- DNA interaction and photonicking properties of DNA-targeted acridine (2,2′-bipyridine)platinum(II) complexes
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Synthesis of two (2,2′-bipyridine)platinum(II) complexes tethered to one or two acridine chromophores is reported. These acridine complexes efficiently unwind and photocleave supercoiled plasmid DNA under physiological conditions of temperature and pH.
- Gude, Lourdes,Fernandez, Maria-Jose,Grant, Kathryn B,Lorente, Antonio
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- Chromium(VI) oxide-mediated oxidation of polyalkyl-polypyridines to polypyridine-polycarboxylic acids with periodic acid
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4,4′-Dicarboxy-2,2′-bipyridine was synthesized quantitatively by chromium(VI) oxide-mediated oxidation of 4,4′-dimethyl-2,2′-bipyridine or 4,4′-diethyl-2,2′-bipyridine with periodic acid as the terminal oxidant in sulfuric acid. 5,5′-Dicarboxy-2,2′-bipyridine and 6,6’-dicarboxy-2,2′-bipyridine were also synthesized by the method from the corresponding dimethyl bipyridines in excellent yields. 4,4′,4″-Tricarboxy-2,2′:6′,2″-terpyridine was obtained in 80% yield from 4,4′,4″-triethyl-2,2′:6′,2″-terpyridine, and 4,4′,4″,4′″-tetracarboxy-2,2′:6′,2″:6″,2′″-quaterpyridine was obtained in 72% yield from 4,4′,4″,4′″-tetraethyl-2,2′:6′,2″:6″,2′″-quaterpyridine by the same procedure.
- Yamazaki, Shigekazu
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- Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs
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The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in neoplastic cell lines.
- Martínez, Mángeles,Carranza, M. Pilar,Massaguer, Anna,Santos, Lucia,Organero, Juan A.,Aliende, Cristina,De Llorens, Rafael,Ng-Choi, Iteng,Feliu, Lidia,Planas, Marta,Rodríguez, Ana M.,Manzano, Blanca R.,Espino, Gustavo,Jalón, Félix A.
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- Synthesis and electrocatalytic water oxidation by electrode-bound helical peptide chromophore-catalyst assemblies
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Artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells requires the assembly of a chromophore and catalyst in close proximity on the surface of a transparent, high band gap oxide semiconductor for integrated light absorption and catalysis. While there are a number of approaches to assemble mixtures of chromophores and catalysts on a surface for use in artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells, the synthesis of discrete surface-bound chromophore-catalyst conjugates is a challenging task with few examples to date. Herein, a versatile synthetic approach and electrochemical characterization of a series of oligoproline-based light-harvesting chromophore-water-oxidation catalyst assemblies is described. This approach combines solid-phase peptide synthesis for systematic variation of the backbone, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) as an orthogonal approach to install the chromophore, and assembly of the water-oxidation catalyst in the final step. Importantly, the catalyst was found to be incompatible with the conditions both for amide bond formation and for the CuAAC reaction. The modular nature of the synthesis with late-stage assembly of the catalyst allows for systematic variation in the spatial arrangement of light-harvesting chromophore and water-oxidation catalyst and the role of intrastrand distance on chromophore-catalyst assembly properties. Controlled potential electrolysis experiments verified that the surface-bound assemblies function as water-oxidation electrocatalysts, and electrochemical kinetics data demonstrate that the assemblies exhibit greater than 10-fold rate enhancements compared to the homogeneous catalyst alone.
- Ryan, Derek M.,Coggins, Michael K.,Concepcion, Javier J.,Ashford, Dennis L.,Fang, Zhen,Alibabaei, Leila,Ma, Da,Meyer, Thomas J.,Waters, Marcey L.
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- A Multi-action and Multi-target RuII–PtIV Conjugate Combining Cancer-Activated Chemotherapy and Photodynamic Therapy to Overcome Drug Resistant Cancers
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PtII complexes are commonly used to treat cancer. To reduce their side effects and improve their pharmacological properties, PtIV complexes are being developed as prodrug candidates that are activated by reduction in cancer cells. Concomitantly, RuII polypyridine complexes have gained much attention as photosensitizers for use in photodynamic therapy due to their attractive characteristics. In this article, a novel PtIV–RuII conjugate, which combines cancer activated chemotherapy with PDT, is presented. Upon entering the cancer cell, the PtIV centre is reduced to PtII and the axial ligands including the RuII complex and phenylbutyrate are released. As each component has its individual targets, the conjugate exerts a multi-target and multi-action effect with (photo-)cytotoxicity values upon irradiation up to 595 nm in the low nanomolar range in various (drug resistant) 2D monolayer cancer cells and 3D multicellular tumour spheroids.
