Hydrolytic and photoinduced degradation of tribenuron methyl studied by HPLC-DAD-MS/MS

The paper studies, with the help of HPLC-DAD-MS/MS technique, the hydrolytic and photoinduced degradation processes that take place in aqueous solutions of tribenuron methyl, both when preserved in the dark and when undergoing solar box irradiation under conditions that simulate sun light. The results indicate that the degradation products formed by hydrolysis alone and by photoirradiation are the same, but kinetics of the hydrolysis reaction is much slower. The degradation products are identified as 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine (P1), methyl 2-aminosulfonylbenzoate (P2), and saccharin (P3) and quantified. Ecotoxicological biotests performed on 0.1 microg L(-1) photoirradiated solutions of the herbicide give a border line toxicity situation comparable to that of the precursor and indicate that the herbicide is characterized by low persistence in the environment, as required. Its degradation, however, does not lead to mineralization but to the formation of products of comparable toxicity. To evaluate the matrix effects, the photodegradation of the herbicide is also studied in the presence of rice paddy waters: the process is slower than in ultrapure water but leads to the same products. Experiments performed for comparison by irradiating ultrapure water solutions with UV lamp (254 nm) show that the degradation process is not only faster with respect to sunlight, but gives a different pathway, without in anyway leading to mineralization.     

Wavy graphene sheets from electrochemical sewing of corannulene

The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.

A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene.     

ZnS bubble clusters with onion-like structures

Following recent studies which showed that the most stable structures for (ZnS)(n) clusters (n= 10-47) are the so-called "bubble clusters", in which all the atoms are three-coordinated, we have used simulated annealing techniques to find the most stable structure for a larger cluster, (ZnS)(60). We find an onion-like structure, with one small cluster enclosed inside a bigger one. The inner cluster has the structure of a sodalite cage. Bonding between the inner and the outer clusters creates a network of four-coordinated atoms.     

UV-induced immobilization of tethered zirconocenes on H-terminated silicon surfaces

A tethered ethylenebis(indenyl) zirconocene was covalently immobilized on H-terminated Si(111) surfaces using UV-mediated alkene hydrosilylation, thus making possible the development of structured catalytic surfaces with highly controlled properties.     

Synthesis and biological evaluation of N-thia-carba-thymidine as an antiherpetic agent

As a continuation of our project aimed at the search for new antiviral agents, the synthesis and biological evaluation of N-thia-carba-thymidine ((1R,2S,4S,5S)-5-methyl-1-{6-thia-4-hydroxy-5-[(hydroxy)-methyl]bicyclo[3.1.0]hex-2-yl}-1,3-dihydropyrimidine-2,4-dione; compound 8) was carried out employing the carbocyclic enantioenriched intermediate (1R,4S)-4-phenylmethoxy-3-[(phenylmethoxy)methyl]cyclopent-2-en-1-ol, which in turn was prepared from (3R,4S) phenylmethoxy-3-[(phenylmethoxy)methyl]-cyclopent-1-ene. The title compound resulted to be a very potent antiherpetic agent exhibiting a similar potency to acyclovir as shown. The synthetic approach to obtain this carbanucleoside required a novel strategy to introduce a thiirane group fused to a functionalized five-membered ring.     

Diphenyltin(IV) complexes of the 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olates: Synthesis and multinuclear NMR, Sn Mössbauer, electrospray ionization MS, X-ray characterization and assessment of in vitro cytotoxicity

A series of cis-bis{5-[(E)-2-(aryl)-1-diazenyl]quinolinolato}diphenyltin(IV) complexes have been synthesized and characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, IR and ^119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. The structures of a ligand L⁶H (i.e., 5-[(E)-2-(4-ethoxyphenyl)-1-diazenyl]quinolin-8-ol) and three diphenyltin(IV) complexes, viz., Ph₂Sn(L¹)₂ · (CH₃)₂CO (1), Ph₂Sn(L⁴)₂ (4) and Ph₂Sn(L⁵)₂ (5) (L = 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-ol: aryl = phenyl - (L¹H); 4′-methylphenyl - (L⁴H) and 4′-bromophenyl - (L⁵H)) were determined by single crystal X-ray diffraction. In general, the complexes were found to adopt a distorted cis-octahedral arrangement around the tin atom. These complexes retain their solid-state structure in non-coordinating solvent as evidenced by ¹¹⁹Sn NMR spectroscopic results. The in vitro cytotoxicity of 1 is reported and compared with Ph₂Sn(Ox)₂ (Ox = deprotonated quinolin-8-ol) against seven well characterized human tumor cell lines.     

