Studies of interfacial regions by sum-frequency generation with a free-electron laser

The use of a Free-Electron Laser (FEL) allows the study of (non)linear optical properties of materials over unsurpassed large spectral intervals. As an example, we report on the use of a FEL as the infrared source in spectroscopic infrared-visible Sum-Frequency Generation (SFG). Employing the extremely wide tunability of the Free-Electron Laser for Infrared eXperiments (FELIX) at Rijnhuizen, we have studied the frequency dependence of the nonlinear susceptibility for sumfrequency generation in gallium phosphide between 20 and 32 m in great detail. We have developed a shortpulse visible laser system that is highly synchronous with FELIX thereby creating a two-color setup that can be broadly applied. Resonantly enhanced SFG in alphaquartz has been used to study the relative timing stability of FELIX and the synchronized picosecond-laser system.Paper presented at the 129th WE-Hearaeus-Seminar on Surface studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Static secondary ion mass spectrometry for organic and inorganic molecular analysis in solids

The use of mass spectra in secondary ion mass spectrometry (S-SIMS) to characterise the molecular composition of inorganic and organic analytes at the surface of solid samples is investigated. Methodological aspects such as mass resolution, mass accuracy, precision and accuracy of isotope abundance measurements, influence of electron flooding and sample morphology are addressed to assess the possibilities and limitations that the methodology can offer to support the structural assignment of the detected ions. The in-sample and between-sample reproducibility of relative peak intensities under optimised conditions is within 10%, but experimental conditions and local hydration, oxidation or contamination can drastically affect the mass spectra. As a result, the use of fingerprinting for identification becomes compromised. Therefore, the preferred way of interpretation becomes the deductive structural approach, based on the use of the empirical desorption–ionisation model. This approach is shown to allow the molecular composition of inorganic and organic components at the surface of solids to be characterised. Examples of inorganic speciation and identification of organic additives with unknown composition in inorganic salt mixtures are given. The methodology is discussed in terms of foreseen developments with respect to the use of polyatomic primary ions.     

The use of high-performance liquid chromatography in the isolation and characterisation of mouse and rat epidermal growth factors and examination of apparent heterogeneity

Various epidermal growth factor preparations obtained from the mouse submaxillary gland (mEGF), have been separated into a number of components by reversed-phase high-performance liquid chromatography (HPLC). It is shown here, however, that when the mEGF is isolated rapidly, using only reversed-phase HPLC for trace enrichment and high-resolution fractionation, it is a single molecular species as determined with several ion-pairing solvent systems, provided that proteolysis is inhibited in the original extracts. This indicates that the minor components of mEGF that have been reported are artefacts formed during the isolation procedure, and are of no biological significance. The products of deliberate mild degradation of mEGF are shown to produce similar chromatographic profiles to those observed in samples of mEGF prepared in the absence of proteolytic inhibitors. Rat EGF has been isolated in a similar manner, and is shown to share many of the properties of the major tryptic digestion product of mEGF.     

Atomic decomposition of the protein solvation free energy and its application to amyloid-beta protein in water

We report the development of an atomic decomposition method of the protein solvation free energy in water, which ascribes global change in the solvation free energy to local changes in protein conformation as well as in hydration structure. So far, empirical decomposition analyses based on simple continuum solvation models have prevailed in the study of protein-protein interactions, protein-ligand interactions, as well as in developing scoring functions for computer-aided drug design. However, the use of continuum solvation model suffers serious drawbacks since it yields the protein free energy landscape which is quite different from that of the explicit solvent model and since it does not properly account for the non-polar hydrophobic effects which play a crucial role in biological processes in water. Herein, we develop an exact and general decomposition method of the solvation free energy that overcomes these hindrances. We then apply this method to elucidate the molecular origin for the solvation free energy change upon the conformational transitions of 42-residue amyloid-beta protein (Aβ42) in water, whose aggregation has been implicated as a primary cause of Alzheimer's disease. We address why Aβ42 protein exhibits a great propensity to aggregate when transferred from organic phase to aqueous phase.     

