- Factors Impacting Electron Transfer in Cyano-Bridged {Fe2Co2} Clusters
-
A cyano-bridged {FeIII2CoII2} complex exhibits reversible thermally and photoinduced intramolecular charge transfer. Its desolvated, MeOH-d4, and other analogues were compared to disclose the impact factors on the electron-transfer behavior of these {FeIII2CoII2} clusters.
- Zheng, Chunyang,Xu, Juping,Yang, Zhixin,Tao, Jun,Li, Dongfeng
-
-
Read Online
- Synthesis of Ortho-Functionalized 1,4-Cubanedicarboxylate Derivatives through Photochemical Chlorocarbonylation
-
The cubane ring has received intense attention as a 3D benzene isostere and scaffold. Mono-and 1,4-disubstituted cubanes are well-described. Here we report a practical procedure for a direct radical-mediated chlorocarbonylation process initially reported by Bashir-Hashemi, to access a range of 2-substituted 1,4-cubanedicarboxylic ester derivatives. A subsequent regioselective ester hydrolysis to give fully differentiated 1,2,4-Trisubstituted cubanes is demonstrated.
- Collin, Diego E.,Kovacic, Kristina,Light, Mark E.,Linclau, Bruno
-
-
Read Online
- Hetero-Bis-Conjugation of Bioactive Molecules to Half-Sandwich Ruthenium(II) and Iridium(III) Complexes Provides Synergic Effects in Cancer Cell Cytotoxicity
-
Four bipyridine-Type ligands variably derivatized with two bioactive groups (taken from ethacrynic acid, flurbiprofen, biotin, and benzylpenicillin) were prepared via sequential esterification steps from commercial 2,2′-bipyridine-4,4′-dicarboxylic acid and subsequently coordinated to ruthenium(II) p-cymene and iridium(III) pentamethylcyclopentadienyl scaffolds. The resulting complexes were isolated as nitrate salts in high yields and fully characterized by analytical and spectroscopic methods. NMR and MS studies in aqueous solution and in cell culture medium highlighted a substantial stability of ligand coordination and a slow release of the bioactive fragments in the latter case. The complexes were assessed for their antiproliferative activity on four cancer cell lines, showing cytotoxicity to the low micromolar level (equipotent with cisplatin). Additional biological experiments revealed a multimodal mechanism of action of the investigated compounds, involving DNA metalation and enzyme inhibition. Synergic effects provided by specific combinations of metal and bioactive fragments were identified, pointing toward an optimal ethacrynic acid/flurbiprofen combination for both Ru(II) and Ir(III) complexes.
- Batchelor, Lucinda K.,Biancalana, Lorenzo,Brabec, Viktor,Degano, Ilaria,Dyson, Paul J.,Hadiji, Mouna,Kostrhunova, Hana,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
-
-
Read Online
- Molecular engineered rhenium(i) carbonyl complexes to promote photoisomerization of coordinated stilbene-like ligands in the visible region
-
Novel fac-[Re(CO)3(dmcb)(trans-stpyR)]+ complexes, dmcb = 4,4′-dimethoxycarbonyl-2,2′-bipyridine, have been judiciously engineered to absorb at lower energies and sensitize trans-4-styrylpyridine (trans-stpy) or trans-4-(4-cyano)styrylpyridine (trans-stpyCN) photoisomerizable ligands up to 436 nm of irradiation. Moreover, these complexes exhibit remarkable photoreversibility, in particular fac-[Re(CO)3(dmcb)(trans-stpyCN)]+ (Φ255 nmcis→trans = 0.26 ± 0.02). Their distinct and noteworthy photochemical and photophysical behavior are described in this work. The main emphasis of this study is that the complexes efficiently sensitize stilbene-like ligand isomerization toward use in potential solar device applications.
- Amaral, Ronaldo C.,Murakami Iha, Neyde Y.
-
-
Read Online
- Synthesis, biomacromolecular interactions, photodynamic no releasing and cellular imaging of two [rucl(Qn)(lbpy)(no)]x complexes
-
Two light-activated NO donors [RuCl(qn)(Lbpy)(NO)]X with 8-hydroxyquinoline (qn) and 2,2′-bipyridine derivatives (Lbpy) as co-ligands were synthesized (Lbpy1 = 4,4′-dicarboxyl-2,2′-dipyridine, X = Cl? and Lbpy2 = 4,4′-dimethoxycarbonyl-2,2′-dipyridine, X = NO3? ), and characterized using ultraviolet–visible (UV-vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (1 H NMR), elemental analysis and electrospray ionization mass spectrometry (ESI-MS) spectra. The [RuCl(qn)(Lbpy2 )(NO)]NO3 complex was crystallized and exhibited distorted octahedral geometry, in which the Ru–N(O) bond length was 1.752(6) ? and the Ru–N–O angle was 177.6(6)? . Time-resolved FT-IR and electron paramagnetic resonance (EPR) spectra were used to confirm the photoactivated NO release of the complexes. The binding constant (Kb ) of two complexes with human serum albumin (HSA) and DNA were quantitatively evaluated using fluorescence spectroscopy, Ru-Lbpy1 (Kb ~106 with HSA and ~104 with DNA) had higher affinity than Ru-Lbpy2 . The interactions between the complexes and HSA were investigated using matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) and EPR spectra. HSA can be used as a carrier to facilitate the release of NO from the complexes upon photoirradiation. The confocal imaging of photo-induced NO release in living cells was successfully observed with a fluorescent NO probe. Moreover, the photocleavage of pBR322 DNA for the complexes and the effect of different Lbpy substituted groups in the complexes on their reactivity were analyzed.
