Ioanna Kyrikou and Demetres Briassoulis, the authors of ''Biodegradation of Agricultural Plastic Films: A Critical Review,'' wish to acknowledge that their project was co-funded by the European Union-European Social Fund & National Resources-O.P. ''Education'' II.
The wide use of titanium in applied materials has prompted pertinent studies targeting the requisite chemistry of that metal's biological interactions. In order to understand such interactions as well as the requisite titanium aqueous speciation, we launched investigations on the synthesis and spectroscopic and structural characterization of Ti(IV) species with the physiological citric acid. Aqueous reactions of TiCl(4) with citric acid in the presence of H(2)O(2) and neutralizing ammonia afforded expediently the red crystalline material (NH(4))(4)[Ti(2)(O(2))(2)(C(6)H(4)O(7))(2)].2H(2)O (1). Complex 1 was further characterized by UV-vis, FT-IR, FT- and laser-Raman, NMR, and finally by X-ray crystallography. Compound 1 crystallizes in the monoclinic space group P2(1)/n, with a = 10.360(4) A, b = 10.226(4) A, c = 11.478(6) A, beta = 107.99(2) degrees, V = 1156.6(9) A(3), and Z = 2. The X-ray structure of 1 reveals a dinuclear anionic complex containing a Ti(IV)(2)O(2) core. In that central unit, two fully deprotonated citrate ligands are coordinated to the metal ions through their carboxylate moieties in a monodentate fashion. The central alkoxides serve as bridges to the two titanium ions. Also attached to the Ti(IV)(2)O(2) core are two peroxo ligands each bound in a side-on fashion to the respective metal ions. NH(4)(+) ions neutralize the 4- charge of the anion in 1, further contributing to the stability of the derived lattice through H-bond formation. The structural similarities and differences with congener vanadium(V)-peroxo-citrate complexes may point out potential implications in the chemistry of titanium with physiological ligands, when the former is present in a biologically relevant medium.
Apart from the conventional polyethylene and the bio-based or mainly bio-based biodegradable in soil mulching films, polyethylene mulching films of controlled degradation in soil are already used in agriculture. The use of special pro-oxidants as additives is expected to accelerate the abiotic oxidation and the subsequent chain scission of the polymer under specific UV radiation or thermal degradation conditions, according to the literature. The role of pro-oxidants in the possible biodegradation of polyethylene has been theoretically supported through the use of controlled laboratory conditions. However, results obtained in real soil conditions, but also several laboratory test results, are not supporting these claims and the issue remains disputed. Mulching films made of linear low-density polyethylene (LLDPE) with pro-oxidants, after being used for one cultivation period in an experimental field with watermelon cultivation, were buried in the soil under real field conditions. This work presents the analysis of the degradation of the mulching films during the cultivation period as compared to the corresponding changes after a long soil burial period of 8.5 years. The combined effects of critical factors on the photochemical degradation of the degradable mulching LLDPE films with pro-oxidants under the cultivation conditions and their subsequent further degradation behaviour in the soil are analysed by testing their mechanical properties and through spectroscopic and thermal analysis.
Three series of ring-substituted ether phospholipids were synthesized carrying N,N,N-trimethylammonium, N-methylpiperidino, or N-methylmorpholino headgroups. The first series is substituted by 2-cyclohexyloxyethyl or 2-(4-alkylidenecyclohexyloxy)ethyl groups, the second series by cyclohexylidenealkyl or adamantylidenealkyl moieties, and the third series by 2-aryloxyethyl or 6-aryloxyhexyl groups in the alkyl portion of the molecule. The antileishmanial activity of the new compounds was evaluated in vitro against the promastigote forms of L. donovani and L. infantum using an MTT (3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide)-based microassay as a marker of cell viability. Analogues 12, 15, 24, 30, 32, 41, 43, and 45 were more potent than the control compound miltefosine (hexadecylphosphocholine) against both L. donovani and L. infantum while, derivatives 13 and 42 were equipotent to miltefosine. Analogues 16, 17, 19, 20 were more potent than miltefosine against L. infantumand compounds 27, 31, 44 were more active than miltefosine against L. donovani. Differential scanning calorimetry (DSC) was used to probe the role of individual ether phospholipids on the physicochemical properties of model membranes. The DSC scans showed that the active compounds have a more profound effect on the thermotropic properties of model membrane bilayers than the less active ones.
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