Irreversible denaturation of proteins through aluminum-induced formation of backbone ring structures.

A combination of ab initio calculations, circular dichroism, nuclear magnetic resonance, and X-ray photoelectron spectroscopy has shown that aluminum ions can induce the formation of backbone ring structures in a wide range of peptides, including neurodegenerative disease related motifs. These ring structures greatly destabilize the protein and result in irreversible denaturation. This behavior benefits from the ability of aluminum ions to form chemical bonds simultaneously with the amide nitrogen and carbonyl oxygen atoms on the peptide backbone.

Orientation-resolved 3d(5/2) binding energy shift of Rh and Pd surfaces: anisotropy of the skin-depth lattice strain and quantum trapping.

Incorporating the BOLS correlation algorithm [Y. Sun, J. Phys. Chem. C, 2009, 113, 14696] into high-resolution XPS measurements [J. N. Andersen, et al., Phys. Rev. B: Condens. Matter, 1994, 50, 17525; A. Baraldi, et al., New J. Phys., 2007, 9, 143] has produced an effective way of determining the 3d(5/2) energy levels of isolated Rh(302.163 +/- 0.003 eV) and Pd (330.261 +/- 0.004 eV eV) atoms and their respective bulk shifts (4.367 and 4.359 eV) with a refinement of the effective atomic coordination numbers of the top (100), (110), and (111) atomic layers (4.00, 3.87, and 4.26, respectively). It is further confirmed that the shorter and stronger bonds between under-coordinated atoms induce local strain and skin-depth charge-and-energy quantum trapping and, hence, dictate globally the positive core level binding energy shifts.

Layer and orientation resolved bond relaxation and quantum entrapment of charge and energy at Be surfaces.

The chemistry and physics of under-coordination at a surface, which determines the process of catalytic reactions and growth nucleation, is indeed fascinating. However, extracting quantitative information regarding the coordination-resolved surface relaxation, binding energy, and the energetic behavior of electrons localized in the surface skin from photoelectron emission has long been a great challenge, although the surface-induced core level shifts of materials have been intensively investigated. Here we show that a combination of the theories of tight binding and bond order-length-strength (BOLS) correlation [C. Q. Sun, Prog. Solid State Chem., 2007, 35, 1-159], and X-ray photoelectron spectroscopy (XPS) has enabled us to derive quantitative information, by analyzing the Be 1s energy shift of Be(0001), (1010), and (1120) surfaces, for demonstration, regarding: (i) the 1s energy level of an isolated Be atom (106.416 ± 0.004 eV) and its bulk shift (4.694 eV); (ii) the layer- and orientation-resolved effective atomic coordination (3.5, 3.1, 2.98 for the first layer of the three respective orientations), local bond strain (up to 19%), charge density (133%), quantum trap depth (110%), binding energy density (230%), and atomic cohesive energy (70%) of Be surface skins up to four atomic layers in depth. It is affirmed that the shorter and stronger bonds between under-coordinated atoms perturb the Hamiltonian and hence the fascinating localization and densification of surface electrons. The developed approach can be applied to other low-dimensional systems containing a high fraction of under-coordinated atoms such as adatoms, atomic defects, terrace edges, and nanostructures to gain quantitative information and deeper insight into their properties and processes due to the effect of coordination imperfection.

Interface quantum trap depression and charge polarization in the CuPd and AgPd bimetallic alloy catalysts.

The ability of a catalyst to accept or donate charge is the key to the process of catalytic reaction. However, the determination of the catalytic nature of a specimen as yet remains a great challenge. Here we report an effective yet simple method for this purpose based on the tight binding theory considerations and XPS monitoring of the evolution of valence and core electrons upon alloy formation. Firstly, we measured the valence and core band charge density of the constituent elements of Cu, Ag, and Pd and then the respective states upon alloy formation. A subtraction of the resultant spectrum of the alloy by the composed elemental spectra gives the residual that shows clearly the occurrence of charge trapping or polarization. We found that the valence and the core electrons of the CuPd alloy shift positively to deeper energies, opposite to the occurrences in the AgPd alloy. Findings clarify for the first time that CuPd serves as an acceptor due to quantum trapping and the AgPd as a donor because of charge polarization, which also explain why AgPd and CuPd perform very differently as important catalysts.

Investigation on Surface Polarization of Al2O3-capped GaN/AlGaN/GaN Heterostructure by Angle-Resolved X-ray Photoelectron Spectroscopy.

The surface polarization of Ga-face gallium nitride (GaN) (2 nm)/AlGaN (22 nm)/GaN channel (150 nm)/buffer/Si with Al2O3 capping layer is investigated by angle-resolved X-ray photoelectron spectroscopy (ARXPS). It is found that the energy band varies from upward bending to downward bending in the interface region, which is believed to be corresponding to the polarization variation. An interfacial layer is formed between top GaN and Al2O3 due to the occurrence of Ga-N bond break and Ga-O bond forming during Al2O3 deposition via the atomic layer deposition (ALD). This interfacial layer is believed to eliminate the GaN polarization, thus reducing the polarization-induced negative charges. Furthermore, this interfacial layer plays a key role for the introduction of the positive charges which lead the energy band downward. Finally, a N2 annealing at 400 °C is observed to enhance the interfacial layer growth thus increasing the density of positive charges.

The stability of aluminium oxide monolayer and its interface with two-dimensional materials.

The miniaturization of future electronic devices requires the knowledge of interfacial properties between two-dimensional channel materials and high-κ dielectrics in the limit of one atomic layer thickness. In this report, by combining particle-swarm optimization method with first-principles calculations, we present a detailed study of structural, electronic, mechanical, and dielectric properties of Al2O3 monolayer. We predict that planar Al2O3 monolayer is globally stable with a direct band gap of 5.99 eV and thermal stability up to 1100 K. The stability of this high-κ oxide monolayer can be enhanced by substrates such as graphene, for which the interfacial interaction is found to be weak. The band offsets between the Al2O3 monolayer and graphene are large enough for electronic applications. Our results not only predict a stable high-κ oxide monolayer, but also improve the understanding of interfacial properties between a high-κ dielectric monolayer and two-dimensional material.