A multifunctional use of bis(methylene)bis(5-bromo-2-hydroxyl salicyloylhydrazone): from metal sensing to ambient catalysis of A3 coupling reactions.

The potential use of bis(methylene)bis(5-bromo-2-hydroxylsalicyloylhydrazone) as a multifunctional fluorescence sensor for Cu, Ni, Co and Fe ions was investigated. The optical behaviour shows an increase in an absorption band at 408 nm which can be ascribed to the d-d transition (UV-vis) of the metal ions and a concomitant decrease in fluorescence intensity at 507 nm. The crystallographic analysis shows the binding site of the sensor to two Cu ions and confirms the stoichiometry of 1 : 2 (ligand to metal) which is in good agreement with a Job plot analysis.

A designed and potentially decadentate ligand for use in lanthanide(iii) catalysed biomass transformations: targeting diastereoselective trans-4,5-diaminocyclopentenone derivatives.

The goal of this study was to design a ligand system which can accommodate single lanthanide(iii)-ions and investigate the properties of the resulting complexes. The complexes of all the accesible lanthanides and yttrium with the new ligand LH = N,N'-dimethyl-N,N'-ethylene-bis(5-bromo-3-(1H-benzimidazol-2-yl)hydrazineylidene)-2-hydroxybenzylamine) were obtained in high yield at room temperature under aerobic reaction conditions. The corresponding compounds were characterised using X-ray diffraction, FT-IR, elemental analysis and the optical properties of all complexes were investigated using UV-vis and fluorescence spectroscopy.

Tetranuclear Cu(ii)-chiral complexes: synthesis, characterization and biological activity.

Tetranuclear chiral Cu(ii)-Schiff-base complexes S-1 and R-1, were synthesised using enantiomerically pure ()-(HvanPheol) and ()-(HvanPheol) ligands respectively in the ratio of 1 : 1 of Cu(NO) to (/)-(HvanPheol) in MeOH at room temperature. A pair of polynuclear chiral Cu(ii)-cluster complexes were characterized using single-crystal X-ray diffraction, elemental analysis, infrared and CD spectroscopy. The results revealed the importance of these chiral ligands encouraging the arrangement of copper metal in non-centrosymmetric polar packing.

1,2,4-Triazine-Modified 2'-Deoxyuridine Triphosphate for Efficient Bioorthogonal Fluorescent Labeling of DNA.

In order to establish the Diels-Alder reaction with inverse electron demand for postsynthetic DNA modification, a 1,2,4-triazine-modified 2'-deoxyuridine triphosphate was synthesized. The bioorthogonally reactive 1,2,4-triazine group was attached at the 5-position of 2'-deoxyuridine by a flexible alkyl linker to facilitate its acceptance by DNA polymerases. The screening of four DNA polymerases showed successful primer extensions, using a mixture of dATP, dGTP, dCTP, and the modified 2'-deoxyuridine triphosphate, by using KOD XL or Vent polymerase.

Polarity Sensitive Bioorthogonally Applicable Far-Red Emitting Labels for Postsynthetic Nucleic Acid Labeling by Copper-Catalyzed and Copper-Free Cycloaddition.

Two series of new, water-soluble, membrane-permeable, far-red/NIR emitting benzothiazolium-based fluorescent labels with large Stokes' shifts were synthesized that can be conjugated to alkyne-modified biomolecules through their azide moiety via azide-alkyne cycloaddition. We have used these azide bearing labels to make fluorescent DNA constructs using copper-catalyzed "click" reaction. All dyes showed good or remarkable fluorescence intensity enhancement upon conjugation to DNA.

Copper-Free Postsynthetic Labeling of Nucleic Acids by Means of Bioorthogonal Reactions.

Postsynthetic modification of nucleic acids has the advantage that the chemical development of only a few building blocks is necessary, each bearing a chosen reactive functional group that is applicable to its reactive counterpart for a variety of different labeling types. The reactive group is either linked to phosphoramidites for chemical synthesis on solid phase or attached to nucleoside triphosphates for application in primer extension experiments and PCR. Chemoselectivity is required for this strategy, together with bioorthogonality to perform these labelings in living cells or even organisms.

Synthesis of gem-difluoromethylenated bicyclo[m.n.0]alkan-1-ols and their ring-expansion to gem-difluoromethylenated macrocyclic lactones.

Fluoride-catalyzed stereoselective nucleophilic addition of PhSCF(2)SiMe(3) (1) to α-carboethoxycycloalkanones 2 followed by intramolecular radical cyclization of the resulting cis-3 adduct afforded the corresponding gem-difluoromethylenated bicyclic compounds 4, which underwent ring-expansion followed by the Baeyer-Villiger-type oxidation of the resulting macrocyclic ketone intermediates to give gem-difluoromethylenated macrocyclic lactones 5.