- Bai, Hehe,Gong, Wenjun,Liu, Chenyang,Song, Luna,Wang, Ai,Wang, Hongfei,Wang, Li,Zhao, Xuan,Zhao, Yi
-
-
Read Online
- Redox Active Ion-Paired Excited States Undergo Dynamic Electron Transfer
-
Ion-pair interactions between a cationic ruthenium complex, [Ru(dtb)2(dea)][PF6]2, C12+ where dea is 4,4′-diethanolamide-2,2′-bipyridine and dtb is 4,4′-di-tert-butyl-2,2′-bipyridine, and chloride, bromide, and iodide are reported. A remarkable result is that a 1:1 iodide:excited-state ion-pair, [C12+, I-]+*, underwent diffusional electron-transfer oxidation of iodide that did not occur when ion-pairing was absent. The ion-pair equilibrium constants ranged 104-106 M-1 in CH3CN and decreased in the order Cl- > Br- > I-. The ion-pairs had longer-lived excited states, were brighter emitters, and stored more free energy than did the non-ion-paired states. The1H NMR spectra revealed that the halides formed tight ion-pairs with the amide and alcohol groups of the dea ligand. Electron-transfer reactivity of the ion-paired excited state was not simply due to it being a stronger photooxidant than the non-ion-paired excited state. Instead, work term, ΔGw was the predominant contributor to the driving force for the reaction. Natural bond order calculations provided natural atomic charges that enabled quantification of ΔGw for all the atoms in C12+ and [C12+, I-]+* presented herein as contour diagrams that show the most favorable electrostatic positions for halide interactions. The results were most consistent with a model wherein the non-ion-paired C12+* excited state traps the halide and prevents its oxidation, but allows for dynamic oxidation of a second iodide ion.
- Troian-Gautier, Ludovic,Beauvilliers, Evan E.,Swords, Wesley B.,Meyer, Gerald J.
-
-
Read Online
- Synthesis of novel tridentate pyrazole–bipyridine ligands for Co-complexes as redox-couples in dye-sensitized solar cells
-
Novel pyrazole bipyridine ligands have been synthesized from 4,4′-substituted bipyridines through oxidation, chlorination and non-catalyzed C–N coupling of potassium pyrazolate with 6-halogen-4,4′-bipyridines in diglyme. These tridentate pyrazole–bipyridine ligands are of interest as components of new redox systems for dye-sensitized solar cells.
- Zavozin, Alexander G.,Ignat'ev, Nikolai V.,Schulte, Michael,Zlotin, Sergei G.
-
-
Read Online
- Dimethyl 2,2′-bipyridine-6,6′-dicarboxyl-ate and bis-(dimethyl 2,2′-bipyridine-6,6′-dicarboxyl-ato-2 N,N′)copper(I) tetra-fluoro-borate
-
The single-crystal X-ray structures of dimethyl 2,2′-bipyridine-6, 6′-dicarboxylate, C14H12N2O4, and the copper(I) coordination complex bis-(dimethyl 2,2′-bipyridine-6,6′-dicarboxylato-2 N,N′)copper(I) tetra-fluoro-borate, [Cu(C14H12N2O4)2]BF4, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anti-cipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter-pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′-bipyridine. International Union of Crystallography 2007.
- Blake, Alexander J.,Champness, Neil R.,Mason, Pamela V.,Wilson, Claire
-
-
Read Online
- A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl-Ligated Gold(I) Centers
-
A combined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C2H4)]+ complexes. The modular nature of this system allowed a systematic assessment of the effects of complex structure. Computational comparisons between cationic gold and the isolobal (neutral) Pd0 and Pt0 complexes revealed similar mechanistic features, but with oxidative addition being significantly favored for the group 10 metals. Further differences between Au and Pd were seen in experimental studies: studying reaction rates as a function of electronic and steric properties showed that ligands bearing more electron-poor functionality increase the rate of oxidative addition; in a complementary way, electron-rich aryl iodides give faster rates. This divergence in mechanism compared to Pd suggests that Ar?X oxidative addition with Au can underpin a broad range of new or complementary transformations.
- Bower, John F.,Cadge, Jamie A.,Russell, Christopher A.
-
supporting information
p. 24976 - 24983
(2021/10/20)
-
- Double-ligand nitrosyl ruthenium complex as well as preparation method and application thereof
-
The invention belongs to the technical field of preparation of nitrosylruthenium complex, and relates to a double-ligand nitrosyl ruthenium complex and a preparation method and application thereof. The chemical formula of the double-ligand nitrosyl ruthenium complex is [RuCl (qn) (Lbpy) (NO)] NO. 3 , qn Is 8 -hydroxyquinoline, Lbpy is 2,2 '-bipyridine -4, 4' - dimethyl formate and the structural formula thereof is shown in the specification. The obtained complex has high purity and low cytotoxicity, and has certain water solubility and sensitive photodynamic activity. Experimental detection shows that the complex can quantitatively regulate the release of nitric oxide through photoexcitation, and can be applied to nitric oxide donors in a nitric oxide donor and cell system in a solution system for preparing light regulation and control.