- Gasser, Gilles,Gibson, Dan,Karges, Johannes,Tharaud, Micka?l,Yempala, Thirumal
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- Preparing a highly dispersed catalyst supported on mesoporous microspheres: Via the self-assembly of amphiphilic ligands for the recovery of ultrahigh concentration wastewater
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A highly dispersed catalyst supported on mesoporous microspheres was prepared via the self-assembly of amphiphilic ligands. In a mixed solvent of water and ethanol, mesoporous microspheres were fabricated using bipyridine-based amphiphilic molecules as structure-directing agents for self-assembly with tetraethoxysilane. The microspheres had an average diameter of 979 nm, and their surface area and pore size were 720 m2 g-1 and 2.86 nm, respectively. Solid-state nuclear magnetic resonance characterization revealed the synthesized mesoporous microspheres display a special coordination effect with ferrous ions. Transmission electron microscopy analysis and energy-dispersive X-ray spectroscopy element mapping indicated that iron oxide was highly decentralized in the mesoporous microspheres after calcination in an O2 atmosphere. Loading iron oxide onto the mesoporous material via the impregnation method produced a completely different effect, with the iron oxide particles larger outside the mesoporous channels. The activity of the obtained catalyst was investigated using a Fenton reaction. In this reaction, the synthesized highly dispersed catalyst displayed strong catalytic activity in dye degradation, even when the dye concentration was as high as 400 ppm. The dye was almost entirely removed within 6 h, and the catalyst could be reused many times.
- Tao, Shengyang,Chen, Yandong,Wang, Huan,Qiu, Jieshan,Wang, Xinkui
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- Detection of NaCN in aqueous media using a calixarene-based fluoroionophore containing ruthenium(ii)-bipyridine as the fluorogenic unit
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A new molecular sensor containing calixarene and ruthenium(ii)-bipyridine as the fluorophore bridged by an amide moiety has been synthesised and characterized, and its anion binding properties have been investigated. It selectively detected cyanide in 95:5 water:acetonitrile when sodium salts of various anions such as F-, Cl-, Br-, I-, PO42-, IO4-, BO3-, CH3COO-, CN- and SO42- were investigated. The recognition event was monitored by fluorescence spectroscopy and the lower detection limit found was 70 ppb. However, when tetrabutylammonium salts of the same anions were used then, in addition to CN-, CH3COO- was also detected under similar experimental conditions. Interestingly, CN- exhibited substantial quenching, whereas CH3COO- showed an enhancement in emission intensity. The interaction of anions with the fluoroionophore was also monitored by electrochemical technique and the result obtained is consistent to that found by fluorogenic method. Binding constants were determined from emission titration, composition of the anion-complexes formed were determined from mass and emission titration data, mechanistic aspects of the interaction have been discussed with the aid of NMR data and the role of cations in the contrast fluorescent off and on behaviour has also been discussed. This sensor has also been used to estimate cyanide in real samples and the result obtained is satisfactory. This journal is
- Maity, Debdeep,Vyas, Gaurav,Bhatt, Madhuri,Paul, Parimal
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- Synthesis and photophysical properties of kinetically stable complexes containing a lanthanide ion and a transition metal antenna group
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A series of bimetallic complexes has been prepared in which an octadentate DOTA-monoamide pocket containing a bound lanthanide ion is linked covalently to a ReI or RuII bipyridyl unit via an alkyl spacer group. The transition metal chromophores incorporated in this way act as effective sensitisers for lanthanide-centred luminescence. The rate and efficiency of energy transfer are dependent upon the nature of the spacer group, and upon the nature of the lanthanide acceptor. For the RuNd diad, there is a long rise-time associated with the energy-transfer step, such that energy transfer is rate determining in H2O, but not in D2O. The results also lead us to suggest that energy transfer may precede formation of the 3M(Ru/Re)L(bpy)CT state and may be a competitive deactivation pathway for the precursor state (1M (Ru/Re)L(bpy)CT). The Royal Society of Chemistry 2010.
