Nanostructural organization and anion effects on the temperature dependence of the optical Kerr effect spectra of ionic liquids

The intermolecular spectra of three imidazolium ionic liquids were studied as a function of temperature by the use of optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids comprise the 1,3-pentylmethylimidazolium cation ([C(5)mim]+), and the anions, bromide (Br-), hexafluorophosphate (PF(6)-), and bis(trifluoromethanesulfonyl)imide (NTf(2)-). Whereas the optical Kerr effect (OKE) spectrum of [C(5)mim][NTf(2)] is temperature-dependent, the OKE spectra of [C(5)mim]Br and [C(5)mim][PF6] are temperature-independent. These results are surprising in light of the fact that the bulk densities of these room temperature ionic liquids (RTILs) are temperature-dependent. The temperature independence of the OKE spectra and the temperature dependence of the bulk density in [C(5)mim]Br and [C(5)mim][PF(6)] suggest that there are inhomogeneities in the densities of these liquids. The existence of density inhomogeneities is consistent with recent molecular dynamics simulations that show RTILs to be nanostructurally organized with nonpolar regions arising from clustering of the alkyl chains and ionic networks arising from charge ordering of the anions and imidazolium rings of the cations. Differences in the temperature dependences of the OKE spectra are rationalized on the basis of the degree of charge ordering in the polar regions of the RTILs.     

Determination of the active and inactive metabolites of prasugrel in human plasma by liquid chromatography/tandem mass spectrometry

Two fast and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based bioanalytical assays were developed and validated to quantify the active and three inactive metabolites of prasugrel. Prasugrel is a novel thienopyridine prodrug that is metabolized to the pharmacologically active metabolite in addition to three inactive metabolites, which directly relate to the formation and elimination of the active metabolite. After extraction and separation, the analytes were detected and quantified using a triple quadrupole mass spectrometer using positive electrospray ionization. The validated concentration range for the inactive metabolites assay was from 1 to 500 ng/mL for each of the three analytes. Additionally, a 5x dilution factor was validated. The interday accuracy ranged from -10.5% to 12.5% and the precision ranged from 2.4% to 6.6% for all three analytes. All results showed accuracy and precision within +/-20% at the lower limit of quantification and +/-15% at other levels. The validated concentration range for the active metabolite assay was from 0.5 to 250 ng/mL. Additionally, a 10x dilution factor was validated. The interbatch accuracy ranged from -7.00% to 5.98%, while the precision ranged from 0.98% to 3.39%. Derivatization of the active metabolite in blood with 2-bromo-3'-methoxyacetophenone immediately after collection was essential to ensure the stability of the metabolite during sample processing and storage. These methods have been applied to determine the concentrations of the active and inactive metabolites of prasugrel in human plasma.     

Cold Sintering: A Paradigm Shift for Processing and Integration of Ceramics

This paper describes a sintering technique for ceramics and ceramic‐based composites, using water as a transient solvent to effect densification (i.e. sintering) at temperatures between room temperature and 200 °C. To emphasize the incredible reduction in sintering temperature relative to conventional thermal sintering this new approach is named the “Cold Sintering Process” (CSP). Basically CSP uses a transient aqueous environment to effect densification by a mediated dissolution–precipitation process. CSP of NaCl, alkali molybdates and V₂O₅ with small concentrations of water are described in detail, but the process is extended and demonstrated for a diverse range of chemistries (oxides, carbonates, bromides, fluorides, chlorides and phosphates), multiple crystal structures, and multimaterial applications. Furthermore, the properties of selected CSP samples are demonstrated to be essentially equivalent as samples made by conventional thermal sintering.     

Bioorthogonal Probes for the Study of MDM2‐p53 Inhibitors in Cells and Development of High‐Content Screening Assays for Drug Discovery

To study the behavior of MDM2‐p53 inhibitors in a disease‐relevant cellular model, we have developed and validated a set of bioorthogonal probes that can be fluorescently labeled in cells and used in high‐content screening assays. By using automated image analysis with single‐cell resolution, we could visualize the intracellular target binding of compounds by co‐localization and quantify target upregulation upon MDM2‐p53 inhibition in an osteosarcoma model. Additionally, we developed a high‐throughput assay to quantify target occupancy of non‐tagged MDM2‐p53 inhibitors by competition and to identify novel chemical matter. This approach could be expanded to other targets for lead discovery applications.     

Electroactive LbL films of metallic phthalocyanines and poly(<Emphasis Type="Italic">0</Emphasis>-methoxyaniline) for sensing

Multilayered nanostructured films have been widely investigated for electrochemical applications as modified electrodes, including the layer-by-layer (LbL) films where properties such as thickness and film architecture can be controlled at the molecular level. In this study, we investigate the electrochemical features of LbL films of poly(o-methoxyaniline; POMA) and tetrasulfonated phthalocyanines containing nickel (NiTsPc) or copper (CuTsPc). The films displayed well-defined electroactivity, with redox pairs at 156 and 347 mV vs SCE, characteristic of POMA, which allowed their use as modified electrodes for detecting dopamine and ascorbic acid at concentrations as low as 10⁻⁵ M. This paper is dedicated to Prof. Francisco Nart, in memoriam.     

Thermal and mechanical properties of PE/organoclay nanocomposites

Polyethylene/montmorillonite clay nanocomposites were obtained via direct melt intercalation. The clay was organically modified with four different types of quaternary ammonium salts. The objective of this work is to study the use of montmorillonite clay in the production of nanocomposites by means on rheological, mechanical and crystallization properties of nanocomposites and to compare to the properties of the matrix and PE/unmodified clay nanocomposites. In general, the tensile test showed that the yield strength and modulus of the nanocomposites are close to the pure PE. Apparently, the mixture with Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay.     

Enhanced aqueous photochemical reaction rates after freezing

Sunlit snow/ice is known to play an important role in the processing of atmospheric species, including photochemical production of NO(x), HONO, molecular halogens, alkyl halides, and carbonyl compounds, among others. It has been shown that a liquid-like (quasi-liquid or disordered) layer exists on the surface of pure ice and that this quasi-liquid layer is also found on the surface of ambient snow crystals and ice at temperatures similar to polar conditions. However, it is unclear what role the liquid-like fractions present in and on frozen water play in potential photochemical reactions, particularly with regard to organic substrates. Here, we report a detailed study of enhanced rates of photochemical nucleophilic substitution of p-nitroanisole (PNA) with pyridine, a well-characterized and commonly used actinometer system. Reaction rates were enhanced by a factor of up to approximately 40 when frozen at temperatures between 236 and 272 K. Reaction rates were dependent on temperature and solute concentration, both variables that control the nature of the liquid-like fraction in frozen water. The results obtained indicate that a major portion of the organic solutes is excluded to the liquid-like layer, significantly impacting the rate of the photochemical nucleophilic substitution reaction studied here. Also, the direct comparison of liquid-phase kinetics to reactions occurring in frozen water systems is drawn into question, indicating that a simple extrapolation of liquid-phase mechanisms to snow/ice may not be valid for certain reactions.