Sol-gel 3-glycidoxypropyltriethoxysilane finishing on different fabrics: The role of precursor concentration and catalyst on the textile performances and cytotoxic activity.

In this paper, the influence of 3-glycidoxypropyltriethoxysilane (GPTES) based organic-inorganic coatings on the properties of treated textile fabrics was studied. All experimental results were deeply analyzed and thereafter correlated with the employed silica precursor concentration and with the presence of the BF3OEt2 (Boron trifluoride diethyl etherate), used as epoxy ring opening catalyst. SEM analysis, FT-IR spectroscopy, X-ray Photoelectron Spectroscopy (XPS), thermogravimetric analysis (TGA) and washing fastness tests of the sol-gel treated cotton fabric samples were firstly exploited in order to characterize the morphological and structural features of the achieved coatings. Finally, the influence of the resulting nanohybrid coatings was explored in terms of abrasion resistance, tensile strength and elongation properties of treated cotton, polyester and silk fabrics. The catalyst amounts seem to strongly improve the formation of coatings, but still they do not influence the wear resistance of treated textile fabrics to the same extent. Indeed, it was found that increasing catalyst/GPTES ratio leads to a more cross linked inorganic 3D-network. GPTES itself was not found to affect the bulk properties of the selected textile and the resulting coatings were not so rigid to hardly modify the mechanical properties of the treated samples. Finally, it is worth mentioning that in all case the obtained 3-glycidoxypropyltriethoxysilane-based chemical finishing have shown no cytotoxic effects on human skin cells.

Role of cyclometalation in controlling the rates of ligand substitution at platinum(II) complexes.

The rates of chloride for triphenylphosphine substitution have been measured in dichloromethane for a series of cyclometalated [Pt(N-N-C)Cl] complexes containing a number of terdentate N-N-C anionic ligands, derived from deprotonated alkyl-, phenyl-, and benzyl-6-substituted 2,2'-bipyridines. These rates have been compared with those of the corresponding [Pt(N-N)(C)Cl] (N-N = 2,2'-bipyridine; C = CH3 or C6H5) complexes having the same set of donor atoms but less constrained arrangements of the ligands. The reactions of the cyclometalated compounds occur as a single-stage conversion from the substrate to the ionic pair [Pt(N-N-C)(PPh3)]Cl products. There is no evidence by 1H and 31P(1H) NMR spectroscopy for the formation of other Pt(II) species or of concurrent ring-opening processes. In contrast, in the monoalkyl- or monoaryl-2,2'-bipyridine complexes, chloride substitution is followed by subsequent slower processes which involve the detachment of one arm of the chelated 2,2'-bipyridine, fast cis to trans isomerization of the cis-[Pt(PPh3)2(eta 1-bipy)(R)]+ transient intermediate, and, eventually, the release of free bipy, yielding trans-[Pt(PPh3)2(R)Cl] (R = Me or Ph). All reactions are first-order with respect to complex and phosphine concentration, obeying the simple rate law kobsd = k2[PPh3]. The values of the second-order rate constant k2 do not seem particularly sensitive to the nature of the bonded organic moiety (alkyl or aryl), to its structure (cyclometalated or not), to the size of the ring, or to the number of alkyl substituents on it. The effects are those foreseen on the basis of an associative mode of activation. The only exception to this pattern of behavior is constituted by the complex [Pt(bipy phi-H)Cl] (bipy phi = 6-phenyl-2,2'-bipyridine), which features a significant rate enhancement with respect to the analogue [Pt(bipy)(Ph)Cl] complex. The results of this work, together with those of a previous paper, suggest that there is not a specific role of cyclometalation in controlling the reactivity, unless an in-plane aryl ring becomes part of the pi-acceptor system of the chelated 2,2-bipyridine, behaving as a cyclometalated analogue of the nitrogen terdentate 2,2':6',2"-terpyridine.

To what extent can cyclometalation promote associative or dissociative ligand substitution at platinum(II) complexes? A combined kinetic and theoretical approach.

The ligand exchange rate constants for the reactions [Pt(bph)(SR2)2] + 2*SR2 --> [Pt(bph)(*SR2)2] + 2SR2 (bph = 2,2'-biphenyl dianion; R = Me and Et) and cis-[PtPh2(SMe2)2] + 2*SMe2 --> cis-[PtPh2(*SMe2)2] + 2SMe2 have been determined in CDCl3 as a function of ligand concentration and temperature, by 1H NMR isotopic labeling and magnetization transfer experiments. The rates of exchange show no dependence on ligand concentration and the kinetics are characterized by largely positive entropies of activation. The kinetics of displacement of the thioethers from [Pt(bph)(SR2)2] with the dinitrogen ligands 2,2'-bipyridine and 1,10-phenanthroline (N-N) to yield [Pt(bph)(N-N)], carried out in the presence of sufficient excess of thioether and N-N to ensure pseudo-first-order conditions, follow a nonlinear rate law k(obsd) = a[N-N]/(b[SR2] + [N-N]). The general pattern of behavior indicates that the rate-determining step for substitution is the dissociation of a thioether ligand and the formation of a three-coordinated [Pt(bph)(SR2)] intermediate. The value of the parameter a, which measures the rate of ligand dissociation, is constant and independent of the nature of N-N, and it is in reasonable agreement with the value of the rate of ligand exchange at the same temperature. Theoretical ab initio calculations were performed for both [Pt(bph)(SMe2)2] and cis-[PtPh2(SMe2)2], and for their three-coordinated derivatives upon the loss of one SMe2 ligand. The latter optimize in a T-shaped structure. Calculations were performed in the HF approximation (LANL2DZ basis set) and refined by introducing the correlation terms (Becke3LYP model). The activation enthalpies from the optimized vacuum-phase geometries are 52.3 and 72.2 kJ moll compared to the experimental values in CDCl3 solution, 80 +/- 1 and 93 +/- 1 kJ mol(-1) for [Pt(bph)(SMe2)2] and cis-[PtPh2(SMe2)2], respectively. The electrostatic potential maps of both parent compounds show a remarkable concentration of negative charge over the platinum atom which exerts a repulsion force on an axially incoming nucleophile. On the other hand, the strength of the organic carbanions trans to the leaving group and the stabilization of the T-shaped intermediate in the singlet ground state may also rationalize the preference for the dissociative mechanism. All of the kinetic and theoretical data support the latter hypothesis and indicate, in particular, that dissociation from the complex containing the planar 2,2'-biphenyl dianion is easier than from its analogue with single aryl ligands. Electron back-donation from filled d orbitals of the metal to empty pi* of the in-plane cyclometalated rings is weak or absent and is not operative in promoting an associative mode of activation.