- Perry, William S.,Pope, Simon J. A.,Allain, Clemence,Coe, Benjamin J.,Kenwright, Alan M.,Faulkner, Stephen
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- Shallow Distance Dependence for Proton-Coupled Tyrosine Oxidation in Oligoproline Peptides
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We have explored the kinetic effect of increasing electron transfer (ET) distance in a biomimetic, proton-coupled electron-transfer (PCET) system. Biological ET often occurs simultaneously with proton transfer (PT) in order to avoid the high-energy, charged intermediates resulting from the stepwise transfer of protons and electrons. These concerted proton-electron-transfer (CPET) reactions are implicated in numerous biological ET pathways. In many cases, PT is coupled to long-range ET. While many studies have shown that the rate of ET is sensitive to the distance between the electron donor and acceptor, extensions to biological CPET reactions are sparse. The possibility of a unique ET distance dependence for CPET reactions deserves further exploration, as this could have implications for how we understand biological ET. We therefore explored the ET distance dependence for the CPET oxidation of tyrosine in a model system. We prepared a series of metallopeptides with a tyrosine separated from a Ru(bpy)32+ complex by an oligoproline bridge of increasing length. Rate constants for intramolecular tyrosine oxidation were measured using the flash-quench transient absorption technique in aqueous solutions. The rate constants for tyrosine oxidation decreased by 125-fold with three added proline residues between tyrosine and the oxidant. By comparison, related intramolecular ET rate constants in very similar constructs were reported to decrease by 4-5 orders of magnitude over the same number of prolines. The observed shallow distance dependence for tyrosine oxidation is proposed to originate in part from the requirement for stronger oxidants, leading to a smaller hole-transfer effective tunneling barrier height. The shallow distance dependence observed here and extensions to distance-dependent CPET reactions have potential implications for long-range charge transfers.
- Koronkiewicz, Brian,Swierk, John,Regan, Kevin,Mayer, James M.
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- DNA Oligomers and Duplexes Containing a Covalently Attached Derivative of Tris(2,2'-bipyridine)ruthenium(II): Synthesis and Characterization by Thermodynamic and Optical Spectroscopic Measurements
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Oligonucleotides having the base sequence 5'-GCA(C*)TCAG-3' and 5'-GCAC(T*)CAG-3' were synthesized where C* and T* equal, respectively, a chemical modified cytidine or thymidine base containing a linker arm terminating in a primary amine.The primary amine of these modified oligomers reacted specifically with the N-hydroxysuccinimide ester of 4-carboxy-4'-methyl-2,2'-bipyridine to form bipyridine-labeled oligomers, and these oligomers reacted with Ru(bpy)2(H2O)2(2+) to give oligonucleotides with covalently attached derivatives of Ru(bpy)3(2+).Oligonucleotideswith nonspecifically bound Ru(bpy)2(H2O)x(2+), where x=0 or 1, were also formed, but were chromatographically separated from the former product.Duplexes of the Ru(bpy)3(2+)-labeled oligonucleotides were formed upon addition of their unmodified complementary strands and were studied by melting temperature behavior as a function of concentration and by absorption and emission optical spectroscopies.Both hybridization behavior and the spectroscopic properties of the ruthenium label itself were retained in these labeled duplexes.This work shows that it is possible to use DNA duplexes as molecular scaffolds to organize covalently attached polypyridyl-substituted transition-metal complexes and constitutes an initial step in the construction of macromolecules with specifically located, redox-active subunits.
- Telser, Joshua,Cruickshank, Kenneth A.,Schanze, Kirk S.,Netzel, Thomas L.
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- Photosensitization of novel ruthenium-functionalized photoconductive polymers: Effect of ruthenium complex as photosensitizer
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Owing to their efficient photo-charge generation, ruthenium derivatives are emerging as an important class of photosensitizers. Despite their promising characteristics, several deficiencies, such as the relatively low quantum yield and short lifetime of t
- Moon, Jong-Sik,Kim, Chuntae,Kim, Won-Geun,Kim, Inhong,Kyhm, Kwangseuk,Oh, Jin-Woo,Kim, Nakjoong
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- Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex
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A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pKa units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.
