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Several complexes of bis(2-pyridyl)amine (‘dpa’) with lead(II) salts have been synthesized and subjected to room-temperature single-crystal X-ray studies. 1:1 Adducts have been obtained with lead(II) bromide and iodide. They have similar unit cells, also similar to those of a variety of other N,N?-heteroaromatic bidentate ligand adducts with metal(II) halides, and the C2/c cell described elsewhere in this series may be regarded as archetypical. [(dpa)PbBr2](?/?) is monoclinic, P 21/a, a 9.791(4), b 9.720(4), c 16.498(4) A, beta 95.96(4), Z = 4 f.u.; conventional R on |F| at convergence was 0.066 for N = 2717 ‘observed’ (I > 3sigma(I)) reflections. [(dpa)PbI2](?/?) is monoclinic. P21/c, a 8.299(2), b 10.229(3), c 16-905(5) A, beta 101.47(2), Z = 4 f.u.; R was 0.044 for N 2140. Both complexes, like their 2,2?-bipyridine and 1,10-phenanthroline analogues, are linear polymers with six-coordinate (cis-N2)Pb(mu-X)4 environments linked in infinite … (mu-X)2Pb(mu-X)2…one-dimensional chains, and with dpa being bidentate. A 2:1 adduct of bis(2-pyridyl)amine with lead(II) acetate (‘Pb(ac)2?) is also described. [(dpa)2Pb(ac)2](?/?) is monoclinic, C 2/c, a 28.835(5), b 10.868(3), c 7.665(2) A, beta 94.21(2), Z = 4; R was 0.029 for N 1854. The complex is a linear polymer along c; the lead atom lies on a crystallographic twofold axis with a coordination environment comprising a pair of symmetry-related dpa ligands, in this case unidentate (Pb-N 3.092(6) A), and a pair of symmetry-related bidentate acetate ligands (Pb-O 2.465(4) and 2.568(5) A) with the first oxygen atom performing an additional bridging function to adjacent symmetry-related lead atoms (Pb-O 2.663(4) A).

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Reactions of CuF2, CuCl2 ? 2H2O and CuBr2 with 2,2?-dipyridylamine (HDPA) in water at room temperature using Cu:HDPA = 2:1 mol yield [Cu(HDPA)(H2O) 2F]F ? 3H2O (1), Cu(HDPA)Cl2 (2) and Cu(HDPA)Br2 (3) respectively. The structures of 2 and 3 are isostructural in spacegroup C2 with cell dimensions; for 2, a = 14.702(8), b = 7.726(2), c = 4.829(6) A, beta = 96.68(8) and for 3, a = 14.2934(8), b = 7.9057(6), c = 5.1982(5) A, beta = 94.049(7). In the X-ray crystal structure, the complex 1 is found to contain tapes of water pentamers. Our DFT calculations at the B3LYP/LanL2DZ level show that the reaction Cu(HDPA)X2 + 2H2O = [Cu(HDPA)(H 2O)2X]X is most exothermic in the gas phase when X – = F-, i.e., the tendency of water uptake is maximum for Cu(HDPA)F2. It seems that the exothermicities of the aquations of Cu(HDPA)Cl2 and Cu(HDPA)Br2 are not sufficient to stabilise the type of ribbons of water observed in 1 and consequently water is eschewed when X- = Cl- or Br-. Cu(2,2?-dipyridylamine)X2 takes up water to produce ribbons of water pentamer, as shown in the accompanied picture (red: O atom of a solvent water molecule), only when X- is F- but not when it Cl- or Br-. The results are rationalised by means of DFT calculations at the B3LYP/LanL2DZ level. [Figure not available: see fulltext.]

