Validity of the law of mass action in three-dimensional coagulation processes

Diffusion-limited reactions are studied in detail on the classical coalescing process. We demonstrate how, with the aid of a recent renormalization group approach, fluctuations can be integrated systematically. We thereby obtain an exact relation between the microscopic physics (lattice structure and particle shape and size) and the macroscopic decay rate in the law of mass action. Moreover, we find a strong violation of the law of mass action. The corresponding term in the kinetic equations originates in long-wavelength fluctuations and is a universal function of the macroscopic decay rate.     

Measurements of F2 and xF(nu)(3) - xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe Data in a Physics Model-Independent Way

We report on the extraction of the structure functions F2 and DeltaxF(3) = xF(nu)(3)-xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe differential cross sections. The extraction is performed in a physics model-independent (PMI) way. This first measurement of DeltaxF(3), which is useful in testing models of heavy charm production, is higher than current theoretical predictions. The ratio of the F2 (PMI) values measured in nu(mu) and mu scattering is in agreement (within 5%) with the predictions of next-to-leading-order parton distribution functions using massive charm production schemes, thus resolving the long-standing discrepancy between the two sets of data.     

Fluctuating semiflexible polymer ribbon constrained to a ring

Twist stiffness and an asymmetric bending stiffness of a polymer or a polymer bundle is captured by the elastic ribbon model. We investigate the effects a ring geometry induces to a thermally fluctuating ribbon, finding bend-bend coupling in addition to twist-bend coupling. Furthermore, due to the geometric constraint the polymer's effective bending stiffness increases. A new parameter for experimental investigations of polymer bundles is proposed: the mean square diameter of a ribbonlike ring, which is determined analytically in the semiflexible limit. Monte Carlo simulations are performed which affirm the model's prediction up to high flexibility.     

Origin and Use of Hydroxyl Group Tolerance in Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Catalysts

The origin of hydroxyl group tolerance in neutral and especially cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes has been investigated. A wide range of catalysts was prepared and tested. Most cationic complexes can be handled in air without difficulty and display an unprecedented stability towards water and alcohols. NHC complexes were successfully used with substrates containing the hydroxyl functionality in acyclic diene metathesis polymerization, homo-, cross and ring-opening cross metathesis reactions. The catalysts remain active even in 2-PrOH and are applicable in ring-opening metathesis polymerization and alkene homometathesis using alcohols as solvent. The use of weakly basic bidentate, hemilabile anionic ligands such as triflate or pentafluorobenzoate and weakly basic aromatic imido ligands in combination with a sterically demanding 1,3-dimesitylimidazol-2-ylidene NHC ligand was found essential for reactive and yet robust catalysts.     

On the critical dynamics of ferromagnets

The dynamic scaling functions for ferromagnets above and below the critical temperature are determined using mode coupling theory. Below the critical temperature we study isotropic ferromagnets taking into account the exchange interaction only and give the first numerical solution of the resulting mode coupling equations. In the paramagnetic phase we examine how the critical dynamics is modified by the addition of the dipoledipole interaction. On the basis of this theory we are able to explain in a unifying fashion the results of different experimental methods; i.e.: neutron scattering, hyperfine interaction and electron-spin resonance. Predictions for new experiments are made.     

Acid-induced degradation of phosphorescent dopants for OLEDs and its application to the synthesis of tris-heteroleptic iridium(III) bis-cyclometalated complexes

Investigations of blue phosphorescent organic light emitting diodes (OLEDs) based on [Ir(2-(2,4-difluorophenyl)pyridine)(2)(picolinate)] (FIrPic) have pointed to the cleavage of the picolinate as a possible reason for device instability. We reproduced the loss of picolinate and acetylacetonate ancillary ligands in solution by the addition of Br?nsted or Lewis acids. When hydrochloric acid is added to a solution of a [Ir(C^N)(2)(X^O)] complex (C^N = 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (diFppy) and X^O = picolinate (pic) or acetylacetonate (acac)), the cleavage of the ancillary ligand results in the direct formation of the chloro-bridged iridium(III) dimer [{Ir(C^N)(2)(μ-Cl)}(2)]. When triflic acid or boron trifluoride are used, a source of chloride (here tetrabutylammonium chloride) is added to obtain the same chloro-bridged iridium(III) dimer. Then, we advantageously used this degradation reaction for the efficient synthesis of tris-heteroleptic cyclometalated iridium(III) complexes [Ir(C^N(1))(C^N(2))(L)], a family of cyclometalated complexes otherwise challenging to prepare. We used an iridium(I) complex, [{Ir(COD)(μ-Cl)}(2)], and a stoichiometric amount of two different C^N ligands (C^N(1) = ppy; C^N(2) = diFppy) as starting materials for the swift preparation of the chloro-bridged iridium(III) dimers. After reacting the mixture with acetylacetonate and subsequent purification, the tris-heteroleptic complex [Ir(ppy)(diFppy)(acac)] could be isolated with good yield from the crude containing as well the bis-heteroleptic complexes [Ir(ppy)(2)(acac)] and [Ir(diFppy)(2)(acac)]. Reaction of the tris-heteroleptic acac complex with hydrochloric acid gives pure heteroleptic chloro-bridged iridium dimer [{Ir(ppy)(diFppy)(μ-Cl)}(2)], which can be used as starting material for the preparation of a new tris-heteroleptic iridium(III) complex based on these two C^N ligands. Finally, we use DFT/LR-TDDFT to rationalize the impact of the two different C^N ligands on the observed photophysical and electrochemical properties.     

Mixed electrolytes in hydrophobic interaction chromatography†

An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins.