Combining the pair distribution function and computational methods to understand lithium insertion in Brookite (TiO2)

X-ray pair distribution function (PDF) methods and first-principles calculations have been combined to probe the structure of electrochemically lithiated TiO(2) Brookite. Traditional powder diffraction studies suggest that Brookite amorphizes upon lithium insertion, with the Bragg reflections disappearing. However, PDF analysis indicates that the TiO(2) framework connectivity is maintained throughout lithium intercalation, with expansions along the a and b axes. The Li(+) ions within the framework are poorly observed in the X-ray PDF, which is dominated by contributions from the more strongly scattering Ti and O atoms. First-principles calculations were used to identify energetically favorable Li(+) sites within the Brookite lattice and to develop a complete structural model of the lithiated material. This model replicates the local structure and decreased intermediate range order observed in the PDF data. The analysis suggests that local structural distortions of the TiO(2) lattice accommodate lithium in five-coordinate sites. This structural model is consistent with the observed electrochemical behavior.     

Adsorption of atrazine from aqueous electrolyte solutions on humic acid and silica

The adsorption of, the still widely used, herbicide atrazine on model soil components, such as humic acid and humic acid-silica gel mixtures, was investigated in a series of batch experiments, under different experimental conditions (ionic strength, temperature, and pH). The investigation aimed at obtaining an estimate of the contribution of each of the soil components on the adsorption of atrazine from aqueous solutions. The kinetics of atrazine adsorption on humic acid showed two steps: a fast step, of a few hours duration, and a second slow step, which continued for weeks. The kinetics of adsorption data gave a satisfactory fit to the Elovich equation. Τhe adsorption of atrazine on the test substrates was found to be reversible in all cases. The atrazine uptake data on the test substrates were fitted best with the Freundlich adsorption isotherm. The ionic strength of the atrazine aqueous solutions did affect the amount of the atrazine adsorbed on the test substrates, suggesting that electrostatic forces between atrazine molecules and soil play a significant role in the adsorption process. An increase of temperature resulted in a decrease of atrazine adsorption on humic acid at low atrazine equilibrium concentrations. However, for higher levels of equilibrium concentrations (≥3 mg/L) the amount of atrazine adsorbed onto the test substrate increased as temperature increased. The calculated isosteric enthalpies of adsorption ranged between slightly exothermic at low atrazine uptake and slightly endothermic at high atrazine uptake, all values being in the range of physisorption.     

Synthesis and properties of conjugated oligoyne-centered π-extended tetrathiafulvalene analogues and related macromolecular systems

Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV-vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.     

Antimicrobial, antileishmanial and cytotoxic compounds from Piper chaba

The petroleum ether and chloroform extracts of the root of Piper chaba showed antimicrobial, antileishmanial and cytotoxic activities. Further bioactivity-guided fractionation led to the isolation of Bornyl piperate (1), piperlonguminine (2) and piperine (3). This is the first report of isolation of compounds (1) and (2) from P. chaba. It was observed that the isolated compounds (1 and 2) showed potent antifungal activity when compared with standard drug Nystatin, and significant cytotoxic activity with the IC?? values of 0.76 and 0.83?μg?mL?1, respectively. These compounds were also found to have weak antibacterial and antileishmanial activities. This is the first report about the antileishmanial activity of Piper isolates.     

Students’ misconceptions about random variables

This article describes some misconceptions about random variables and related counter-examples, and makes suggestions about teaching initial topics on random variables in general form instead of doing it separately for discrete and continuous cases. The focus is on post-calculus probability courses.     

Dynamics of the collective excitations of the quantum Hall system

Using the non linear optical technique of 3-pulse 4-wave mixing, we study the dynamics of the collective excitations of the quantum Hall system. We excite the system with 100 fs pulses propagating in directions k₁ and k₃ and then probe its time evolution with a delayed pulse k₂. We measure the non-linear optical response from the lowest Landau level along the direction k₁+k₂−k₃. As function of the time delay of pulse k₂, this signal shows striking beats for short time delays (500 fs), followed by a rise (20 ps) and then a decay (100 ps). We identify the microscopic origin of this dynamics by extending the standard theory of ultra fast nonlinear optics to include the effects of the correlations.     

Pyrimidine Derivatives and Related Compounds II: Synthesis of some derivatives of pyrimido[1,2:2′,3′]pyrazolo[1,5-a]pyrimidines,a new ring system

3,5-Diamino-4-phenylazo-pyrazoles ( 1a–1c ) react with acetylacetone and with ethyl acetoacetate to yield the corresponding pyrazolo[1,5-a]pyrimidine derivatives 2a–2c and 3a–3c , respectively. Whereas 1a–1c add readily to methyl acrylate yielding the 4,5,6,7-tetrahydropyrazolo[1,5-a]-pyrimidine derivatives 5a–5c, 1a–1c add to methylacrylonitrile or methyl methacrylate only under drastic conditions to yield 5d–5f . The pyrimido[1,2:2′,3′]pyrazolo[1,5-a]pyrimidine derivatives 10a–10c are prepared by the action of acrylonitrile on 2a–2c . Compounds 10a–10c are readily converted into the corresponding oxo derivatives 12a–12c on treatment with acetic acid-hydrochloric acid mixture.     

Inelastic incoherent neutron scattering studies of water interacting with biological macromolecules.

The interaction between water and biological macromolecules in living organisms is of fundamental importance in a range of processes. We have studied water-DNA and water-proteolipid membrane systems over a range of hydration states using inelastic incoherent neutron scattering. We find a relatively sharp transition for both systems at a water concentration above which bulk solvent can be detected. Below this concentration, bulk water is essentially absent, i.e., all the water in the system is interacting with the biological macromolecules. This water is strongly perturbed as judged by its energy transfer spectrum, with a broader and lower energy transition than bulk water in the 50-75 meV (approximately 400-600 cm(-1)) range. Taking into account the differing geometry of (cylindrical) DNA and (planar) membranes, the number of water shells perturbed by each system was estimated. A conclusion is that in living organisms a large proportion of the cellular water will be in a state quite distinct from bulk water. The data add to the growing evidence that water structure in the vicinity of biological macromolecules is unusual and that the proximal water behaves differently compared to the bulk solvent.     

Capillary electrophoresis-mass spectrometry in impurity profiling of pharmaceutical products

Generally reversed-phase high-performance liquid chromatography (RP-HPLC) methods are extensively applied during quality control of pharmaceutical products. Since capillary electrophoresis (CE) is based on a different separation principle and consequently results in a unique selectivity compared to RP-HPLC, it can advantageously be used as an orthogonal technique. CE equipped with a mass spectrometer detector provides even more information that can be helpful for identification and structural elucidation purposes. CE-MS was recently implemented in the method development approach to support impurity profiling of pharmaceutical products. In this paper the application of CE-electrospray ionization (ESI)-MS/MS to the impurity profiling of galantamine hydrobromide in stressed Reminyl Extended Release (ER) capsules is discussed. Reminyl ER samples were stressed at different storing conditions. The impurity profile of these samples was compared with the current RP-HPLC and chiral CE method, but also with CE-ESI-MS/MS. The combination of these three methods provided valuable data that allowed understanding comprehensively the impurity profile of these samples. Two impurities were detected at concentrations lower than 0.05%, which did not occur in nonstressed samples. Chromatographic data and the fragmentation patterns of galantamine and related compounds were also examined for identification of these two degradation products.