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The present invention relates to mononuclear and dinuclear coordination compounds of Ru and Ga, pharmaceutical formulations based thereof, the relative method of synthesis and encapsulation of the compounds in macromolecules, supramolecular aggregates or nanostructures, as well as their use for the diagnosis and/or treatment of neoplasia. Advantageously, such coordination compounds and/or formulations may contain carbohydrates which act as “cancer-targeting moieties” thereby increasing therapeutic selectivity. Said compounds and formulations are characterized by a promising toxicological profile, a remarkable and highly-selective anti-cancer activity, as well as stability and solubility in the physiological means.

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The potential of N(Me)-alkoxyamine glycosylation as a DNA-templated ligation has been studied. On a hairpin stem-template model, a notable rate enhancement and an increased equilibrium yield are observed compared to the corresponding reaction without a DNA catalyst. The N-glycosidic connection is dynamic at pH 5, whereas it becomes irreversible at pH 7. The N(Me)-alkoxyamine glycosylation may hence be an attractive pH controlled reaction for the assembly of DNA-based dynamic products.

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A composition including a Rh or Ru metailoinsertor complex specifically targets mismatch repair (MMR)~deficient cells. Selective cytotoxicity is induced in MMR-deficient cells upon uptake of the inventive metailoinsertor complexes.

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Partially protected monosaccharides, having the anomeric hydroxyl group underivatized, react with poly(hydrogen fluoride) to yield the corresponding glycosyl fluorides.

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The reaction between di-(2-pyridyl)amine and butyl nitrite produced N-nitrosodi-(2-pyridyl)amine, (5-nitro-2-pyridyl)-2-pyridylamine and (3-nitro-2-pyridyl)-2-pyridylamine of which the likely conformations are evinced from spectral data.Structural elucidation of N-nitrosodi-(2-pyridyl)amine in the solid state by X-ray diffraction excluded any substantial contribution of the rings to resonance structures.

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New 5,5-diethylbarbiturate (barb) complexes of Ni(ii), Cu(ii) and Zn(ii) with 1,10-phenanthroline (phen) and 2,2?-dipyridylamine (dpya), namely [Ni(phen-kappaN,N?)3]Cl(barb)·7H2O (1), [Cu(barb-kappaN)(barb-kappa2N,O)(phen-kappaN,N?)]·H2O (2), [Cu(barb-kappaN)2(phen-kappaN,N?)] (2a), [Zn(barb-kappaN)2(phen-kappaN,N?)]·H2O (3), [Ni(barb-kappa2N,O)(dpya-kappaN,N?)2]Cl·2H2O (4), [Cu(barb-kappa2N,O)2(dpya-kappaN,N?)]·2H2O (5) and [Zn(barb-kappaN)2(dpya-kappaN,N?)] (6), were synthesized and characterized by elemental analysis, UV-vis, FT-IR and ESI-MS. The structures of the complexes were determined by X-ray crystallography. Notably, 3 and 6 were fluorescent in MeOH:H2O at rt. The interaction of the complexes with fish sperm (FS) DNA and bovine serum albumin (BSA) was investigated in detail by various techniques. The complexes exhibited groove binding along with a partial intercalative interaction with DNA, while the hydrogen bonding and hydrophobic interactions played a major role in binding to BSA. It is noteworthy that 2 exhibited the highest affinity towards DNA and BSA. Enzyme inhibition assay showed that 1-4 show a preference for both A/T and G/C rich sequences in pUC19 DNA, while 5 and 6 display a binding specificity to the G/C and A/T rich regions, respectively. These findings were further supported by molecular docking. The cellular uptake studies suggested that 2 was deposited mostly in the membrane fraction of the cells. Among the present complexes, 2 exhibited a very strong cytotoxic effect on A549, MCF-7, HT-29 and DU-145 cancer cells, being more potent than cisplatin. Moreover, 2 induces cell death through the apoptotic mode obtained by flow cytometry.