A simple taste analyzing system design for visual and quantitative analysis of different tastes using multi-array chemical sensors and pattern recognition techniques

In this paper, we describe design of a simple taste analyzing system using sensory system based on a multi-array chemical sensor (MACS) and personal digital assistant (PDA) for visual and quantitative analysis of different tastes using pattern recognition techniques. The sensory system is communicated with PDA, which has several interesting benefits for data analysis and display, via wireless using the Bluetooth. A various pattern recognition techniques are adapted including spider map, principal component analysis (PCA) and fuzzy C-means (FCM) algorithm to classify visually data patterns detected by the sensory system. The proposed techniques can be determined the cluster centers and membership grade of patterns through the unsupervised way. The membership grade of an unknown pattern, which does not shown previously, can be visually and analytically determined. Throughout the experimental trails, the taste analyzing system is demonstrated robust performance through data acquisition via wireless communication and visual and quantitative analysis of different tastes for the liquids. The system, which is implemented as a simple hand-held taste analyzing instrument, can be applicable to on-site taste monitoring.     

Cyclodipeptide-bridged porphyrin dimer supramolecular assemblies

A cyclodipeptide-bridged porphyrin dimer has formed fibrous and toroidal multi-porphyrin array systems by hydrogen bonding-mediated self-assembly.     

Facile one-step synthesis of Ru doped NiCoP nanoparticles as highly efficient electrocatalysts for oxygen evolution reaction

Transition metal phosphides (TMPs) as ever-evolving electrocatalytic materials have attracted increasing attention in water splitting reactions owing to their cost-effective, highly active and stable catalytic properties. This work presents a facile synthetic route to NiCoP nanoparticles with Ru dopants which function as highly efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media. The Ru dopants induced a high content of Ni and Co vacancies in NiCoP nanoparticles, and the more defective Ru doped NiCoP phase than undoped NiCoP ones led to a greater number of catalytically active sites and improved electrical conductivity after undergoing electrochemical activation. The Ru doped NiCoP catalyst exhibited high OER catalytic performance in alkaline media with a low overpotential of 281 mV at 10 mA cm⁻² and a Tafel slope of 42.7 mV dec⁻¹.     

Comparison of laser desorption and matrix-assisted laser desorption/ionization for ruthenium and osmium trisbipyridine complexes using Fourier transform mass spectrometry

Metal-bipyridine complexes are a vehicle for developing approaches for studying the fluorescence of gas-phase ions; however, conclusions regarding fluorescence behavior depend on explicitly identifying the ionic species in the gas phase. [Ru(bpy)(3)]X(2) and [Os(bpy(3))]X(2), (where bpy = 2,2'-bipyridine and X = Cl or PF(6)), were studied using direct laser desorption (LD) and matrix-assisted laser desorption/ionization (MALDI) using Fourier transform mass spectrometry (FTMS). LD spectra of the PF(6) salt of the Ru and Os complexes reveal counterion attachment, fluoride transfer, and significant losses of H for a number of peaks. LD of the chloride salt complexes produced loss of a single bpy ligand, chloride attachment, and losses of H. Spectra of [Ru(bpy(3)]X(2) where X = BF(4)(-), CF(3)SO(3)(-), and SCN(-) were also collected using LD and compared with the spectra for Cl(2) and PF(6) salts. Regardless of counterion, loss of H is observed in LD spectra. MALDI spectra of the trisbipyridyl complexes using 2,5-dihydroxybenzoic acid (DHB) and sinapinic acid (SA) as the matrix were also obtained. The spectra using SA as matrix show intact molecular ion peaks with very little fragmentation and no counterion attachment. Unlike SA, the spectra obtained using DHB look similar to LD spectra with significant losses of H. Our results are consistent with a reaction scheme for hydrogen loss from a carbon that also involves breaking of the metalz.sbnd;nitrogen bond, rotation of a pyridine ring, and re-formation of an ortho-metallated complex by a metalz.sbnd;C bond. These results demonstrate the importance of ion generation method and the utilization of FTMS for correct characterization of metal poly(pyridyl) complexes.     

Synthesis of functionalized organotrifluoroborates via the 1,3-dipolar cycloaddition of azides

[reaction: see text] We have successfully prepared potassium azidoalkyltrifluoroborates from the corresponding halogen compounds in 94-98% yields through a nucleophilic substitution reaction with NaN(3). In the presence of various alkynes and Cu(I) as a catalyst, these azidotrifluoroborates easily formed 1,4-disubstituted organo-[1,2,3]-triazol-1-yl-trifluoroborates in 85-98% yields. This method was then developed into a facile one-pot synthesis for the preparation of various organo-[1,2,3]-triazol-1-yl-trifluoroborates using haloalkyltrifluoroborates as the starting materials.