Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

Supramolecular nanocapsule 1 ?(BArF)₈ is able to sequentially and selectively entrap recently discovered U₂@C₈₀ and unprecedented Sc₂CU@C₈₀, simply by soaking crystals of 1 ?(BArF)₈ in a toluene solution of arc‐produced soot. These species, selectively and stepwise absorbed by 1 ?(BArF)₈, are easily released, obtaining highly pure fractions of U₂@C₈₀ and Sc₂CU@C₈₀ in one step. Sc₂CU@C₈₀ represents the first example of a mixed metal actinide‐based endohedral metallofullerene (EMF). Remarkably, the host–guest studies revealed that 1 ?(BArF)₈ is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations.     

Rapid characterization of alkylpolyphosphonates by CZE with indirect photometric and mass spectrometric detection

Methods for the rapid characterization of industrial alkylpolyphosphonates (APPs) by infusion MS and CZE with indirect photometric (IPD) and MS detection are described. Technical-grade APPs, including alkylaminepolyphosphonates with 3-5 phosphonate groups and different hydrocarbon skeletons, hydroxyethyl-amino-bis(methylenephosphonic acid), hydroxyethylidene-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid, were examined. A 10 mM solution of adenosine triphosphate disodium salt at pH 2.2 was used as BGE. The nominal compounds of the industrial APPs and their impurities were well resolved in less than 15 min. The peaks were identified by using extracted ion electropherograms, which were obtained at the m/z values indicated by the peaks of the infusion spectra. Low concentrations of esters, anhydrides, and APPs having different hydrocarbon skeletons compared to nominal compounds, and lacking phosphonate and methylene-phosphonate groups with respect to them, were found. Also, hydroxyethyl-aminobis(methylenephosphonic acid) contained an intramolecular ester at a concentration close to that of the nominal compound. Application of CZE-IPD and CZE-MS to the quality control of industrial APPs, and of CZE-MS to the identification and characterization of APPs in cleaning products, was demonstrated.     

Production of cellulolytic and hemicellulolytic enzymes from Aureobasidium pulluans on solid state fermentation

This article investigates a strain of the yeast Aureobasidium pullulans for cellulase and hemicellulase production in solid state fermentation. Among the substrates analyzed, the wheat bran culture presented the highest enzymatic production (1.05 U/mL endoglucanase, 1.3 U/mL beta-glucosidase, and 5.0 U/mL xylanase). Avicelase activity was not detected. The optimum pH and temperature for xylanase, endoglucanase and beta-glucosidase were 5.0 and 50, 4.5 and 60, 4.0 and 75 degrees C, respectively. These enzymes remained stable between a wide range of pH. The beta-glucosidase was the most thermostable enzyme, remaining 100% active when incubated at 75 degrees C for 1 h.     

Synthesis and structure of some azo coupled cyclic beta-enaminones

The reaction of 3-phenylaminocyclopent-2-en-1-one with 4-methyl, 4-methoxy and 4-chlorobenzenediazonium tetrafluoroborates was used to prepare the azo coupling products 3a-c. It was found that these compounds are present in both CDCl(3) solution and solid phase practically exclusively as (E)-3-phenylamino-2-(4-subst.phenyldiazenyl)cyclopent-2-en-1-ones with N--H...N intramolecular hydrogen bond. The substitution of the phenyl residue of the diazonium salt has no effect on the position of the tautomeric equilibrium. On the other hand, the compounds 4a, b formed by the reaction of 3-phenylamino-1H-inden-1-one with 4-methylbenzene- or benzenediazonium tetrafluoroborates exist in CDCl(3) solution and in solid phase as hydrazone compounds. In the solution they occur as a mixture of three forms, out of which two were identified as E/Z isomers with different types of hydrogen bonds. Compound 5 formed by the reaction of 3-amino-5,5-dimethylcyclohex-2-en-1-one with 4-methoxybenzenediazonium tetrafluoroborate is converted into a stable hydrochloride 5.HCl on standing in CHCl(3) solution; this product exhibits a high degree of delocalization of the positive charge. Its structure was studied by means of X-ray.     

Ultrathin zirconium disulfide nanodiscs

We present a colloidal route for the synthesis of ultrathin ZrS(2) (UT-ZrS(2)) nanodiscs that are ~1.6 nm thick and consist of approximately two unit cells of S-Zr-S. The lateral size of the discs can be tuned to 20, 35, or 60 nm while their thickness is kept constant. Under the appropriate conditions, these individual discs can self-assemble into face-to-face-stacked structures containing multiple discs. Because the S-Zr-S layers within individual discs are held together by weak van der Waals interactions, each UT-ZrS(2) disc provides spaces that can serve as host sites for intercalation. When we tested UT-ZrS(2) discs as anodic materials for Li(+) intercalation, they showed excellent nanoscale size effects, enhancing the discharge capacity by 230% and greatly improving the stability in comparison with bulk ZrS(2). The nanoscale size effect was especially prominent for their performance in fast charging/discharging cycles, where an 88% average recovery of reversible capacity was observed for UT-ZrS(2) discs with a lateral diameter of 20 nm. The nanoscale thickness and lateral size of UT-ZrS(2) discs are critical for fast and reliable intercalation cycling because those dimensions both increase the surface area and provide open edges that enhance the diffusion kinetics for guest molecules.     

