Ru(IV)-catalyzed isomerization of allylamines in water: a highly efficient procedure for the deprotection of N-allylic amines

A general and efficient method for the deprotection of N-allylic substrates in aqueous media, using catalytic amounts of the bis(allyl)-ruthenium(IV) complexes [Ru(eta3:eta2:eta3-C12H18)Cl2] and [{Ru(eta3:eta3-C10H16)(micro-Cl)Cl}2], has been developed.     

Mechanism of action of 4-hydroxymethyl-1,6,8-trimethylfuro[2,3-h]quinolin-2(1H)-one, a very active angular furocoumarin-like sensitizer

The molecular structure of 1,4,6,8-tetramethylfuro[2,3-h]quinolin-2(1H)-one (FQ), a recent furocoumarin-like photosensitizer, has been modified with the aim of reducing its strong genotoxicity, by replacing the methyl group at 4 position with a hydroxymethyl one, and so obtaining 4-hydroxymethyl-1,6,8-trimethylfuro[2,3-h]quinolin-2(1H)-one (HOFQ). This modification gave rise to a strong reduction of lipophilicity and dark interaction with DNA. The formation of monoadducts (MA) was deeply affected, whereas the induction of bifunctional adducts between DNA and proteins (DPC(L>0)) was replaced by an efficient production of DNA-protein cross-links at zero length (DPC(L=0)), probably via guanine damage. Because of its angular molecular structure, HOFQ does not form interstrand cross-links (ISC): therefore, DPC(L=0) and MA represent the main lesions induced by HOFQ in DNA. In comparison with FQ (which induces MA and DPC(L>0)) and 8-methoxypsoralen (8-MOP) (MA, ISC, DPC(L>0)), HOFQ seems to be a more selective agent. In fact, contrary to FQ and 8-MOP, HOFQ, together with a noticeable antiproliferative activity, shows low levels of point mutations in bacteria and of clastogenic effects in mammalian cells. HOFQ is also an efficient apoptosis inducer, especially in comparison with 8-MOP, when tested at equitoxic experimental conditions; this property might be correlated with the complete HOFQ inability of inducing skin erythemas, a well-known side effect of classic furocoumarin photosensitization.     

Ab initio analytical potential energy surface and quasiclassical trajectory study of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+))-->OH(+)(X (3)Sigma(-))+H((2)S) reaction and isotopic variants

An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes.     

Cross sections of the O+ + H2 --> OH+ + H ion-molecule reaction and isotopic variants (D2, HD): quasiclassical trajectory study and comparison with experiments

A dynamics study [cross section and microscopic mechanism versus collision energy (E(T))] of the reaction O+ + H2 --> OH+ + H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E(T) = 0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E(T), and considering the influence of the collinear [OHH]+ absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies.     

Thermodynamics of liquid mixtures containing n-alkanes and strongly polar components: VE and C P E of mixtures with either pyridine or piperidine

Excess molar volumes V _E and excess molar heat capacities C _P ^/E at constant pressure have been obtained, as a function of mole fraction x₁, for several binary liquid mixtures belonging either to series I: pyridine+n-alkane (C_lH_2l+2), with l=7, 10, 14, 16, or series II: piperidine+n-alkane, with l=7, 8, 10, 12, 14. The instruments used were a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. V ^E of pyridine+n-heptane shows a S-shaped composition dependence with a small negative part in the region rich in pyridine (x₁>0.90). All the other systems show positive V ^E only. The excess volumes increase with increasing chain length l of the n-alkane. The excess molar heat capacities of the mixtures belonging to series II are all negative, except for a small positive part for piperidine+n-heptane in the region rich in piperidine (x₁>0.87). The C _P ^/E at the respective minima, C _P ^/E (x_1,min ), become more negative with increasing l, and the x_1,min values range from about 0.26 (l=7) to 0.39 (l=14). Most interestingly, mixtures of series I exhibit curves of C _P ^/E against x₁ with two minima and one maximum, the so-called W-shape curves.Dedicated to Professor A. Néckel on the occasion of his 65^th birthday. Communicated in part at the XVII^èmes Journées de Calorimétrie, d'Analyse Thermique et de Thermodynamique Chimique, Ferrara, Italy, 27–30 October, 1986.     

Mechanisms of peroxidic oxygen transfer to organic substrates : Oxidation of organic sulphides by chromium(vi)oxide diperoxide

The oxidation of organic sulphides (n-Bu₂S, PhSCH₃, Tolyl-SCH₃, p-Cl-C₆H₄SCH₃, and Ph₂S by (HMPT)CrO(O₂)₂1′ in CHCl₃ has been studied. The reaction produces the corresponding sulphoxides in nearly quantitative yields according to a 2:1 stoichiometry of sulphide to metaldiperoxide. A second-order-overall (order one in each of the reagents) kinetic law is obeyed. In parallel, the oxidation of organic sulphides by (HMPT)MoO(O₂)₂1' has been studied. Kinetic data, the observed rate laws, and the effect of inhibitors (HMPT, DABCO) have pointed out that-although 1' is significantly more reactive than 1′—considerable similarity exists between the two metaldiperoxides, in that both appear to act as electrophilic oxidizers. Also, through ¹H, ³¹P and ¹³C NMR investigations have permitted to assess the relevance of equilibria (HMPT)MO(O₂₂ MO(O₂)₂ + HMPT [with M = Mo(VI) or Cr(VI)]in solution, whereas no NMR evidence could be found for significant substrate coordination under the given conditions.     