- -
-
Paragraph 0017-0018
(2021/10/20)
-
- Synthesis of a Water-Soluble, Soft N-Donor BTzBP Ligand Containing only CHON
-
A hydrophilic ligand that contains only C, H, O, and N substituents and uses a 6,6′-bis(1 H -1,2,3-triazol-4-yl)-2,2′-bipyridine (BTzBP) structural core has been synthesized. The effect of adding water-soluble groups onto extractant ligands has been extensively studied to facilitate the efficient partitioning of 4f and transuranic 5f elements for the treatment of spent nuclear fuel. Soft, N-donor ligands exhibit greater binding affinities for the trivalent actinides over the trivalent lanthanides, making BTzBP ligands an ideal candidate in the search for extractants to be used on an industrial scale. To date, hydrophobic BTzBPs have been shown to exhibit physical and chemical properties that might be conducive to nuclear waste processing conditions. However, hydrophilic BTzBPs have yet to be reported. Herein, we show the synthesis of a hydrophilic BTzBP ligand featuring cationic water solubilizing groups attached to the bipyridal rings.
- Albright, Savannah G.,Ali, Bakr,Chapman, Hayley A.,Cheng, Yijie,Cusic, Rachel M.,Friese, Seth J.,Hartlove, Nathan B.,Labb, Samantha A.,Marr, Alissa N.,Masteran, Conner J.,Timmons, Miranda
-
supporting information
p. 1384 - 1388
(2020/08/03)
-
- Rational Design of Phosphorescent Iridium(III) Complexes for Selective Glutathione Sensing and Amplified Photodynamic Therapy
-
It is a huge challenge to avoid irreversible damage to normal tissues during irradiation in photodynamic therapy (PDT) for cancer. An effective strategy is to develop smart photosensitizers, which exhibit amplified generation of reactive oxygen species (ROS) through triggering specific reaction in the tumor microenvironment. In this work, we designed a class of glutathione (GSH)-activatable photosensitizers (Ir1 and Ir4) based on an effective strategy of GSH-induced nucleophilic substitution reaction. The addition of GSH, induced changes in both phosphorescence intensity and lifetime of photosensitizers with high sensitivity. Importantly, the amount of singlet oxygen generated was increased significantly by GSH-induced activation reaction. Hence, the photosensitizers can selectively distinguish cancer cells from normal cells through luminescence and lifetime imaging, and can amplify PDT effects in cancer cells, owing to the evidently higher level of GSH compared to normal cells. This work presents a novel paradigm for GSH-amplified PDT against cancer cells and provides a new avenue for smart-responsive theranostic systems that can avoid nonspecific damage to normal cells.
- Huang, Tianci,Yu, Qi,Liu, Shujuan,Zhang, Kenneth Yin,Huang, Wei,Zhao, Qiang
-
p. 576 - 586
(2018/11/23)
-
- Identification of novel lysine demethylase 5-selective inhibitors by inhibitor-based fragment merging strategy
-
Histone lysine demethylases (KDMs) have drawn much attention as targets of therapeutic agents. KDM5 proteins, which are Fe(II)/α-ketoglutarate-dependent demethylases, are associated with oncogenesis and drug resistance in cancer cells, and KDM5-selective inhibitors are expected to be anticancer drugs. However, few cell-active KDM5 inhibitors have been reported and there is an obvious need to discover more. In this study, we pursued the identification of highly potent and cell-active KDM5-selective inhibitors. Based on the reported KDM5 inhibitors, we designed several compounds by strategically merging two fragments for competitive inhibition with α-ketoglutarate and for KDM5-selective inhibition. Among them, compounds 10 and 13, which have a 3-cyano pyrazolo[1,5-a]pyrimidin-7-one scaffold, exhibited strong KDM5-inhibitory activity and significant KDM5 selectivity. In cellular assays using human lung cancer cell line A549, 10 and 13 increased the levels of trimethylated lysine 4 on histone H3, which is a specific substrate of KDM5s, and induced growth inhibition of A549 cells. These results should provide a basis for the development of cell-active KDM5 inhibitors to highlight the validity of our inhibitor-based fragment merging strategy.
