- Modifying a composite based on silica molecular sieve and a Ru(II)-based probe with Fe3O4 particles: Construction and oxygen sensing performance
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This paper reported a composite based on silica molecular sieve MCM-41 and a Ru(II)-based probe which was further functionalized with magnetic Fe3O4 so that site-specific guiding could be achieved. A core–shell structure was applied in this composite, with Fe3O4 as core and MCM-41 as shell, respectively. By means of electron microscope images, XRD analysis, IR spectra, N2 adsorption/desorption measurement and thermal degradation analysis, this composite was analyzed and confirmed. Emission monitoring of this composite under various O2 concentrations suggested that its emission was quenchable by O2 through a dynamic mechanism with good stability. Sensitivity of 11.5 and short response time of 10 s were obtained with a linear working plot.
- Chen, Lin,Sun, Shuai,Li, Jia,Fang, Zhigang
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Read Online
- Polynuclear heteroleptic ruthenium(II) photoredox catalysts: Evaluation in blue-light-mediated, regioselective thiol-ene reactions
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Polynuclear heteroleptic ruthenium(II) photosensitisers combining either imine or amine-functionalised bipyridyl ligands were synthesised (via Schiff-base condensation/reductive amination reactions), characterised and investigated for their photoreactivity in the hydrothiolation reaction. Furthermore, electrochemical, electronic absorption and emission studies of the complexes were conducted. All the ligand-modified, heteroleptic complexes show red-shifted emission spectra (614–633 nm) relative to the canonical [Ru(bpy)3](PF6)2 complex (609 nm), attributed to the transition from the triplet MLCT excited state (3MLCT) to the ground state. The complexes were evaluated as visible-light photoredox catalysts in the radical hydrothiolation reaction of olefins (thiol-ene coupling) to afford thioethers. Control reactions performed in the absence of the photocatalyst resulted in either significantly lower yields (6%) or no product formation, demonstrating the role of the complexes as photoredox catalysts. The reactions carried out using trinuclear complexes (Ered (Ru2+*/+) = +0.300 V vs Ag/Ag+) resulted in increased yields in comparison with their respective mononuclear congeners and greater than those reported for [Ru(bpy)3](PF6)2, demonstrating the benefits of using polynuclear photocatalysts for photoinitiated redox catalysis reactions.
- Motimani, Nozuko M.,Ngubane, Siyabonga,Smith, Gregory S.
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- Physical, spectroscopic, and biological properties of ruthenium and osmium photosensitizers bearing diversely substituted 4,4′-di(styryl)-2,2′-bipyridine ligands
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Capitalising on the previous identification of a distyryl coordinated Ru(ii) polypyridine complex as a promising photosensitizer for photodynamic therapy, eight new complexes were synthesized by modifications of the ligands or by changing the metal coordinated. We report in this work the effects of these modifications on the physical, spectroscopic, and biological properties of the synthesized complexes. Subtle structural modifications of the distyryl ligand only had a moderate effect on the corresponding complexes' visible light absorption and singlet oxygen quantum yield. These modifications however had a significant effect on the lipophilicity, the cellular uptake and the phototoxicity of the complexes. Although the lipophilicity of the complexes had a somewhat expected effect on their cellular uptake, this last parameter could not be directly correlated to their phototoxicity, revealing other underlying phenomena. Overall, this work allowed identification of two promising ruthenium complexes as photosensitisers for photodynamic therapy and provides some guidance on how to design better photosensitizers. This journal is
- Cariou, Kevin,Gasser, Gilles,Karges, Johannes,Tharaud, Micka?l,Vinck, Robin
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p. 14629 - 14639
(2021/11/03)
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- Photorelease of a metal-binding pharmacophore from a Ru(ii) polypyridine complex
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The adoption of compounds that target metalloenzymes comprises a relatively low (5%) percentage of all FDA approved therapeutics. Metalloenzyme inhibitors typically coordinate to the active site metal ions and therefore contain ligands with charged or highly polar functional groups. While these groups may generate highly water-soluble compounds, this functionalization can also limit their pharmacological properties. To overcome this drawback, drug candidates can be formulated as prodrugs. While a variety of protecting groups have been developed, increasing efforts have been devoted towards the use of caging groups that can be removed upon exposure to light to provide spatial and temporal control over the treatment. Among these, the application of Ru(ii) polypyridine complexes is receiving increased attention based on their attractive biological and photophysical properties. Herein, a conjugate consisting of a metalloenzyme inhibitor and a Ru(ii) polypyridine complex as a photo-cage is presented. The conjugate was designed using density functional theory calculations and docking studies. The conjugate is stable in an aqueous solution, but irradiation of the complex with 450 nm light releases the inhibitor within several minutes. As a model system, the biochemical properties were investigated against the endonucleolytic active site of the influenza virus. While showing no inhibition in the dark in anin vitroassay, the conjugate generated inhibition upon light exposure at 450 nm, demonstrating the ability to liberate the metalloenzyme inhibitor. The presented inhibitor-Ru(ii) polypyridine conjugate is an example of computationally-guided drug design for light-activated drug release and may help reveal new avenues for the prodrugging of metalloenzyme inhibitors.
- Karges, Johannes,Stokes, Ryjul W.,Cohen, Seth M.
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supporting information
p. 2757 - 2765
(2021/03/09)
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- Time Resolved Ligand Loss: Flash Photolysis and UV–Vis Spectroscopic Studies of cis-[Ru(bpy)2(py)2]2+ Complex
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Abstract: A preliminary study on photoinduced ligand loss from [Ru(bpy)2(py)2]2+ has been made. The photolysis of cis-[Ru(bpy)2(py)2]2+ in the presence of trifluoroacetic acid, using broad band, white light excitation, leads to a shift in λmax from 458 nm to 472 nm, consistent with a substitution reaction of the pyridine by THF. A flash photolysis study was also performed to investigate the excited state changes of [Ru(bpy)2(py)2]2+ in THF.
- Rahman, Mohammad Aminur
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p. 2341 - 2347
(2021/11/11)
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- Ruthenium ruthenium complex as well as preparation method and pharmaceutical application thereof
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The invention provides an iridium ruthenium complex and a preparation method and pharmaceutical application thereof, and belongs to the field of pharmacy. The structure of the ruthenium complex is shown in the formula I. The ruthenium complex provided by the invention can effectively inhibit breast cancer cells. A plurality of tumor cells including liver cancer cells, lung adenocarcinoma cells and esophageal cancer cells are grown. , Compound 1 is MDA-MB - 231 for breast cancer cells IC. 50 3.20 ±0.06 μm, To A549 for lung adenocarcinoma cell IC50 Low to 2.95 ±0.04 μm. The ruthenium complex provided by the invention can be used for preparing prevention and/or treatment of breast cancer. The medicine for treating various tumors such as liver cancer, lung adenocarcinoma and esophagus cancer has a wide application prospect.
