Phase diagram and phase transitions of Krypton on graphite in the extended monolayer regime

We report high resolution x-ray diffraction studies of the structures and phase transitions of monolayer krypton, adsorbed on both powder and single crystal graphite substrates. A comprehensive series of powder diffraction profiles is used to construct the two dimensional phase diagram. The melting of the commensurate solid is shown to be strongly first order throughout the region where tricritical behavior was previously thought to occur; fluid solid coexistence extends up to the termination of the commensurate phase at 130 K. A disordered weakly incommensurate phase is shown to be a reentrant fluid, a system which may be described as a disordered network of domain walls and which evolves continuously into a more conventional 2D fluid. This evolution is marked by the disappearance of satellite peaks which are caused by the modulation of the overlayer by the substrate. The freezing of the reentrant fluid into the commensurate phase is shown to be consistent with a chiral Potts transition, its freezing into the incommensurate solid consistent with a dislocation binding transition.Single crystal experiments reveal the orientation of the weakly incommensurate phase. The reentrant fluid is found to have no visible orientational fluctuations, manifesting isotropic diffraction peaks. This is attributed to the strong epitaxy of domain walls. The incommensurate solid is shown to undergo an aligned-rotated transition which is well described by zerotemperature calculations.     

Direct measurement of forces due to solvent structure

Forces measured between two molecularly smooth solid surfaces separated by inert organic liquids exhibit spatial oscillations with periodicity equal to the size of the liquid molecules. Between five and ten oscillations are measurable, and their amplitude is large compared with the conventional van der Waals force.     

Experimental studies of pressure/temperature dependence of protein adsorption equilibrium in reversed-phase high-performance liquid chromatography

The effect of the average pressure and temperature of the column on the adsorption equilibrium of insulin variants on a C₈ bonded silica was studied in isocratic reversed-phase HPLC. Analytical injections of samples of four different insulins (bovine, porcine, Lys–Pro and human recombinant) were carried out at constant flow-rate but under increased average pressure. The temperature dependence of the retention parameters over the range 25–50 °C was studied under two different average column pressures (47 and 147 bar). Substantial increases of the retention time (up to 300%) were observed when the pressure and/or the temperature were increased. Similar adsorption-induced changes in the partial molar volume at constant temperature (ΔV_m≈102 ml/mol) were found for all the variants studied. Furthermore, ΔV_m was revealed to be practically independent of the temperature, which suggests that the temperature has no or very little influence on the mechanism of the pressure induced perturbations in the molecular structure of the solute. This conclusion was also derived from the observed temperature dependence of the logarithm of the retention factor (k) measured under different pressures. The relation between the temperature and ln k was nonlinear with a parabolic shape. Moreover, the shapes of the plots corresponding to the low and high pressures were found to be exactly the same, except that the curves were vertically shifted, due to the difference between the two average column pressures. These results indicate that pressure and temperature affect the retention behavior of insulins in a different and separate way.     

Computation of molecular parity violation using the coupled-cluster linear response approach

In memoriam, Nicholas C. Handy.

We report the implementation of a coupled-cluster linear response approach for the computation of molecular parity violation (in the framework of the PSI3 code, in particular). The approach is applied first to molecules such as hydrogen peroxide (HOOH), hydrogen disulfide (HSSH) and dichlorinedioxide (ClOOCl), which have been studied previously. The importance of including correlation is demonstrated for these examples, also including selected variations of geometry providing parity violation as a function of torsional angles. For the substituted allenes, 1,3 difluoroallene (CHF=C=CHF), 1,fluoro,3 chloroallene (CHF=C=CHCl) and 1,3 dichloroallene (CHCl=C=CHCl), we find that in particular the last molecule may be a suitable candidate for the experimental study of molecular parity violation.     

Laplacesche Integrale und Gammaquotientenreihen in der Theorie der linearen Differentialgleichungen und Volterraschen Integralgleichungen

Ohne Zusammenfassung     

Zur Theorie der Systeme linearer Differentialgleichungen mit einer unabhängigen Veränderlichen. II

Ohne Zusammenfassung     

Bis­[N‐phenyl­(di­cyclo­hexyl­thiophos­phinoyl)­thio­methan­amido‐S,S′]copper(II)

The ligands in [Cu(C₁₉H₂₇NPS₂)₂] adopt an S,S′‐chelation mode leading to an S₄ donor set which defines a square‐planar geometry about the Cu atom, which lies on an inversion centre.     

Two Tags in One Probe: Combining Fluorescence- and Biotin-based Detection of the Trypanosomal Cysteine Protease Rhodesain

Rhodesain is the major cysteine protease of the protozoan parasite Trypanosoma brucei and a therapeutic target for sleeping sickness, a fatal neglected tropical disease. We designed, synthesized and characterized a bimodal activity-based probe that binds to and inactivates rhodesain. This probe exhibited an irreversible mode of action and extraordinary potency for the target protease with a k_inac/K_i value of 37,000 M⁻¹s⁻¹. Two reporter tags, a fluorescent coumarin moiety and a biotin affinity label, were incorporated into the probe and enabled highly sensitive detection of rhodesain in a complex proteome by in-gel fluorescence and on-blot chemiluminescence. Furthermore, the probe was employed for microseparation and quantification of rhodesain and for inhibitor screening using a competition assay. The developed bimodal rhodesain probe represents a new proteomic tool for studying Trypanosoma pathobiochemistry and antitrypanosomal drug discovery.