Accurate vertical ionization energy and work function determinations of liquid water and aqueous solutions

The absolute-scale electronic energetics of liquid water and aqueous solutions, both in the bulk and at associated interfaces, are the central determiners of water-based chemistry. However, such information is generally experimentally inaccessible. Here we demonstrate that a refined implementation of the liquid microjet photoelectron spectroscopy (PES) technique can be adopted to address this. Implementing concepts from condensed matter physics, we establish novel all-liquid-phase vacuum and equilibrated solution–metal-electrode Fermi level referencing procedures. This enables the precise and accurate determination of previously elusive water solvent and solute vertical ionization energies, VIEs. Notably, this includes quantification of solute-induced perturbations of water''s electronic energetics and VIE definition on an absolute and universal chemical potential scale. Defining and applying these procedures over a broad range of ionization energies, we accurately and respectively determine the VIE and oxidative stability of liquid water as 11.33 ± 0.03 eV and 6.60 ± 0.08 eV with respect to its liquid-vacuum-interface potential and Fermi level. Combining our referencing schemes, we accurately determine the work function of liquid water as 4.73 ± 0.09 eV. Further, applying our novel approach to a pair of exemplary aqueous solutions, we extract absolute VIEs of aqueous iodide anions, reaffirm the robustness of liquid water''s electronic structure to high bulk salt concentrations (2 M sodium iodide), and quantify reference-level dependent reductions of water''s VIE and a 0.48 ± 0.13 eV contraction of the solution''s work function upon partial hydration of a known surfactant (25 mM tetrabutylammonium iodide). Our combined experimental accomplishments mark a major advance in our ability to quantify electronic–structure interactions and chemical reactivity in liquid water, which now explicitly extends to the measurement of absolute-scale bulk and interfacial solution energetics, including those of relevance to aqueous electrochemical processes.

A generalised liquid-phase photoelectron spectroscopy approach is reported, allowing accurate, absolute energy scale ionisation energies of liquid water and aqueous solutions, as well as liquid water''s work function to be reported.     

Chemical,Thermal and Antioxidant Properties of Lignins Solubilized during Soda/AQ Pulping of Orange and Olive Tree Pruning Residues

Some agroforestry residues such as orange and olive tree pruning have been extensively evaluated for their valorization due to its high carbohydrates content. However, lignin-enriched residues generated during carbohydrates valorization are normally incinerated to produce energy. In order to find alternative high added-value applications for these lignins, a depth characterization of them is required. In this study, lignins isolated from the black liquors produced during soda/anthraquinone (soda/AQ) pulping of orange and olive tree pruning residues were analyzed by analytical standard methods and Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (solid state ¹³C NMR and 2D NMR) and size exclusion chromatography (SEC). Thermal analysis (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) and antioxidant capacity (Trolox equivalent antioxidant capacity) were also evaluated. Both lignins showed a high OH phenolic content as consequence of a wide breakdown of β-aryl ether linkages. This extensive degradation yielded lignins with low molecular weights and polydispersity values. Moreover, both lignins exhibited an enrichment of syringyl units together with different native as well as soda/AQ lignin derived units. Based on these chemical properties, orange and olive lignins showed relatively high thermal stability and good antioxidant activities. These results make them potential additives to enhance the thermo-oxidation stability of synthetic polymers.     

Towards a proteome signature for invasive ductal breast carcinoma derived from label-free nanoscale LC-MS protein expression profiling of tumorous and glandular tissue

As more and more alternative treatments become available for breast carcinoma, there is a need to stratify patients and individual molecular information seems to be suitable for this purpose. In this study, we applied label-free protein quantitation by nanoscale LC-MS and investigated whether this approach could be used for defining a proteome signature for invasive ductal breast carcinoma. Tissue samples from healthy breast and tumor were collected from three patients. Protein identifications were based on LC-MS peptide fragmentation data which were obtained simultaneously to the quantitative information. Hereby, an invasive ductal breast carcinoma proteome signature was generated which contains 60 protein entries. The on-column concentrations for osteoinductive factor, vimentin, GAP-DH, and NDKA are provided as examples. These proteins represent distinctive gene ontology groups of differentially expressed proteins and are discussed as risk markers for primary tumor pathogenesis. The developed methodology has been found well applicable in a clinical environment in which standard operating procedures can be kept; a prerequisite for the definition of molecular parameter sets that shall be capable for stratification of patients.     

Interaction of torsion and lateral bending in aircraft nose landing gear shimmy

In this paper we consider the onset of shimmy oscillations of an aircraft nose landing gear. To this end we develop and study a mathematical model with torsional and lateral bending modes that are coupled through a wheel-mounted elastic tyre. The geometric effects of a positive rake angle are fully incorporated into the resulting five-dimensional ordinary differential equation model. A bifurcation analysis in terms of the forward velocity and the vertical force on the gear reveals routes to different types of shimmy oscillations. In particular, we find regions of stable torsional and stable lateral shimmy oscillations, as well as transient quasiperiodic shimmy where both modes are excited.     

New Evaluation Algorithm in Diode-Array Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography (TLC). It is a simple...     

Symmetric Spaces of Matter and Real Fermion Manifolds

The geometric algebra Cl_3,1 generated by the Minkowski spacetime with signature {+++− } possesses a natural ternary partition which provides the Lie algebra of the standard model symmetry in an improved form. The symmetric spaces of matter embed a differentiable manifold of primitive idempotents which represents a real valued fermion space as an 8-dimensional real unitsphere in a 10-dimensional subspace with positive definite signature. The algebraic properties of the present theory of spacetime-matter are developed, beginning with the definiteness of the stabilizer algebra of neutrinos, investigating the orthogonality between fermions and neutrinos and ending with the curvature of the symmetric spaces of the strong force. The model brings together the quantum theory and relativity, as we conceive it at present, such that the standard model turns out to be a definite property of the spacetime algebra.