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Paragraph 0048-0052
(2021/08/25)
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- Preparation method of ruthenium-based photosensitizer and application of ruthenium-based photosensitizer in photodynamic therapy of breast cancer
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The invention relates to a preparation method of a ruthenium-based photosensitizer and an application thereof in photodynamic therapy of breast cancer, in particular to a ruthenium-based photosensitizer [Ru (bpy). 2 PYIP] Cl2 Preparation method and application of ruthenium complex [Ru (bpy) in photodynamic therapy of breast cancer2 PYIP] Cl2 The aqueous solution has good dispersibility, strong red fluorescence and higher singlet oxygen quantum yield under the action 640 nm laser, and can be used for photodynamic therapy of breast cancer.
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Paragraph 0033-0034; 0036; 0039-0040; 0042; 0044-0045; 0047
(2021/09/01)
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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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supporting information
p. 12106 - 12118
(2020/08/06)
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- A lysosome-targeted ruthenium(II) polypyridyl complex as photodynamic anticancer agent
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Polypyridyl ruthenium complexes as novel photosensitizers had drawn attention due to its high selectivity towards cancer cells and low toxicity to normal cells. Herein, we synthesized a lysosome-targeted polypyridyl ruthenium complex Rhein-Ru(bpy)3 (bpy = 2,2′-bipyridine, rhein = 4,5-dihydroxy-9,10-dioxoanthracene-2-carboxylic acid), tethering with the Chinese medicine herb rhein. Rhein-Ru(bpy)3 exhibited high phototoxicity with short time of irradiation against tumor cell lines with the IC50 value of 2.4– 8.7 μM, and higher cytotoxicity against cisplatin-resistant A2780 cell lines, suggesting that Rhein-Ru(bpy)3 could overcome the cisplatin resistance. Moreover, Rhein-Ru(bpy)3 displayed low cytotoxicity towards cell lines in dark incubation, which was beneficial to reduce the toxic side effects towards normal cell lines. Besides, the confocal imaging and western blotting assay results suggested that Rhein-Ru(bpy)3 could induce cancer cell death through the autophagy pathway. These results inspired us that lysosome-targeted photosensitizers based on ruthenium complexes showed great potential for photodynamic therapy (PDT) application in cancer treatment.
- Chen, Jun,Liu, Hong-Ke,Qian, Yong,Su, Zhi,Tao, Qin,Wang, Mengmeng,Wang, Yan,Wu, Jian,Xue, Xuling,Yu, Tao
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- Novel ruthenium complex as well as preparation method and application thereof in detection of 5-formylcytosine
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The invention discloses a novel ruthenium complex as well as a preparation method and application thereof in detection of 5-formylcytosine. The invention provides the novel ruthenium complex and the preparation method thereof. The invention further provides a fluorescent molecular probe for detecting the 5-formylcytosine. The invention also provides a method for detecting the 5-formylcytosine by adopting the novel ruthenium complex or the ruthenium complex prepared by the preparation method or the fluorescent molecular probe. The ruthenium complex can be uniquely combined with 5fC in DNA (deoxyribonucleic acid); therefore, the 5fC in the double-stranded DNA can be specifically recognized; good fluorescence response and chemical stability are realized; the novel ruthenium complex has the advantages of good thermodynamic stability, realization of real-time detection and distribution positioning of the 5fC in the double-stranded DNA in cells, low cost, low equipment requirements, no enrichment of the 5-formylcytosine, direct detection, wide application conditions, simple and mild conditions, and high sensitivity.
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Paragraph 0046; 0047
(2020/04/22)
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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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- Two photoactive Ru (II) compounds based on tetrazole ligands for photodynamic therapy
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Ru (II) compounds have potential application in photodynamic therapy (PDT). In the current study, two Ru (II) compounds based on the auxiliary ligand 2,2′-bipyridine (bipy) by changing main ligands 5-(2-pyridyl) tetrazole (Hpytz) and di(2H-tetrazol-5-yl) amine (H2datz) have been successfully synthesized and characterized, [Ru (pytz)(bipy)2][PF6] (1) and [Ru(Hdatz)(bipy)2][PF6] (2). These compounds can form nanoparticles (NPs) by nano-precipitation. And [Ru(pytz)(bipy)2][PF6] NPs with a lower half maximal inhibitory concentration (IC50) of 37 μg/mL on HeLa cells than that of [Ru(Hdatz)(bipy)2][PF6] NPs (65 μg/mL). Meanwhile, negligible dark toxicity has been also observed for these NPs even under high concentrations. The results show that [Ru(pytz)(bipy)2][PF6] (1) and [Ru(Hdatz)(bipy)2][PF6] (2) NPs can inhibit cell proliferation in vitro, and may be potential candidates for photodynamic therapy.
- Chen, Jianjiao,He, Xin,Ke, Zhen,Wei, Bo,Yang, Jie,Zou, Dengfeng,Zou, Jianhua,Zou, Zhenyuan
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- A Ru - BSA hydrogel and its preparation method and application
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The invention discloses a Ru - BSA hydrogel and its preparation method and application. The Ru - BSA hydrogel shown in the following formula: ; Wherein . In the invention, the Ru - BSA hydrogel is more easily cancer cell uptake, and the hydrogel in the Ru - BSA bovine serum protein can in vivo environment continuously enzymolysis, thus sustained release drug molecules, which improves the utilization ratio, greatly improving the medicine to the curative effect of the tumor.
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Paragraph 0027; 0028
(2019/04/10)
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- Experimental and density functional theory insights into the effect of withdrawing ligands on the fluorescence yield of Ru(II)-based complexes
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The quality of emission spectra of metal complexes gives good insights into their performance in many optoelectronic applications. Herein, the effect of the number and position of various ligand structures on the emission spectra of Ru bipyridine complexes was studied. Specifically, the use of a different number of withdrawing groups (COOH) was investigated in detail. The complexes were first investigated using density functional theory (DFT) and time-dependent DFT calculations and then confirmed experimentally. The bandgap energy, reactivity, emission spectra and Stokes shift were found to depend on the number and position of the withdrawing groups attached to the Ru(bpy)22+ complexes. Upon increasing the number of withdrawing groups, the electrons were found to be withdrawn from the carbon orbitals and resonated to reach the metal, and accumulated around it, thus enhancing the metal-to-ligand charge transfer mechanism instead of the ligand-to-ligand charge transfer mechanism. The complexes with more withdrawing groups showed spectra with more intense emission peaks with shorter lifetime, indicating the enhancement in the photoactivity of the complexes. Ligands with ring nitrogens with two COOH groups showed the greatest effect on the enhancement of the emission spectra with a lifetime of 0.5359?ns. The resulting collective emission spectra covered a wide wavelength range, making the investigated complexes a good choice for many optoelectronic applications.
