The mechanism of double proton transfer in dimers of uracil and 2-thiouracil--the reaction force perspective

The intermolecular double proton transfer in dimers of uracil and 2-thiouracil is studied through density functional theory calculations. The reaction force framework provides the basis for characterizing the mechanism that in all cases has been associated to a dynamic balance between polarization and charge transfer effects. It has been found that the barriers for proton transfer depend upon the nature of the acceptor atoms and its position within the seminal monomer. Actually, the change in the nature of the hydrogen bonds connecting the two monomers along the reaction coordinate may favor or disfavor the double-proton transfer.     

Clonal structure and variation in virulence of Salmonella enteritidis isolated from mice, chickens, and humans

The clonal analysis of a diverse collection of Salmonella Enteritidis indicates that most strains belong to a single multilocus genotype (i.e., ET-3) regardless of phage type, geographic origin, or time of isolation that spanned over 2 decades (1978 to 2004). Attachment and invasion assays, however, indicate that, among ET-3 isolates, there is a distinct invasive bacterial subpopulation that is more readily recovered from eggs and clinical cases in humans than from chicken cecal samples. These observations support the hypothesis that the specialized ability of S. Enteritidis to infect the avian reproductive tract and contaminate eggs has been critical in its emergence as a frequent cause of human illness.     

Image structure preserving denoising using generalized fractional time integrals

A generalization of the linear fractional integral equation u(t)=u₀+∂^−αAu(t), 1<α<2, which is written as a Volterra matrix-valued equation when applied as a pixel-by-pixel technique is proposed in this paper for image denoising (restoration, smoothing, etc.). Since the fractional integral equation interpolates a linear parabolic equation and a hyperbolic equation, the solution enjoys intermediate properties. The Volterra equation we propose is well-posed for all t>0, and allows us to handle the diffusion by means of a viscosity parameter instead of introducing nonlinearities in the equation as in the Perona-Malik and alike approaches. Several experiments showing the improvements achieved by our approach are provided.     

Fair content dissemination in participatory DTNs

Thanks to advances in the computing capabilities and added functionalities of modern mobile devices, creating and consuming digital media on the move has never been so easy and popular. Most of the DTN routing protocols proposed in the literature to enable content sharing have been exploiting users’ mobility patterns, in order to maximise the delivery probability, while minimising the overall network overhead (e.g., number of message replicas in the system, messages’ path length). Common to all these protocols has been the assumption that devices are willing to participate in the content distribution network; however, because of battery constraints, participation cannot be taken for granted, especially if the very same subset of devices are continuously selected as content carriers, simply because of their mobility properties. Indeed, we demonstrate that state-of-the-art DTN routing protocols distribute load in a highly unfair manner, with detrimental effects on delivery once the assumption of unconditional participation is lifted. To overcome this limitation, we propose a load-balancing mechanism whereby nodes maintain local estimates of network workload, and use them to direct traffic towards the least loaded portion of the network. We implement the mechanism on top of a source-based DTN routing protocol, and demonstrate, by means of simulation using a variety of real mobility traces, that high delivery is now achieved without compromising fairness.     

In situ aberration measurement technique based on multi-illumination settings and principal component analysis of aerial images

The impact of lens aberrations becomes severe when the critical dimensions (CDs) shrink. The accurate measurement of both low- and high-order Zernike aberrations is important during a photolithographic process. Based on the multi-illumination settings and principal component analysis of aerial images, a novel in situ aberration measurement technique that can accurately measure all the Zernike aberrations, except for the sinusoidal 2-θ and sinusoidal 4-θ terms (under polar coordinates, and Z 1 to Z 4 are not considered) is proposed in this letter. The estimated maximum error of the Zernike aberrations ranges from 0.43 to 0.78 mλ when the amplitudes of the Zernike coefficients range from -20 to 20 mλ. The standard and root mean square errors are both in the range from 0.14 to 0.4 mλ.     

