Spectroscopic study of maghemite nanoparticles surface-grafted with DMSA

Nanosized maghemite (below 10 nm average diameter), surface-functionalized with meso-2,3-dimercaptosuccinic acid (DMSA), was investigated with respect to the content of DMSA molecules attached onto its surface and the onset of S-S bridges due to oxidation of neighboring S-H groups. To support our investigation, we introduced the use of photoacoustic spectroscopy to monitor thiol groups (S-H) conjugated with Raman spectroscopy to monitor the disulfide bridges (S-S). The normalized intensity (N(R)) of the Raman feature peaking at 500 cm(-1) was used to probe the S-S bridge whereas the normalized intensity (N(P)) of the photoacoustic band-S (0.42-0.65 μm) was used to probe the S-H moiety. The perfect linearity observed in the N(R) versus (1 - N(P)) plot strongly supports the oxidation process involving neighboring S-H groups as the DMSA surface grafting coefficient increases whereas the approach used in this report allows the evaluation of the [S-H]/[S-S] ratio. The observation of the reduction of the hydrodynamic diameter as the nominal DMSA-grafting increases supports the proposed model picture, in which the intraparticle (interparticle) S-S bridging takes place at higher (lower) DMSA-grafting values.     

Influence of OH⋯N and NH⋯O inter- and intramolecular hydrogen bonds in the conformational equilibrium of some 1,3-disubstituted cyclohexanes through NMR spectroscopy and theoretical calculations

The analysis of concentration effects in the (1)H NMR data of cis-3-aminocyclohexanol (ACOL) showed that its diequatorial conformer changes from 60% at 0.01 mol L(-1) to 70% at 0.40 mol L(-1) in acetone-d(6). A similar increase was also observed for the diequatorial conformer of cis-3-N-methylaminocyclohexanol (MCOL), from 32% (CDCl(3) 0.01 mol L(-1)) to 55% (CDCl(3) 0.40 mol L(-1)). The increase in solvent basicity leads to a large stabilization effect for the diequatorial conformer of both compounds too. For ACOL, it changes from 47% (ΔG(eqeq-axax)=0.06 kcal mol(-1)) in CCl(4) to 93% (ΔG(eqeq-axax)=-1.53 kcal mol(-1)) in DMSO, while for MCOL it goes from 7% (ΔG(eqeq-axax)=1.54 kcal mol(-1)) in CCl(4) to 82% (ΔG(eqeq-axax)=-0.88 kcal mol(-1)) in pyridine-d(6). These results indicate that the intramolecular hydrogen bonds (IAHB) OH?N and NH?O stabilize the diaxial conformers of these compounds in a non-polar solvent. For cis-3-amino-1-methoxycyclohexane (ACNE) and cis-3-N-methylamino-1-methoxy-cyclohexane (MCNE) no changes were observed in equilibrium with the variation of solvent polarity. These results indicate for the first time that the IAHB NH?O is not strong enough to stabilize the diaxial conformer of these compounds and that the conformation equilibria of the cis isomers of compounds ACOL and MCOL are influenced only by the IAHB OH?N. Moreover, the presence of a secondary amino group (93% of diaxial conformer in CCl(4)) leads to an IAHB OH?N stronger than in primary and tertiary amino-derivatives (53 and 54% of diaxial conformer, respectively) for 1,3-disubstituted cyclohexanes. Values obtained from the theoretical data through the B3LYP functional are in agreement with the experimental results and indicate that the IAHB strength that influences the conformational equilibrium of these compounds is the IAHB OH?N. Thus, the IAHB NH?O do not stabilize the diaxial conformer of the cis isomer of compounds ACNE and MCNE showing that the diequatorial conformer will always be more stable than the diaxial conformer, independent of concentration or solvent.     

Global dynamics and integrity of a two-dof model of?a?parametrically excited cylindrical shell

In this paper the global dynamics and topological integrity of the basins of attraction of a parametrically excited cylindrical shell are investigated through a two-degree-of-freedom reduced order model. This model, as shown in previous authors?? works, is capable of describing qualitatively the complex nonlinear static and dynamic buckling behavior of the shell. The discretized model is obtained by employing Donnell shallow shell theory and the Galerkin method. The shell is subjected to an axial static pre-loading and then to a harmonic axial load. When the static load is between the buckling load and the minimum post-critical load, a three potential well is obtained. Under these circumstances the shell may exhibit pre- and post-buckling solutions confined to each of the potential wells as well as large cross-well motions. The aim of the paper is to analyze in a systematic way the bifurcation sequences arising from each of the three stable static solutions, obtaining in this way the parametric instability and escape boundaries. The global dynamics of the system is analyzed through the evolution of the various basins of attraction in the four-dimensional phase space. The concepts of safe basin and integrity measures quantifying its magnitude are used to obtain the erosion profile of the various solutions. A detailed parametric analysis shows how the basins of the various solutions interfere with each other and how this influences the integrity measures. Special attention is dedicated to the topological integrity of the various solutions confined to the pre-buckling well. This allows one to evaluate the safety and dynamic integrity of the mechanical system. Two characteristic cases, one associated with a sub-critical parametric bifurcation and another with a super-critical parametric bifurcation, are considered in the analysis.     