- Ali, Basant A.,Sharmoukh, Walid,Elnagar, Mohamed M.,Hassan, Zeinab M.,Allam, Nageh K.
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- Metalated Chromene and Chromone Complexes: pH Switchable Metal–Carbon Bonding Interaction, Photo-triggerable Chromone Delivery Application, and Antioxidative Activity
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The two families of RuII-chromene and -chromone complexes isolated in this work represent the first examples of metalated chromene and chromone complexes synthesized through transition-metal-mediated cyclization of phenol-tethered ynone. These unprecedented metalated heterocyclic compounds exhibit remarkable features, such as pH-switchable metal–carbon bonding interactions, photo-triggerable release of organic chromone upon visible-light irradiation, and superior antioxidative property to their organic analogue (1,4-benzopyrone). These findings not only offer mechanistic insights into metal-induced activation of functionalized alkynes, but also add a new dimension to rational design of antioxidants and photo-responsive drug delivery systems.
- Ng, Sze-Wing,Chung, Lai-Hon,Yeung, Chi-Fung,Lo, Hoi-Shing,Shek, Hau-Lam,Kang, Tian-Shu,Leung, Chung-Hang,Ma, Dik-Lung,Wong, Chun-Yuen
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p. 1779 - 1783
(2018/02/10)
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- Ruthenium-diimine type complex as well as preparation method and application thereof
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The invention relates to a ruthenium-diimine type complex as well as a preparation method and application thereof. The method comprises the following steps: i, dissolving 2-pyridine carboxaldehyde and2-aminochrysene into absolute ethyl alcohol, and heating and stirring under the protection of nitrogen gas; adding a ruthenium complex precursor Ru(bpy)2Cl2; heating and refluxing overnight under theprotection of the nitrogen gas; after raw materials are completely transformed, stopping heating; cooling to room temperature and concentrating; adding a methanol saturated solution of ammonium hexafluorophosphate into a concentrated solution; transferring a reaction mixture into a sand plate funnel for suction filtration, and washing; dissolving a crude product into acetone and taking n-hexane as a dispersion agent for recrystallizing, so as to obtain a ruthenium-diimine type complex pure product. The ruthenium-diimine type complex provided by the invention has the advantages of simple preparation method and relatively high yield and purity; after a ligand is synthesized, the ligand does not need to be subjected to separation treatment and can directly react with a ruthenium precursor toobtain a target product. The ruthenium-diimine type coordination complex has a wide application prospect in the fields including catalysis, sensing, molecular recognition and the like.
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Paragraph 0031-0032
(2020/01/25)
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- A self-deformable gel system with asymmetric shape change based on a gradient structure
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A self-deformable gel system is constructed by coupling a gradient structured gel with a chemical oscillating reaction. The system exhibits periodic and asymmetric shape change. The asymmetric shape change of the gel is based on the gradient structure.
- Li, Jie,Li, Xiuchen,Xu, Guohe,Zheng, Zhaohui,Deng, Jinni,Ding, Xiaobin
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supporting information
p. 11594 - 11597
(2018/11/10)
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- Membrane-targeted photosensitizer capable of realizing photodynamic therapy as well as preparation method and application thereof
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The invention discloses a membrane-targeted photosensitizer capable of realizing photodynamic therapy as well as a preparation method and application thereof, and belongs to the technical field of organic photoelectric materials. The preparation method comprises the following steps: preparing a C9 dichlorodipyridine bridge through reactions among dipyridine, ruthenium trichloride and lithium chloride; enabling the dichlorodipyridine bridge to react with a dipyridine auxiliary ligand b to obtain a ruthenium complex. The photosensitizer can specifically target the cell membrane of a cancer cell,and under irradiation of specific exciting light, generates reactive oxygen and damages the surface of the cell membrane to cause cell apoptosis finally; moreover, the photosensitizer realizes a goodphotodynamic therapy effect, thereby adding a new idea for photodynamic therapy. The membrane-targeted photosensitizer capable of realizing photodynamic therapy has a great potential in future biomedicine application.
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Paragraph 0053; 0054; 0055
(2019/01/15)
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- Low-Energy and Long-Lived Emission from Polypyridyl Ruthenium(II) Complexes Having A Stable-Radical Substituent
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Novel polypyridyl ruthenium(II) complexes having a 2,2′-bipyridine (bpy) derivative which possesses a 1,5-dimethyl-6-oxoverdazyl radical (OV) group as a stable-radical substituent were designed and synthesized. The radical-ruthenium(II) complexes showed low-energy/intense MLCT absorption and low-energy/long-lived MLCT emission, and these characteristics of the complexes were explained by the electron-withdrawing nature of the OV group. Furthermore, the radical-substituent effects were enhanced by the presence of the electron-donating methyl groups at the 4- and 4′-positions of bpy in the ancillary ligands. The detailed electrochemical, spectroscopic, and photophysical properties of the complexes were discussed in terms of the systematic modification of the second coordination sphere in the main and ancillary ligands.
- Ito, Akitaka,Kobayashi, Nozomi,Teki, Yoshio
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supporting information
p. 3794 - 3808
(2017/04/10)
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- Ruthenium complex with characteristic of strengthening aggregation state induced phosphorescence as well as preparation method and application of ruthenium complex
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The invention discloses a ruthenium complex with the characteristic of strengthening aggregation state induced phosphorescence as well as a preparation method and application of the ruthenium complex. The ruthenium complex has a structure shown by a formula I shown as follows, wherein N^N bidentate ligand is a first ligand, X^X bidentate ligand is a second ligand, the first ligand comprises 2, 2-bipyridine or 1, 10-phenanthroline, and the second ligand comprises a 2, 2-distyrylbenzene derivative. The ruthenium complex can emit stronger phosphorescence in an aggregation state and does not need to be doped in a host material as a guest material when being used for preparing an electroluminescent device, and thus the preparation process of the device can be simplified, the preparation cost of the device can be lowered, the electroluminescence efficiency of the device can be improved, and industrialization is facilitated. Meanwhile, the method of preparing the ruthenium complex is simple, is easy in controlling the condition and is beneficial to large-scale implementation.
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Paragraph 0071
(2017/08/28)
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- Polypyridine ruthenium metal complex as well as preparation method and application thereof
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The invention relates to a polypyridine ruthenium metal complex which has a structure as shown in the specification. The complex is compounded by causing 2',2-dipyridyl and 3-thiophene-1,2,4-triazine [5,6-f]1, 10-o-phenanthroline react with ruthenium chloride hydrate. The polypyridine ruthenium metal complex provided by the invention has excellent water solubility and can detect high-expression miR-185 in peripheral blood of a patient suffering from gastric carcinoma.
