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Structures and Fluorescent Properties of Cadmium(II) Complexes with 1D and 2D Structures Based on Tridentate Benzimidazole Ligands

The cadmium(II) complexes [CdL1(m-nba)2] (1), [CdL1(p-nba)2]¡¤C2H5OH (2), [CdL2(p-nba)2]¡¤CH3OH (3), and [CdL2(p-nbat)2] (4) containing the ligands L1 and L2 [L1 = 2,6-bis(benzimidazol-2-yl)pyridine, L2 = bis(2-benzimidazolylmethyl)amine] were synthesized and characterized (m-nba, p-nba, and p-nbat are the anions of p-nitrobenzoic acid, m-nitrobenzoic acid, and p-nitrobenzeneacetic acid, respectively). The complexes were investigated by X-ray single crystal diffraction, elemental analysis as well as IR and fluorescence spectroscopy. Compounds 1-3 contain a distorted pentagonal bipyramidal coordination sphere with CdII coordinated by two carboxylate ligands in bidentate-chelating mode, whereas complex 4 exhibits a distorted octahedral arrangement with one carboxylate ligand in bidentate-chelating and the other in monodentate coordination mode. 1 and 2 form a 1D chain interplayed by hydrogen bonding and strong pi-pi stacking interactions. 3 and 4 vary from 1D chain into 2D single-layer and double-layer networks because of more extensive hydrogen bonding interactions. The complexes show emission maxima in the blue region in the solid state and emission bands are red-shifted compared to those of the free ligands.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Reference of 14220-64-5, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.14220-64-5, Name is Bis(benzonitrile)palladium chloride, molecular formula is C14H10Cl2N2Pd. In a Article£¬once mentioned of 14220-64-5

Synthesis, magnetic and spectral studies of Co(II) picrate complexes with heterocyclic nitrogen donors

New mixed-ligand picrate complexes of cobalt(II), formed by interaction of cobalt(II) picrate with 2-aminobenzothiazole (ABZT), 2-(2′- aminophenyl)benzothiazole (2′-AMPHBZT), 2-(3′-aminophenyl)benzothiazole(3′- AMPHBZT), bipyridyl(Bipy), o-phenonthroline (Phen), and 2,6- bis(benzimidazole-2’yl)pyridine(BBZLY) are described. The complexes have been characterised by elemental analyses, molar conductances, magnetic and decomposition temperature measurements, electron spin resonance, infrared and electronic spectral studies. They have the composition [Co(PA)2(L-L)2], where L – L= ABZT, 2′-AMPHBZT, 3’AMPHBZT, Bipy, Phen or BBZLY. A trans octahedral structure has been tentatively proposed for these complexes.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Synthesis, characterization and theoretical studies of the heteroleptic Ruthenium(II) complexes of 2,6-bis(benzimidazolyl)pyridine

Four new Ruthenium(II) complexes [Ru(bbp)(pyterpy)](PF6)2 (1), [Ru(bbp)(bip)Cl]PF6 (2), [Ru(bbp)(biq)Cl]PF6 (3) and [Ru(bbp)(phen)Cl]PF6 (4) have been synthesized and characterized by spectroscopic techniques (IR, NMR and mass) and single crystal X-ray diffraction study of one of them (4) (where bbp = 2,6-bis(benzimidazolyl)pyridine, pyterpy = 4(4-pyridyl)terpyridine, phen = 1,10-phenanthroline, bip = 2-(benzimidazolyl)pyridine, biq = 2,2?-biquinoline). The electronic spectra of all the complexes show significant bathochromic shift of their lowest energy Metal to Ligand Charge Transfer band position with respect to [Ru(bpy)3]2+. The position of the MLCT band is modulated by the nature of the coligand, the 2,6-bis(benzimidazolyl)pyridine ligand being present in all the complexes. The change in the RuIII/II potential is also explained on the basis of the sigma/pi donor characteristic of the ligands.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Anticancer activity of two novel ruthenium compounds in gastric cancer cells