- Miyake, Yuka,Itoh, Yukihiro,Hatanaka, Atsushi,Suzuma, Yoshinori,Suzuki, Miki,Kodama, Hidehiko,Arai, Yoshinobu,Suzuki, Takayoshi
-
p. 1119 - 1129
(2019/02/13)
-
- Synthesis and characterization of novel heteroleptic Ru(II) bipyridine complexes for dye-sensitized solar cell applications
-
Abstract: Four heteroleptic ruthenium(II) complexes, [Ru(L1)(L2)(NCS)2] (where L1 = 4,4′-bis[2-(1,1′-biphenyl)-4-ylethenyl]-2,2′-bipyridine (bpbpy) or 4,4′-bis[2-(3,4-dimethoxyphenyl)ethenyl]-2,2′-bipyridine (dmpbpy); L2 = 4,4′-dicarboxy-2,2′-bipyridine (dcbpy) or 4,4′-bis(E-carboxyvinyl)-2,2′-bipyridine (dcvbpy)), were synthesized from a one-pot reaction of [RuCl2(p-cymene)]2 and L1 followed by the addition of the anchoring ligand, L2. From these new heteroleptic ruthenium(II) complexes containing carboxylic acid-functionalized ligands, the tetrabutylammonium salt forms of the ruthenium(II) complexes, [Ru(L1)(L2)(NCS)2][TBA], were obtained in reasonable yields and applied as dyes in dye-sensitized solar cell (DSSC) devices. Among the DSSCs fabricated with the [Ru(L1)(L2)(NCS)2][TBA] dyes, a DSSC fabricated with the [Ru(bpbpy)(dcbpy)(NCS)2][TBA] dye exhibited the best power conversion efficiency (η) of 4.27%, while the cells fabricated with other dyes had η between 1.94 and 2.68%. Graphic abstract: [Figure not available: see fulltext.].
- Seo, Jinhyung,Jeong, Mingyeong,Na, Seo Yeong,Lee, Eugin,Kim, Yang-Rae,Park, Byoungchoo,Kim, Byeong Hyo
-
p. 1445 - 1452
(2019/07/29)
-
- Xylose derivatives and process for preparation thereof
-
Disclosure of the present invention relates to a method for synthesis of a xylose derivative, which comprises protecting a xylose with a protective group, followed by incorporating to a halogen atom as a leaving group; removing the protective groups and using water-soluble ligands to carry out a Suzuki cross-couplings reaction with a palladium catalyst in a water solution. Ten new xylose derivatives as obtained by the method are also provided.
- -
-
Page/Page column 9
(2019/09/01)
-
- XYLOSE DERIVATIVES AND PROCESS FOR PREPARATION THEREOF
-
Disclosure of the present invention relates to a method for synthesis of a xylose derivative, which comprises protecting a xylose with a protective group, followed by incorporating to a halogen atom as a leaving group removing the protective groups and using water-soluble ligands to carry out a Suzuki cross-couplings reaction with a palladium catalyst in a water solution. Ten new xylose derivatives as obtained by the method are also provided.
- -
-
Paragraph 0076-0078
(2020/04/10)
-
- Control of Excited-State Supramolecular Assembly Leading to Halide Photorelease
-
Ground- and excited-state control of halide supramolecular assembly was achieved through the preparation of a series of ester- and amide-functionalized ruthenium polypyridyl complexes in CH2Cl2. Hydrogen-bonding amide and alcohol groups on the receptor ligand were found to direct interactions with halide, while halide association with the ethyl ester groups was not observed. The various functional groups on the receptor ligands tuned the ground-state equilibrium constants over 2 orders of magnitude (1 × 105 to 1 × 107 M-1), and the fractional contribution of each hydrogen-bond donor to the total equilibrium constant was determined. Pulsed-laser excitation of the complexes resulted in excited-state localization on the ester- or amide-functionalized ligands. In the case where the excited state was oriented toward an associated halide ion (the amide complexes), an 80 ± 10 meV Coulombic repulsion was induced that lowered the excited-state equilibrium constant (K?eq) and resulted in halide photorelease. The rate constants for excited-state halide release (k?21) were determined, and the values varied based on the functional groups present in the receptor ligand. Complexes with more hydrogen-bonding donors had smaller rate constants for halide photorelease. In a complex without a specific receptor ligand, the excited-state dipole was not oriented toward the associated halide, and the excited state was therefore found to have a larger equilibrium constant for halide association than the ground state.
- Turlington, Michael D.,Troian-Gautier, Ludovic,Sampaio, Renato N.,Beauvilliers, Evan E.,Meyer, Gerald J.
-
p. 3316 - 3328
(2019/05/25)
-
- Chromium(VI) oxide-mediated oxidation of polyalkyl-polypyridines to polypyridine-polycarboxylic acids with periodic acid
-
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
-
supporting information
p. 2210 - 2218
(2019/06/25)
-
- Visible Photosensitization of trans-Styrylpyridine Coordinated to fac-[Re(CO)3(dcbH2)]+: New Insights
-
A strategic methodology has been developed to effectively synthesize the fac-[Re(CO)3(dcbH2)(trans-stpy)]+ complex, where dcbH2 = 2,2′-bipyridine-4,4′-dicarboxylic acid and trans-stpy = trans-4-styrylpyridine, which has been designed to efficiently absorb visible light. The complex exhibits outstanding trans-to-cis photoisomerization with 436 nm irradiation (φtrans→cis = 0.50 ± 0.03), in contrast to the photochemical behavior previously reported in the literature (Faustino, L. A.; et al. Inorg. Chem. 2018, 57, 2933-2941). The main emphasis here is to address the synthetic strategy for obtaining the actual complex, its characterization, and an accurate description of its photochemical and photophysical behavior, which reveal new insights into this complex.