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Paragraph 0044
(2017/08/28)
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- Fluorescent probe for identifying heavy metal copper ions and synthesis and application thereof
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The invention relates to a ruthenium complex and a preparation method thereof and application. The specific structure of the ruthenium complex is as shown in general formula (I). The ruthenium complex can be used for detection of the copper ions. The ruthenium complex has quick specificity response to Cu2+, and an in vitro detection limit reaches 30 nmol.L; the ruthenium complex is good in biocompatibility and small in cytotoxicity and can be evenly distributed in whole cells, the Cu2+ level in the cells can be detected; and the content and distribution of in vivo Cu2+ can be monitored in real time.
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Paragraph 0056-0059
(2017/11/18)
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- Kinetico-mechanistic Studies on the Substitution Reactivity on the {RuII(bpy)2} Core with Nucleosides and Nucleotides at Physiological pH
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The kinetico-mechanistic study of the substitution reactions of the aquo ligands in cis-[Ru(bpy)2(H2O)2]2+ by different nucleotides and nucleosides has been conducted at pH close to the physiological value. The concentration dependence and thermal and pressure activation parameters have been measured to ascertain the activation via which reactions take place. Substitution processes are found associatively activated for nitrogen-bonded nucleosides or nucleotides, with outer-sphere hydrogen-bonded aggregates being determinant. For reactions leading to oxygen-bonded nucleotides, the process is clearly dissociatively activated. A selectively induced lability of the inert {RuII(bpy)2} core is observed on the formation of nitrogen(amide)-bonded complexes at relatively low pH values, which might be relevant for the effective intercalation of designed, ruthenium(II)-bonded, aromatic rings.
- Vázquez, Marta,Martínez, Manuel
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supporting information
p. 6731 - 6738
(2016/07/16)
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- LUMINESCENT RUTHENIUM (II) COMPLEXES AND THEIR USE IN PH SENSORS
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The invention provides luminescent Ru(ll) complexes that can be used in pH sensors to provide pH sensitivity over a wide pH range. The complexes have at least one polypyridyl ligand having at least one proton-accepting group with a pKa in the range 4 to less than 6, wherein the luminescence intensity and/or luminescence lifetime of the complex varies depending on the protonation state of the proton-accepting group; and at least one polypyridyl ligand having at least one proton-donating group with a pKa in the range 6 to 8, wherein the at least one proton-donating group is covalently linked to a ring carbon atom of the at least one polypyridyl ligand by a spacer group having the formula -(CH2)q- wherein q may be 1, 2, or 3, and wherein the luminescence intensity and/or luminescence lifetime of the complex varies depending on the protonation state of the proton-donating group.
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Page/Page column 25; 26
(2016/06/01)
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- Observation of cascade f → d → f energy transfer in sensitizing near-infrared (NIR) lanthanide complexes containing the Ru(ii) polypyridine metalloligand
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Distinguishable d → f or f → d energy transfer processes depending on lanthanide ions are observed in isomorphous d-f heterometallic complexes containing the Ru(ii) metalloligand (LRu), which lead to sensitized NIR emission (for Nd3+ and Yb3+) or enhanced red emission of LRu (for Eu3+ and Tb3+), and represent the first eye-detectable evidence of f → d energy transfer processes in Ln-Ru bimetallic complexes. Based on the systematic luminescence and decay lifetime study, cascade f → d → f energy transfer has been proposed in Ln1-Ru-Ln2 trimetallic systems for improved NIR sensitization.
- Zhang, Lu-Yin,Li, Kang,Pan, Mei,Fan, Ya-Nan,Wang, Hai-Ping,Su, Cheng-Yong
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p. 5379 - 5386
(2016/07/06)
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- Design, synthesis, structural characterization and in vitro cytotoxic activity of mononuclear Ru(II)complexes
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The synthesis and characterization of ruthenium complexes (Ru-1–Ru-6) of the type [Ru(R)2(K)]2+ (where R = 1,10-phenanthroline/2,2′-bipyridyl and K = acetyl coumarin-inh, pyrazole-tch, acetyl coumarin-tsz, are described. These ligand
- Thota, Sreekanth,Vallala, Srujana,Yerra, Rajeshwar,Rodrigues, Daniel Alencar,Barreiro, Eliezer J.
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p. 2127 - 2132
(2016/10/25)
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- Manipulating pH using near-infrared light assisted by upconverting nanoparticles
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Near-infrared light can be used to manipulate the pH of aqueous solutions by using upconverting nanoparticle-assisted photocleavage of a ruthenium complex photobase. Upconverting nanoparticles and the photobase were also introduced into a pH-responsive hydrogel, in which near-infrared irradiation induced swelling of the hydrogel.
- Chen, Zhijun,Xiong, Yubing,Etchenique, Roberto,Wu, Si
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supporting information
p. 13959 - 13962
(2016/12/07)
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- A new method for the utilization of compounds of the type [Ru(bpy)2(CO)Cl]+ as a starting material for the synthesis of [Ru(N6)]2+ type compounds
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[Ru(R-bpy)2Cl2] is an important starting material for the synthesis of [Ru(N6)]2+ complexes. During the conventional synthesis procedure of [Ru(R-bpy)2Cl2], yield loss of up to 50% occurs, due to the formation of the side product [Ru(R-bpy)2(CO)Cl]+. The CO ligand hinders further conversion to [Ru(N6)]2+. Here we describe a simple and efficient removement of the CO ligand followed by a complexation of a third chelating ligand generating [Ru(N6)]2+. Complete removal of the CO ligand and formation of an intermediate state is verified by ESI-MS spectrometry and IR spectroscopy. After complexation of the third chelating ligand bpy, pure [Ru(R-bpy)3]2+ was formed with complete conversion. Purity of [Ru(R-bpy)3]2+ was ensured by IR-, NMR-spectroscopy and MS spectrometry.
- Zabarska, Natalia,Vos, Johannes G.,Rau, Sven
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p. 173 - 175
(2015/10/29)
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- CATALYTIC CONVERSION OF ALCOHOLS
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The disclosure provides methods of converting a lower alcohol (e.g., ethanol) to a higher alcohol (e.g., butanol) in the presence of a water stable transition metal catalyst comprising a Group VIII transition metal and a polydentate nitrogen donor ligand. The methods described in the disclosure can be carried out in the presence of water and achieve high purities of the higher alcohols.
