Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.     

Charge-density oscillations at (1 1 1) noble metal surfaces

Induced charge-density oscillations at noble metal surfaces caused by an external static impurity are studied within linear response theory. The calculation takes into account such properties of realistic surface electronic structure as an energy gap for three-dimensional (3D) bulk electrons and a s − p_z surface state that forms two-dimensional (2D) electron system. It is demonstrated that the coexistence of these 2D and 3D electron systems has profound impact on the induced charge-density in the surface region. Thus, the oscillations with the 1/R² decay as a function of lateral distance, R, are established in both electron systems with characteristic chess-board-like structure. Additionally, the charge-density penetrates into the solid at a finite angle with respect to the surface normal in contrast to that in jellium model. The origin of both these findings is investigated.     

劣化变压器油中硅胶吸附物的分离分析

利用红外光谱法、气相色谱法（GC）和色－质联用（GC-MS)技术分析测定了投运一年后的劣质变压器油中硅胶吸附物的呈色成分，分析了硅胶吸附变色的原因。     

吡嗪分子在硅(100)面吸附构型的XPS和NEXAFS谱理论研究

本文利用X射线谱研究了吡嗪(C₄H₄N₂)分子共价吸附于硅(100)面的几种吸附构型的几何结构和电子结构. 利用密度泛函理论结合团簇模型,对预测的吸附结构的碳K壳层(1s)X射线光电子能谱(XPS)和近边X射线吸收精细结构(NEXAFS)谱进行了模拟. 计算结果阐明了XPS和NEXAFS谱与不同吸附构型的对应关系. 与XPS谱相比,NEXAFS谱对所研究的吡嗪/硅(100)体系的结构有明显的依赖性,可以很好地用于结构鉴定. 根据碳原子的分类,研究了在NEXAFS光谱中不同化学环境下碳原子的光谱成分.     

New experimental set-ups for studying nanoconfined water on the AILES beamline at SOLEIL

Three ensembles designed to investigate condensed matter in complex environments have been developed recently on the AILES beamline at SOLEIL. They have been exploited for studies aiming at understanding the properties of water molecules and their network in various confining systems, namely:

• -a hydration and temperature-controlled cell for the study of water confined in nanoporous Vycor,
• -a high pressure set-up allowing the study of the evolution of water molecules network trapped in Faujasite through the pressure-induced amorphisation of the matrix material,
• -a temperature resolved electrochemical cell used to record FIR difference spectra of metalloproteins interacting with water molecules.

By combining the high infrared flux and collimation of the AILES beamline with these optimized sample environments, it is possible to measure the infrared and THz spectra for minute quantities of samples in precise physical conditions.     

Surface enhanced infrared absorption on Au nanoparticle films deposited on SiO2/Si for optical biosensing: Detection of the antibody-antigen reaction

The specific antibody-antigen reaction was detected by taking advantage of the effect of surface enhanced infrared absorption (SEIRA). For the SEIRA active film, single Au nanoparticles (AuNP) deposited on the SiO₂/Si wafer surface were used. After immobilizing specific antibodies onto the AuNP, these samples were then exposed to specific antigens (unspecific antigens, respectively); then the samples were investigated with infrared spectroscopy. In addition, the same kind of sample preparation was done using a 40 nm thick non-enhancing Au film, in order to compare the SEIRA transmission spectra to the infrared reflection absorption spectra (IRRAS) and therefore to determine the factor of the SEIRA enhancement. In both geometries, SEIRA transmission and IRRAS, the antibody-antigen coupling could clearly be detected; a comparison of the spectra showed, that the enhancement factor due to the Au nanoparticles is roughly 25.     

Direct SCF direct static-exchange calculations of electronic spectra

Applications of the direct SCF direct static-exchange method are reviewed for three different types of systems (free molecules, polymers, and surface adsorbates) and for six types of spectroscopy (X-ray absorption-, -emission-, and -shake-up spectroscopy, ultraviolet photoelectron emission, X-ray Raman and circular dichroism spectroscopy. Received: 28 December 1996 / Accepted: 8 April 1997     

Phase Diagram of 2 × 2 Adsorbates at Surfaces with Hexagonal Symmetry

The phase diagram of a lattice-gas model for 2 2 2 adsorbates at surfaces with hexagonal symmetry has been investigated by Monte Carlo simulations. The model relies on repulsive interactions between the particles for distances up to second nearest neighbor sites. It is shown that first- or second-order phase transitions take place depending on the strength of the interactions. Strong first- or second-neighbor interactions are responsible for a first-order transition while for intermediate interaction strength a second-order transition is possible. The critical exponent for the susceptibility shows the expected value of the four-states Potts model in case of a second-order transition. The value of the critical exponent is reduced when the transition changes from first to second order.     

Adsorption and electro-oxidation of <Emphasis Type="Italic">N</Emphasis>-alkyl and <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’-dialkyl thioureas on gold electrodes in acid solutions. A combined FTIRRAS and voltammetry study

The adsorption and electro-oxidation of N-alkyl and N,N’-dialkyl thioureas on polycrystalline gold in aqueous acid solutions is studied by Fourier-transformed infrared reflection absorption spectroscopy (FTIRRAS) and voltammetry. The potential ranges for different electrochemical processes, including electrodissolution of gold and electro-oxidation of thioureas, are determined by cyclic voltammetry. The gradual depletion of thioureas and the progressive formation of products from adsorbed and soluble species in the thin solution layer in contact with the electrode are followed through changes in band intensity of infrared (IR) spectra. Adsorbates of thioureas are formed at 0.05 V and remain on the surface up to E = 1.2 V, a potential at which their electro-oxidation takes place. Irrespective of the type of thiourea, the first electro-oxidation process from soluble thioureas starts at ca. 0.45 V with the formation of their respective disulphide. This process is preceded by the electrodissolution of gold via the formation of gold–thiourea soluble complex species. From ca. 1.2 V upwards the second electro-oxidation process results in the formation of carbon dioxide, sulphate ions and C≡N-containing species. The latter are produced only from N-alkyl thioureas, in which the presence of free amine groups makes the formation of a C≡N bond possible, as a previous stage to the production of carbon dioxide and sulphate ions as final products. From the correlation between voltammetric and spectroscopic data a general reaction pathway for the adsorption of thioureas and their electro-oxidation on gold is advanced. This work is dedicated to Prof. Teresa Iwasita on the occasion of her 65th birthday.     

Challenges and errors: interpreting high resolution images in scanning tunneling microscopy

With the availability of first principles methods to simulate the operation of a scanning tunneling microscope (STM) theory has moved from the qualitative and topographic to the quantitative and dynamic. Simulations in effect predict the influence of a model-tip or chemical interactions between tip and sample in the actual imaging process. By comparing experiments and simulations, the information about the analyzed system can be substantially extended. We give an overview of recent work, where the combination of first principles simulations with high resolution measurements was decisive to arrive at consistent results. This concerns the resolution of single wavefunctions by STM, force effects in high resolution scans, contrast reversal due to the field of the tip, the imaging of magnetic properties by spin-polarized STM, and the analysis of dynamic processes on surfaces.