Enantioseparations of polyhalogenated 4,4’-bipyridines on polysaccharide-based chiral stationary phases and molecular dynamics simulations of selector–selectand interactions

2’-(4-Pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs (TCIBP = 3,3’,5,5’-tetrachloro-2-iodo-4,4’-bipyridyl) are chiral compounds that showed interesting inhibition activity against transthyretin fibrillation in vitro. We became interested in their enantioseparation since we noticed that the M-stereoisomer is more effective than the P-enantiomer. Based thereon, we recently reported the enantioseparation of 2’-substituted TCIBP derivatives with amylose-based chiral columns. Following this study, herein we describe the comparative enantioseparation of both 2’-(4-pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs on four cellulose phenylcarbamate-based chiral columns aiming to explore the effect of the polymer backbone, as well as the nature and position of substituents on the side groups on the enantioseparability of these compounds. In the frame of this project, the impact of subtle variations of analyte and polysaccharide structures, and mobile phase (MP) polarity on retention and selectivity was evaluated. The effect of temperature on retention and selectivity was also considered, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van ’t Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal were observed. In particular, the EEO was shown to be dependent on polysaccharide backbone, the elution sequence of the two analytes being P-M and M-P on cellulose and amylose tris(3,5-dimethylphenylcarbamate), respectively. In this regard, a theoretical investigation based on molecular dynamics (MD) simulations was performed by using amylose and cellulose tris(3,5-dimethylphenylcarbamate) nonamers as virtual models of the polysaccharide-based selectors. This exploration at the molecular level shed light on the origin of the enantiodiscrimination processes.     

Mixed micellar systems of octyl β,d-glucopyranoside with a nonionic surfactant and a water-soluble polymer

We have made a comparative study between the micellar regions of the octyl -d-glucoside (OG)–tetraethylene glycol monododecyl ether and the OG–poly(ethylene glycol) 20,000 systems by means of surface tension and viscosimetric measurements. The incorporation of the tetraethylene glycol monododecyl ether nonionic surfactant in the OG micelles decreases the critical micelle concentration, whereas the presence of polymer increases it. The nonionic surfactant mixture exhibits nonideal mixing behaviour. The data fit to Rubinghs treatment with a value of –5.1, which implies a modest attraction between both surfactants. The surfactant–poly(ethylene glycol) 20,000 system does not form mixed micelles. The incorporation of polymer increases the critical micelle concentration of the surfactant. The viscosity for the surfactant–polymer system is higher than that for the pure polymer, demonstrating a surfactant-induced structuring.     

Reaction of singlet oxygen with some benzylic sulfides

Product distribution, total quenching rate (k_T), and rate of chemical reaction (k_r) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines.     

UVB irradiation of normal human skin favors the development of type-2 T-cells in vivo and in primary dermal cell cultures

To determine the effect of UVB exposure on the balance of type-1 or type-2 T-cells in skin, we examined the expression of key markers interferon (IFN)-gamma and interleukin (IL)-4 in cryostat sections. IFN-gamma mRNA was clearly detectable in nonirradiated control skin, and IFN-gamma protein was found in 2% of the dermal CD3pos T-cells, whereas IL-4 mRNA was hardly detectable, and no IL-4 protein was found. In contrast, IL-4 mRNA expression increased upon irradiation, and IL-4 was found in 2% of the T-cells at day 2 after UVB-exposure. Concomitantly, IFN-gamma mRNA expression decreased, and IFN-gamma protein became absent. We also analyzed T-cells present in primary dermal cell cultures, which were used as an in vitro equivalent of the in vivo situation. As compared with T-cells from control skin, T-cells in dermal cell cultures from UVB-exposed skin displayed an increased IL-4 and decreased IFN-gamma expression. No such skewing occurred when the T-cells from irradiated skin were cloned in the absence of a dermal microenvironment. Except for an occasional positive T-cell, type-1-associated cell-surface markers (CCR5, CXCR3) or type-2 markers (CCR3, CD30, CRTH2) were undetectable in situ. But these markers were expressed on cultured dermal T-cells from UVB-exposed and control skin at a comparable level, but did not correlate with the IFN-gamma and IL-4 production. Altogether, UVB-induced changes of the dermal microenvironment favor the development of type-2 T-cells.