Competition between van der Waals and hydrogen bonding interactions: structure of the trans-1-naphthol/N(2) cluster

The excitation energy in the multiphoton ionization spectrum of the trans-1-naphthol/N(2) cluster shows only a small red shift with respect to isolated naphthol, indicating a van der Waals pi-bound structure rather than a hydrogen-bonded one. To confirm this interpretation, high-level electronic structure calculations were performed for several pi- and hydrogen-bonded isomers of this cluster. The calculations were carried out at the second order M?ller-Plesset (MP2) level of perturbation theory with the family of correlation consistent basis sets up to quintuple-zeta quality including corrections for the basis set superposition error and extrapolation to the MP2 complete basis set (CBS) limit. We report the optimal geometries, vibrational frequencies, and binding energies (D(e)), also corrected for harmonic zero-point energies (D(0)), for three energetically low-lying isomers. In all calculations the lowest energy structure was found to be an isomer with the N(2) molecule bound to the pi-system of the naphthol ring carrying the OH group. In the CBS limit its dissociation energy was computed to be D(0) = 2.67 kcal/mol (934 cm(-1)) as compared to D(0) = 1.28 kcal/mol (448 cm(-1)) for the H-bound structure. The electronic structure calculations therefore confirm the assignment of the experimental electronic spectrum corresponding to a van der Waals pi-bound structure. The energetic stabilization of the pi-bound isomer with respect to the hydrogen-bonded one is rather unexpected when compared with previous findings in related systems, in particular phenol/N(2).     

Colorimetric determination of reactive primary amino groups of macro- and microsolid supports

The several factors that could affect the sensitivity and the accuracy of the determination of solid-supported amino groups using 2-iminothiolane (Traut's reagent) and 5,5′-dithiobis-(2-nitrobenzoic acid) (Ellman's reagent) are described. The authors found that by using 0.1M phosphate buffer, pH 8.0, instead of ethanol as solvent for the reaction of the solid supports with the 2-iminothiolane, using 0.1M phosphate buffer adjusted at pH 7.27 instead of 8.0 as diluent of 5,5′-dithiobis-(2-nitrobenzoic acid), and selecting carefully the concentration of the latter reagent, it was possible to produce a very sensitive assay capable of quantitatively determining the surface amino groups of very different types of samples. The assay is well adapted for quantitative determination of amino-carrying plastic beads, permitting the determination of nanomolar quantities. In addition, the assay is well suited for microparticulated solid supports (e.g., AH-Sepharose).     

High-level ab initio calculations for the four low-lying families of minima of (H2O)20. I. Estimates of MP2/CBS binding energies and comparison with empirical potentials

We report estimates of complete basis set (CBS) limits at the second-order M?ller-Plesset perturbation level of theory (MP2) for the binding energies of the lowest-lying isomers within each of the four major families of minima of (H(2)O)(20). These were obtained by performing MP2 calculations with the family of correlation-consistent basis sets up to quadruple zeta quality, augmented with additional diffuse functions (aug-cc-pVnZ, n=D, T, Q). The MP2/CPS estimates are -200.1 (dodecahedron, 30 hydrogen bonds), -212.6 (fused cubes, 36 hydrogen bonds), -215.0 (face-sharing pentagonal prisms, 35 hydrogen bonds), and -217.9 kcal/mol (edge-sharing pentagonal prisms, 34 hydrogen bonds). The energetic ordering of the various (H(2)O)(20) isomers does not follow monotonically the number of hydrogen bonds as in the case of smaller clusters such as the different isomers of the water hexamer. The dodecahedron lies ca. 18 kcal/mol higher in energy than the most stable edge-sharing pentagonal prism isomer. The TIP4P, ASP-W4, TTM2-R, AMOEBA, and TTM2-F empirical potentials also predict the energetic stabilization of the edge-sharing pentagonal prisms with respect to the dodecahedron, albeit they universally underestimate the cluster binding energies with respect to the MP2/CBS result. Among them, the TTM2-F potential was found to predict the absolute cluster binding energies to within <1% from the corresponding MP2/CBS values, whereas the error for the rest of the potentials considered in this study ranges from 3% to 5%.     

Restricted diffusion in silica particles measured by pulsed field gradient NMR

The restricted diffusion coefficient of water through porous silica is measured by pulsed field gradient (PFG) NMR as a function of loading in order to develop a model for self-diffusion at full pore filling in sol-gel-made porous silica particles. This model describes the pore or intraparticle diffusion coefficient as a function of particle porosity, tortuosity, and the steric hindrance applied on the molecules by the pore space. The particle morphology is characterized by nitrogen adsorption and an appropriate tortuosity model is chosen in comparison with literature data. To characterize the material, NMR relaxation and diffusion studies at different degrees of pore filling were carried out in relation to the silica/water adsorption isotherm.     