Synthesis of novel dispiro-oxindoles via 1,3-dipolar cycloaddition reactions of azomethine ylides

The 1,3-dipolar cycloaddition of 1-allyl-5-haloisatin derivatives as dipolarophiles with the azomethine ylides generated in situ from N-allylisatin and l-proline to furnish novel dispiro-oxindoles has been investigated. The structures and relative stereochemistry of both types of cycloadducts were confirmed by single crystal X-ray diffraction, ¹H and ¹³C NMR spectroscopy and mass spectrometry.     

Unexpected acidity enhancement triggered by AlH3 association to phosphines

The complexes formed by the interaction between a series of phosphines R-PH(2) (R = H, CH(3), c-C(3)H(5), C(6)H(5)) and AlH(3) have been investigated through the use of high-level G4 ab initio calculations. These very stable complexes behave as much stronger acids than the isolated phosphines. This dramatic acidity enhancement, which can be as high as 174 kJ mol(-1), results from a much greater stabilization of the anionic deprotonated species with respect to the neutral one, upon AlH(3) association. This effect depends quantitatively on the nature of the substituent R and is smaller for R = C(6)H(5) because of the conjugation of the P lone pair with the aromatic system. More unexpectedly, however, the phosphine-alane complexes, RPH(2):AlH(3), are more acidic than the corresponding phosphine-borane RPH(2):BH(3) analogues. This unexpected result is due to the enhanced stability of the anionic deprotonated species for complexes involving AlH(3), because the delocalization of the newly created P lone pair with the P-Al bonding density is more favorable when the Lewis acid is aluminum trihydride than when it is borane.     

Engineered mesoporous ionic‐modified γ‐Fe2O3@hydroxyapatite decorated with palladium nanoparticles and its catalytic properties in water

A new mesoporous organic–inorganic nanocomposite was formulated and then used as stabilizer and support for the preparation of palladium nanoparticles (Pd NPs). The properties and structure of Pd NPs immobilized on prepared 1,4‐diazabicyclo[2.2.2]octane (DABCO) chemically tagged on mesoporous γ‐Fe₂O₃@hydroxyapatite (ionic modified (IM)‐MHA) were investigated using various techniques. The synergistic effects of the combined properties of MHA, DABCO and Pd NPs, and catalytic activity of γ‐Fe₂O₃@hydroxyapatite‐DABCO‐Pd (IM‐MHA‐Pd) were investigated for the Heck cross‐coupling reaction in aqueous media. The appropriate surface area and pore size of mesoporous IM‐MHA nanocomposite can provide a favourable hard template for immobilization of Pd NPs. The loading level of Pd in the nanocatalyst was 0.51 mmol g^?1. DABCO bonded to the MHA surface acts as a Pd NP stabilizer and can also lead to colloidal stability of the nanocomposite in aqueous solution. The results reveal that IM‐MHA‐Pd is highly efficient for coupling reactions of a wide range of aryl halides with olefins under green conditions. The superparamagnetic nature of the nanocomposite means that the catalyst to be easily separated from solution through magnetic decantation, and the catalytic activity of the recycled IM‐MHA‐Pd showed almost no appreciable loss even after six consecutive runs.     

Use of iodide and silver/sulfide ion-selective electrodes for the determination of some tertiary amines and alkaloids

Summary Some tertiary amines and alkaloides were determined by reaction with methyl iodide at 43 °C. The produced quaternary ammonium iodide salts were potentiometrically titrated with standard silver nitrate solution using either the iodide or silver/sulfide ion-selective electrode. The effects of solvent, temperature and time of reaction were examined. An average recovery of 99.0% and 98.9% with standard deviations of 0.73 and 0.52 were obtained for the studied amines and alkaloides, respectively.

---

Verwendung der Iodid-bzw. Silber/Sulfid-selektiven Elektrode zur Bestimmung einiger tertiärer Amine und Alkaloide