Aims: Ruthenium (II) complexes are promising anticancer molecules due its pharmacological properties and selectivity to cells tumor. The aim of this work was to study the cytotoxic activity, and apoptosis induction of two new ruthenium complexes on a human gastric cancer cell line. Main methods: Two ruthenium(II) complexes were synthesized: [(H2pbbzim)Ru(tpy-Ph-COOCH3)](Cl)2 (Ru-UCN1), and [(tpy)Ru(tpy-Ph-bzH)](Cl)2 (Ru-UCN3), and their anticancer capacity determined by cytotoxic assays, gene expression analysis, caspase activation and confocal microscopy. Key findings: Ru-UCN3 is more notably cytotoxic than cisplatin in human gastric cancer cells AGS at 24 h, while Ru-UCN1 is more active against gastric cancer cells than cisplatin at 48 h. The complexes induce apoptosis as shown by RT-qPCR, protease activity, and confocal microscopy. Ru-UCN1 induces the overexpression of pro-apoptotic genes at 3 and 6 h, whereas Ru-UCN3 induces overexpression of these genes at 12 and 24 h. Ru-UCN1 treatment shows a strong activation of caspases 3/7 at 24 h, which was not observed for Ru-UCN3 treatment in the same timeframe. Significance: Taken together, this data suggests that Ru-UCN1 and to a lesser extent, Ru-UCN3, may be interesting anticancer agents for gastric cancer.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Partitioning of 2,6-Bis(1H-Benzimidazol-2-yl)pyridine fluorophore into a phospholipid bilayer: Complementary use of fluorescence quenching studies and molecular dynamics simulations

Successful use of fluorescence sensing in elucidating the biophysical properties of lipid membranes requires knowledge of the distribution and location of an emitting molecule in the bilayer. We report here that 2,6-bis(1H-benzimidazol-2-yl)pyridine (BBP), which is almost non-fluorescent in aqueous solutions, reveals a strong emission enhancement in a hydrophobic environment of a phospholipid bilayer, making it interesting for fluorescence probing of water content in a lipid membrane. Comparing the fluorescence behavior of BBP in a wide variety of solvents with those in phospholipid vesicles, we suggest that the hydrogen bonding interactions between a BBP fluorophore and water molecules play a crucial role in the observed “light switch effect”. Therefore, the loss of water-induced fluorescence quenching inside a membrane are thought to be due to deep penetration of BBP into the hydrophobic, water-free region of a bilayer. Characterized by strong quenching by transition metal ions in solution, BBP also demonstrated significant shielding from the action of the quencher in the presence of phospholipid vesicles. We used the increase in fluorescence intensity, measured upon titration of probe molecules with lipid vesicles, to estimate the partition constant and the Gibbs free energy (DeltaG) of transfer of BBP from aqueous buffer into a membrane. Partitioning BBP revealed strongly favorable DeltaG, which depends only slightly on the lipid composition of a bilayer, varying in a range from – 6.5 to – 7.0 kcal/mol. To elucidate the binding interactions of the probe with a membrane on the molecular level, a distribution and favorable location of BBP in a POPC bilayer were modeled via atomistic molecular dynamics (MD) simulations using two different approaches: (i) free, diffusion-driven partitioning of the probe molecules into a bilayer and (ii) constrained umbrella sampling of a penetration profile of the dye molecule across a bilayer. Both of these MD approaches agreed with regard to the preferred location of a BBP fluorophore within the interfacial region of a bilayer, located between the hydrocarbon acyl tails and the initial portion of the lipid headgroups. MD simulations also revealed restricted permeability of water molecules into this region of a POPC bilayer, determining the strong fluorescence enhancement observed experimentally for the membrane-partitioned form of BBP.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Gold(III) complexes containing N-heterocyclic carbene ligands: Thiol “switch-on” fluorescent probes and anti-cancer agents

Illuminating results: Activation of non-emissive [AuIII(N N N)(NHC)]+ complexes (such as 1) through reduction by intracellular glutathione gives active AuI-NHC complexes, which show promising anti-cancer properties, accompanied by release of the highly fluorescent ligand. The high fluorescence “switch-on” efficiency makes these Au III complexes excellent probes for cellular thiol detection. Copyright

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Crystal Structures and Luminescence Spectra of Ten-co-ordinate Lanthanide(III) Complexes (Ln = Ce, Sm, Eu or Tb) with 2,6-Bis(benzimidazol-2-yl)pyridine

The complexes NO3*nMeOH have been characterized by single-crystal X-ray diffraction, IR and 1H NMR spectroscopy and molar conductivity.They are ten-co-ordinate with six nitrogen atoms from two tridentate L ligands and four oxygen atoms from two bidentate nitrates, crystallizing in the triclinic system, space group P<*>, Z = 2; 1, a = 10.907(1), b = 14.498(1), c = 16.187(2) Angstroem, alpha = 63.02(1), beta = 75.54(1), gamma = 74.54(1) deg; 3, a = 10.864(8), b = 14.57(1), c = 15.95(1) Angstroem, alpha = 116.92(8), beta = 90.46(8), gamma = 106.32(8) deg; 4, a = 10.847(1), b = 14.567(2), c = 15.847(2) Angstroem, alpha = 117.25(1), beta = 90.39(1), gamma = 106.37(1) deg.The luminescence spectra of complexes 2 (Ln = Sm), 3 and 4 were recorded at room temperature in the solid state, and the quantum yields measured in methanol solution were in the order Eu > Tb > Sm.In the luminescence spectrum of complex 3, the electric dipole transitions 5D0 -> 7F2 and 5D0 -> 7F4 are more intense than is the magnetic dipole transition 5D0 -> 7F1, and the latter comprises three bands, suggesting a low C1 symmetry for the Eu(3+) ion, consistent with the crystallographic results.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Self-assembly of small gold nanoparticles through interligand interaction