- Matos, Lais S.,Amaral, Ronaldo C.,Murakami Iha, Neyde Y.
-
p. 9316 - 9326
(2018/08/17)
-
- Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′-Bis((E)-styryl)-2,2′-bipyridine as Ancillary Ligand and Application for Dye-Sensitized Solar Cells
-
Heteroleptic Ru(II) complexes were designed based on 4,4′-bis((E)-styryl)-2,2′-bipyridine (bsbpy) as an ancillary ligand for dye-sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)2][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one-pot reaction of [RuCl2(p-cymene)]2 with the corresponding anchoring ligands (where L?=?4,4′-dicarboxy-2,2′-bipyridine (dcbpy), 4,4′-bis((E)-carboxyvinyl)-2,2′-bipyridine (dcvbpy), 4,7-dicarboxy-1,10-phenanthroline (dcphen), or 4,7-bis((E)-carboxyvinyl)-1,10-phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)2][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red-shifted bands over the overall UV/VIS region relative to the absorption spectra of N719. A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)2][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719, 4.82%).
- Lee, Jihoon,Seo, Jinhyung,Choi, Yong Rack,Oh, Hyunju,Huh, Jun Nyeong,Park, Byoungchoo,Tak, Jungae,Kim, Byeong Hyo
-
-
- Ionic type iridium complex with double phosphorescence emission properties as well as preparation method and application of ionic type iridium complex
-
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.
- -
-
Paragraph 0051; 0053; 0055
(2018/01/11)
-
- Synthetic method for 2,2'-bipyridine-4,4'-methyl formate
-
The invention provides a synthetic method for 2,2'-bipyridine-4,4'-methyl formate. The synthetic method comprises the following steps: 1) mixing 2,2'-bipyridine, methyl chloroformate, an acid-binding agent, a solvent and a catalyst, introducing protective gas, and carrying out a reaction at 90 to 120 DEG C under a pressure of 3 to 4 MPa for 5 to 9 h; and 2) after completion of the reaction, carrying out cooling, separating and purifying so as to obtain a product namely 2,2'-bipyridine-4,4'-methyl formate. The synthetic method provided by the invention uses 2,2'-bipyridine as a raw material, and the raw material is easily available and cheap; the reaction has short steps and is a one-step reaction, so operation is more simple; the use of strongly-corrosive substances like dichromic acid and sulfuric acid can be avoided, so operation is safe and simple; the yield is high and reaches 98% or above; meanwhile, the process has low cost; and simple postprocessing and less pollution are realized.
- -
-
Paragraph 0017
(2017/08/31)
-
- Pyridinium-based ionic phosphorescent iridium complex probe and preparation method and biotechnological application thereof
-
The invention relates to a pyridinium-based ionic phosphorescent iridium complex probe and a preparation method and biotechnological application thereof, in particular to phosphorescent iridium complex for detecting and reducing glutathione, cysteine, hydrogen sulfide and other sulfydryl containing reductive substances and application of the phosphorescent iridium complex in detecting the redox state in cells, and belongs to the technical field of organic photoelectric functional materials. The complex material is prepared from cyclometalated ligand, a metal center (iridium) and pyridinium group modified auxiliary ligand, and the structure of the complex is shown as the following formula. The complex has wide application prospects on the technical aspects of detecting the redox state in the cells, phosphorescence lifetime imaging and time resolution. The formula can be seen in the specification.
- -
-
Paragraph 0023; 0025; 0028
(2017/11/07)
-
- PT(IV) COMPLEXES CONTAINING 4,4'-DISUBSTITUTED-2,2'-BIPYRIDYL AND THEIR USE IN CANCER THERAPY
-
Platinum-containing compounds for the treatment of disease, such as, for example, cancer, are provided herein. Specifically, platinum Pt(IV) complexes with a substituted 2,2'-bipyridine ring structure are provided, as are methods for using the complexes.
- -
-
Paragraph 00109; 00214-00215
(2016/02/29)
-
- Post-synthetic modifications of cadmium-based knots and links
-
Three topologically non-trivial cadmium(ii)-based complexes - Cd-[2]C, Cd-TK and Cd-SL - were simultaneously self-assembled in a dynamic library, individually isolated and fully characterized using solid-state, gas-phase and solution-phase techniques. Post-synthetic modifications, including reduction and transmetalation, were subsequently achieved. Imine bond reduction followed by demetallation led to the isolation of the corresponding organic molecules [2]C, TK and SL. Transmetalation of Cd-TK and Cd-SL with the zinc(ii) cation resulted in isolation of the corresponding zinc(ii)-containing complexes Zn-TK and Zn-SL.