On the decay of solutions for porous-elastic systems with history

In this paper we study the asymptotic behavior to an one-dimensional porous-elasticity problem with history. We show the lack of exponential stability when the porous dissipation or the elastic dissipation is absent. And we show the lack of analyticity and exponential stability when the porous viscosity and the elastic dissipation are present.     

A geometric approach to error estimates for conservation laws posed on a spacetime

We consider a hyperbolic conservation law posed on an (N+1)-dimensional spacetime, whose flux is a field of differential forms of degree N. Generalizing the classical Kuznetsov’s method, we derive an L¹ error estimate which applies to a large class of approximate solutions. In particular, we apply our main theorem and deal with two entropy solutions associated with distinct flux fields, as well as with an entropy solution and an approximate solution. Our framework encompasses, for instance, equations posed on a globally hyperbolic Lorentzian manifold.     

New Approaches to 6‐Oxoisoaporphine and Tetrahydroisoquinoline Derivatives

2,3‐Dihydro‐6‐hydroxy‐5‐methoxy‐7H‐dibenzo[de,h]quinolin‐7‐one, 6‐hydroxy‐5‐methoxy‐7H‐dibenzo[de,h]quinolin‐7‐one, and 2‐(6,7‐dimethoxy‐3,4‐dihydroisoquinolin‐1‐yl)benzyl benzoate, easily available by a Bischler–Napieralski cyclization, were used as starting materials to afford 6‐oxoisoaporphine and 2,3‐dimethoxy‐5,6,8,12b‐tetrahydroisoindolo[1,2‐a]isoquinoline as the main products. However, the catalytic hydrogenation of the benzyl benzoate derivative afforded, under mild conditions, 1,2,3,4‐tetrahydro‐6,7‐dimethoxy‐1‐(2‐methylphenyl)isoquinoline.     

How does dielectric solvation affect the size of an ion?

The effect of solvation by a continuum dielectric on the size of an ion is examined using electronic structure calculations. Various measures correlated with size are considered, including the root-mean-square radius of the electronic charge density, the amount of solute charge penetrating outside the cavity, the electronic radial distribution function, the nucleus-electron potential energy, and the electron-electron potential energy. Calculations are made on several representative ionic solutes, and it is found that every measure indicates that the application of a dielectric makes the cations larger and the anions smaller. These counterintuitive trends are examined, and a plausible explanation is offered for the observed behavior.     

An exact method for computing the nadir values in multiple objective linear programming

In this paper we propose a new method to determine the exact nadir (minimum) criterion values over the efficient set in multiple objective linear programming (MOLP). The basic idea of the method is to determine, for each criterion, the region of the weight space associated with the efficient solutions that have a value in that criterion below the minimum already known (by default, the minimum in the payoff table). If this region is empty, the nadir value has been found. Otherwise, a new efficient solution is computed using a weight vector picked from the delimited region and a new iteration is performed. The method is able to find the nadir values in MOLP problems with any number of objective functions, although the computational effort increases significantly with the number of objectives. Computational experiments are described and discussed, comparing two slightly different versions of the method.     

Rotaxanes capable of recognising chloride in aqueous media

A new, versatile chloride-anion-templating synthetic pathway is exploited for the preparation of a series of eight new [2]rotaxane host molecules, including the first sulfonamide interlocked system. (1)H NMR spectroscopic titration investigations demonstrate the rotaxanes' capability to selectively recognise the chloride anion in competitive aqueous solvent media. The interlocked host's halide binding affinity can be further enhanced and tuned through the attachment of electron-withdrawing substituents and by increasing its positive charge. A dicationic rotaxane selectively binds chloride in 35% water, wherein no evidence of oxoanion binding is observed. NMR spectroscopy, X-ray structural analysis and computational molecular dynamics simulations are used to account for rotaxane formation yields, anion binding strengths and selectivity trends.