Stable and monodisperse Au nanoparticles smaller than 2 nm are easily prepared by the reduction of HAuCl4-4H2O in DMF/H 2O in the presence of a series of bidentate ligands, 2,6-bis(1?-(n-thioalkyl)benzimidazol-2-yl)pyridine (TCnBIP, n = 3, 6, 8, 10, 12). The TCnBIP ligands afford stronger coordination ability than alkanethiols due to their bidentate nature. These small nanoparticles form hexagonal close-packed (hcp) two-dimensional (2D) superlattices with tunable interparticle spacings (from 1.2 to 2.5 nm), produced by changing the length of the ligand at both the hydrophobic amorphous carbon and the air-water interface. Long-range-ordered hep 2D superlattices were fabricated through the cleavage and construction of interligand pi-pi interactions formed via an annealing process at the air-water interface.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Controlling the Direction of the Molecular Axis of Rod-Shaped Binuclear Ruthenium Complexes on Single-Walled Carbon Nanotubes

We report the synthesis of a mixed-valence ruthenium complex, bearing pyrene moieties on one side of the ligands as anchor groups. Composites consisting of mixed-valence ruthenium complexes and SWNTs were prepared by noncovalent pi-pi interactions between the SWNT surface and the pyrene anchors of the Ru complex. In these composites, the long axis of the Ru complexes was aligned in parallel to the principal direction of the SWNT. The optimized conformation of these complexes on the SWNT surface was calculated by molecular mechanics. The composites were examined by UV/Vis absorption and FT-IR spectroscopy, XPS, and SEM analysis. Furthermore, their electrochemical properties were evaluated. Cyclic voltammograms of the composites showed reversible oxidation waves at peak oxidation potentials (Epox) = 0.86 and 1.08 V versus Fc+/Fc, which were assigned to the RuII-RuII/RuII-RuIII and the RuII-RuIII/RuIII-RuIII oxidation events of the dinuclear ruthenium complex, respectively. Based on these observations, we concluded that the electrochemical properties and mixed-valence state of the dinuclear ruthenium complexes were preserved upon attachment to the SWNT surface. A mixed-valence ruthenium complex was developed, bearing pyrene moieties on one side of the ligands as anchor groups. Composites consisting of mixed-valence ruthenium complexes and single-walled carbon nanotubes (SWNTs) were prepared by noncovalent pi-pi interactions between the SWNT surface and the pyrene anchors of the Ru complex (see figure). The long axis of the Ru complexes was aligned in parallel to the principal direction of the SWNT.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Copper(II)-benzimidazole complexes as efficient fluorescent probes for l-cysteine in water

Copper(ii) complexes [Cu(L1)(H2O)2](SO3CF3)21 and [Cu(L2)(H2O)2](SO3CF3)22 based on 2,6-bis(benzimidazolyl)pyridine were synthesized and are reported herein as highly selective “turn-on” optical probes for l-cysteine. The Cu(ii)/Cu(i) redox potential of probe 1 (0.14 V vs. NHE) was lower than that of 2 (0.233 V vs. NHE) in water. The molecular structure of 2 adopted a square pyramidal geometry (tau = 0.2545), with the Cu-Npy bond (1.958 A) of its middle pyridine unit being shorter than the other two Cu-Nbenzim bonds (Cu-N, 1.995, 2.000 A). The axial Cu-O2 bond distance (2.247 A) was slightly longer than the equatorial Cu-O1 bond distance (1.953 A). The square-based geometry was further supported by the A? value of 156 ¡Á 10-4 cm-1 in EPR at 70 K. The d-d and ligand-based transitions appeared at 662 and 314-356 nm for 1 and 651 and 313-360 nm for 2, respectively, in HEPES buffer at pH 7.34. These probes showed selective and efficient “turn-on” fluorescence behaviour towards Cys over other natural amino acids with a binding constant for 1 of 5.4 ¡Á 104 and 1.30 ¡Á 104 M-1 for 2 and a limit of detection of 2.9 ¡Á 10-8 M and 3.32 ¡Á 10-8 M, respectively, for 1 and 2 at pH 7.34. The quantum yield for the detection of Cys by 1 (14.7%) was much lower than by 2 (23%). The fluorescence intensity of 1 and 2 were also slightly enhanced by histidine, but at a relatively lower level than that exhibited by Cys.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method