Preparation and characterization of chloroaluminum phthalocyanine-loaded solid lipid nanoparticles by thermal analysis and powder X-ray diffraction techniques

Solid lipid nanoparticles (SLN) without drug and SLN loaded with chloroaluminum phthalocyanine (AlClPc) were prepared by solvent diffusion method in aqueous system and characterized by thermal analyses and X-ray diffraction (XRD) in this study. Determination of particle size, zeta potential (ZP), and encapsulation efficiency were also evaluated. SLN containing AlClPc of nanometer size with high encapsulation efficiency and ZP were obtained. The results indicated that the size of SLN loaded with AlClPc is larger than that of the inert particle, but ZP is not changed significantly with incorporation of the drug. In differential scanning calorimetry (DSC) curves, it was observed that the melting point of stearic acid (SA) isolated and in SLN occurred at 55 and 64 °C, respectively, suggesting the presence of different polymorphs. DSC also shows that the crystallinity state of SLN was much less than that of SA isolated. The incorporation of drug in SLN may have been favored by this lower crystallinity degree of the samples. XRD techniques corroborated with the thermal analytic techniques, suggesting the polymorphic modifications of stearic acid.     

Inherent Electrochemistry and Activation of Chemically Modified Graphenes for Electrochemical Applications

Graphene research is currently at the frontier of electrochemistry. Many different graphene‐based materials are employed by electrochemists as electrodes in sensing and in energy‐storage devices. Because the methods for their preparation are inherently different, graphene materials are expected to exhibit different electrochemical behaviors depending on the functionalities and density of defects present. Electrochemical treatment of these “chemically modified graphenes” (CMGs) represents an easy approach to alter surface functionalities and consequently tune the electrochemical performance. Herein, we report a preliminary electrochemical characterization of four common chemically modified graphenes, namely: graphene oxide, graphite oxide, chemically reduced graphene oxide, and thermally reduced graphene oxide. These CMGs were compared with graphite as a reference material. Cyclic voltammetry was used to ascertain the chemical functionalities present and to understand the potential ranges in which the materials were electroactive. Electrochemical treatment with either an oxidative or a reductive fixed potential were then carried out to activate these chemically modified graphenes. The effects of such electrochemical treatments on their electrocatalytic properties were then investigated by cyclic voltammetry in the presence of well‐known redox probes, such as [Fe(CN)₆]^4?/3?, Fe^3+/2+, [Ru(NH₃)₆]^2+/3+, and ascorbic acid. Thermally reduced graphene oxide exhibited the best electrochemical behavior amongst all of the CMGs, with the fastest rate of heterogeneous electron transfer (HET) and the lowest overpotentials. These findings will have far‐reaching consequences for the evaluation of different CMGs as electrode materials in electrochemical devices.     

Rhenium(V) and technetium(V) nitrido complexes with mixed tridentate π-donor and monodentate π-acceptor ligands

Mixed-ligand [M(N)(SNS)(PPh(3))] complexes (M = Tc, Re) (1, 2) were prepared by reaction of the precursor [M(N)Cl(2)(PPh(3))(2)] with ligand 2,2'-dimercaptodiethylamine [H(2)SNS = NH(CH(2)CH(2)SH)(2)] in refluxing dichloromethane/ethanol mixtures. In these compounds, 2,2'-dimercaptodiethylamine acts as a dianionic tridentate chelating ligand bound to the [M≡N](2+) group through the two π-donor deprotonated sulfur atoms and the protonated amine nitrogen atom. Triphenylphosphine completes the coordination sphere, acting as a monodentate ligand. [M(N)(NS(2))(PPh(3))] complexes can assume two different isomeric forms depending on the syn and anti orientations of the hydrogen atom bound to the central nitrogen atom of the SNS ligand with respect to the M≡N moiety. X-ray crystallography of the syn isomer of complex 2 demonstrated that it has a distorted trigonal bipyramidal geometry with the nitrido group and the two sulfur atoms defining the equatorial plane, the phosphorus atom of the monophosphine and the protonated amine nitrogen of the tridentate ligand spanning the two reciprocal trans positions along the axis perpendicular to the trigonal plane. Synthesis of the analogous Tc derivatives with tris(2-cyanoethyl)phosphine, [Tc(N)(SNS)(PCN)] [(PCN = P(CH(2)CH(2)CN)(3)], required the preliminary preparation of the new precursor [Tc(N)(PCN)(2)Cl(2)](2) (3), which was prepared by reacting [n-NBu(4)][Tc(N)Cl(4)] with a high excess of PCN. The crystal structure of compound 3 consists of a noncrystallographic centrosymmetric dimer of Tc(V) nitrido complexes having an octahedral geometry. In this arrangement, the apical positions are occupied by two tris(2-cyanoethyl)phosphine groups and the equatorial positions by the nitrido group whereas the two Cl(-) anions and one cyano ligand belong to the other octahedral component of the dimer. By reacting the new precursor [Tc(N)(PCN)(2)Cl(2)](2) with the ligand H(2)SNS the complex [Tc(N)(SNS)(PCN)] (5) was finally obtained in acetonitrile solution. The new Tc(III) complex trans-[Tc(PCN)(2)Cl(4)][n-NBu(4)] (4) was also isolated from the reaction solution used for preparing complex 3 as side product and characterized by X-ray diffraction. The crystal structure of 4 consists of independent trans-[TcCl(4)(PCN)(2)](-) anions situated on crystallographic centers of symmetry and tetrabutylammonium cations in general positions.     