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Paragraph 0134; 0135
(2015/03/16)
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- Synthesis, characterization and in-vitro cytotoxic studies of 5,10,15,20 tetra pyridyl porphyrin coordinated to four [Ru (bipy)2 Cl]+ groups
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Ruthenium possesses several favorable properties suited to rational anticancer drug design when conjugation with the porphyrin moiety was accomplished through peripheral pyridyl rings. The ruthenium porphyrin conjugates are soluble at least moderately in
- Uthayanila,Neeraja
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p. 867 - 873
(2015/10/28)
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- Phosphonic acid anchored ruthenium complexes for ZnO-based dye-sensitized solar cells
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We report on the development of ruthenium dyes for the application in flexible ZnO based dye-sensitized solar cells. The ZnO based solar cells were prepared by electrodeposition using eosin Y as a structure-directing agent. The newly synthesized ruthenium dyes differed in the complexity of the extended π-donor-system and in their anchor moieties. As alternatives to carboxylic acids as anchor groups, dyes carrying phosphonic acids were studied. Comparison of the dyes contrary to what could be expected showed that the phosphonic acid anchored dyes were not superior to the carboxylic anchored dyes. A surprising second effect was that the dyes with the least sophisticated ligands performed best. Exploring possible reasons we established a simple model that allows pre-evaluation of the applicability of the dyes before testing them in real solar cells.
- Neuthe, Katja,Bittner, Florian,Stiemke, Frank,Ziem, Benjamin,Du, Juan,Zellner, Monika,Wark, Michael,Schubert, Thomas,Haag, Rainer
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- Synthesis and electron-transfer processes in a new family of ligands for coupled Ru-Mn2 complexes
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A series of [Ru(bpy)3]2+-type (bpy=2,2 ′-bipyridine) photosensitisers have been coupled to a ligand for Mn, which is expected to give a dinuclear complex that is active as a water oxidation catalyst. Unexpectedly, photophysical studies showed that the assemblies had very short lived excited states and that the decay patterns were complex and strongly dependent on pH. One dyad was prepared that was capable of catalysing chemical water oxidation by using [Ru(bpy)3]3+ as an oxidant. However, photochemical water oxidation in the presence of an external electron acceptor failed, presumably because the short excited-state lifetime precluded initial electron transfer to the added acceptor. The photophysical behaviour could be explained by the presence of an intricate excited-state manifold, as also suggested by time-dependent DFT calculations.
- Karlsson, Erik A.,Lee, Bao-Lin,Liao, Rong-Zhen,Akermark, Torbjoern,Kaerkaes, Markus D.,Becerril, Valeria Saavedra,Siegbahn, Per E. M.,Zou, Xiaodong,Abrahamsson, Maria,Akermark, Bjoern
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p. 936 - 950
(2014/08/05)
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- Structural and optical properties of new cyclometalated Ru(II) derived compounds
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The electronic spectra of 4 cyclometalated ruthenium compounds built up from cycloruthenated 2-phenylpyridine with monodentate and bidentate ligands, namely 1 [Ru(MeCN)2(phen)(PhPy)]1+ (RDC11), 2 [Ru(phen)2(PhPy)]1+ (RDC34), 3 [Ru(MeCN) 2(PhPy)(dppz)]1+ (RDC11Z), 4 [Ru(bpy)(PhPy)(dppz)] 1+ (RDCbpZ), the last two being newly synthesized, have been recorded and calculated together with that of 5 [Ru(bpy)2(dppz)]2+ (RDNbpZ). Recently synthesized variants of RDC34 where the phenylpyridine ligand is substituted with an electro-attractor or an electro-donor group, 6 [Ru(phen)2(NO2PhPy)]1+ RDC40 and 7 [Ru(phen)2(NH2PhPy)]1+ RDC41 respectively, and the dicationic reference complex [Ru (phen)2(bpy)]2+ (RDN34) have been investigated as well for comparison. The global structures of RDC34 and RDN34 are very similar despite of the substitution of one N atom by one C atom. As expected a shortening of the Ru-C bond as compared to the Ru-N bond is observed. The calculated structures of the investigated complexes point to a rather rigid structure whatever their environment. The introduction of a strong Ru-C bond has a minor effect on the coordination sphere around the metal atom keeping the other Ru-N bonds and bond angles similar, the only noticeable alteration being an increase of the Ru-N bond trans to the Ru-C bond. The experimental spectra are characterized by an intense band in the UV domain centered at 270 nm and corresponding to a strong intra-ligand (IL) absorption. Low-lying MLCT states contribute to a weak shoulder around 370 nm and to a large band between 550 nm and 400 nm. The tail of this band, towards 650 nm, is a characteristic of the cyclometalated complexes. This series of molecules, as other polypyridyl complexes, are characterized by a high density of excited states in the vis/UV energy domain, a large mixing between MLCT/IL and LLCT states in the upper part of the spectrum, and a significant sensitivity to the environment of the IL state localized on the dppz ligands.
- Finck, Sidonie,Issenhuth, Jean-Thomas,Despax, Stéphane,Sirlin, Claude,Pfeffer, Michel,Poidevin, Corentin,Gourlaouen, Christophe,Boeglin, Alex,Daniel, Chantal
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supporting information
p. 248 - 259
(2014/05/06)
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- A TiO2 immobilized Ru(ii) polyazine complex: A visible-light active photoredox catalyst for oxidative cyanation of tertiary amines
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A chemically functionalized nanocrystalline TiO2 grafted ruthenium(ii) polyazine complex was found to be an efficient visible light photoredox catalyst for the oxidative cyanation of tertiary amines to the corresponding α-aminonitriles in high to excellent yields, using molecular oxygen as an oxidant and sodium cyanide in acetic acid as a cyanide source. The developed photoredox catalyst could be easily recovered by simple filtration and reused for several runs with consistent catalytic activity.
- Kumar, Pawan,Varma, Sanny,Jain, Suman L.
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p. 4514 - 4519
(2014/03/21)
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- Photocatalytic reduction of carbon dioxide to methanol using a ruthenium trinuclear polyazine complex immobilized on graphene oxide under visible light irradiation
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A ruthenium trinuclear polyazine complex was synthesized and subsequently immobilized through complexation to a graphene oxide support containing phenanthroline ligands (GO-phen). The developed photocatalyst was used for the photocatalytic reduction of CO2 to methanol, using a 20 watt white cold LED flood light, in a dimethyl formamide-water mixture containing triethylamine as a reductive quencher. After 48 h illumination, the yield of methanol was found to be 3977.57 ± 5.60 μmol gcat -1. The developed photocatalyst exhibited a higher photocatalytic activity than graphene oxide, which provided a yield of 2201.40 ± 8.76 μmol gcat-1. After the reaction, the catalyst was easily recovered and reused for four subsequent runs without a significant loss of catalytic activity and no leaching of the metal/ligand was detected during the reaction.
- Kumar, Pawan,Sain, Bir,Jain, Suman L.
