Influence of the aggregation state in solution on the supramolecular organization of adsorbed type I collagen layers

In the last years, adsorbed collagen was shown to form layers with a supramolecular organization depending on the substrate surface properties and on the preparation procedure. If the concentration of collagen and the duration of adsorption are sufficient, fibrillar collagen structures are formed, corresponding to assemblies of a few molecules. This occurs more readily on hydrophobic compared to hydrophilic surfaces. This study aims at understanding the origin of such fibrillar structures and in particular at determining whether they result from the deposition of fibrils formed in solution or from the building of assemblies at the interface. Therefore, type I collagen solutions with an increasing degree of aggregation were prepared, using the “neutral-start” approach, by ageing pH 5.8 solutions at 37 °C for 15 min, 2 or 7 days. The obtained solutions were used to investigate the influence of collagen aggregation in solution on the supramolecular organization of adsorbed collagen layers, which was characterized by X-ray photoelectron spectroscopy and atomic force microscopy. Polystyrene and plasma-oxidized polystyrene were chosen as substrates for the adsorption. The size and the density of collagen fibrils at the interface decreased upon increasing the degree of aggregation of collagen in solution. This is explained by a competitive adsorption process between monomers and aggregates of the solution, turning at the advantage of the monomers. More aggregated solutions, which are thus depleted in free monomers, behave like less concentrated solutions, i.e. lead to a lower adsorbed amount and less fibril formation at the interface. This study shows that the supramolecular fibrils observed in adsorbed collagen layers, especially on hydrophobic substrates, are not formed in the solution, prior to adsorption, but are built at the interface, through the assembly of free segments of adsorbed molecules.     

ToF‐SIMS studies of the oxidation of Fe by D2O vapour: comparison with XPS

The oxidation of iron (Fe) by water (D₂O) vapour at low pressures and room temperature was investigated using time‐of‐flight (ToF) SIMS. The results supported those found previously using XPS and the QUASES^? program in that a duplex oxide structure was found containing a thin outer surface hydroxide (Fe(OD)₂) layer over an inner oxide (FeO) layer. The extraordinary depth resolution of the ToF‐SIMS profiles assisted in identifying the two phases; this resolution was achieved by compensation for surface roughness. A substantial concentration of deuterium was found in the subsurface oxide layer. This observation confirmed previous assessments that the formation of FeO was from the reaction of Fe(OD)₂ with outward‐diffusing Fe, leaving deuterium as a reaction product. Copyright © 2005 John Wiley & Sons, Ltd.     

Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Chemical stability of TiN,TiAlN and AlN layers in aggressive SO2 environments

In this paper, we have studied, using X‐ray photoelectron spectroscopy (XPS), the chemical stability of TiN, TiAlN and AlN layers produced by magnetron sputtering on Si wafer substrates, against humid, SO₂‐polluted atmospheres. The results have indicated that the TiN layers suffer almost no degradation after seven days of exposure to the aggressive environment. The degradation of the TiAlN layers is small, and this is evidenced by the appearance of signals corresponding to N? O bonds in the N 1s spectra, after seven days of exposure to the corrosive atmosphere and the increase in the Ti 2p spectra of the contribution corresponding to TiO₂. In contrast, the degradation experienced by the AlN layers is quite large. The spectra reveal dramatic changes after just one day of exposure to the aggressive conditions. This is related to the preferential growth of the AlN layers, which gives rise to an open, columnar structure. Copyright © 2005 John Wiley & Sons, Ltd.     

加氢脱硫催化剂各组分的相互作用与催化性能

石油化工生产中广泛使用的加氢脱硫催化剂往往是以v－A120。作为载体,Moo或WOs为主要活性组分,少量Nio或Coo为助剂的多组分负载型催化剂．由于它在生产中所起的重要作用,此类催化剂的研究一直受到科学工作者的关注．本文分别考察了几种不同组分的催化剂,研究了催化剂组分间的相互作用对活性组分的分散状态、还原性能以及加氢脱硫活性的影响,旨在为进一步改进催化剂的性能提供有益的信息．且实验部分Ni－MO体系催化剂样品是以银酸钦和硝酸镍及v－AI。0。为原料,采用浸渍方法制备．C。M。／AJ。0。和W－Ni／AJ。0。分别用硝酸钻…     

GaAs(100)解理面的能带弯曲

在真空中解理后,用XPS测得了GaAs样品（110）断面能带弯曲的动态过程．两组重掺杂n型和p型GaAs样品的费米能级分别向禁带中间的方向移动了0.4eV和0．3eV.实验测得重掺杂n型和p型GaAs样品费米能级之差为1．3eV,它们的禁带宽度理论值为1．42eV,这说明结果是合理的．根据实验结果,对引起GaAs表面能带弯曲的可能原因进行了分析讨论．排除了本征表面态、真空中残留气体和X射线辐射等原因,认为解理过程在表面产生的缺陷和解理后表面晶格弛豫过程中产生的缺陷可能是导致能带弯曲的主要原因．     

The electrochemical behavior of some podands at a benzo[c]cinnoline modified glassy carbon electrode

This paper describes the grafting of benzo[c]cinnoline (BCC) molecules on glassy carbon (GC) electrode surface. The attachment of BCC molecules to carbon substrate is induced by the electrochemical reduction of the corresponding diazonium salt. The modification of GC with BCC diazonium salt was done in aprotic solution and proved by blocking of dopamine electron transfer. The presence of BCC at the GC surface was characterized by cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). On modified surface, the electrochemical behavior of two different types of podands and the catalytic effects of the GC-BCC surface were studied. The XPS was used to monitor element characteristics of the adsorbates on the GC surface and confirm the attachment of BCC molecules to the GC surface.     

Spectroscopic characterization of alkaline earth uranyl carbonates

A series of alkaline uranyl carbonates, M[UO₂(CO₃)₃]·nH₂O (M=Mg₂, Ca₂, Sr₂, Ba₂, Na₂Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba₂[UO₂(CO₃)₃]·6H₂O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO₂)(CO₃)₃ clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90±0.02 Å.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces.     

Classification of oxide glasses: A polarizability approach

A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability α_O2−(n₀), optical basicity Λ(n₀), metallization criterion M(n₀), interaction parameter A(n₀), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials.     

A Stable Porphyrin Functionalized Graphite Electrode Used at the Oxygen Evolution Reaction Potential

Many researches have been devoted to rechargeable power generators that can store (but also release) energy. This availability is ensured through (e. g.) the oxygen evolution reaction (OER). However, (i) large values of the overpotentials and (ii) a progressive detriment of the anode (graphite) electrode limit the ultimate device. In view of enhancing the electrode performances, graphite was protected by following different strategies, which oblige to follow precise preparation protocols. Here, we prove that a thin layer of free-base porphyrin molecules is able to protect the underneath graphite electrode from detriment even if many (about 100) electrochemical cycles are performed.