The Formation of Imidazolium Salt Intimate (Contact) Ion Pairs in Solution

1‐n‐Butyl‐2,3‐dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2‐Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl₃ and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D₂O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.     

On investigation of high Tc superconductors with Electron Paramagnetic Resonance spectrometers

Following the discovery of high T_c superconductors, many researchers have applied EPR spectrometers to investigate their properties using the regular instructions to operate the spectrometer. As no substantial information was obtained it was soon practically abandoned. Investigations performed recently with the EPR technique, using a different operating method than the conventional one and the introduction of a detailed theoretical study related to the interaction of the JV with the microwave magnetic field lead to new and important results related to properties of high anisotropy superconductors indicating that the EPR spectrometer can be used to investigate properties of high anisotropy superconductors. The failures when using conventional operating method to obtain meaningful results and the method used in the present work to carry out the measurements in a proper manner are presented. Some important results obtained in investigating high anisotropy superconductors by the EPR technique are presented.     

In Situ Detection of Particle Aggregation on Electrode Surfaces

Partially blocked electrodes (PBEs) are important; many applications use non‐conductive nanoparticles (NPs) to introduce new electrode functionalities. As aggregation is a problem in NP immobilization, developing an in situ method to detect aggregation is vital to characterise such modified electrodes. We present chronoamperometry as a method for detection of NP surface aggregation and semi‐quantitative sizing of the formed aggregates, based on the diffusion limited current measured at PBEs as compared with the values calculated numerically for different blocking feature sizes. In contrast to voltammetry, no approximations on electrode kinetics are needed, making chronoamperometry a more general and reliable method. Sizing is shown for two modification methods. Upon drop casting, significant aggregation is observed, while it is minimized in electrophoretic NP deposition. The aggregate sizes determined are in semi‐quantitative agreement with ex situ microscopic analysis of the PBEs.     

Bioactivity and chemical composition of the essential oil from the leaves of Guatteria australis A.St.-Hil

Essential oil from the leaves of Guatteria australis was obtained by hydrodistillation, analyzed by Gas Chromatography coupled to Mass Spectromery (GC–MS) and their antiproliferative, antileishmanial, antibacterial, antifungal and antioxidant activities were also evaluated. Twenty-three compounds were identified among which germacrene B (50.66%), germacrene D (22.22%) and (E)-caryophyllene (8.99%) were the main compounds. The highest antiproliferative activity was observed against NCI-ADR/RES (TGI = 31.08 μg/ml) and HT-29 (TGI = 32.81 μg/ml) cell lines. It also showed good antileishmanial activity against Leishmania infantum (IC₅₀ = 30.71 μg/ml). On the other hand, the oil exhibited a small effect against Staphylococcus aureus ATCC 6538, S. aureus ATCC 14458 and Escherichia coli ATCC 10799 (MIC = 250 μg/ml), as well as small antioxidant activity (457 μmol TE/g) assessed through ORAC_FL assay. These results represent the first report regarding chemical composition and bioactivity of G. australis essential oil.     

Nonvisual Opsins and the Regulation of Peripheral Clocks by Light and Hormones

The molecular clock machinery is conserved throughout evolution. However, how environmental cues are perceived has evolved in such a way that peripheral clocks in mammals require a variety of signals, including hormones. On the other hand, in nonmammalian cells able to directly detect light, light seems to play a major role in the synchronization of the clock. The interaction between perception of circadian light by nonvisual opsins and hormones will be discussed under the perspective of clock synchronization at the molecular level.     

Thermal desorption spectra of hydrogen from the bulk: ZrV2Hx

Thermal desorption of hydrogen from the bulk of the system ZrV₂H_x, 0.3 ? x ? 4.27, shows spectra which develop from a single peak, for x < 1, to a spectrum that consists of 3 peaks and a shoulder for x ? 4.27. A model is proposed to explain the origin of these peaks and relates them to a consecutive desorption of the hydrogens from the different interstitial sites, in agreement with neutron diffraction data on the sites' occupancy. However, neutron diffraction indicates that up to x ≈ 2.5 the hydrogens occupy the tetrahedral sites formed by 2 Zr and 2 V, nevertheless our results show that there is a large difference in the bonding energy of these sites for hydrogens with x < 1 and hydrogens with 1 < x < 2.5.     