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p. 11246 - 11253
(2014/07/21)
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- Synthesis, spectroscopic characterization, in vitro cytotoxic and structure activity relationships of some mononuclear Ru(II) complexes
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New mononuclear Ru(II) complexes [Ru(A)2(B)}2+, where A= 2,2'-bipyridine/1,10-phenanthroline and B= 3,4,5-tri-OCH3-DPC, 4-CH3-DPC, 4-N(CH3)2-DPC, 4-NO2-DPC, N-BITSZ, PTSZ and PINH, were prepared and characterized by spectroscopic methods. The in vitro cytotoxic activities of the complexes and their corresponding ligands were investigated against the human cancer TlyMPhocyte cell lines molt 4/c8 and CEM and the murine tumor leukemia cell line L1210, human promyelocytic leukemia cells (HL-60) and Bel-7402 liver cancer cells by MTT assay. The complexes [Ru(A)2(B)}2+ (A= 1,10-phenanthroline, B= 3,4,5-tri-OCH3-DPC) exerts rather more potent activities against all of these cell lines, especially for CEM and L1210. Ru complexes and structure-activity relationships and anticancer mechanisms are also discussed.
- Thota, Sreekanth,Vallala, Srujana,Imran, Mohammad,Mekala, Sravani,Anchuri, Shyam Sunder,Karki, Subhas Somalingappa,Yerra, Rajeshwar,Balzarini, Jan,De Clercq, Erik
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p. 1031 - 1045
(2013/07/28)
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- New supramolecular structural motif coupling a ruthenium(II) polyazine light absorber to a rhodium(I) center
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Two new complexes, [(bpy)2Ru(dpp)RhI(COD)](PF 6)3 and [(Me2bpy)2Ru(dpp)Rh I(COD)](PF6)2(BF4) (bpy = 2,2′-bipyridine, Me2bpy = 4,4′-dimethyl-2,2′- bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine, and COD = 1,5-cyclooctadiene), representing a new Ru(II),Rh(I) structural motif, have been prepared and characterized by mass spectrometry, 1H NMR spectroscopy, electrochemistry, electronic absorption spectroscopy, and emission spectroscopy. These two complexes represent a new type of supramolecular complex with a [(TL)2Ru(dpp)]2+ (TL = terminal ligand) light absorber (LA) coupled to a Rh(I) center and are models for Ru(II),Rh(I) intermediates in the photochemical reduction of water using dpp-bridged Ru(II),Rh(III) photocatalysts. Electrochemical study reveals overlapping reversible Ru II/III and irreversible RhI/II/III oxidations and a quasi-reversible dpp0/- reduction, demonstrating that the lowest unoccupied molecular orbital (LUMO) is dpp(π*) based. The COD ligand is sterically bulky, displaying steric repulsions between hydrogen atoms on the alkene of COD and dpp about the square planar Rh(I) center. An interesting reactivity occurs in coordinating solvents such as CH3CN, where Rh(I) substitution leads to an equilibrium between the Ru(II),Rh(I) bimetallic and [(TL)2Ru(dpp)]2+ and [RhI(COD)(solvent) 2]+ monometallic species. The electronic absorption spectra of both complexes feature transitions at ca. 500 nm attributed to a Ru(dπ) → dpp(π*) metal-to-ligand charge transfer (MLCT) transition that is slightly red-shifted from the Ru synthon upon Rh(I) complexation. The methylation of TL on the Ru impacts the electrochemical and optical properties in a minor but predictable manner. The photophysical studies, by comparison with the model complex [{Ru(bpy)2}2(dpp)] (PF6)4 and related Rh(III) complex [(bpy) 2Ru(dpp)RhIIICl2(phen)](PF6) 3, reveal the expected absence of a Ru(dπ) → Rh(dσ*) 3MMCT state (metal-to-metal charge transfer) in the title complexes, which is present in Rh(III) systems. The absence of this 3MMCT state in Ru(II),Rh(I) complexes results in a longer lifetime and higher emission quantum yield for the Ru(dπ) → dpp(π*) 3MLCT state than [(bpy)2Ru(dpp)RhIIICl 2(phen)](PF6)3. Both complexes display photocatalytic hydrogen production activity in the presence of water and a sacrificial electron donor, with the [(bpy)2Ru(dpp)Rh I(COD)](PF6)3 possessing a higher catalytic activity than the methyl analogue. Both display low activities, hypothesized to occur due to steric crowding about the Rh(I) site.
- Zhou, Rongwei,Sedai, Baburam,Manbeck, Gerald F.,Brewer, Karen J.
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p. 13314 - 13324
(2014/01/06)
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- An efficient light-driven P450 BM3 biocatalyst
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P450s are heme thiolate enzymes that catalyze the regio-and stereoselective functionalization of unactivated C-H bonds using molecular dioxygen and two electrons delivered by the reductase. We have developed hybrid P450 BM3 heme domains containing a covalently attached Ru(II) photosensitizer in order to circumvent the dependency on the reductase and perform P450 reactions upon visible light irradiation. A highly active hybrid enzyme with improved stability and a modified Ru(II) photosensitizer is able to catalyze the light-driven hydroxylation of lauric acid with total turnover numbers of 935 and initial reaction rate of 125 mol product/(mol enzyme/min).
- Tran, Ngoc-Han,Nguyen, Daniel,Dwaraknath, Sudharsan,Mahadevan, Sruthi,Chavez, Garrett,Nguyen, Angelina,Dao, Thanh,Mullen, Sarah,Nguyen, Thien-Anh,Cheruzel, Lionel E.
