Charge-Transfer Promoted Fixation of Glyphosate on TiO2 - a Multiscale Approach

In the present manuscript we used atomistic simulation methodsto investigate the adsorption of GGG on the titania rutile-(110)surface. The molecule showed a high adsorption to the surface es-pecially in its bidentate-⊥mode. This configuration was furtherinvestigated both in terms of charge transfer and strain analysis.In the first case a transfer of roughly one electron was observedfrom the functional groups binding to the surface atoms, leavingthe molecule at the phosphate and carboxylic groups. This chargeis distributed into the rutile’s bulk, where it gets then dissipated.To get a hint on the location of the bond break, the strain analysis identified the C-C bond as the major strain location. This presump-tion can not be confirmed in this work. In order to understand pho-tocaltalytic degradation of GGG in further investigations, a clustermodel was developed for TD-DFT simulations. The cluster simu-lations are in good agreement with the DFT simulations in termsof ground state properties (band gap and HOMO-levels) as well as geometrically optimized structures. <br>Here not only the DOS showeda reduction of the band gap upon adsorption, but also the TD-DFTspectrum lied in the same regime. Hence, there is a high likelihoodfor GGG to proceed in a photocatalytic reaction

Charge-Transfer Promoted Fixation of Glyphosate on TiO2 - a Multiscale Approach

In the present manuscript we used atomistic simulation methodsto investigate the adsorption of GGG on the titania rutile-(110)surface. The molecule showed a high adsorption to the surface es-pecially in its bidentate-⊥mode. This configuration was furtherinvestigated both in terms of charge transfer and strain analysis.In the first case a transfer of roughly one electron was observedfrom the functional groups binding to the surface atoms, leavingthe molecule at the phosphate and carboxylic groups. This chargeis distributed into the rutile’s bulk, where it gets then dissipated.To get a hint on the location of the bond break, the strain analysis identified the C-C bond as the major strain location. This presump-tion can not be confirmed in this work. In order to understand pho-tocaltalytic degradation of GGG in further investigations, a clustermodel was developed for TD-DFT simulations. The cluster simu-lations are in good agreement with the DFT simulations in termsof ground state properties (band gap and HOMO-levels) as well as geometrically optimized structures. <br>Here not only the DOS showeda reduction of the band gap upon adsorption, but also the TD-DFTspectrum lied in the same regime. Hence, there is a high likelihoodfor GGG to proceed in a photocatalytic reaction

Bis(4-phenyl-2-sulfanylidene-2,3-dihydro-1,3-thiazol-3-ido-κ2 S 2,N)(4-phenyl-1,3-thiazole-2-thiolato-κS 2)bismuth

The title compound, [Bi(C9H6NS2)3], was prepared by reacting BiCl3 and 2-mercapto-4-phenylthiazole (LH) at room temperature in a stoichiometric ratio of 1:4. The molecular structure reveals a slightly distorted square-pyramidal environment around the BiIII atom. Two of the three monoanionic ligands L − coordinate in an N,S-bidentate mode, while one shows a monodentate mode through an S atom. There are no significant intermolecular interactions present in the crystal.

How to complete the tautomerization and substrate-assisted activation prior to C–C bond fission by meta-cleavage product hydrolase LigY?

Two feasible binding modes could complete the C–C bond fission of the substrate. One is the bidentate mode and five-coordination, and the other is the monodentate mode and five-coordination.

Bis(μ-N,N-diallyldithiocarbamato)bis[(N,N-diallyldithiocarbamato)cadmium]

The title compound, [Cd2(C7H10NS2)4], is a neutral dinuclear cadmium(II) complex bearing four bisN,N-diallyldithiocarbamate ligands coordinating to two CdIIcations. In each of the monomeric subunits, there are four S atoms of two dithiocarbamate ligands [Cd—S = 2.5558 (3), 2.8016 (3), 2.6050 (3) and 2.5709 (3) Å] that coordinate to one CdIIatom in a bidentate mode. The dimers are located over an inversion centre bridged by two additional bridging Cd—S bonds [2.6021 (3) Å], leading to a substantial distortion of the geometry of the monomeric subunit from the expected square-planar geometry. The five-coordinate environment around each of the CdIIions in the dimer is best described as substantially tetragonally distorted square pyramidal. The dithiocarbamate groups are themselves planar and are also coplanar with the CdIIions. The negative charge on these groups is delocalized by resonance across the S atoms bound to the CdIIcation. This delocalization of the π electrons in the dithiocarbamate groups also extends to the C—N bonds as they reveal significant double bond character [C—N = 1.3213 (16) and 1.3333 (15) Å].

The CO release properties of κ2N1,N2Mn(i) tricarbonyl photoCORMs with tridentate benzimidazole coligands

The κ2N1,N2bidentate mode of tridentate benzimidazole ligand is changed into meridional, tridentate one upon illumination at 468 nm.