Two nickel complexes stabilized by nitrate counter‐ions

Two new nickel nitrates, di­aqua­bis(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ²N,N′)­nickel(II) dinitrate methanol solvate, [Ni(C₁₆H₁₆N₂)₂(H₂O)₂](NO₃)₂·CH₄O, (I), and tri­aqua­[2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine‐κ³N¹,N²,N⁶]nickel(II) di­ni­trate trihydrate, [Ni(C₁₈H₁₂N₆)(H₂O)₃](NO₃)₂·3H₂O, (II), are reported. In both structures, the cation is octahedrally coordinated, to two bidentate 3,4,7,8‐tetra­methyl‐1,10‐phenanthroline (tmp) and two water mol­ecules in (I), and to one tridentate 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tpt) and three water mol­ecules in (II). Both structures are stabilized by extensive hydrogen‐bonding interactions.     

Bis(1,10‐phenanthroline)(thio­sulfato)­manganese(II) methanol solvate and catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phenanthroline)­manganese(II)]‐μ‐thio­sulfato]

The structure of bis(1,10‐phenanthroline‐κ²N,N′)(thio­sulfato‐κ²O:S)­manganese(II) methanol solvate, [Mn(S₂O₃)(C₁₂H₈N₂)₂]·CH₃OH, is made up of Mn²⁺ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thio­sulfate anion, forming monomeric entities. The structure of catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phen­anthro­line‐κ²N,N′)­manganese(II)]‐μ‐thio­sulfato‐κ²O:S], [Mn(S₂O₃)(C₁₄H₁₂N₂)(H₂O)₂]_n, is polymeric, consisting of Mn(dmph)(H₂O)₂ units (dmph is 2,9‐di­methyl‐1,10‐phenanthroline) linked by thio­sulfate anions acting in an S,O‐chelating manner.     

Si-Fluoro substituted quasisilatranes (N → Si) FYSi(OCH2CH2)2NR

The reaction of fluorosilanes XYSiF₂ (X = Y = F; X = F, Y = Ph; X = Ph, Y = Me) with diethanolamines and their O-trimethylsilyl derivatives affords novel Si-fluoro substituted quasisilatranes 3, 5 and 9. These compounds were characterized by the multinuclear NMR spectroscopy and X-ray diffraction analysis. Experimental and theoretically calculated electron density distribution functions in crystal structure of 9 have shown that the N → Si coordination bond corresponds to polar bond with pronounced ionic contribution. Calculated N → Si bond order in the compound 9 does not exceed 1/3 of the normal Si-N bond. A strong N → Si coordination bond exists in compounds 3, 5 and 9 the length of which varies in the range 1.98-2.175 Å.     

Mixed Co/Fe oxide nanoparticles in block copolymer micelles

Small iron oxide and Co-doped iron oxide nanoparticles (NPs) were synthesized in a commercial amphiphilic block copolymer, poly(ethylene oxide)-b-poly(methacrylic acid) (PEO 68-b-PMAA8), in aqueous solutions. The structure and composition of the micelles containing guest molecules (metal salts) or NPs (metal oxides) were studied using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The enlarged micelle cores after incorporation of metal salts are believed to be formed by both PMAA blocks containing metal species and penetrating PEO chains. The nanoparticle size distributions in PEO 68-b-PMAA8 were determined using small-angle X-ray scattering (SAXS) in bulk. Two independent methods for SAXS data interpretation for comprehensive analysis of volume distributions of metal oxide NPs showed presence of both small particles and larger entities containing metal species which are ascribed to organization of block copolymer micelles in bulk. The magnetometry measurements revealed that the NPs are superparamagnetic and their characteristics depend on the method of the NP synthesis. The important advantage of the PEO 68-b-PMAA8 stabilized magnetic nanoparticles described in this paper is their remarkable solubility and stability in water and buffers.