The crystalline electric field in some non-magnetic dialuminides compounds

Magnetization measurements performed in powdered LuAl₂:RE (RE = Dy, Er) and single crystals of YAl₂:Er and LaAl₂:Nd are reported. The results yield information concerning the levels scheme of the paramagnetic impurities in these compounds. The results in YAl₂:Er are discussed in view of recent measurements.     

The Biochemical Mechanisms of Antimicrobial Photodynamic Therapy†

The unbridled dissemination of multidrug-resistant pathogens is a major threat to global health and urgently demands novel therapeutic alternatives. Antimicrobial photodynamic therapy (aPDT) has been developed as a promising approach to treat localized infections regardless of drug resistance profile or taxonomy. Even though this technique has been known for more than a century, discussions and speculations regarding the biochemical mechanisms of microbial inactivation have never reached a consensus on what is the primary cause of cell death. Since photochemically generated oxidants promote ubiquitous reactions with various biomolecules, researchers simply assumed that all cellular structures are equally damaged. In this study, biochemical, molecular, biological and advanced microscopy techniques were employed to investigate whether protein, membrane or DNA damage correlates better with dose-dependent microbial inactivation kinetics. We showed that although mild membrane permeabilization and late DNA damage occur, no correlation with inactivation kinetics was found. On the other hand, protein degradation was analyzed by three different methods and showed a dose-dependent trend that matches microbial inactivation kinetics. Our results provide a deeper mechanistic understanding of aPDT that can guide the scientific community toward the development of optimized photosensitizing drugs and also rationally propose synergistic combinations with antimicrobial chemotherapy.     

Increasing the output length of zero‐error dispersers

Let $\cal{C}$ be a class of probability distributions over a finite set Ω. A function $D : \Omega \mapsto\{0,1\}^{m}$ is a disperser for $\cal{C}$ with entropy threshold $k$ and error $\epsilon$ if for any distribution X in $\cal{C}$ such that X gives positive probability to at least $2^{k}$ elements we have that the distribution $D(X)$ gives positive probability to at least $(1-\epsilon)2^{m}$ elements. A long line of research is devoted to giving explicit (that is polynomial time computable) dispersers (and related objects called “extractors”) for various classes of distributions while trying to maximize m as a function of k. For several interesting classes of distributions there are explicit constructions in the literature of zero‐error dispersers with “small” output length m. In this paper we develop a general technique to improve the output length of zero‐error dispersers. This strategy works for several classes of sources and is inspired by a transformation that improves the output length of extractors (which was given by Shaltiel (CCC'06; Proceedings of the 21st Annual IEEE Conference on Computational Complexity, (2006) 46–60.) building on earlier work by Gabizon, Raz and Shaltiel (SIAM J Comput 36 (2006) 1072–1094). Our techniques are different than those of Shaltiel (CCC'06; Proceedings of the 21st Annual IEEE Conference on Computational Complexity (2006) 46–60) and in particular give non‐trivial results in the errorless case. Using our approach we construct improved zero‐error 2‐source dispersers. More precisely, we show that for any constant $\delta >0$ there is a constant $\eta >0$ such that for sufficiently large n there is a poly‐time computable function $D :\{0,1\}^{n}\times\{0,1\}^{n}\mapsto\{0,1\}^{\eta n}$ such that for every two independent distributions $X_1,X_2$ over $\{0,1\}^{n}$ each with support size at least $2^{\delta n}$ , the output distribution $D(X_1,X_2)$ has full support. This improves the output length of previous constructions by Barak, Kindler, Shaltiel, Sudakov and Wigderson (Proceedings of the 37th Annual ACM Symposium on Theory of Computing (2005) 1–10) and has applications in Ramsey theory and in improved constructions of certain data structures from the work of Fiat and Naor [SIAM J Comput 22 (1993)]. We also use our techniques to give explicit constructions of zero‐error dispersers for bit‐fixing sources and affine sources over polynomially large fields. These constructions improve the best known explicit constructions due to Rao (unpublished data) and Gabizon and Raz [Combinatorica 28 (2008)] and achieve $m=\Omega(k)$ for bit‐fixing sources and $m=k-o(k)$ for affine sources over polynomial size fields. © 2011 Wiley Periodicals, Inc. Random Struct. Alg., 2011