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supporting information
p. 14484 - 14487
(2013/10/22)
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- Silane: A new linker for chromophores in dye-sensitised solar cells
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A series of ruthenium(II) polypyridyl complexes, with novel silane functionalisation, [Ru(bipy)2(bipy-sil)](PF6)2 (3), [Ru(bipy-sil)2Cl2] (6), and [Ru(bipy-sil) 2(NCS)2] (7) have been synthesised and tested as chromophores (dyes) in TiO2 and WO3 based dye-sensitised solar cells (DSSCs). The performance of the respective DSSCs were compared to analogous dyes with ionic carboxylate ([Ru(bipy)2(dcbipy)](PF 6)2 (1), [Ru(dcbipy)2Cl2] (4), [Ru(dcbipy)2(NCS)2] (5)) or phosphonate ([Ru(bipy) 2(dpipy)](PF6)2 (2)) linking groups. The covalent silane-metal oxide linkage offers much needed improvement to the operating conditions, and lifetime of DSSCs, in terms of pH range and choice of solvent. UV-Vis spectroscopy of the deep-red solutions showed that the bis-bipy-sil complexes absorbed more visible light than the tris-bipy complex, as indicated by the presence of two absorption bands and higher ε values. The UV-Vis spectrum of (3) contained a single broad absorption at 400-600 nm with: λmax = 457 nm; ε = 10 520 ± 440 L mol -1 cm-1, whereas two intense broad absorption bands were observed for novel bis-bipy-sil complexes (6): 340-370 nm (λ max(1) = 365 nm, ε(1) = 12 716 ± 180 L mol-1 cm-1); and 440-540 nm (λmax(2) = 485 nm, ε(2) = 11 070 ± 150 L mol-1 cm -1), and (7): 340-400 nm (λmax = 371 nm, ε(1) = 20 690 ± 485 L mol-1 cm-1), and 460-530 nm (λmax = 500 nm and ε(2) = 20 750 ± 487 L mol-1 cm-1). The bands in (7) being significantly more defined. A 10-fold improvement in the efficiency of the bipy-sil TiO2-based DSSCs was observed from (3) to (6) to (7). This performance was lower than that of the commercial N3 dye, [Ru(dcbipy) 2(NCS)2] (5), but the current of (7) on WO3, was comparable to that of the carboxylate system (4). There is considerable potential for further improvement by modification of the silyl linker, reducing the long non-conjugated propyl chain between the amide group and the silatrane (bipy-sil), to a short, conjugated link. During an extensive synthetic study, the most promising strategy was identified as direct linkage, the formation of a direct Si-C bond, using butyllithium with 4,4′-dibromo-2,2′- bipyridine and either trimethylsilane or 1-ethoxysilatrane, provided that the product can be captured and stabilised prior to binding to a metal oxide coated DSSC substrate.
- Szpakolski, Katherine,Latham, Kay,Rix, Colin,Rani, Rozina A.,Kalantar-Zadeh, Kourosh
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p. 719 - 732
(2013/06/26)
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- Ruthenium-bipyridine complexes bearing fullerene or carbon nanotubes: Synthesis and impact of different carbon-based ligands on the resulting products
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This paper discusses the synthesis of two carbon-based pyridine ligands of fullerene pyrrolidine pyridine (C60-py) and multi-walled carbon nanotube pyrrolidine pyridine (MWCNT-py) via 1,3-dipolar cycloaddition. The two complexes, C60-Ru and MWCNT-Ru, were synthesized by ligand substitution in the presence of NH4PF6, and Ru(ii)(bpy)2Cl2 was used as a reaction precursor. Both complexes were characterized by mass spectroscopy (MS), elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy (IR), ultraviolet/visible spectroscopy (UV-VIS) spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and cyclic voltammetry (CV). The results showed that the substitution way of C 60-py is different from that of MWCNT-py. The C60-py and a NH3 replaced a Cl- and a bipyridine in Ru(ii)(bpy) 2Cl2 to produce a five-coordinate complex of [Ru(bpy)(NH3)(C60-py)Cl]PF6, whereas MWCNT-py replaced a Cl- to generate a six-coordinate complex of [Ru(bpy) 2(MWCNT-py)Cl]PF6. The cyclic voltammetry study showed that the electron-withdrawing ability was different for C60 and MWCNT. The C60 showed a relatively stronger electron-withdrawing effect with respect to MWCNT. The Royal Society of Chemistry 2011.
- Wu, Zhen-Yi,Huang, Rong-Bin,Xie, Su-Yuan,Zheng, Lan-Sun
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p. 8353 - 8360
(2011/10/10)
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- PHOTOSENSITIVE AMINOACID-MONOMER LINKAGE AND BIOCONJUGATION APPLICATIONS IN LIFE SCIENCES AND BIOTECHNOLOGY
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This invention is related to preparation of photosensitive ruthenium based aminoacid monomers and oligomers, aminoacid monomer-protein cross- linking using photo sensitat ion and conjugation on micro and nano-structures by ruthenium-chelate based monomers. Its vast range biotechnolgy applications of multifunctional, biocompatible, stabilE and specific micro and nanobio-conjugates, which will stand-alone or simultaneously enable (i) both purification and determination, (ii) both targeting and imaging and theranostics and (iii) catalysis and determination. The construction and method of preparation is applicable to silica materials, superparamagnetic particles, QDs, CNTs, Ag/ Au nanoparticles and Au surfaces and polymeric materials. The photosensitive aminoacid monomer linkers can react via chemically and biocompatible to a lot of different micro and nano-surface and then to the protein when they act as a single-step cross-linking reaction using irradiation. The photosensitive conjugation based on click biochemistry can be carried out at mild conditions, independent of pH and temperature, without affecting conformation and function of protein.
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Page/Page column 14
(2011/06/26)
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- Anthracene-bridged binuclear ruthenium complexes: Electrochemical and spectroscopic evidence of electronic communication through the Π system
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Six dinuclear cyclometalated ruthenium complexes, 1-6, based on diphenylanthracene (DPA) and anthracene (AN) as bridging ligands have been synthesized and fully characterized electrochemically and spectroscopically. The anodic electrochemistry of the homobinuclear ruthenium complexes, 1 -6, has been examined in three different nonaqueous solvents (ACN, DMF, and CH 2CI2). The ability of the anthracene derivatives to transmit electronic effects between the two redox units has been demonstrated by the observed splitting of the voltammetric signals ascribed to the metal centers. The electronic communication has also been evidenced by the presence of intervalence charge transfer transition bands in the near-infrared region of the spectrum due to an intramolecular electron transfer process mediated by the bridge when the mixed valence species (RuII/RuIII) are electrochemically generated. Cyclic voltammetric measurements have been carried out under different conditions of solvent and supporting electrolyte. Differences in ?,E°′ the potential separation of the formal potentials of the metal-based anodic processes, have been observed and found to depend on the medium employed. These differences have been ascribed to different degrees of ion pairing. Such effects can be, in turn, modulated as a function of not only the polarity and donor strength of the solvent but also of the coordinating capacity of the anion employed as a supporting electrolyte.
- Vila, Neus,Zhong, Yu-Wu,Henderson, Jay C.,Abrun, Hector D.
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p. 796 - 804
(2010/04/04)
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- SUPRAMOLECULAR METALLIC COMPLEXES EXHIBITING BOTH DNA BINDING AND PHOTOCLEAVAGE
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Supramolecular complexes that target and cleave DNA are provided. The supramolecular complexes include at least one metal-to-ligand charge transfer (MLCT) light absorbing unit, at least one Pt based DNA binding unit, and at least one bridging unit that serves to connect the components. The Pt-based DNA binding unit binds the complex to DNA, and the MLCT unit absorbs light, thereby sensitizing molecular oxygen to produce reactive oxygen species in close proximity to the complex and the bound DNA. The reactive oxygen species cleave the bound DNA.
