Supramolecular study,Hirshfeld analysis and theoretical study of 6‐methoxyquinoline N‐oxide dihydrate

In the crystal structure of 6‐methoxyquinoline N‐oxide dihydrate, C₁₀H₉NO₂·2H₂O, (I), the presence of two‐dimensional water networks is analysed. The water molecules form unusual water channels, as well as two intersecting mutually perpendicular columns. In one of these channels, the O atom of the N‐oxide group acts as a bridge between the water molecules. The other channel is formed exclusively by water molecules. Confirmation of the molecular packing was performed through the analysis of Hirshfeld surfaces, and (I) is compared with other similar isoquinoline systems. Calculations of bond lengths and angles by the Hartree–Fock method or by density functional theory B3LYP, both with 6‐311++G(d,p) basis sets, are reported, together with the results of additional IR, UV–Vis and theoretical studies.     

A SIMPLE METHOD FOR THE INCORPORATION OF LOW MOLECULAR WEIGHT DYES IN ULTRATHIN FILMS

A simple method for the fabrication of ultrathin films containing low molecular weight dye material is introduced(post-adsorption technique). The chromophore used is 4-nitro-4'-decyloxy azobenzene quaternary ammonium salt (azo-10Q).In classical layer-by-layer (LBL) procedures, where the substrate is dipped alternately into the chromophore solution and thecomplementary polyelectrolyte, the chromophore tends to desorb from the film during subsequent immersion in thepolyanion solution, and there is little or no indication of multilayer growth. The extent of desorption depends somewhat onthe selection of polyelectrolyte, the ionic strength and the pH of solution. An alternative approach is to first prepareconventional LBL films from a pair of oppositely charged polyelectrolytes, and then to soak this film into the chromophoresolution, where adsorption by penetration into the LBL film may take place. In preliminary results, a linear dependence ofUV absorbance on layer number of LBL film thus prepared was found, demonstrating the apparent effectiveness of the post-adsorption technique for the preparation of azo-10Q-containing ultrathin films.     

On the different roles of anions and cations in the solvation of enzymes in ionic liquids

The solvation of the enzyme Candida antarctica lipase B (CAL-B) was studied in eight different ionic liquids (ILs). The influence of enzyme-ion interactions on the solvation of CAL-B and the structure of the enzyme-IL interface are analyzed. CAL-B and ILs are described with molecular dynamics (MD) simulations in combination with an atomistic empirical force field. The considered cations are based on imidazolium or guanidinium that are paired with nitrate, tetrafluoroborate or hexafluorophosphate anions. The interactions of CAL-B with ILs are dominated by Coulomb interactions with anions, while the second largest contribution stems from van der Waals interactions with cations. The enzyme-ion interaction strength is determined by the ion size and the magnitude of the ion surface charge. The solvation of CAL-B in ILs is unfavorable compared to water because of large formation energies for the CAL-B solute cages in ILs. The internal energy in the IL and of CAL-B increases linearly with the enzyme-ion interaction strength. The average electrostatic potential on the surface of CAL-B is larger in ILs than in water, due to a weaker screening of charged enzyme residues. Ion densities increased moderately in the vicinity of charged residues and decreased close to non-polar residues. An aggregation of long alkyl chains close to non-polar regions and the active site entrance of CAL-B are observed in one IL that involved long non-polar decyl groups. In ILs that contain 1-butyl-3-methylimidazolium cations, the diffusion of one or two cations into the active site of CAL-B occurs during MD simulations. This suggests a possible obstruction of the active site in these ILs. Overall, the results indicate that small ions lead to a stronger electrostatic screening within the solvent and stronger interactions with the enzyme. Also a large ion surface charge, when more hydrophilic ions are used, increases enzyme-IL interactions. An increase of these interactions destabilizes the enzyme and impedes enzyme solvation due to an increase in solute cage formation energies.     

