Influence of exchange fields in hybrid pairing superconductors II. Selfconsistent ground states

A previously investigated model of a two band superconductor with hybrid pairing and molecular fields is enlarged by exchange interactions generating those fields. The fields are calculated selfconsistently in molecular field approximation at zero temperature. They turn out to stabilise the previously found new state of gapless superconductivity and non vanishing spin polarization for a wide range of exchange couplings, in particular for zero external field.Dedicated to B. Mühlschlegel on the occasion of his 60th birthdayWork performed within the research program of Sonderforschungsbereich 125 Aachen-Jülich-Köln     

Interaction of acetic acid with solid water

The interaction of acetic acid (AA, CH(3)COOH), with solid water, deposited on metals, tungsten and gold, at 80 K, was investigated. We have prepared acid/water interfaces at 80 K, namely, acid layers on thin films of solid water and H(2)O adlayers on thin acid films; they were annealed between 80 and 200 K. Metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy UPS(HeII) were utilized to obtain information on the electronic structure of the outermost surface from the study of the electron emission from the weakest bound MOs of the acids, and of the molecular water. Temperature-programmed desorption (TPD) provided information on the desorption kinetics, and Fourier-transformed infrared spectroscopy (FTIR) provided information on the identification of the adsorbed species as well as on the water and acid crystallization. The results are compatible with the finding of ref 1 (preceding paper), made on the basis of DFT calculations, that AA adsorbs on ice as cyclic dimers. Above 120 K, a rearrangement of the AA dimers is suggested by a sharpening of the spectral features in the IR spectra and by spectral changes in MIES and UPS; this is attributed to the glass transition in AA around 130 K. Above 150 K the spectra transform into those characteristic for polycrystalline polymer chains. This structure is stable up to about 180 K; desorption of water takes place from underneath the AA film, and practically all water has desorbed through the AA film before AA desorption starts. There is no indication of water-induced deprotonation of the acid molecules. For the interaction of H(2)O molecules adsorbed on amorphous AA films, the comparison of MIES with the DFT results of ref 1 shows that the initial phase of exposure does not lead to the formation of a top-adsorbed closed water film at 80 K. Rather, the H(2)O molecules become attached to or incorporated into the preexisting AA network by H bonding; no water network is formed in the initial stage of the water adsorption. Also under these conditions no deprotonation of the acid can be detected.     

Stable isotope-free quantitative shotgun proteomics combined with sample pattern recognition for rapid diagnostics

Mass spectrometry (MS) has become a powerful tool for the quantitative analysis of complex protein samples. A high-throughput strategy for the comparative analysis of multiple protein samples with high complexity becomes more and more important. Two strategies, spectral count and peak intensity, for label-free MS analysis of prefractionated complex mixtures have been described recently to be useful for quantitation. Here we compare both strategies for rapid and quantitative 1-D shotgun LC/MS/MS analyses of highly complex protein mixtures using silica-based monolithic columns. First, we validated linearity and sensitivity of these methods by spiking varying amounts of an internal standard protein in a complex plant protein extract. Secondly, quantitative data of proteins of Medicago truncatula nodules were visualized with independent components analysis using data either obtained from spectral count or peak integration performed with commercial software. Spectral count showed apparent advantages over peak integration because several peptides per protein are automatically averaged, the linear dynamic range of quantitation increases in complex matrices and the number of quantified proteins surpasses the number of proteins using peak integration. Thus, for the need of rapid comparative analysis of highly complex protein samples, spectral count enables sample pattern recognition and identification of biomarkers in nongel based proteomic studies.     

Transfer of parahydrogen-induced hyperpolarization to 19F

Homogeneous hydrogenations of unsaturated substrates with parahydrogen yield strong NMR signal enhancements of the transferred 1H nuclei if the symmetry of H2 is broken in the resulting hydrogenated products. This chemically induced hyperpolarization known as Parahydrogen-induced polarization (PHIP) is also transferred to other protons and heteronuclei (2H, 13C, 29Si, 31P) when the hydrogenation is initiated at low magnetic fields. Hydrogenating various fluorinated styrenes and phenylacetylenes, we show that PHIP-derived hyperpolarization is transferred to 19F not only in the Earth's magnetic field (ALTADENA condition) but also in a strong magnetic field, e.g., when carrying out the reaction in the NMR spectrometer (PASADENA condition). Upon conducting a systematic analysis of the observed PHIP transfer to 1H, 13C, and 19F in the hydrogenation products to elucidate the mechanisms that govern this parahydrogen-aided resonance transfer (PART), we conclude that high- and low-field PHIP transfer mechanisms differ in detail depending on either through-bond or through-space interactions. Substrates with high hydrogenation rates and long spin-lattice relaxation times (T1) yield the highest degree of heteronuclear hyperpolarization. Possible medical applications for hyperpolarized 19F-containing molecules as "active" contrast agents for magnetic resonance imaging (MRI) are outlined.     

A water-soluble hexa-peri-hexabenzocoronene: synthesis, self-assembly and role as template for porous silica with aligned nanochannels

A water-soluble hexa-peri-hexabenzocoronene was prepared and shown to undergo ordered columnar self-assembly either in water solution or bulk and therefore served as template for the fabrication of porous silica with aligned nanochannels.     

Long-term integrated surgery room optimization and recovery ward planning,with a case study in the Brazilian National Institute of Traumatology and Orthopedics (INTO)

This paper proposes an integrated approach for the long-term planning and surgery allocation problem with downstream constraints. It is motivated by a case study in the Brazilian National Institute of Traumatology and Orthopedics, which provides elective high complexity surgeries for patients from the Brazilian public health system. We introduce an optimization problem that designs a periodic surgery allocation schedule as well as a recovery ward utilization plan, with a view at balancing patient arrivals and releases in the long term, in such a way that all surgeries are performed in a timely manner.