130897-00-6Relevant articles and documents
Engineering of Highly Luminescent Lanthanide Tags Suitable for Protein Labeling aad Time-Resolved Luminescence Imaging
Weibel, Nicolas,Charbonniere, Loic J.,Guardigli, Massimo,Roda, Aldo,Ziessel, Raymond
, p. 4888 - 4896 (2004)
The synthesis of a new ligand LH4 based on a glutamic acid skeleton bis-functionalized on its nitrogen atom by 6-methylene-6′ -carboxy-2,2′-bipyridine chromophoric units is described. UV-vis spectrophotometric titrations revealed the formation of 1:1 M:L complexes with lanthanide(III) cations, and complexation of LH4 with equimolar amounts of hydrated LnCl3 salts (Ln = Eu, Gd, and Tb) gave water-soluble and stable complexes of the general formula [LnL(H 2O)]Na, which were characterized by elemental analysis, IR, UV-vis absorption spectroscopy, 1H NMR (Ln = Eu), and mass spectrometry. The conditional stability constant for formation of the [EuL(H2O)]Na complex was determined by competitive complexation experiments to be log K= 16. 5 ± 0.6 in 0.01 M TRIS/HCl buffer (pH = 7.0). In water solution, the [EuL(H2O)]Na and [TbL(H2O)]Na complexes were highly luminescent with quantum yields of 8% and 31%, respectively, despite the presence of ca. one water molecule in the first coordination sphere of the metal ions. Activation of the appended carboxylate function of the glutamate moiety in the form of an N-hydroxysuccinimidyl ester allows for the covalent linking of the complexes to primary amino groups of biological compounds. Bovine serum albumin (BSA) was labeled with both Eu or Tb complexes, and the Ln-BSA conjugates were characterized by UV-vis absorption and emission spectroscopy and MALDI-TOF mass spectrometry. Labeling ratios (number of complex molecules per BSA) of ca. 8:1 and 7:1 were established for Eu-BSA and Tb-BSA, respectively. The suitability of the tagged compound for use in bioanalytical time-resolved luminescence microscopy was established by comparison with fluorescein-labeled probes.
Sulfur(IV)-Mediated Unsymmetrical Heterocycle Cross-Couplings
Zhou, Min,Tsien, Jet,Qin, Tian
supporting information, p. 7372 - 7376 (2020/04/09)
Despite the tremendous utilities of metal-mediated cross-couplings in modern organic chemistry, coupling reactions involving nitrogenous heteroarenes remain a challenging undertaking – coordination of Lewis basic atoms into metal centers often necessitate elevated temperature, high catalyst loading, etc. Herein, we report a sulfur (IV) mediated cross-coupling amendable for the efficient synthesis of heteroaromatic substrates. Addition of heteroaryl nucleophiles to a simple, readily-accessible alkyl sulfinyl (IV) chloride allows formation of a trigonal bipyramidal sulfurane intermediate. Reductive elimination therefrom provides bis-heteroaryl products in a practical and efficient fashion.
Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds
Gil-Sepulcre, Marcos,Axelson, Jordan C.,Aguiló, Joan,Solà-Hernández, Lluís,Francàs, Laia,Poater, Albert,Blancafort, Lluís,Benet-Buchholz, Jordi,Guirado, Gonzalo,Escriche, Lluís,Llobet, Antoni,Bofill, Roger,Sala, Xavier
, p. 11216 - 11229 (2016/11/17)
A RuII-pentadentate polypyridyl complex [RuII(κ-N5-bpy2PYMe)Cl]+ (1+, bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6-2,2′-bipyridyl)ethane) and its aqua derivative [RuII(κ-N5-bpy2PYMe)(H2O)]2+ (22+) were synthesized and characterized by experimental and computational methods. In MeOH, 1+ exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-12+ generates a [RuIII(κ-N4-bpy2PYMe)Cl2]+ intermediate after the exchange of a pyridyl ligand by a Cl- counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-12+ is in direct equilibrium with trans-12+, with absence of the κ-N4-bis-chlorido RuIII-intermediate. All these equilibria were modeled by density functional theory calculations. Interestingly, the aqua derivative is obtained as a pure trans-[RuII(κ-N5-bpy2PYMe)(H2O)]2+ isomer (trans-22+), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [RuII(κ-N5-bpy(bpyMe)PYMe)Cl]+ (3+) and [RuII(κ-N5-bpy(bpyMe)PYMe)(H2O)]2+ (42+) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [RuII(PY5Me2)X]n+ system (X = Cl, n = 1 (5+); X = H2O, n = 2 (62+)), which also contains a κ-N5-RuII coordination environment, and to the newly synthesized [RuII(PY4Im)X]n+ complexes (X = Cl, n = 1 (7+); X = H2O, n = 2 (82+)), which possess an electron-rich Hκ-N4C-RuII site due to the replacement of a pyridyl group by an imidazolic carbene.
NOVEL MICROBIOCIDES
-
Page/Page column 165, (2013/03/26)
The present invention relates to methods of controlling or preventing phytopathogenic diseases on useful plants or on propagation material thereof comprising applying to useful plants, the locus thereof or propagation material thereof a compound of formula (I) wherein Q, Q', L1, L2, L3, L4, L5, L6 and X are as defined in claim 1. The invention also relates to novel compounds that may be used in said methods, as well as intermediates useful for the preparation of the novel compounds.