Probing phase transitions under extreme conditions by ultrafast techniques: Advances at the Fermi@Elettra free-electron-laser facility

Novel possibilities for studying matter under extreme conditions are opened by the forthcoming availability of free electron laser (FEL) facilities generating subpicosecond photon pulses of high intensity in the VUV and X-ray range, which are able to heat thin samples up to the warm dense matter (WDM) regime. Pump-and-probe ultrafast techniques can be used to study the dynamics of phase transitions and characterize the states under extreme and metastable conditions. Ultrafast (10-100 fs) bulk heating is seen as a novel route for accessing extremely high temperature regimes as well as the transition region between low-density and high density fluids, that is presently considered a no man's land in simple liquids and glasses. Here we briefly describe the present status of the TIMEX end-station devoted to those experimental activities at the Fermi@Elettra FEL facility, and some preliminary results obtained in a pilot ultrafast experiment using a laser source as a pump and a supercontinuum probe aimed to characterize the melting process of Silicon.     

Single-atom optical clock with high accuracy

For the past 50 years, atomic standards based on the frequency of the cesium ground-state hyperfine transition have been the most accurate time pieces in the world. We now report a comparison between the cesium fountain standard NIST-F1, which has been evaluated with an inaccuracy of about 4 x 10(-16), and an optical frequency standard based on an ultraviolet transition in a single, laser-cooled mercury ion for which the fractional systematic frequency uncertainty was below 7.2 x 10(-17). The absolute frequency of the transition was measured versus cesium to be 1,064,721,609,899,144.94 (97) Hz, with a statistically limited total fractional uncertainty of 9.1 x 10(-16) the most accurate absolute measurement of an optical frequency to date.     

CsF-promoted acetyl dance at the narrow rim of p-tert-butyl[3.1.3.1]homooxacalixarene

In the acetylation of an oxygenated calix[4]arene homologue in the presence of CsF as a base, relaxation of the reaction system to the equilibrium composition takes place through several intra- and intermolecular steps that can be easily controlled to obtain the various acetyl derivatives. The effect of different bases is also discussed.     

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS

The coordination polymer [Zn(BDC)(H₂O)₂]_n was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 μg g⁻¹) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H₂O)₂]_n sorbent. Detection and quantification limits ranged from 0.02 to 0.07 μg g⁻¹ and from 0.05 to 0.1 μg g⁻¹, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 μg g⁻¹), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H₂O)₂]_n and the commercial phase C₁₈-bonded silica showed good performance of the [Zn(BDC)(H₂O)₂]_n polymeric sorbent for the pesticides tested.     

Pd complexes of iminophosphine ligands: A homogeneous molecular catalyst for Suzuki–Miyaura cross-coupling reactions under mild conditions

The complexes formed by combining Pd(OAc)₂ and iminophosphine ligands (P^N) are active catalysts in Suzuki–Miyaura cross-coupling reactions under mild conditions. Aryl bromides and iodides, as well as benzyl chlorides give the corresponding coupled products in high yields at low temperatures (25–50 °C) using these catalysts. Iminophosphines containing the most sterically demanding groups attached to the N-imino moiety were the most effective ligands. New divalent Pd complexes of known iminophosphines were synthesised and their activity was compared with the in situ generated catalyst system. The complex resulting from the oxidative addition of 4-bromo anisole [Pd(4-CH₃OC₆H₄)Br(P^N)] was more active than the in situ generated system. However, palladacycles containing the iminophosphine ligand (e.g., {[C₆H₄CH(Me)₂St-Bu]Pd(P^N)}⁺PF₆⁻) were less active than the in situ generated catalyst due to the greater stability of the complexes that involve two bidentate ligands. Poisoning tests demonstrated that homogeneous mononuclear palladium species containing the iminophsophine ligand were responsible for the catalytic activity.     

Quantifying time-varying coordination of multimodal speech signals using correlation map analysis

This paper demonstrates an algorithm for computing the instantaneous correlation coefficient between two signals. The algorithm is the computational engine for analyzing the time-varying coordination between signals, which is called correlation map analysis (CMA). Correlation is computed around any pair of points in the two input signals. Thus, coordination can be assessed across a continuous range of temporal offsets and be detected even when changing over time due to temporal fluctuations. The correlation algorithm has two major features: (i) it is structurally similar to a tunable filter, requiring only one parameter to set its cutoff frequency (and sensitivity), (ii) it can be applied either uni-directionally (computing correlation based only on previous samples) or bi-directionally (computing correlation based on both previous and future samples). Computing instantaneous correlation for a range of time offsets between two signals produces a 2D correlation map, in which correlation is characterized as a function of time and temporal offset. Graphic visualization of the correlation map provides rapid assessment of how correspondence patterns progress through time. The utility of the algorithm and of CMA are exemplified using the spatial and temporal coordination of various audible and visible components associated with linguistic performance.