Synthesis, Characterization and Antibacterial of 2,3-Dihydrobenzo Thiazole-2-Carboxylic Acid Complexes with Some Selected Metal Ions

A new ligand 2,3-dihydrobenzo [d] thiazole-2-carboxylic acid (L) has been prepared from the reaction of ortho amino phenyl thiol with dichloroacetic acid in mole ratio (1:1). It has been characterized by elemental analysis (C.H.N.), IR, UV- Vis.spectraand 1H, 13C-NMR. A new series complexes of the bivalent ions (Co, Ni, Cu, Pd, Cd, Hg and Pb) and the trivalent (Cr) have been prepared and characterized too. The structural has been established by elemental analysis (C.H.N.), IR, UV-Vis. spectra, molar conductivity, atomic absorption and magnetic susceptibility measurements. The synthesized complexes were prepared in (1:2) ratio correspond to (Co(II), Ni(II), Cu(II), Pd(II), Cd(II), Hg(II) and Pb(II) complexes while in case Cr(III) complex is (1:1) ratio (M:L). ?, Kf for (Cr(III), Co(II), Ni(II) and Cu(II)) were estimated too. The complexes showed characteristics octahedral geometry with the (O,N) ligand coordinated in bidentate mode except with Pd showed square planer. The study of biological activity of ligand (L) and its complexes showed various activities toward Staphylococcus aureusand E. coli.

Synthesis and Characterization of some Ternary Metal Complexes of Curcumin with 1,10-phenanthroline and their Anticancer Applications

Some ternary complexes of curcumin have been synthesized by the reaction of M(II) nitrate with curcumin as primary ligand and 1,10-phenanthroline (phen) as supporting ligand in water/ethanol solution under a nitrogen atmosphere. The composition of the complexes has been characterized by elemental analysis, molar conductivity, thermogravimetric analysis, IR, UV–vis spectroscopy. The results reveal that curcumin ligand coordinates with M(II) in bidentate mode after deprotonation. The supporting ligand (phen) uses its two N atoms in coordination with metal ions in bidentate mode. The general formula of the complexes is [M(Cur)(phen)]NO3 (M = Ni(II), Co(II), Cu(II) and Z(II)). The results of antibacterial activity indicated that the complexes have good antibacterial ability for the testing bacterium than that of curcumin. Furthermore, the [M(Cur)(phen)]NO3 complexes were evaluated for its in vitro anticancer activity against hepatocellular carcinoma. © 2014 JSR Publications. ISSN: 2070-0237 (Print); 2070-0245 (Online). All rights reserved. doi: http://dx.doi.org/10.3329/jsr.v6i3.18750 J. Sci. Res. 6 (3), 509-519 (2014)

A three-dimensional zinc-based coordination polymer built from 5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium with a 4-connectedsratopology

A novel three-dimensional ZnIIcomplex, poly[aqua(μ4-5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium)zinc(II)], [Zn(C8H5NO4)(H2O)]n, has been prepared by hydrothermal assembly of Zn(CH3COO)2·2H2O and 5-carboxy-1-(carboxymethyl)pyridin-1-ium-2-olate (H2ccop). The ccop2−anions bridge the ZnIIcations in a head-to-tail fashionviamonodentate aromatic carboxylate and phenolate O atoms to form an extended zigzag chain which runs parallel to the [011] direction. One O atom of the aliphatic carboxylate group of the ccop2−ligand coordinates to the ZnIIatom of a neighbouring chain thereby producing undulating layers which lie parallel to the (01-1) plane. A similar parallel undulating planar structure can be obtained if a path involving the other O atom of the aliphatic carboxylate group is considered. Thus, the aliphatic carboxylate group acts in a bridging bidentate mode to give extended –Zn–O–C–O–Zn– sequences running parallel to [001] which link the layers into an overall three-dimensional framework. The three-dimensional framework can be simplified as a 4-connected sra topology with a Schläfli symbol of 42.63.8 if all the ZnIIcentres and ccop2−anions are regarded as tetrahedral 4-connected nodes. The three-dimensional luminescence spectrum was measured at room temperature with excitation and emission wavelengths of 344–354 and 360–630 nm, respectively, at intervals of 0.15 and 2 nm, respectively.

The synthesis, structure and physical properties of lanthanide(III) complexes with nicotinic acid

This article reports the synthesis of novel, rare-earth coordination complexes with nicotinic acid. Three compounds with the general formula Ln2[(C5H4NCOO)6(H2O)4] (Ln = Yb, 1; Ln = Gd, 2; Ln = Nd, 3) were prepared from relatively cheap and readily available reactants. Their compositions and structure were characterized by IR spectroscopy and single-crystal X-ray diffraction. The magnetic and thermogravimetric properties were also studied. The complexes consist of centrosymetric, dimeric molecules having all six nicotinato ligands coordinated with the central atom in the bidentate mode. The coordination environment of the Ln3+ for all three compounds is 8. Here we describe the crystal structure of Yb and Gd complexes with nicotinic acid.