Omega-halonitriles: domino cyclizations to oxa- and carbocyclic nitriles

t-BuOK-induced deprotonation of omega-haloalkylnitriles generates remarkably stable potassiated nitriles. In situ deprotonation and alkylation of omega-chloroalkylnitriles with aldehyde electrophiles trigger sequential nucleophilic-electrophilic alkylations generating substituted tetrahydrofuranyl and tetrahydropyranyl nitriles. Redirecting the cyclization manifold with 5-iodopentanenitrile and a ketone causes a complementary electrophilic-nucleophilic cyclization to the corresponding carbonitrile. Collectively these cyclizations provide rapid assembly of five- and six-membered oxa- and carbocyclic nitriles demonstrating the utility of omega-halonitriles in domino alkylations.     

Surfactant driven flows overlying a hydrophobic epithelium: film rupture in the presence of slip

Both for tear films and along the airways within the lung, one has an extremely thin fluid layer overlying a biological substrate; in both cases surfactants either of natural origin, or artificially introduced, are important in driving fluid flows. There is evidence that slip can occur when hydrophilic liquids, similar to mucus or aqueous tear films, overlie hydrophobic epithelium. Utilizing results from recent experimental findings we examine the possible influence of slip upon tear film rupture, important in so-called dry eye, and upon surfactant-induced flows within the lung, used in surfactant replacement therapy.     

Low-energy effects in brane worlds: Liennard–Wiechert potentials and Hydrogen Lamb shift

Testing extra dimensions at low-energies may lead to interesting effects. In this work a test point charge is taken to move uniformly in the 3D subspace of a (3 + n)-brane embedded in a (3 + n + 1)-space with n compact and one warped infinite spatial extra dimensions. We found that the electromagnetic potentials of the point charge match standard Liennard–Wiechert’s at large distances but differ from them close to it. These are finite at the position of the charge and produce finite self-energies. We also studied a localized Hydrogen atom and take the deviation from the standard Coulomb potential as a perturbation. This produces a Lamb shift that is compared with known experimental data to set bounds for the parameter of the model. This work provides details and extends results reported in a previous Letter. We are pleased to dedicate this work to Professor Octavio Obregón on occasion of his 60th birthday. H. A. Morales-Técotl is an associate member of the Abdus Salam ICTP, Trieste Italy.     

NIR spectroscopic properties of aqueous acids solutions

Acid content is one of the important quality attributes in determining the maturity index of agricultural product, particularly fruits. Despite the fact that much research on the measurement of acidity in fruits through non-destructive spectroscopy analysis at NIR wavelengths between 700 to 1,000 nm has been conducted, the same response towards individual acids is not well known. This paper presents NIR spectroscopy analysis on aqueous citric, tartaric, malic and oxalic solutions through quantitative analysis by selecting a set of wavelengths that can best be used to measure the pH of the solutions. The aquaphotomics study of the acid solutions has generated R2 above 0.9 for the measurement of all acids. The most important wavelengths for pH are located at 918-925 nm and 990-996 nm, while at 975 nm for water.     

Energy Levels of Neutral Atoms Via a New Perturbation Method

The energy levels of neutral atoms supported by potential V (r) = -Zexp(-ar)/r (Yukawa potential) are studied, using both dimensional and dimensionless quantities, via a new analytical methodical proposal (devised to solve for nonexactly solvable Schrödinger equation). Using dimensionless quantities, by scaling the radial Hamiltonian through y = Zr and = /Z, we report that the scaled screening parameter is restricted to have values ranging from zero to less than 0.4. On the other hand, working with the scaled Hamiltonian enhances the accuracy and extremely speeds up the convergence of the energy eigenvalues. The energy levels of several new eligible scaled screening parameter values are also reported.     

Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks

The dihydrogen adsorption isotherms of eight metal-organic frameworks (MOFs), measured at 77 K up to a pressure of 1 atm, have been examined for correlations with their structural features. All materials display approximately Type I isotherms with no hysteresis, and saturation was not reached for any of the materials under these conditions. Among the six isoreticular MOFs (IRMOFs) studied, the catenated materials exhibit the largest capacities on a molar basis, up to 9.8 H(2) per formula unit. The addition of functional groups (-Br, -NH(2), -C(2)H(4)-) to the phenylene links of IRMOF-1 (MOF-5), or their replacement with thieno[3,2-b]thiophene moieties in IRMOF-20, altered the adsorption behavior by a minor amount despite large variations in the pore volumes of the resulting materials. In contrast, replacement of the metal oxide units with those containing coordinatively unsaturated metal sites resulted in greater H(2) uptake. The enhanced affinities of these materials, MOF-74 and HKUST-1, were further demonstrated by calculation of the isosteric heats of adsorption, which were larger across much of the range of coverage examined, compared to those of representative IRMOFs. The results suggest that under low-loading conditions, the H(2) adsorption behavior of MOFs can be improved by imparting larger charge gradients on the metal oxide units and adjusting the link metrics to constrict the pore dimensions; however, a large pore volume is still a prerequisite feature.     

Fabrication of Alginate-Based O/W Nanoemulsions for Transdermal Drug Delivery of Lidocaine: Influence of the Oil Phase and Surfactant

Transdermal drug delivery of lidocaine is a good choice for local anesthetic delivery. Microemulsions have shown great effectiveness for the transdermal transport of lidocaine. Oil-in-water nanoemulsions are particularly suitable for encapsulation of lipophilic molecules because of their ability to form stable and transparent delivery systems with good skin permeation. However, fabrication of nanoemulsions containing lidocaine to provide an extended local anesthetic effect is challenging. Hence, the aim of this study was to address this issue by employing alginate-based o/w nanocarriers using nanoemulsion template that is prepared by combined approaches of ultrasound and phase inversion temperature (PIT). In this study, the influence of system composition such as oil type, oil and surfactant concentration on the particle size, in vitro release and skin permeation of lidocaine nanoemulsions was investigated. Structural characterization of lidocaine nanoemulsions as a function of water dilution was done using DSC. Nanoemulsions with small droplet diameters (d < 150 nm) were obtained as demonstrated by dynamic light scattering (DLS) and cryo-TEM. These nanoemulsions were also able to release 90% of their content within 24-h through PDMS and pig skin and able to the drug release over a 48-h. This extended-release profile is highly favorable in transdermal drug delivery and shows the great potential of this nanoemulsion as delivery system.     

Characterization of H2 binding sites in prototypical metal-organic frameworks by inelastic neutron scattering

The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. Similarities in the spectral features as a function of H(2) loading and correlations with recent crystallographic studies were used to assign transitions ranging in rotational barrier from <0.04 to 0.6 kcal/mol as corresponding to localized adsorption sites on the organic and inorganic components of these frameworks. We find that binding of H(2) at the inorganic cluster sites is affected by the nature of the organic link and is strongest in IRMOF-11 in accord with our adsorption isotherm data. The sites on the organic link have lower binding energies, but a much greater capacity for increases in H(2) loading, which demonstrates their importance for hydrogen uptake by these materials.