(II) [Zn(II)–PCRed] or Lu(III) [Lu(III)–PCRed]. The complexation of these two diamagnetic heavy metal ions to PCRed improved the properties of the free photosensitizer as a PDT drug. We discovered that the 1:1 complex between PCRed and Lu(III) significantly increases the cellular uptake, ROS production and antiproliferative capacity in four cancer cell lines. Our study shows that metal complexation is a useful strategy to potentiate iso-pentaphyrin as a PDT drug.

Synthesis and Characterization of the Heptanuclear [MnIII 6 CoIII]3+ Triplesalen Complex: Evidence for Exchange Pathways Involving Low-spin CoIII

The reaction of the tert-butyl-substituted triplesalen ligand H6talent-Bu2 with MnII(OAc)2・ 4H2O and K3[CoIII(CN)6] results in the formation of the heptanuclear complex [{(talent-Bu2 )- (MnIII(MeOH))3}2{CoIII(CN)6}](PF6)2(OAc)・11MeOH ([MnIII 6 CoIII](PF6)2(OAc)・11MeOH, 1 ・11MeOH), which has been characterized by FT-IR spectroscopy, elemental analysis, ESI-MS, single-crystal X-ray diffraction, and magnetic measurements. The molecular structure of the [MnIII 6 CoIII]3+ complex is closely related to the already published analogs [MnIII 6CrIII]3+ and [MnIII 6 FeIII]3+. Variable-temperature variable-field and μeff vs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction, taking into account the relative orientation of the D tensors. This allowed a careful inspection of the MnIII-MnIII exchange interaction involving a diamagnetic central metal ion. A satisfactory reproduction of the magnetic data required the incorporation not only of an exchange interaction between the MnIII ions belonging to one triplesalen half unit, but also of an exchange coupling between MnIII ions belonging to different triplesalen subunits. Satisfactory reproduction of the experimental data has been obtained for the parameter set J1 = −(0.50±0.04) cm−1, J2 = +(0.05±0.02) cm−1, and D = −(2.5±0.5) cm−1. A detailed analysis of the J1 coupling taking into account the molecular structures of the three available heptanuclear complexes [MnIII 6MIII]3+ (M = Cr, Fe, Co) indicates that the exchange interaction between the MnIII ions belonging to the same triplesalen subunit involves not only an exchange pathway through the central phloroglucinol unit but also an exchange pathway through the central metal ion.

A homologous heterospin series of mononuclear lanthanide/TCNQF4 organic radical complexes

Reactions between trivalent rare earth ions (M(III) = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er and Yb) and the radical anion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF(4)) produce a family of mononuclear complexes {M[(TCNQF(4))](2)[H(2)O](x)}.(TCNQF(4))(3H(2)O), x = 6, 7. The cationic complex {M(III)([TCNQF(4)](-) )(2)[H(2)O](x)}(+) cocrystallizes with one [TCNQF(4)](-) radical anion and three water molecules. One of the coordinated [TCNQF(4)](-) radicals is involved in pi-pi stacking interactions with the uncoordinated [TCNQF(4)](-) radicals which leads to the antiferromagnetic coupling for these ((TCNQF(4))(2))(2-)pi-dimers. The second coordinated [TCNQF(4)](-) remains as a radical ligand and is not involved in pi-pi interactions. Magnetic studies indicate that the Sm compound magnetically orders at 4.4 K and that a fraction of the Gd and Dy samples undergo magnetic ordering at 3.7 K and 4.3 K respectively due to partial dehydration (loss of interstitial water molecules). Diamagnetic metal ions were used to generate magnetically dilute Gd, and Dy compounds that do not exhibit any signs of magnetic ordering.