- Lennox, J. Christian,Dempsey, Jillian L.
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- Synthesis and characterization of oligoproline-based molecular assemblies for light harvesting
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Helical oligoproline arrays provide a structurally well-defined environment for building photochemical energy conversion assemblies. The use of solid-phase peptide synthesis (SPPS) to prepare four such arrays, consisting of 16, 17, 18, and 19 amino acid residues, is described here. Each array contains the chromophore [Rub′2m](PF6)2 (b′ = 4,4′-diethylamidocarbonyl-2,2′-bipyridine; m = 4-methyl-2,2′- dipyridine-4′-carboxylic acid) and the electron transfer donor PTZ (phenothiazine). The arrays differ systematically in the distance between the redox-active metal complex and PTZ sites. They have been used in photophysical studies to provide insight into the distance dependence of electron transfer. (J. Am. Chem. Soc. 2004, 126, 14506-14514). This work describes the synthesis, purification, and characterization of the oligoproline arrays, including a general procedure for the synthesis of related arrays.
- Aldridge III, W. Steven,Hornstein, Brooks J.,Serron, Scafford,Dattelbaum, Dana M.,Schoonover, Jon R.,Meyer, Thomas J.
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- 4'-Aminomethyl-2,2'-bipyridyl-4-carboxylic acid (Abc) and related derivatives: Novel bipyridine amino acids for the solid-phase incorporation of a metal coordination site within a peptide backbone
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The novel bipyridyl amino acid, 4'-aminomethyl-2,2'-bipyridyl-4- carboxylic acid (Abc), and related Boc- and Fmoc-protected derivatives were synthesized to provide high-affinity bidentate metal-binding amino acid modules for the solid-phase peptide synthesis (SPPS) of metallopeptides. Since the bipyridyl group of Abc is inserted into the peptide mainchain and not in the sidechain, its presence in a peptide should impart distinct conformational constraints to the backbone geometry, influencing local secondary structure. To demonstrate its amenability for SPPS and its capacity for metal complexation, Abc was incorporated into the hexapeptide Ac-Ala-Abc- Ahx-Ahx-Abc-Gly-NH2 (peptide Aha; where Ahx=aminohexanoic acid) and subsequently used as a tetradentate ligand to octahedrally coordinate and asymmetrically encapsulate a ruthenium(II) ion, creating a novel peptide- caged redox-active metal complex. (C) 2000 Elsevier Science Ltd.
- Bishop, Barney M.,McCafferty, Dewey G.,Erickson, Bruce W.
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- Persistent photoconductivity in chemically modified single-wall carbon nanotubes
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Control of the conductivity of single wall carbon nanotubes (SWNTs) is crucial for the use of carbon nanotubes in molecular electronics. We report a new fundamental characteristic of semiconducting SWNTs: the persistent photoconductivity of chemically modified carbon nanotube films. Illumination of carboxylated semiconducting SWNTs with ultraviolet or visible light causes a persistent decrease in the conductivity of semiconducting films. The photoinduced conductivity persists in the dark with a characteristic half-life of 35 s to 1.2 ?? 103 s at room temperature and an activation energy of 0.35 eV. Infrared illumination restores the conductivity of SWNT films. Ultraviolet and visible light illumination partially refills empty valence band states of chemically modified SWNTs by electron injection from the dopant sites. Photoinduced injection of electrons is accompanied by a decrease of the conductivity of the p-doped SWNT film, because of neutralization of holes by injected electrons. Covalent attachment of ruthenium(II)-tris(2,2a?2- bipyridine) (Ru(bpy)32+) to SWNTs makes carbon nanotubes sensitive to light that has been absorbed by the ruthenium complex and makes the carbon nanotubes persistently photoconductive. The photoconductivity of Ru(bpy)32+-SWNT films is presumably due to the injection of holes from *Ru(bpy)32+ to SWNT with a quantum yield of 0.55. Persistently photoconductive SWNTs have potential uses as nanosized optical switches, photodetectors, electrooptical information storage devices, and chemical sensors.