- Prakasam, Thirumurugan,Bilbeisi, Rana A.,Lusi, Matteo,Olsen, John-Carl,Platas-Iglesias, Carlos,Trabolsi, Ali
-
supporting information
p. 7398 - 7401
(2016/06/14)
-
- Ruthenium bipyridyl tethered porous organosilica: A versatile, durable and reusable heterogeneous photocatalyst
-
A versatile heterogeneous photocatalysis protocol was developed by using ruthenium bipyridyl tethered porous organosilica (Ru-POS). The versatility of the Ru-POS catalyst in organo-photocatalysis was explored by (i) oxidative aromatization of Hantzsch ester, (ii) reductive dehalogenation of alkyl halides, and (iii) functional group interconversion (FGI) of alcohols to alkyl halides. This journal is
- Jana, Avijit,Mondal, John,Borah, Parijat,Mondal, Sujan,Bhaumik, Asim,Zhao, Yanli
-
supporting information
p. 10746 - 10749
(2015/06/30)
-
- Dynamic stereoisomerization in inherently chiral bimetallic [2]catenanes
-
Stereoisomerization and the unprecedented phenomenon of metal translocation in the absence of redox processes were probed in two inherently chiral bimetallic [2]catenanes by using a combination of variableerature 1H NMR and CD spectroscopies, X-ray crystallography, and DFT calculations.
- Prakasam, Thirumurugan,Lusi, Matteo,Nauha, Elisa,Olsen, John-Carl,Sy, Mohamadou,Platas-Iglesias, Carlos,Charbonnière, Lo?c J.,Trabolsi, Ali
-
supporting information
p. 5840 - 5843
(2015/03/31)
-
- Study of asymmetric aldol and Mannich reactions catalyzed by proline-thiourea host-guest complexes in nonpolar solvents
-
A proline-thiourea host-guest complex has been described as a good catalyst for asymmetric reactions such as aldol and Mannich reactions. High stereoselectivities were obtained under optimal conditions. Thiourea was observed to have an important effect on the reactivity and selectivity, even in an unconventional nonpolar reaction medium and without the need to utilize low temperatures. This proline-thiourea host-guest system has the ability to participate in a hydrogen bonding network.
- Demir, Ayhan Sitki,Basceken, Sinan
-
p. 515 - 525
(2013/06/26)
-
- Simultaneous self-assembly of a [2]catenane, a trefoil knot, and a solomon link from a simple pair of ligands
-
A topological triptych: Three molecular links, a [2]catenane, a trefoil knot, and a Solomon link, were obtained in one pot through the self-assembly of two simple ligands in the presence of ZnII (see picture). The approach relied on dynamic covalent chemistry and metal templation.
- Prakasam, Thirumurugan,Lusi, Matteo,Elhabiri, Mourad,Platas-Iglesias, Carlos,Olsen, John-Carl,Asfari, Zouhair,Cianferani-Sanglier, Sarah,Debaene, Francois,Charbonniere, Loic J.,Trabolsi, Ali
-
supporting information
p. 9956 - 9960
(2013/10/01)
-
- Inhibition of histone demethylases by 4-Carboxy-2,2'-Bipyridyl compounds
-
Exploiting epigenetics: 2-Oxoglutarate (2OG)-dependent histone lysine demethylases, such as JMJD2E, are potential therapeutic targets in a range of diseases. Through structure-activity relationship studies and analyses, we identified a potent 4-carboxy-2,2'-bipyridyl compound, which inhibits JMJD2E with an IC50 value of 110nM, representing a 66-fold improvement over the lead compound. These bipyridyl derivatives bind in the 2-oxoglutarate binding site.
- Chang, Kai-Hsuan,King, Oliver N. F.,Tumber, Anthony,Woon, Esther C. Y.,Heightman, Tom D.,Mcdonough, Michael A.,Schofield, Christopher J.,Rose, Nathan R.
-
scheme or table
p. 759 - 764
(2012/01/06)
-
- Synthesis and characterization of cross-linkable ruthenium dye with ion coordinating property for dye-sensitized solar cells
-
Crosslinkable ruthenium complex dye, Ru(2,2′-bipyridine-4,4′- bicarboxylic acid)(4,4′-bis((4-vinyl benzyloxy)methyl)-2,2′- bipyridine)(NCS)2 (denoted as Ru-S dye), was synthesized and characterized using 1H-NMR, 13C-NMR, Fourier transform infrared (FTIR) and UV/vis spectroscopies.The power conversion efficiency of dye-sentitized solar cell (DSSC) using Ru-S and liquid electrolyte containing lithium iodide (LiI) reached 7.53% under standard global AM 1.5 full sunlight, which is partly attributed to Li+ being coordinated by Ru-S as verified by ATR-FTIR spectroscopy. As Ru-S was further crosslinked with glycerol propoxylate triacrylate (GPTA), not only 89% of dye retained on TiO2 mesoporous surface after rinsed by 0.1 N NaOH aqueous solution, the power efficiency was also increased to 7.88%. As poly(methyl acrylate) was used to gel the electrolyte system, the power efficiency of DSSC with Ru-S dye was 6.96% but increased to 7.57% after crosslinking with GPTA. Notably, both DSSCs showed a good long-term stability after one month storage.
