Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A Combined ARXPS and Pendant Drop Study**

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C₄C₁Im][PF₆] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our previous angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5 %_mol down to 1 %_mol and present complementary surface tension pendant drop (PD) measurements under ultraclean vacuum conditions. This combination allows for connecting the microscopic information on the IL/gas interface derived from ARXPS with the macroscopic property surface tension. The surface enrichment of the Pt complexes is found to be most pronounced at 1 %_mol. It also displays a strong temperature dependence, which was not observed for 5 %_mol and above, where the surface is already saturated with the complex. The surface enrichment deduced from ARXPS is also reflected by the pronounced decrease in surface tension with increasing concentration of the catalyst. We furthermore observe by ARXPS and PD a much stronger surface affinity of the buoy-complex as compared to the free ligands in solution. Our results are highly interesting for an optimum design of IL-based catalyst systems with large contact areas to the surrounding reactant/product phase, such as in supported IL phase (SILP) catalysis.     

A Fast and Efficient Track to Allosteric Modulators of Muscarinic Receptors: Microwave-Assisted Syntheses

By using microwave irradiation bisammonium-and bispyridinium-type allosteric modulators of muscarinic receptors can be obtained fast and efficiently.     

Factorization of the (relative) Chern character through Lie algebra homology

Karoubi's relative Chern character is constructed as a chain map factoring through Lie algebra chains.This is part of the author's doctoral thesis, Stanford University 1990.     

Test of an optical parametric oscillator (OPO) as a compact and fast tunable stokes source in coherent anti-stokes raman spectroscopy (CARS)

An optical parametric oscillator (OPO), as a novel kind of broadband Stokes source, is employed for coherent anti-Stokes Raman spectroscopy (CARS). Compared to the conventional dye laser configuration OPO-CARS offers practical advantages. The tunable OPO allows a fast and comfortable frequency tuning. The excitation bandwidth of about 35 cm^–1 (FWHM) limits the spectral range of effective and stable single pulse CARS generation but can be used to enhance selected spectral structures.     

Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer

Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components.     

Quantitative evaluation of mechanosensing of cells on dynamically tunable hydrogels

Thin hydrogel films based on an ABA triblock copolymer gelator [where A is pH-sensitive poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) and B is biocompatible poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC)] were used as a stimulus-responsive substrate that allows fine adjustment of the mechanical environment experienced by mouse myoblast cells. The hydrogel film elasticity could be reversibly modulated by a factor of 40 via careful pH adjustment without adversely affecting cell viability. Myoblast cells exhibited pronounced stress fiber formation and flattening on increasing the hydrogel elasticity. As a new tool to evaluate the strength of cell adhesion, we combined a picosecond laser with an inverted microscope and utilized the strong shock wave created by the laser pulse to determine the critical pressure required for cell detachment. Furthermore, we demonstrate that an abrupt jump in the hydrogel elasticity can be utilized to monitor how cells adapt their morphology to changes in their mechanical environment.