- Khairoutdinov, Rafail F.,Doubova, Larissa V.,Haddon, Robert C.,Saraf, Laxmikant
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- Synthesis and electrochemical characterization of a transition-metal- modified ligand - Receptor pair
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The energetics of weak interactions (van der Waals forces, hydrogen bonding) are difficult to quantify in biological ligand-receptor pairs. Insight into the biochemical role these forces play is critical to an understanding of signal transduction events and the drug discovery process. Ruthenium pentaammine and iron tetracyano complexes modified with either biotin or desthiobiotin have been synthesized and characterized. These modified biological ligands bind to the protein avidin in a manner similar to that of native biotin. Experiments using redox mediators show that the avidin-bound complexes are electrochemically accessible. Copyright
- Eckermann, Amanda L.,Barker, Kylie D.,Hartings, Matthew R.,Ratner, Mark A.,Meade, Thomas J.
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- Metal-triggered radial self-assembly of collagen peptide fibers
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A metal-triggered self-assembling collagen peptide was designed and synthesized to generate fibers through a radial growth mechanism. The assembly of the fibers was made possible through the placement of a bipyridine ligands within the center of the triple helix and was triggered by the addition of Fe(II). Copyright
- Przybyla, David E.,Chmielewski, Jean
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- Synthesis of redox derivatives of lysine and their use in solid-phase synthesis of a light-harvesting peptide
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Redox-active amino acids were synthesized for incorporation into peptide assemblies to study photoinitiated electron or energy transfer. 4'-Methyl-2,2'-bipyridine-4-carboxylic acid was obtained in 72% yield by consecutive SeO2 and Ag2O oxidation without isolation of intermediates. The side chain ε-amino group of Boc-L-lysine methyl ester or γ-carboxyl group of Boc-L-glutamic acid α-methyl ester was coupled to a redox moiety (transition-metal chromophore, electron donor, electron acceptor, metal ligand, or triplet-energy transmitter) using 4-(dimethylamino)pyridine, (1-benzotriazoleoxy)tris(dimethylamino)phosphonium hexafluorophosphate, N-methylmorpholine, and 1-hydroxybenzotriazole. Use of one equivalent of 4-(dimethylamino)pyridine provided the amide coupling product in 80-97% isolated yield. Selective hydrolysis of the methyl esters with lithium hydroxide provided the redox Boc-amino acids in 70-98% yield. These redox modules are suitable for solid-phase assembly of light-harvesting peptides, as illustrated by the synthesis of the partially α-helical 11-residue redox triad that contains a phenothiazine electron donor, a ruthenium(II)tris(bipyridine) chromophore, and an anthraquinone electron acceptor. Upon laser excitation at 420 nm, the peptide triad underwent photoinduced electron transfer to create a charge-separated state with a lifetime of 53 ns and decayed with a first-order rate constant of 1.9 x 108 s-1.
- McCafferty, Dewey G.,Bishop, Barney M.,Wall, Craig G.,Hughes, Solon G.,Mecklenberg, Sandra L.,Meyer, Thomas J.,Erickson, Bruce W.
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- Covalent hybrids based on Re(i) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: Synthesis, characterization and electronic properties
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A series of [Re(CO)3Br(N^N)] (N^N = substituted 2,2′-bipyridine ligand) complexes based on polypyridine-functionalized Dawson polyoxometalate (1-3) has been synthesized. The new hybrids (4-6) were characterized by various analytical techniques, including absorption, vibrational and luminescence spectroscopies as well as electrochemistry. Both units, the polyoxometalate and the transition metal complex, retain their intrinsic properties. Their combination in the newly prepared hybrids results in improved photosensitization in the high-energy visible region. However, a complete quenching of the emission for the [Re(CO)3Br(N^N)] complexes is observed due to formation of a charge separated state, Re(ii)-POM-, as shown by quenching experiments as well as theoretical modelling via DFT.
- Auvray, Thomas,Santoni, Marie-Pierre,Hasenknopf, Bernold,Hanan, Garry S.
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- Nitrogen-containing ligand iridium complex as well as preparation method and application thereof
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The invention provides a nitrogen-containing ligand iridium complex as well as a preparation method and application thereof. Belong to inorganic material synthesis and application technical field. After the iridium complex, 4, 4 '- dimethyl -2 and 2' - bipyridyl are oxidized to bipyridine formaldehyde by using iridium trichloride, and then hydroxylamine hydrochloride is added to form a novel nitrogen-containing ligand iridium complex after the third ligand is reacted with the benzoquinoline iridium dimer. The complex is simple in synthesis process. The prepared hypochlorite ion fluorescent probe is high in sensitivity, good in selectivity, good in anti-interference performance, wide in concentration detection range and low in detection limit.
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Paragraph 0031; 0048; 0050; 0053; 0055; 0058; 0060; ...
(2021/11/14)
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- Double-phosphorescence emission probe and preparation method thereof
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The invention discloses a double-phosphorescence emission probe and a preparation method thereof; the double-phosphorescence emission probe capable of detecting oxygen and metal ions is constructed byutilizing the response of a bis(2-pyridylmethyl)amine structure to metal ions and the response of a double-phosphorescence emission iridium complex to oxygen. Compared with a single-phosphorescence emission iridium complex probe disclosed in the prior art, the double-phosphorescence emission probe provides a new idea for simultaneous detection of multiple detection targets by a single probe; thepreparation process of the double-phosphorescence emission iridium complex is simple, reaction conditions are mild, and operability is high.
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Paragraph 0036; 0040; 0044; 0045
(2020/06/16)
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- Peptide-Ruthenium Conjugate as an Efficient Photosensitizer for the Inactivation of Multidrug-Resistant Bacteria
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Antimicrobial photodynamic therapy (APDT) has gained increased attention because of its broad spectrum activity and lower likelihood to elicit bacterial resistance. Although many photosensitizers excel at eradicating Gram-positive bacterial infections, they are generally less potent when utilized against Gram-negative bacteria. We hypothesized that conjugating the DNA-targeting, antimicrobial peptide buforin II to a metal-based photosensitizer would result in a potent APDT agent. Herein, we present the synthesis and characterization of a buforin II-[Ru(bpy)3]2+ bioconjugate (1). The submicromolar activity of 1 against the multidrug-resistant strains Escherichia coli AR 0114 and Acinetobacter baumannii Naval-17 indicates strong synergy between the ruthenium complex and buforin II. Our mechanistic studies point to an increased rate of DNA damage by 1 compared to [Ru(bpy)3]2+. These results suggest that conjugating metal complexes to antimicrobial peptides can lead to potent antimicrobial agents.
- Angeles-Boza, Alfredo M.,Jennings, Murphy P.,Juliano, Samuel A.,Pierce, Scott
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supporting information
p. 14866 - 14870
(2020/11/02)
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- Preparation method of ruthenium complex and acquired immune deficiency syndrome virus reverse transcriptase inhibition application of ruthenium complex
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The invention belongs to the field of researches and development of acquired immune deficiency syndrome virus inhibitors and discloses a preparation method of a ruthenium complex and acquired immune deficiency syndrome virus reverse transcriptase inhibition application of the ruthenium complex. The invention designs a novel synthesis method of a polypyridine ruthenium complex; the complex has highpurity and high yield and has good water solubility and excellent light spectrum property. The polypyridine ruthenium complex provided by the invention has a capability of selectively combining a TARregion on acquired immune deficiency syndrome virus RNA (Ribonucleic Acid), and can be used for blocking a reverse transcription process of the reverse transcriptase on the virus RNA to inhibit the copying of the virus RNA. The polypyridine ruthenium complex provided by the invention is an acquired immune deficiency syndrome virus RNA selective binding reagent with high affinity and an acquired immune deficiency syndrome virus reverse transcriptase inhibitor with high activity, and is an acquired immune deficiency syndrome virus medicine with extremely good application potential.
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Paragraph 0019
(2019/02/06)
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- Phosphorescence iridium complex with singlet oxygen detection effect and preparation method and applications thereof
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The invention provides a phosphorescence iridium complex with a singlet oxygen detection effect and a preparation method and applications thereof. The complex is composed of a cyclo-metal ligand, a metal center, and an auxiliary ligand of a singlet oxygen detection functional group. The structural formula of the complex is represented in the description. The provided complex can be combined with singlet oxygen under the light radiation and can be used to detect singlet oxygen; after the complex is combined with singlet oxygen, the complex can be deeply co-dyed with a commercial mitochondrion dye, thus the complex can be used to target mitochondria; and moreover, the complex can be applied to biological imaging and can be used to detect the change of singlet oxygen in live cells. The provided phosphorescence iridium complex has an important application prospect in the fields of bio-imaging and singlet oxygen detection.
