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Recently, the use of lime mortars in the restoration of historic buildings has found a renewed interest because they can guarantee the required mechanical, chemical and physical compatibility with the existing substrate. Spontaneous occurrence of self-healing phenomena in lime-based mortars is well known; the possibility of engineering the self-healing capacity, through tailored additions, is therefore of the utmost interest with the aim of enhancing the durability of the building masonry restoration works. This work proposes a system for the evaluation of the self-healing capacity with reference to traditional and advanced lime mortars. The autogenous healing capacity of a reference lime mortar has been first of all evaluated. Then, the possibility of engineering the aforementioned capacity has also assessed, through both commercial crystalline admixtures and tailored encapsulated additives. These should work according to a twofold mechanism: first, the coated granules envelope a core of lime mortar with purpose of making it inert during the hardening phase. Secondly, once the coated granules rupture upon cracking and damage of the mortar, the reactive binder is released and undergoes a delayed hardening, which is responsible of the healing phenomena. The results show that the mortar is able to heal micro-cracks; moreover, the addition of the crystalline admixture enhances this capacity. The different kinds of employed coated granules were also able to induce a sensible self-healing, but they decrease the instantaneous compressive strength. [ABSTRACT FROM AUTHOR]

Reaction rates and equilibrium constants of indole dimerization and trimerization in aqueous sulfuric acid at 298 K are reported. The equilibrium of oligomerization is attained in about 4–5 h, and formation of oligomers with more than three monomeric unit is not observed. The equilibrium of formation of the indole dimer is influenced by the protonation equilibrium of indole, which means the pKIH values of indole strongly influences equilibria and kinetics of the whole process. In the evaluation of the kinetic constants, the pKIH values of indole have been taken into account; in this way, the kinetic constant of formation of the dimer (kD) results almost four order of magnitude larger than that of the trimer (kT), suggesting a higher electrophilicity of the 3H-indolium cations with respect to the protonated dimer (which is an aliphatic ammonium salt). Further indole addition to the trimer, which is a protonated 2-alkyl-aniline, does not occur, since the anilinium ion is ineffective as an electrophile. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 107–112, 2009 [ABSTRACT FROM AUTHOR]

Abstract: In recent studies regarding acid-catalysed Beckmann rearrangement of cyclohexanone oxime in aprotic solvents it has been observed that a quite surprising hydrolysis of the starting material, i.e., cyclohexanone oxime, occurs even if the experimental conditions and the water concentration in the reaction mixture can not justify such a side-reaction. Being this apparent hydrolysis critical for catalyst selectivity and poisoning, a computational DFT study on a possible secondary reaction pathway, involving a bi-molecular reaction between two cyclohexanone oxime molecules in acid media as the primary step, is here reported to explain the experimental results. [Copyright &y& Elsevier]

Consecutive, parallel reactions and equilibria affecting the selectivity in cyclohexanone oxime. • Nitrobenzene hydrogenation catalyzed by Pd/C in the presence of NH 2 OH HCl forms Aniline and cyclohexanone oxime. • The best solvent are ethers followed by dichloromethane and dimethylcarbonate. • NH 2 OH HCl hydrogenates to NH 4 Cl in the presence of Pd/C as a catalyst. • Aniline in the presence of NH 2 OH HCl gives cyclohexanone oxime and NH 4 Cl favors the selectivity to cyclohexanone oxime. • An imine intermediate on catalyst surface gives CON, COX and PCNA all in equilibrium. We studied the influence of temperature, solvent, pressure, catalysts type on the selectivity of nitrobenzene hydrogenation to cyclohexanone oxime (COX) in the presence of NH 2 OH. The best reaction conditions are: pressure 0.8 MPa, temperature 333 K, solvent ethers, and catalyst Pd/C5%. Other hydrogenation metal catalysts did not give comparable results. The amount of Pd/C influences the yield in COX, which rises above to 90 % at the highest load. The reaction profile shows that aniline is the reaction intermediate. Indeed, aniline as a substrate gives COX, though in lower yield than that achieved employing nitrobenzene. The NH 2 OH parallel hydrogenation to NH 4 Cl, influences positively the selectivity to COX. It has been observed that COX, cyclohexanone and N-cyclohexylideneaniline are in equilibrium in the reaction solution and all likely derive from nucleophilic substitutions to a common imine intermediate formed on the Pd surface, whose high activity does not need any further metal catalyst. [ABSTRACT FROM AUTHOR]