- Liu, Ken-Yen,Ko, Chih-Yang,Ho, Kuo-Chuan,Lin, King-Fu
-
scheme or table
p. 3318 - 3324
(2012/05/31)
-
- HISTONE LYSINE DEMETHYLASE INHIBITORS
-
The invention provides a compound which is an iV-oxalylglycine derivative of formula (I): a hydroxamic acid derivative of formula (II): or a heteroaryl derivative of fomula (III): wherein n; Z1; Z2; Y1; Y2; A; p; X1; X2; m; R4; B; R5; R6; R7; R8; R9; X3; R10; R11 and R12 are as defined herein, or a pharmaceutically acceptable salt thereof. These compounds are inhibitors of the human 2-oxoglutarate-dependant JMJD2 subfamily of histone demethylases, in particular JMJD2E. Such inhibitors are useful in changing the epigenetic state of cells resulting in the inhibition / activation of chromatin remodelling, multiple gene activation / deactivation, and in treating cancer and other conditions characterised by undesirable cellular proliferation, and psychiatric disorders including depression.
- -
-
Page/Page column 80
(2010/04/30)
-
- Catalytic atom-transfer radical cyclization by copper/bipyridine species encapsulated in polysiloxane gel
-
Novel polysiloxane gel, in which CuCl/bipyridine species are immobilized, is prepared by treatment of polymethylhydrosiloxane with 4,4′-bis[(2- propenyl)oxy]-2,2′-bipyridine and 1,5-hexadine in the presence of Karstedt′s catalyst followed by addition of CuCl. This polysiloxane gel acts as a reusable catalyst in the atom-transfer radical cyclization of α-halogenated acetamide derivatives in high turnover numbers without allowing leakage of the metal species.
- Motoyama, Yukihiro,Kamo, Kazuyuki,Yuasa, Akihiro,Nagashima, Hideo
-
supporting information; experimental part
p. 2256 - 2258
(2010/07/09)
-
- Selective protein-surface sensing using Ruthenium(II) Tris(bipyridine) complexes
-
"Chemical Equation Presented" Protein surface recognition: Functionalised RuII tris-(bipyridine) complexes are shown to act as high-affinity (2 nM) and selective receptors for the surface of cytochrome c (see figure) as compared to a panel of other proteins
- Muldoon, James,Ashcroft, Alison E.,Wilson, Andrew J.
-
experimental part
p. 100 - 103
(2010/04/02)
-
- Highly soluble dichloro, dibromo and dimethyl dioxomolybdenum(VI)- bipyridine complexes as catalysts for the epoxidation of olefins
-
The reaction of solvent substituted MoO2X2(S) 2 (X = Cl, S = THF; X = Br, S = DMF) complexes with one equivalent of bidentate nitrogen donor ligands at room temperature leads within a few minutes to the quantitative formation of complexes of the type [MoO2X 2L2] (L = 4,4′-bis-methoxycarbonyl-2,2′- bipyridine, 5,5′-bis-methoxycarbonyl-2,2′-bipyridine, 4,4′-bis-ethoxycarbonyl-2,2′-bipyridine, 5,5′-bis- ethoxycarbonyl-2,2′-bipyridine). Treatment of the complexes [MoO 2Cl2L2] with Grignard reagents at low temperatures yields dimethylated complexes of the formula [MoO 2(CH3)2L2]. [MoO2Br 2(4,4′-bis-ethoxycarbonyl-2,2′-bipyridine)], [MoO 2Br2(5,5′-bis-methoxycarbonyl-2,2′-bipyridine) ] and [MoO2Br2(5,5′-bis-ethoxycarbonyl-2,2′- bipyridine)] have been exemplary examined by single crystal X-ray analysis. The complexes were applied as homogenous catalysts for the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free conditions. The complexes containing L = Cl have been additionally investigated with room temperature ionic liquids (RTILs) as solvents. The catalytic activity of the [MoO2X2L2] complexes in olefin epoxidation with tert-butyl hydroperoxide is on average very good. The main advantage of the synthesised complexes in comparison to previously reported complexes is their high solubility. This good solubility is apparently the reason that the catalytic potential of the compounds can unfold. The turnover frequencies (TOFs) in RTILs are even higher, showing the performance of the catalysts under optimised conditions.
- Günyar, Alev,Betz, Daniel,Drees, Markus,Herdtweck, Eberhardt,Kühn, Fritz E.
-
experimental part
p. 117 - 124
(2011/01/07)
-
- Protein surface recognition by dendritic ruthenium(II) tris(bipyridine) complexes
-
We report protein surface binding of dendritic ruthenium(II) tris(bipyiridine) complexes to α-chymotrypsin, resulting in a 1:1 and 1:2 protein complex formation as well as inhibition of the enzyme activity. The Royal Society of Chemistry 2009.
- Ohkanda, Junko,Satoh, Ritsuko,Kato, Nobuo
-
supporting information; experimental part
p. 6949 - 6951
(2010/04/25)
-
- Inhibitor scaffolds for 2-oxoglutarate-dependent histone lysine demethylases
-
The dynamic methylation of histone lysyl residues plays an important role in biology by regulating transcription, maintaining genomic integrity, and by contributing to epigenetic effects. Here we describe a variety of inhibitor scaffolds that inhibit the human 2-oxoglutarate-dependent JMJD2 subfamily of histone demethylases. Combined with structural data, these chemical starting points will be useful to generate small-molecule probes to analyze the physiological roles of these enzymes in epigenetic signaling.
