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A Pt(ii) complex with a glucosylated carbene shows very high in vitro cytotoxicity and selectivity toward malignant cells.

relevant role. They can be transformed into methyl esters for production of biodiesel or functionalized to produce surfactants, plasticizers, monomers, and new solvents [2,3]. These include cis-9-octadecenoic acid (oleic acid, OA in Scheme 1), which is a very interesting raw material, since it is renewable, inexpensive, and available in different geographical areas.Its most common transformations are epoxidation, hydroxylation, and oxidative cleavage of the double bond. The latter reaction is particularly interesting because it selectively produces azelaic acid (AA) and pelargonic acid (PA) (Scheme 1).Azelaic acid has important applications in textiles (polyesters and polyamides) and pharmaceuticals (antiacne). Industrially, oxidative cleavage of the double bond is carried out by ozonolysis [4]. However, use of ozone and molecular oxygen at high temperatures represents a serious drawback of this process, since these oxidants present combustion hazards. It is therefore required to find new processes that meet the standards of sustainability.A valid alternative is hydrogen peroxide, because it is capable of oxidizing with excellent atom economy and is safer than gaseous reactants [5]. Many of the known strategies couple H 2 O 2 with catalytic systems such as RuO 2 , Na 3 PO 4 {[WO(O 2 ) 2 ]}, H 2 WO 4 /Co(OAc) 2 , and Re 2 O 7 [6][7][8][9][10][11][12][13][14][15][16]. These synthetic routes (path i of Scheme 1) typically include a first step of dihydroxylation that gives 9,10-dihydroxystearic acid (DSA). In a second step (ii) a new catalyst is introduced, either in the same reaction environment [14] or on the purified diol [15], for oxidative cleavage of the CH(OH)-CH(OH) bond.Recently, an efficient one-pot strategy (iii in Scheme 1) was proposed with a catalyst based on the quaternary ammonium salt Q 3 {PO 4 [WO(O 2 ) 2 ] 4 } [17]. Even in this case, there are some disadvantages, namely high catalyst Abstract This work describes two sustainable methods for production and purification of azelaic acid (AA) to replace the current process of ozonolysis of oleic acid (OA). The first proceeds in two steps, coupling smooth oxidation of OA to 9,10-dihydroxystearic acid (DSA) with subsequent oxidative cleavage by sodium hypochlorite. An alternative methodology is also proposed, using a chemocatalytic system consisting of H 2 O 2 /H 2 WO 4 for direct oxidative cleavage of the double bond of OA at 373 K. A convenient technique for separation and purification of azelaic acid is also proposed.

This article describes the synthesis and characterization of novel cationic five-coordinate Pt(II) complexes containing nitrogen sugar-based ligands. The cytotoxicity of the complexes was evaluated on different cell lines with the expectation that both the coordinative saturation and the sugar moiety cooperate to enhance their biological activity. In fact, the complexes resulted to be more active than cisplatin but still with little selectivity. They activate the apoptosis pathway. Binding of representative compounds with DNA was studied by ethidium bromide displacement assay and circular dichroism. Binding to model proteins was also investigated; the X-ray structure of the adduct formed in the reaction between a representative compound and the model protein bovine pancreatic ribonuclease was obtained. The structure discloses an unprecedented interaction between a five-coordinate Pt(II) moiety and a His side chain.

The coordinated olefin in dicationic platinum(II) and palladium(II) complexes [M(PNP)(olefin)](SbF 6 ) 2 (M ) Pt, Pd; PNP ) 2,6-bis(diphenylphosphinomethyl)pyridine; olefin ) ethene, propene) is electrophilic enough to react with benzene rings activated by methoxy substituents. If the proton released by the aromatic ring is trapped by a base, stable σ-alkyl derivatives of the type [M(PNP)CH 2 CH(R)Ar](SbF 6 ) or [M(PNP)CH(R)CH 2 Ar](SbF 6 ) (R ) H, Me) are formed; otherwise the M-C σ-bond can be cleaved by the proton, setting up a catalytic cycle that leads to the alkylated aromatic compound. The molecular structure of the σ-alkyl derivative [(PNP)PtCH 2 CH 2 -C 6 H 2 (OMe) 3 ](BF 4 ) has been determined by X-ray diffraction analysis, and the factors affecting the mechanism and the rates of the catalytic reaction have been qualitatively investigated and rationalized, showing that the rates of C-C bond formation and M-C bond cleavage are inversely correlated.

The coordinated ethylene molecule in the dicationic complex [(PNP)Pt(CH2=CH2)](BF4)2 (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) undergoes nucleophilic attack by free internal alkenes, giving the isolable complexes [(PNP)Pt(CH2=CHCH(Me)CMeRR'](BF4)2 (R, R' = H, Me) and providing a new effective pathway for a chemo- and regio-selective catalytic hydrovinylation reaction.

Cardoon seed oil (CO), derived from the nonedible Cynara cardunculus plant, growing in marginal and contaminated soils of Mediterranean regions, was successfully epoxidized (ECO) in a fed-batch modality. The cost-effective and environmentally friendly oils have been used as bioplasticizers of poly­(lactic acid) (PLA), to improve the overall properties and broaden its industrial applications as a biodegradable packaging material. Hence, physical blends and films of PLA, containing 3% by weight of CO and ECO, were prepared by melt extrusion and compression molding, and the effect of the both bioplasticizers on structural, thermal, and mechanical properties of the obtained films was investigated. Cardoon oils induced the decreasing of glass transition temperature due to PLA free volume enhancement. This effect was particularly marked in PLA–ECO film. Thermal stability of PLA was meaningfully improved upon addition of the oils, and the mechanical properties made evident the increase of PLA ductility, particularly enhanced in the PLA–ECO system, where the polymeric matrix and the oil showed stronger physical interaction and improved phase compatibility, as also revealed by spectroscopic and morphological analyses. Therefore, the plasticization action exerted by very low concentrations of epoxidized cardoon oil efficiently overcomes PLA drawbacks, thus encouraging the feasibility of its use as a bioplastic for packaging material.