Abstract: The cationic complexes trans-[Pd(COOR)(H2O)(PPh3)2](TsO) have been synthesised by reacting cis-[Pd(H2O)2(PPh3)2](TsO)2·2H2O with CO in ROH (R=Me and Et), practically under room conditions, or by methathetical exchange of trans-[Pd(COOMe)Cl(PPh3)2] with Ag(TsO) (R= n-Pr, iso-Pr, n-Bu, iso-Bu, sec-Bu). They have been characterised by IR, 1H NMR and 31P NMR spectroscopies. The X-ray investigation of trans-[Pd(COOMe)(TsO)(PPh3)2] reveals that the palladium center is surrounded in a virtually square planar environment realized by two PPh3 trans to each other, the carbon atom of the carbomethoxy ligand and an oxygen atom of the p-toluensulfonate anion, with two crystallization molecules of CHCl3. The Pd–O–S angle, 151.9 (3)°, is very wide, probably due to the interaction of one CHCl3 molecule with the complex inner core. The carbomethoxy derivatives react with R′OH yielding the corresponding R′ carboalkoxy derivative (R′=Et, n-Pr and iso-Pr); ethene does not insert into the Pd–COOMe bond; decarbomethoxylation occurs when treated with TsOH/H2O in MeOH at 50°C. All the carboalkoxy are precursors for the catalytic carboalkoxylation of ethene if used in combination of PPh3 and TsOH, better in the presence of some water. Experimental evidences are more in favor of the so-called “hydride” mechanism rather than the “carbomethoxy” mechanism. [Copyright &y& Elsevier]

Today, polymeric drug delivery systems (DDS) appear as an interesting solution against bacterial resistance, having great advantages such as low toxicity, biocompatibility, and biodegradability. In this work, two polyketones (PK) have been post-functionalized with sodium taurinate (PKT) or potassium sulfanilate (PKSK) and employed as carriers for Vancomycin against bacterial infections. Modified PKs were easily prepared by the Paal-Knorr reaction and loaded with Vancomycin at a variable pH. All polymers were characterized by FT-IR, DSC, TGA, SEM, and elemental analysis. Antimicrobial activity was tested against Gram-positive Staphylococcus aureus ATCC 25923 and correlated to the different pHs used for its loading (between 2.3 and 8.8). In particular, the minimum inhibitory concentrations achieved with PKT and PKSK loaded with Vancomycin were similar, at 0.23 μg/mL and 0.24 μg/mL, respectively, i.e., six times lower than that with Vancomycin alone. The use of post-functionalized aliphatic polyketones has thus been demonstrated to be a promising way to obtain very efficient polymeric DDS.

Indole and its derivatives are molecules which play important roles in different fields, from biology to pharmacology. Here we report a thorough investigation on the anharmonic force fields of indole as well as the ab initio determinations of its gas phase basicity and aqueous pK(a) value. For the geometry optimizations, the calculations have been performed using both density functional (DFT) and second-order Møller-Plesset (MP2) levels of theory employing different basis sets. Anharmonic force fields have been obtained employing both the B3LYP and the B97-1 functionals and an hybrid approach: the best agreement to the experimental data has been determined employing the B3LYP functional combined with the recently developed N07D basis set (mean unsigned error, MUE, of 5.1 cm(-1) and a root-mean-square error, RMSE, of 7.2 cm(-1)). Gas phase basicity and proton affinity have been computed employing several computational schemes, namely the G3 and G4 Gaussian models, the complete basis set (CBS) extrapolation methods of Petersson and co-workers, several DFT calculations, and different hybrid extrapolation schemes based on combining single-point energy calculations performed at MP2 as well as at coupled cluster level of theory with single, double and perturbative triple excitations, CCSD(T). Regarding the aqueous pK(a) computations, two implicit solvation models (SMD and SM8) have been employed to determine the free energy of solvation and the corresponding pKa value.