Isolation of Volatile Compounds with Repellent Properties against Aedes albopictus (Diptera: Culicidae) Using CPC Technology

The present work describes the use of Centrifugal Partition Chromatography (CPC) for the bio-guided isolation of repellent active volatile compounds from essential oils. Five essential oils (EOs) obtained from three Pinus and two Juniperus species were initially analyzed by gas chromatography–mass spectrometry (GC/MS) and evaluated for their repellent properties against Aedes albopictus. The essential oil from needles of P. pinea (PPI) presented the higher activity, showing 82.4% repellency at a dose of 0.2 μL/cm². The above EO, together with the EO from the fruits of J. oxycedrus subsp. deltoides (JOX), were further analyzed by CPC using the biphasic system n-Heptane/ACN/BuOH in ratio 1.6/1.6/0.2 (v/v/v). The analysis of PPI essential oil resulted in the recovery of (−)-limonene, guaiol and simple mixtures of (−)-limonene/β-pheladrene, while the fractionation of JOX EO led to the recovery of β-myrcene, germacrene-D, and mixtures of α-pinene/β-pinene (ratio 70/30) and α-pinene/germacrene D (ratio 65/45). All isolated compounds and recovered mixtures were tested for their repellent activity. From them, (−)-limonene, guaiol, germacrene-D as well the mixtures of (−)-limonene/β-pheladrene presented significant repellent activity (>97% repellency) against Ae. albopictus. The present methodology could be a valuable tool in the effort to develop potent mosquito repellents which are environmentally friendly.     

Homogeneous ZnO Nanoparticles by Flame Spray Pyrolysis

Zinc oxide (ZnO) nanoparticles were made by flame spray pyrolysis (FSP) of zinc acrylate–methanol–acetic acid solution. The effect of solution feed rate on particle specific surface area (SSA) and crystalline size was examined. The average primary particle diameter can be controlled from 10 to 20nm by the solution feed rate. All powders were crystalline zincite. The primary particle diameter observed by transmission electron microscopy (TEM) was in agreement with the equivalent average primary particle diameter calculated from the SSA as well as with the crystalline size calculated from the X-ray diffraction (XRD) patterns for all powders, indicating that the primary particles were rather uniform in diameter and single crystals. Increasing the solution feed rate increases the flame height, and therefore coalescence and/or surface growth was enhanced, resulting in larger primary particles. Compared with ZnO nanoparticles made by other processes, the FSP-made powder exhibits some of the smallest and most homogeneous primary particles. Furthermore, the FSP-made powder has comparable BET equivalent primary particle diameter with but higher crystallinity than sol–gel derived ZnO powders.     

Waiting Time for an Almost Perfect Run and Applications in Statistical Process Control

A natural and intuitively appealing generalization of the runs principle arises if instead of looking at fixed-length strings with all their positions occupied by successes, we allow the appearance of a small number of failures. Therefore, the focus is on clusters of consecutive trials which contain large proportion of successes. Such a formation is traditionally called “scan” or alternatively, due to the high concentration of successes within it, almost perfect (success) run. In the present paper, we study in detail the waiting time distribution for random variables related to the first occurrence of an almost perfect run in a sequence of Bernoulli trials. Using an appropriate Markov chain embedding approach we present an efficient recursive scheme that permits the construction of the associated transition probability matrix in an algorithmically efficient way. It is worth mentioning that, the suggested methodology, is applicable not only in the case of almost perfect runs, but can tackle the general discrete scan case as well. Two interesting applications in statistical process control are also discussed.     

Optimal policy and holding cost stability regions in a periodic review inventory system with manufacturing and remanufacturing options

In this paper a periodic review inventory model with finite horizon and remanufacturing, manufacturing options is studied. It is assumed that demand and cost parameters are constant and a sufficiently large quantity of used products is available at the beginning of the horizon. The model is studied within the class of policies with given remanufacturing and manufacturing set up and the optimal policy is obtained within this class. The policy specifies the period of switching from remanufacturing to manufacturing (switching period), the periods where remanufacturing and manufacturing activities take place and the corresponding lot sizes. An explicit formula for the cost function and some of its properties are established. Based on these, an algorithm which partitions the set of holding cost parameters into subsets, computes the optimal policy and constructs its corresponding stability regions on every such subset is proposed.     

Positive solutions for fractional differential systems with nonlocal Riemann–Liouville fractional integral boundary conditions

In this paper, we study the positive solutions of fractional differential system with coupled nonlocal Riemann–Liouville fractional integral boundary conditions. Our analysis relies on Leggett–Williams and Guo–Krasnoselskii’s fixed point theorems. Two examples are worked out to illustrate our main results.     

On Perturbed Fractional Differential Inclusions with Nonlocal Multi-point Erdélyi–Kober Fractional Integral Boundary Conditions

In this paper, by using a nonlinear alternative for a sum of compact upper semicontinuous and contractive multivalued operators, we establish sufficient conditions for the existence of solutions for perturbed fractional differential inclusions with nonlocal multi-point Erdélyi–Kober fractional integral boundary conditions. For the applicability of the main result, we include an example.