Trapping and release of citrate-capped gold nanoparticles

An electrical method to trap and release charged gold nanoparticles onto and from the surface of gold electrodes modified by an alkanethiol self-assembled monolayer (SAM) is presented. To form electrodes coated with gold nanoparticles (GNPs), amine-terminated SAMs on gold electrodes were immersed in a solution of negatively charged citrate-capped GNPs. Accumulation of GNPs on the electrode surface was monitored by a decrease in the impedance of the SAM-modified electrode and by an increase in the electrochemical activity at the electrode as shown through cyclic voltammetry (CV). Electrostatic interactions between the GNPs and the amine-terminated SAM trap the GNPs on the electrode surface. Application of a subsequent negative bias to the electrode initiated a partial release of the GNPs from the electrode surface. Impedance spectroscopy, cyclic voltammetry, ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM) were used to monitor and confirm the attraction of GNPs to and release from the aminealkanethiolated gold electrodes. This work describes a method of trapping and release for citrate-capped GNPs that could be used for on-demand nanoparticle delivery applications such as in assessing and modeling nanoparticle toxicology, as well as for monitoring the functionalization of gold nanoparticles.     

Computer Modelling and Synthesis of Deoxy and Monohydroxy Analogues of a Ribitylaminouracil Bacterial Metabolite that Potently Activates Human T Cells

5-(2-Oxopropylideneamino)-6-d -ribitylaminouracil (5-OP-RU) is a natural product formed during bacterial synthesis of vitamin B2. It potently activates mucosal associated invariant T (MAIT) cells and has immunomodulatory, inflammatory, and anticancer properties. This highly polar and unstable compound forms a remarkably stable Schiff base with a lysine residue in major histocompatibility complex class I–related protein (MR1) expressed in antigen-presenting cells. Inspired by the importance of the ribityl moiety of 5-OP-RU for binding to both MR1 and the T cell receptor (TCR) on MAIT cells, each OH was removed in silico. DFT calculations and MD simulations revealed a very stable hydrogen bond between the C3′−OH and uracil N1H, which profoundly restricts flexibility and positioning of each ribityl-OH, potentially impacting their interactions with MR1 and TCR. By using deoxygenation strategies and kinetically controlled imine formation, four monodeoxyribityl and four monohydroxyalkyl analogues of 5-OP-RU were synthesised as new tools for probing T cell activation mechanisms.     

Differentiation of polycyclic aromatic hydrocarbons using electron capture negative chemical ionization

A number of isomeric polycyclic aromatic hydrocarbons may be distinguished using electron capture negative chemical ionization when methane is used as a buffer gas, including benzo[a]pyrene and benzo[e]pyrene. The ionization behavior of these compounds may be predicted, on the basis of their electron afinities, allowing compounds to be distinguished without the use of standards.     

Isocein-a new fluorescent reagent for calcium

A metallofluorescent indicator, isocein, has-been synthesized from 7-hydroxy-2-methylisoflavone, iminodiacetic acid and formaldehyde. It is readily obtained in pure form and in alkaline solutions is excited by light of 339 nm. It is recommended for use as a spectrofluorimetric reagent for calcium.     

Mid-infrared second-order susceptibility of alpha-quartz and its application to visible-infrared surface sum-frequency spectroscopy

We provide the first account of the second-order susceptibility of quartz down to 10 mum (1000 cm(-1)) and show how this data may be used along with the sum-frequency response of an amorphous gold surface to elucidate the nonlinear susceptibility of any material in the mid-infrared region. Crystalline quartz is an established material for use in second-harmonic and sum-frequency generation studies of new systems, on account of its well-characterized linear and nonlinear optical properties. Previous knowledge of its nonlinear susceptibility has been limited to its transparent region, wavelengths shorter than about 3 mum. Longer wavelength chi((2)) values for quartz are particularly important for techniques such as vibrational sum-frequency spectroscopy which are expanding into the mid-IR with the increasing availability of widely tunable infrared laser sources.