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Page/Page column 6; 3/17
(2008/06/13)
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- BINUCLEAR METAL COMPLEX, METAL COMPLEX DYE, PHOTOELECTRIC TRANSDUCER AND PHOTOCHEMICAL BATTERY
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A novel binuclear metal complex according to the present invention is an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n, wherein M1 and M2, which may be identical or different, represent a transition metal; L1 and L2, which are different, represent a chelate ligand capable of polydentate coordination and two L1s may be different and two L2s may be different; BL represents a bridge ligand having at least two heteroatom-containing cyclic structures, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1 and M2; X represents a counter ion; and n is the number of counter ions needed to neutralize the charge of the complex. And the binuclear metal complex is useful as a metal complex dye.
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Page/Page column 23-24
(2008/06/13)
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- Efficient synthesis of ruthenium complexes of the type (R-bpy) 2RuCl2 and [(R-bpy)2Ru(L-L)]Cl2 by microwave-activated reactions (R: H, Me, tert-But) (L-L: Substituted bibenzimidazoles, bipyrimidine, and phenanth
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Complexes of the type (R-bpy)2RuCl2 (R: H, Me, tert-but) were synthesised by microwave-activated reactions of [Ru(cod)Cl 2]n with substituted 2,2′-bipyridines in dimethylformamide in high yields and high purity.
- Rau, Sven,Sch?fer, Bernhard,Grü?ing, André,Schebesta, Sebastian,Lamm, Katja,Vieth, Jana,G?rls, Helmar,Walther, Dirk,Rudolph, Manfred,Grummt, Ulrich W.,Birkner, Eckard
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p. 4496 - 4503
(2008/10/09)
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- Electropolymerisable bipyridine ruthenium(II) complexes: Synthesis, spectroscopic and electrochemical characterisation of 4-((2-thienyl) ethenyl)- and 4,4′-di((2-thienyl) ethenyl)-2,2′ -bipyridine ruthenium complexes
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Four new ruthenium polypyridyl complexes with mono- or di-((2-thienyl) ethenyl) substituted bipyridines have been synthesized. The complexes were characterized by NMR, elemental analysis, UV-Vis absorption and electrochemistry (differential pulse and cyclic voltammetry). Electroactive polymer films of these complexes have been prepared by oxidative electropolymerisation and characterized by UV-Vis absorption spectroscopy and electrochemistry. The electrochemically induced polymerisation of the complexes resulted in a significant shift of the oxidation potential of the Ru(II)-Ru(III) process towards more positive potentials. Also, MLCT absorption band of the polymeric complexes is shifted towards shorter wavelengths. These results are interpreted in terms of an interruption of the conjugated system of the (2-thienyl)ethenyl-substituted bipyridine ligands due to a radical polymerisation mechanism affecting rather the ethenyl part of the ligand than the thienyl.
- Aranyos, Viviane,Hagfeldt, Anders,Grennberg, Helena,Figgemeier, Egbert
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p. 589 - 598
(2008/10/09)
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- Tuning the properties of ruthenium bipyridine dyes for solar cells by substitution on the ligands - Characterisation of bis[4,4′-di(2-(3- methoxyphenyl)ethenyl)-2,2′ -bipyridine] [4,4′-dicarboxy-2,2′- bipyridine]ruthenium(II) dihexafluorophosphate
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The new dye complex bis[4,4′-di(2-(3-methoxyphenyl)ethenyl)-2, 2′-bipyridine][4,4′-dicarboxy-2,2′-bipyridine]-ruthenium(II) dihexafluorophosphate (1) has been prepared, characterised by absorption spectroscopy and adsorbed onto nanocrystalline TiO2 electrodes. The resulting system was studied by absorption spectroscopy, electrochemistry and photoelectrochemistry and the results were compared to those for a reference system with bis[2,2′-bipyridine]-[4,4′-dicarboxy-2,2′- bipyridine]ruthenium(II) (2). The system with 1 displays a broader and red-shifted UV-vis absorption compared to that with 2. Moreover, the system with 1 is less sensitive towards the water content in the electrolyte, and an adsorbed monolayer of 1 remains on the electrode surface after days even in aqueous NaOH (0.1 M), while 2 desorbs immediately.
- Aranyos, Viviane,Hjelm, Johan,Hagfeldt, Anders,Grennberg, Helena
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p. 1280 - 1283
(2007/10/03)
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- Ligand selective monosubstitution with complete enantiomeric retention in ruthenium bis(bipyridine) complexes
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Ligand selective monosubstitution with complete enantiomeric retention in Δ and Λ-cis-[Ru(bpy)2(DMSO)(Cl)]PF6 has been achieved photochemically. Irradiation in the presence of various ligands, including 4,4′-bipyridine, results in th
- Hesek,Hembury,Drew,Taniguchi,Inoue
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p. 2478 - 2479
(2008/10/08)
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- Surface functionalization of cadmium sulfide quantum confined nanoclusters 6: Evidence of facile electronic communication between remote surface sites
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The preparation and derivatization of a series of surface functionalized ~ 30 ? cadmium sulfide nanoclusters possessing surfaces of varied electron demand, tethered covalently to an electroactive fluorescent ruthenium polypyridyl complex, are described. Electrochemical analyses of these nanoclusters bearing ruthenium moieties yield a monotonic relationship between the Ru(II/III) oxidation potential and the electron withdrawing nature of the cluster surface, indicating that the electron density at the electroactive ruthenium center is indeed influenced by remote electropositive and electronegative substituents attached to the nanocluster. Further evidence of cluster mediated electronic interactions between remote surface moieties presents itself in the form of a dependence of the integrated ruthenium based MLCT emission intensity on the mole per cent of attached thiolate capping agent possessing an electron withdrawing substituent in the position para to the point of cluster attachment. (C) 2000 Elsevier Science Ltd.
- Veinot,Farah,Galloro,Zobi,Bell,Pietro
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p. 331 - 341
(2008/10/08)
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- Synthesis, X-ray structures, spectroscopic and electrochemical properties of ruthenium(II) complexes containing 2,2'-bipyrimidine
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Ruthenium polypyridyl complexes containing 2,2'-bipyrimidine, [Ru(bpy)2bpm](PF6)2 (I) and [Ru(phen)2bpm](PF6)2 (II), were synthesized with high yield and purity. An extensive characterization was carried out using ESMS, UV-Vis, 1H and 13C NMR, electrochemistry and X-ray single crystal diffraction analysis. The experimental results show that the spectroscopic and electrochemical properties of I and II are similar to those of their parent complexes [Ru(bpy)3](PF6)2 and [Ru(phen)3](PF6)2. This indicates that both I and II can be used as building blocks for the construction of molecular devices. (C) 2000 Elsevier Science S.A.
- Ji, Zhiqin,Huang, Songping D.,Guadalupe, Ana R.
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p. 127 - 134
(2008/10/08)
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