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Paragraph 0058; 0062; 0063
(2019/01/08)
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- Ionic type iridium complex with double phosphorescence emission properties as well as preparation method and application of ionic type iridium complex
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The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an ionic type iridium complex with double phosphorescence emission properties as well as a preparation method and an application of the ionic type iridium complex. The complex comprises a metal center and cyclometalated ligands. The preparation method comprises steps as follows: dichloro bridge is prepared from a phenylpyridine derivative and iridium(III) chloride trihydrate through a coordination reaction, and the ionic type iridium complex with the double phosphorescence emission properties is prepared from dichloro bridge and a dipyridyl derivative or sodium carbonate through coordination reaction. The ionic type iridium complex with the double phosphorescence emission properties can be applied to the fields of biological detection and biological imaging for hypoxic oxygen-enriched conditions; a diagnosis and treatment integrated multifunctional probe based on the ionic type iridium complex with the double phosphorescence emission properties has great potential in further biomedicine application.
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Paragraph 0036; 0038; 0040
(2018/01/11)
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- COLLAGEN PEPTIDE CONJUGATES AND USES THEREFOR
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Described herein are conjugates of collagen peptides and metal binding agents and compositions resulting therefrom, useful in various tissue engineering and regeneration applications, in cell culture, cell adhesion, cosmetic surgery, construction of artificial skin substitutes, management of severe burns and burn surgery, reconstruction of bone and a wide variety of dental, orthopedic and surgical purposes, as drug delivery vehicles and in delivering populations of cells to a site of disease or injury.
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Paragraph 0121
(2016/08/23)
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- Membrane staining dyes containing phosphorescent transition metal polypyridine complexes
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The present invention is concerned with a staining dye for staining a biological cell, comprising dye molecules with a positively charged polar head group for attraction to cell membrane of the cell and for refraining the dye molecules from entering the cytoplasm, and one or more hydrophobic groups for interaction with phospholipids of the cell membrane. The dye molecules are phosphorescent transition metal polypyridine complexes having a metal center and ligands which are non-organic fluorophores.
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Page/Page column 5; 9
(2016/09/28)
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- Ligand-directed selective protein modification based on local single-electron-transfer catalysis
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A photocatalyst ([Ru(bpy)3]2+) bound to a protein ligand was essential for the title method. Local single-electron transfer from the catalyst resulted in the formation of tyrosyl radicals. N′-Acetyl-N,N- dimethyl-1,4-phenylenediamine was used as the tyrosyl radical trapping agent and used in a radical addition to afford selective modification of the target protein. Copyright
- Sato, Shinichi,Nakamura, Hiroyuki
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supporting information
p. 8681 - 8684
(2013/09/12)
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- Interfacial electron transfer dynamics of two newly synthesized catecholate bound RuII polypyridyl-based sensitizers on TiO2 nanoparticle surface - A femtosecond pump probe spectroscopic study
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Two new catecholate-bound RuII-polypyridine based sensitizers, (2,2′-bipyridine){ethyl 3-(4-hydroxyphenyl)-2-[(4′-methyl-2, 2′-bipyridinyl-4-carbonyl)amino]propionate}{4-[2-(4′-methyl-2, 2′-bipyridinyl-4-yl)vinyl]benzene-1,2-diol)}ruthenium(II) hexafluorophosphate (5) and [(2,2′-bipyridine)-(4-2,2′-bipyridinyl- 4-yl-phenol)-(4-{2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl}benzene-1, 2-diol)]ruthenium(II) hexafluorophosphate (6) with secondary electron-donating groups (tyrosine and phenol, respectively) were synthesized and characterized. Steady-state optical absorption and emission studies confirm strong coupling between the sensitizers and TiO2 nanoparticles. Femtosecond visible transient absorption spectroscopy has been employed to study interfacial electron transfer (IET) dynamics in the dye-nanoparticle systems to explore the influence of the secondary electron-donating groups on IET dynamics. Electron injection into the conduction band of nanoparticulate TiO2 has been confirmed by detection of the conduction band electrons in TiO2 ([e-]TiO2CB) and radical cation of the adsorbed dye (D·+) in real time monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (2 and by the recovery of the ground state bleach. BET dynamics in dye-TiO2 systems for complexes 5 and 6 have been compared with those of [bis(2,2′-bpy)-(4-{2-(4′-methyl-2, 2′-bipyridinyl-4-yl)vinyl}benzene-1,2-diol)]ruthenium(II) hexafluorophosphate (7), which does not have a secondary electron-donating group.
