One-pot assembling of selenazolines from elemental selenium,alkenes and acetonitrile

A new method for assembling 1,3-selenazolines by the iodine- mediated reaction of the simplest building blocks such as elemental selenium, alkenes and acetonitrile has been discovered. A proposed mechanism includes the addition of the intermediate selenium iodides to alkene with subsequent solvent interception by the formed seleniranium ion.     

Investigating How Organic Solvents Affect Tissue Culture Polystyrene Surfaces through Responses of Mesenchymal Stem Cells

Polymer coating of tissue culture polystyrene (TCPS) surfaces promotes their biofunctionality, which can aid manipulation of cellular functions. However, the effect of the solvent used for polymer coating is yet to be elucidated. In this study, solvent‐treated TCPS surfaces using water, methanol, ethanol, 2‐propanol, and dimethyl sulfoxide are fabricated. Solvent treatment of TCPS surfaces is performed by spreading solvents onto the surfaces and allowing them to dry. Solvent treatment changes the surface roughness and wettability, depending on the kind of solvents. In addition, these surface property changes affected the extension, proliferation, and differentiation of human bone marrow–derived mesenchymal stem cells. These results suggest that solvent selection for polymer coating is crucial in the regulation of cell responses. Further, treatment with an appropriate solvent can result in a more suitable culture environment for modulating cellular functions.     

Comparison of the stability of thymine tautomers and the interaction of its tautomers with Na+, K+, Mg2+ and Ca2+ in gas and solvent phases

The present study compared the interactions among Na ⁺, K ⁺, Mg²⁺ and Ca²⁺, thymine and its tautomers in the gas and solvent phase, an interaction dependent upon the electronic construction of the tautomers. Three types of cation interaction with thymine and its tautomers were observed. In the first one, the metal cations interacted with a lone pair of nitrogen or oxygen of the tautomers. In the second type, there was an interaction among the cations, nitrogen and oxygen at the same time; the last one was that of cations with the electron density of thymine π-system, where the cations were perpendicular to the ring of thymine. The interaction of metals cation with tautomers was studied in the gas and solvent phases; a comparison was then made between interactions in two phases. The interaction energy for all complexes indicated the stability of complexes, an energy which was higher in Ca²⁺ and Mg²⁺ compared with Na⁺ and K⁺. Concerning K⁺ and Na⁺, the stability of all complexes of tautomers was greater than that of thymine complexes; however, the stability of certain Ca²⁺ and Mg²⁺ complexes was lower than the complexes of thymine.     

Calculating nuclear magnetic resonance chemical shifts in solvated systems

The nuclear magnetic resonance (NMR) chemical shift is extremely sensitive to molecular geometry, hydrogen bonding, solvent, temperature, pH, and concentration. Calculated magnetic shielding constants, converted to chemical shifts, can be valuable aids in NMR peak assignment and can also give detailed information about molecular geometry and intermolecular effects. Calculating chemical shifts in solution is complicated by the need to include solvent effects and conformational averaging. Here, we review the current state of NMR chemical shift calculations in solution, beginning with an introduction to the theory of calculating magnetic shielding in general, then covering methods for inclusion of solvent effects and conformational averaging, and finally discussing examples of applications using calculated chemical shifts to gain detailed structural information.     

Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Excited-State Dynamics of Thienoguanosine,an Isomorphic Highly Fluorescent Analogue of Guanosine

Thienoguanosine (^thG) is an isomorphic analogue of guanosine with promising potentialities as fluorescent DNA label. As a free probe in protic solvents, ^thG exists in two tautomeric forms, identified as the H1, being the only one observed in nonprotic solvents, and H3 keto–amino tautomers. We herein investigate the photophysics of ^thG in solvents of different polarity, from water to dioxane, by combining time-resolved fluorescence with PCM/TD-DFT and CASSCF calculations. Fluorescence lifetimes of 14.5–20.5 and 7–13 ns were observed for the H1 and H3 tautomers, respectively, in the tested solvents. In methanol and ethanol, an additional fluorescent decay lifetime (≈3 ns) at the blue emission side (λ≈430 nm) as well as a 0.5 ns component with negative amplitude at the red edge of the spectrum, typical of an excited-state reaction, were observed. Our computational analysis explains the solvent effects observed on the tautomeric equilibrium. The main radiative and nonradiative deactivation routes have been mapped by PCM/TD-DFT calculations in solution and CASSCF in the gas phase. The most easily accessible conical intersection, involving an out-of plane motion of the sulfur atom in the five-membered ring of ^thG, is separated by a sizeable energy barrier (≥0.4 eV) from the minimum of the spectroscopic state, which explains the large experimental fluorescence quantum yield.     

Concomitant cocrystal and salt: no interconversion in the solid state

A cocrystal and a molecular salt of β‐alanine and dl ‐tartaric acid, C₃H₈NO₂⁺·C₄H₄O₆^?, of the same chemical composition, were studied over a wide temperature range by single‐crystal and powder X‐ray diffraction. Neither the interconversion between the two phases nor any polymorphic transitions were observed in the temperature range from 100 K to the melting points. This contrasts with the solvent‐mediated phase transition from the salt to the cocrystal in a slurry that has been documented earlier.     

Novel and Rapid Deep Eutectic Solvent (DES) Homogeneous Liquid–Liquid Microextraction (HLLME) with Flame Atomic Absorption Spectrometry (FAAS) Detection for the Determination of Copper in Vegetables

Novel and fast deep eutectic solvent (DES)-based homogeneous liquid–liquid microextraction (HLLME) was applied for the extraction of copper from vegetable samples followed by flame atomic absorption spectrometry (FAAS). 1,5-diphenyl carbazone (DPC) was used as the chelating agent, and a DES was used as the extraction media. The utilized DES was based on benzyl triphenyl phosphonium bromide and ethylene glycol in a 1:8?mole ratio. The phase separation phenomenon was occurred by changing of sample temperature. Several factors influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, an enhancement factor of 64 was obtained. The limit of detection, based on three signal-to-noise ratio, and limit of quantification were found to be 0.13?µg L^?1 and 5.0?µg L^?1, respectively. The calibration curve was linear within the range of 5.0–250?µg L^?1 with r² > 0.9957. Intra- and inter-day relative standard deviations (%) of 2.1% and 2.6% were obtained at the concentration of 25?µg L^?1. The accuracy of the proposed method was evaluated by analyzing a tomato leaves certified reference material and the results were to be in agreement with the certified value. Finally, the feasibility of the method was successfully confirmed by determination of copper in spinach, lettuce, broccoli, potato, carrot and parsley samples.