- Rose, Nathan R.,Ng, Stanley S.,Mecinovi?, Jasmin,Liénard, Beno?t M. R.,Bello, Simon H.,Sun, Zhe,McDonough, Michael A.,Oppermann, Udo,Schofield, Christopher J.
-
supporting information; experimental part
p. 7053 - 7056
(2009/11/30)
-
- Artificial G-wire switch with 2,2′-bipyridine units responsive to divalent metal ions
-
Development of a guanine nanowire (G-wire) that is controllable and can be switched by external signals is important for the creation of molecular electronic technologies. Here, we constructed a G-wire in which the thymines of the main chain of d(G4T4G4) were replaced with 2,2′-bipyridine units, which have two aromatic rings that rotate arbitrarily upon coordination with metal ions. Circular dichroism of the DNA oligonucleotides with or without the 2,2′-bipyridine unit showed that divalent metal ions induce the bipyridine-containing oligonucleotide to switch from an antiparallel to a parallel G-quadruplex. Native polyacrylamide gel electrophoresis showed that the parallel-stranded G-quadruplex DNA had a high-order structure. Circular dichroism and native gel electrophoresis analyses suggested that adding Na2EDTA causes a reverse structural transition from a parallel-stranded high-order structure to an antiparallel G-quadruplex. Moreover, atomic force microscopy showed a long nanowire (~200 nm) in the presence of Ni2+ but no significant image in the absence of Ni 2+ or in the presence of both Ni2+ and Na2EDTA. These observations revealed that the parallel-stranded high-order structure is a G-wire containing numerous DNA oligonucleotide strands bound together via divalent metal ion-2,2′-bipyridine complexes. Finally, we found that alternating addition of Ni2+ and Na2EDTA can cycle the G-wire between the high-order and disorganized structures, with an average cycling efficiency of 0.95 (i.e., 5% loss per cycle). These results demonstrate that a DNA oligonucleotide incorporating the 2,2′-bipyridine unit acts as a G-wire switch that can be controlled by chemical input signals, namely, divalent metal ions.
- Miyoshi, Daisuke,Karimata, Hisae,Wang, Zhong-Ming,Koumoto, Kazuya,Sugimoto, Naoki
-
p. 5919 - 5925
(2008/02/06)
-
- Syntheses, characterizations, and properties of electronically perturbed 1,1′-dimethyl-2,2′-bipyridinium tetrafluoroborates
-
The syntheses of three new 2,2′-bipyridinium tetrafluoroborate sensitizers are reported. Their preliminary electrochemical and photophysical properties are compared to the properties of the more widely used pyrylium cation sensitizers. In addition, the first examples of triplet-triplet absorption spectra of 2,2′-bipyridinium ions are presented.
- Zhang, Dong,Dufek, Eric J.,Clennan, Edward L.
-
p. 315 - 319
(2007/10/03)
-
- Synthesis and recognition behaviour of allosteric hemicarcerands
-
Bipyridine bridged bis(resorcinarenes) have been prepared. Upon co-ordinating to a transition metal ion, e.g. Ag+, the respective metal complex forms a hemicarcerand-like structure with the two resorcinarene moieties capable of binding non-polar organic molecules in a co-operative fashion, as shown qualitatively by NMR spectroscopy.
- Lützen, Arne,Ha?, Oliver,Bruhn, Torsten
-
p. 1807 - 1811
(2007/10/03)
-
- Synthesis of C3-cyclotriveratrylene ligands for iron(II) and iron(III) coordination
-
The design and synthesis of a new family of siderophores based on cyclotriveratrylene is described. The ligands consist of a C3-cyclotriveratrylene unit provided with three arms (spacers) ending with hydroxamate, catecholate, bipyridine, or iminopyridine units suitable for the octahedral coordination of transition metals and particularly for the complexation of iron(II) and iron(III).
- Veriot, Gilles,Dutasta, Jean-Pierre,Matouzenko, Galina,Collet, Andre
-
p. 389 - 400
(2007/10/02)
-
- Novel polytopic macrocyclic receptor molecules containing multiple bipyridyl and dibenzo-18-crown-6 units
-
New polytopic macrocycles (7)-(11) containing multiple 4,4′-disubstituted-2,2′-bipyridyl and dibenzo-18-crown-6 units are described. Preliminary coordination studies reveal these novel ligands form polymetallic complexes with ruthenium and potassium guest cations.
- Kocian, Oldrich,Mortimer, Roger J.,Beer, Paul D.
-
p. 5069 - 5072
(2007/10/02)
-
- Synthesis of 4,4'-Divinyl-2,2'-bipyridine
-
4,4'-Divinyl-2,2'-bipyridine (2) was prepared in 12 percent overall yield from 4,4'-dimethyl-2,2'-bipyridine (3) via a 5 step reaction sequence involving the intermediate 4,4'-R2-2,2'-bipyridines: R=COOH, 4; CO2CH3, 5; CH2OH, 6; CHO, 7.The newly synthesized compounds 2, 6 and 7 were characterized by melting point, infrared, 1H nmr, mass spectrometry and elemental analysis.
- Ciana, Leopoldo Della,Dressick, Walter J.,Zelewsky, A. von
-
p. 163 - 165
(2007/10/02)
-