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The transformation of simple hydrocarbons into more complex and valuable products has revolutionised modern synthetic chemistry. This type of reactivity has quickly become one of the cornerstones of modern catalysis . 499-40-1, Name is (2R,3S,4R,5R)-2,3,4,5-Tetrahydroxy-6-(((2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)hexanal, molecular formula is C12H22O11. In a Article,once mentioned of 499-40-1, Application of 499-40-1

Copper(I) thiocyanate derivatives were prepared by the reaction of CuNCS with pyridine (py) and tertiary monophosphine ligands [PR3 in general; in detail: PPh3, triphenylphosphine, P(4-FPh)3, tris(4-fluorophenyl)phosphine)], as well as the potentially bidentate ligand diphenyl(2-pyridyl)phosphine (PPh2py). Mechanochemical methods were used in some cases to investigate stoichieometries that were not easily accessible by conventional solution syntheses. Three forms of the resulting adducts of CuNCS/PR3/py-base (1:3-n:n) stoichiometry-all containing four-coordinate copper(I) atoms and monodentate N-thiocyanate groups-were confirmed crystallographically. Mononuclear arrays are defined for [(PPh2py)3-n(py)nCuNCS], n = 0, 1, 2, the monodentate thiocyanate being N-coordinated in all; two polymorphs are observed for the n = 2 complex, both crystallizing in monoclinic P21 (Z = 2) cells with similar cell dimensions, but with aromatic components eclipsed about the Cu-P bond in the PPh3 complex, and staggered in the PPh2py complex. Bridging thiocyanate groups are found in the 1:1:1 CuNCS/PPh2py/2-methylpyridine (mpy) and P(4-FPh)3/mpy complexes, wherein centrosymmetric dimers with eight-membered central rings are obtained: [(R3P)(mpy)Cu(NCS)2Cu(PR3)(mpy)], as is also the case in the parent 1:2 CuNCS/PPh2py adduct [(pyPh2P)2Cu(NCS)2Cu(PPh2py)2]. For the 1:1:1 CuNCS/P(4-FPh)3/py and PPh3/Brmpy (Brmpy = 3-bromo-4-methylpyridine) adducts, and, likely, CuNCS/PPh2py/py (1:1:1), single-stranded polymers of the form [?Cu(NCS)(PR3)(py-base)(Cu)?](?|?) with linearly bridging NCS ligands were obtained. Some derivatives, representative of all forms, display medium to strong green to blue luminescence when excited with radiation at 365 nm. The 31P CPMAS NMR spectroscopic data clearly differentiate the inequivalent phosphorus positions within each system, showing a wide range of 1J(31P,63/65Cu) values ranging from 965 Hz for [Cu(NCS)(PPh2py)3] to 1540 Hz for dimeric [(4-FPh)3P(mpy)Cu(NCS)2Cu(P(4-FPh)3)(mpy)], reflecting the large variations in the Cu-P bond length.

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A novel process is disclosed herein for the preparation of N-substituted halopyrrolidones of the formula STR1 in which X is selected from the group consisting of hydrogen, chlorine, and methyl; Y is selected from the group consisting of hydrogen, chlorine, and bromine; Z is selected from the group consisting of chlorine and bromine; R1 is selected from the group consisting of hydrogen and C1 -C4 alkyl; and R2 is selected from the group consisting of C1 -C6 alkyl, C3 -C6 alkenyl, C1 -C6 haloalkyl, C3 -C7 cycloalkyl, C4 -C8 cycloalkylalkyl, benzyl, chlorobenzyl, and STR2 in which R3 is selected from the group consisting og hydrogen, C1 -C4 alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyan, C1 -C4 alkoxy, C1 -C4 alkylthio, C1 -C4 alkylsulfinyl, C1 -C4 alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, and 3-methylureido; and R4 is selected from the group consisting of hydrogen, C1 -C4 alkyl, chlorine, and trifluoromethyl; WHICH COMPRISES THE INTRAMOLECULAR CYCLIZATION OF AN alpha-HALOGEN-CONTAINING N-2-alkenyl amide at a temperature of from about 60 C to about 200 C in the presence of a catalytic amount of a transition-metal-containing catalyst in which the transition metal is selected from the group consisting of vanadium, molybdenum, ruthenium, silver, and copper.

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