Trigonal-Bipyramidal Metal Cyanide Complexes: A Versatile Platform for the Systematic Assessment of the Magnetic Properties of Prussian Blue Materials

Pentanuclear cyanide-bridged clusters of the general formula {[M(tmphen)(2)](3)[M'(CN)(6)](2)} (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been under investigation in our laboratories for a number of years. These related molecules are conveniently prepared by a building block approach that involves the reaction of mononuclear {M(tmphen)(2)X(2)}(0/2+) species (M = Cr, Mn, Fe, Co, Ni, Zn; X = anion, solvent) with [M'(CN)(6)](3-) anions (M' = Cr, Mn, Fe, Co, Os). The resulting trigonal-bipyramidal (TBP) clusters, consisting of M and M' centers in the equatorial and axial positions, respectively, exhibit diverse properties including those that had previously been observed only for Prussian blue extended phases; these properties include single-molecule magnetism, spin crossover, charge-transfer-induced spin transitions, cyanide linkage isomerism, and magnetic coupling through diamagnetic metal ions. Given that a series of clusters with identical axial cyanometallate units can be prepared, we have been able to establish trends in magnetic coupling for families of clusters with different equatorial metal ions. The crystal packing of the clusters, which involves supramolecular pi-stacking interactions, reveals the origin of the observed differences in the coordination environments and, in several cases, the physical properties of the metal ions in the equatorial sites. Recent work has focused on the use of these molecules as building blocks for magnetic chains and the incorporation of highly anisotropic 5d metal ions such as Os(III) into the TBP core. Such comprehensive studies of small clusters are valuable for understanding and modeling the magnetic behavior of more complicated cyanide materials.

Oxidation of oleuropein studied by EPR and spectrophotometry

AbstractThe autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg2+) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters Km = 0.34 ± 0.03 mM and Vmax = 0.029 ± 0.002 ΔA400 min–1 were determined for oleuropein.

Effect of the substituents on the spin coupling between iminosemiquinone π-radicals mediated by diamagnetic metal ions: l.s. Co(iii) vs Ga(iii)

Exchange coupling between the radical iminosemiquinone ligands changes from ferromagnetic to antiferromagnetic in l.s. Co(III) complexes, whereas the same coupling in Ga(III) complexes is always antiferromagnetic.

The chemistry, photophysics and photosensitizing properties of phthalocyanines.

Phthalocyanines (Pcs) and naphthalocyanines (Ncs) are being extensively studied as photosensitizers for photodynamic therapy (PDT) of cancer. They strongly absorb clinically useful red light, with maxima around 670 nm and 770 nm respectively. Chelated with appropriate diamagnetic metal ions, they exhibit high triplet yields and long triplet lifetimes. Energy transfer from the triplet dye to ground-state oxygen to yield singlet oxygen appears to be the main photosensitizing pathway in biological systems. Underivatized Pcs and Ncs can be incorporated in liposomes for in vivo administration. Sulphonation renders the dyes water soluble but also enhances dimerization to yield photochemically inactive aggregates. Tumour retention and cell membrane penetration of the dyes are strongly affected by the polarity of the macrocycle as well as the nature of the central metal ion and axial ligands. Among the sulphonated dyes, amphiphilic mono- and disulphonated derivatives exhibit particularly good cell membrane-penetrating properties, although the more highly sulphonated dyes show better tumour retention in vivo. At least in vitro, Pc dyes are more photoactive than the corresponding Nc dyes, which probably reflects the lower photostability of the latter.

A DNAzyme Catalytic Beacon Sensor for Paramagnetic Cu2+ Ions in Aqueous Solution with High Sensitivity and Selectivity

Copper is a key metal ion both in environment monitoring and in biology, and exposure to high concentration of copper can cause adverse health effects. Although significant progresses have been made in designing fluorescent sensors for diamagnetic metal ions, few effective Cu2+ sensors are known because of the paramagnetic nature of the metal ion. We herein report a highly sensitive and selective “turn-on” fluorescent Cu2+ sensor based on an in vitro selected DNAzyme (also known as catalytic DNA or deoxyribozyme). The substrate strand of the DNAzyme was labeled with a fluorophore on the 3‘-end and a quencher on the 5‘-end, and the enzyme strand was labeled with a second quencher on the 5‘-end. Initially, the fluorescence was quenched. Addition of Cu2+ induced oxidative cleavage of the substrate, and the fluorescence intensity increased by 13-fold. The sensor has a detection limit of 35 nM and a dynamic range up to 20 μM. The sensor selectivity is more than 2000-fold for Cu2+ over Fe2+ and UO22+ and more than 10 000-fold over any other metal ions. The DNAzyme catalytic beacon method demonstrated here can be applied to designing turn-on fluorescent sensors for other paramagnetic metal ions.