- Banerjee, Tanmay,Rawalekar, Sachin,Das, Amitava,Ghosh, Hirendra N.
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experimental part
p. 4187 - 4197
(2011/12/05)
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- Facile synthesis of size dependent Ru(ii)-carbohydrate dendrimers via click chemistry
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A facile and flexible approach for the preparation of Ru(ii) complexes containing different carbohydrates based on the Cu(ii)-catalyzed Huisgen-[3+2] cycloaddition is described.
- Kikkeri, Raghavendra,Liu, Xinyu,Adibekian, Alexander,Tsai, Yu-Hsuan,Seeberger, Peter H.
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supporting information; scheme or table
p. 2197 - 2199
(2010/07/08)
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- DYE AND DYE-SENSITIZED SOLAR CELL
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A novel dye which has high conversion efficiency, excellent weatherability and heat resistance when it is used in a dye-sensitized solar cell and a dye-sensitized solar cell comprising this dye. This dye is represented by the following formula (1): ????????ML1L2X1X2?????(1) wherein M is an element of any one of the groups 8 to 10 of the long form of the periodic table, L1 and L2 are each independently a bidentate ligand composed of a specific bipyridine, and X1 and X2 are each independently a monovalent atomic group or unidentate ligand.
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Page/Page column 6; 12
(2010/11/26)
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- Methods of synthesis of halogen base-modified oligonucleotides and subsequent labeling with a metal-catalyzed reaction
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The present invention provides metal-containing purines, pyrimidines, nucleosides, nucleotides and oligonucleotides; including phosphoramidite and photolabile derivatives thereof, including methods of making and method of using same. The present invention provides a method for detection of nucleic acid sequences via electrochemical or photochemical means.
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- Light-Induced Electron-Transfer Reactions Involving the Tris(2,2'-bipiridine)ruthenium Dication and Related Complexes. III Improved Synthesis of 2,2'-Bipyridine-4,4'-dicarboxylic Acid and Photoreduction of Water by Bis(2,2'-bipyridine)(2,2'-bipyridine-4,4'-dicarboxylic acid)ruthenium(II)
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The oxidation of 4,4'-dimethyl-2,2'-bipyridine with potassium permanganate in water gives 2,2'-bipyridine-4,4'-dicarboxylic acid and 4'-methyl-2,2'-bipyridine-4-carboxylic acid.The latter acid is oxidized to the diacid by boiling nitric acid.Complexes of the type Ru(Bpy)2L2+ have been prepared where L is 2,2'-bipyridine-4,4'-dicarboxylic acid, diethyl 2,2'-bipyridine-4,4'-dicarboxylate, 4'-methyl-2,2'-bipyridine-4-caroxylic acid and ethyl 4'-methyl-2,2'-bipyridine-4-carboxylate.These complexes have been compared with 2+ as sensitizers for the photoreduction of water.Stern-Volmer analysis has been applied to the quenching of their luminescence by methylviologen (mv2+), 3+ (sep is 1,3,6,8,10,13,16,19-octaazabicycloicosane) and 3+ (CLsar is 1-chloro-3,6,10,13,16,19-hexaazabicycloicosane).Changes in the Stern-Volmer constants have been related to the free energy changes associated with the oxidative quenching and the overall charges of the ruthenium complexes.The rates of formation of hydrogen compared favourably in sacrificial cycles with the ruthenium complexes as sensitizers, mv2+, Co(sep)3+ as electron-transfer agents, platinum/poly(vinyl alcohol) as catalyst, and ethylenediaminetetraacetic acid as electron donor.The results obtained have been discussed in terms of variations in the efficiencies of cage escape in the oxidative quenching and competition between electron transfer and energy transfer.
- Launikonis, Anton,Lay, Peter A.,Mau, Albert W.-H.,Sargeson, Alan M.,Sasse, Wolfgang H. F.
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p. 1053 - 1062
(2007/10/02)
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