Optimization of the ultrasound-assisted synthesis of allyl 1-naphthyl ether using response surface methodology

Allyl 1-naphthyl ethers are useful compounds for different purposes, but reported methods to synthesize them require long reaction times. In this work, we have obtained allyl 1-naphthyl ether in good yield using ultrasonic-assisted methodology in a 1-h reaction. A central composite design was used to obtain a statistical model and a response surface (p<0.05; R(2)=0.970; R(2)(adj)=0.949; R(2)(pred)=0.818) that can predict the optimal conditions to maximize the yield, validated experimentally.     

Resonance Tongues and Spectral Gaps in Quasi-Periodic Schrödinger Operators with One or More Frequencies. A Numerical Exploration

In this article we investigate numerically the spectrum of some representative examples of discrete one-dimensional Schrödinger operators with quasi-periodic potential in terms of a perturbative constant b and the spectral parameter a. Our examples include the well-known Almost Mathieu model, other trigonometric potentials with a single quasi-periodic frequency and generalisations with two and three frequencies. We computed numerically the rotation number and the Lyapunov exponent to detect open and collapsed gaps, resonance tongues and the measure of the spectrum. We found that the case with one frequency was significantly different from the case of several frequencies because the latter has all gaps collapsed for a sufficiently large value of the perturbative constant and thus the spectrum is a single spectral band with positive Lyapunov exponent. In contrast, in the cases with one frequency considered, gaps are always dense in the spectrum, although some gaps may collapse either for a single value of the perturbative constant or for a range of values. In all cases we found that there is a curve in the (a, b)-plane which separates the regions where the Lyapunov exponent is zero in the spectrum and where it is positive. Along this curve, which is b = 2 in the Almost Mathieu case, the measure of the spectrum is zero.     

The condensation and ordering of models of empty liquids

We consider a simple model consisting of particles with four bonding sites ("patches"), two of type A and two of type B, on the square lattice, and investigate its global phase behavior by simulations and theory. We set the interaction between B patches to zero and calculate the phase diagram as the ratio between the AB and the AA interactions, ε(AB)*, varies. In line with previous work, on three-dimensional off-lattice models, we show that the liquid-vapor phase diagram exhibits a re-entrant or "pinched" shape for the same range of ε(AB)*, suggesting that the ratio of the energy scales--and the corresponding empty fluid regime--is independent of the dimensionality of the system and of the lattice structure. In addition, the model exhibits an order-disorder transition that is ferromagnetic in the re-entrant regime. The use of low-dimensional lattice models allows the simulation of sufficiently large systems to establish the nature of the liquid-vapor critical points and to describe the structure of the liquid phase in the empty fluid regime, where the size of the "voids" increases as the temperature decreases. We have found that the liquid-vapor critical point is in the 2D Ising universality class, with a scaling region that decreases rapidly as the temperature decreases. The results of simulations and theoretical analysis suggest that the line of order-disorder transitions intersects the condensation line at a multi-critical point at zero temperature and density, for patchy particle models with a re-entrant, empty fluid, regime.     

Antimicrobial activity of diterpenes from Viguiera arenaria against endodontic bacteria

Six pimarane-type diterpenes isolated from Viguiera arenaria Baker and two semi-synthetic derivatives were evaluated in vitro against a panel of representative microorganisms responsible for dental root canal infections. The microdilution method was used for the determination of the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against Porphyromonas gingivalis, Prevotella nigrescens, Prevotella intermedia, Prevotella buccae, Fusobacterium nucleatum, Bacteroides fragilis, Actinomyces naeslundii, Actinomyces viscosus, Peptostreptococcus micros, Enterococcus faecalis and Aggregatibacter actinomycetemcomitans. The compounds ent-pimara-8(14),15-dien-19-oic acid, its sodium salt and ent-8(14),15-pimaradien-3β-ol were the most active, displaying MIC values ranging from 1 to 10 μg mL-1. The results also allow us to conclude that minor structural differences among these diterpenes significantly influence their antimicrobial activity, bringing new perspectives to the discovery of new chemicals for use as a complement to instrumental endodontic procedures.     

Local nonreflecting boundary condition for time-dependent multiple scattering

Starting from a high-order local nonreflecting boundary condition (NBC) for single scattering [25], we derive a local NBC for time-dependent multiple scattering problems in three space dimensions, which is completely local both in space and time. To do so, we first develop an exterior evaluation formula for a purely outgoing wave field, given its values and those of certain auxiliary functions needed for the local NBC at the artificial boundary. By combining that evaluation formula with the decomposition of the total scattered field into purely outgoing contributions, we obtain a completely local NBC for time-dependent multiple scattering problems. The accuracy and stability of this new local NBC are evaluated by coupling it to a standard finite difference method.