Intracellular lectins are involved in quality control of glycoproteins

Glycoprotein quality control is categorized into three kinds of reactions; the folding of nascent glycoproteins, ER-associated degradation of misfolded or unassembled glycoproteins, and transport and sorting of correctly folded glycoproteins. In all three processes, N-glycans on the glycoproteins are used as tags that are recognized by intracellular lectins. We analyzed the functions of these intracellular lectins and their sugar-binding specificities. The results clearly showed that the A, B, and C-arms of high mannose-type glycans participate in the folding, transport and sorting, and degradation, respectively, of newly synthesized peptides. After correctly folded glycoproteins are transported to the Golgi apparatus, N-glycans are trimmed into Man₃GlcNAc₂ and then rebuilt into various complex-type glycans in the Golgi, resulting in the addition of diverse sugar structures that allow glycoproteins to play various roles outside of the cells.     

Interaction élastique de défauts ponctuels dans un cristal hexagonal semi-infini avec ou sans adsorbat

The energy of elastic interaction between a point defect and the (0001) surface of a hexagonal crystal is calculated, as well as the energy of the elastic interaction between two defects near such a surface. The defects are represented by the superposition of three mutually perpendicular double forces without moment. The calculation is done by means of a Green function method. As for an isotropic medium, the energy of a point defect presents a variation in x₃^?3 with the distance x₃ to the surface. On the other hand, the mutual interaction between two defects depends upon different geometric parameters, and not simply on an image factor. We also study the effect of a thin adlayer on these elastic interactions. This is done by showing that the presence of the adlayer is equivalent to effective boundary conditions at the surface of the substrate. We derive these conditions and then the elastic energies to the first order in the thickness h of the layer. Finally we present the mean square displacements of atoms in the presence of a clean or adsorbed surface.     

Surface-induced magnetism of the solids with impurities and vacancies

Using the quantum-mechanical approach combined with the image charge method we calculated the lowest energy levels of the impurities and neutral vacancies with two electrons or holes located in the vicinity of flat surface of different solids. Unexpectedly we obtained that the magnetic triplet state is the ground state of the impurities and neutral vacancies in the vicinity of surface, while the nonmagnetic singlet is the ground state in the bulk, for e.g. He atom, Li⁺, Be⁺⁺ ions, etc. The energy difference between the lowest triplet and singlet states strongly depends on the electron (hole) effective mass μ, dielectric permittivity of the solid ε₂ and the distance from the surface z₀. For z₀=0 and defect charge ∣Z∣=2 the energy difference is more than several hundreds of Kelvins at μ=(0.5−1)m_e and ε₂=2-10, more than several tens of Kelvins at μ=(0.1−0.2)m_e and ε₂=5-10, and not more than several Kelvins at μ<0.1m_e and ε₂>15 (m_e is the mass of a free electron). Pair interaction of the identical surface defects (two doubly charged impurities or vacancies with two electrons or holes) reveals the ferromagnetic spin state with the maximal exchange energy at the definite distance between the defects (∼5-25 nm). We estimated the critical concentration of surface defects and transition temperature of ferromagnetic long-range order appearance in the framework of percolation and mean field theories, and RKKY approach for semiconductors like ZnO. We obtained that the nonmagnetic singlet state is the lowest one for a molecule with two electrons formed by a pair of identical surface impurities (like surface hydrogen), while its next state with deep enough negative energy minimum is the magnetic triplet. The metastable magnetic triplet state appeared for such molecule at the surface indicates the possibility of metastable ortho-states of the hydrogen-like molecules, while they are absent in the bulk of material. The two series of spectral lines are expected due to the coexistence of ortho- and para-states of the molecules at the surface. We hope that obtained results could provide an alternative mechanism of the room temperature ferromagnetism observed in TiO₂, HfO₂, and In₂O₃ thin films with contribution of the oxygen vacancies. We expect that both anion and cation vacancies near the flat surface act as magnetic defects because of their triplet ground state and Hund's rule. The theoretical forecasts are waiting for experimental justification allowing for the number of the defects in the vicinity of surface is much larger than in the bulk of as-grown samples.     

Excess electrons in reduced rutile and anatase TiO2

As a prototypical photocatalyst, TiO₂ is a material of scientific and technological interest. In photocatalysis and other applications, TiO₂ is often reduced, behaving as an n-type semiconductor with unique physico-chemical properties. In this review, we summarize recent advances in the understanding of the fundamental properties and applications of excess electrons in reduced, undoped TiO₂. We discuss the characteristics of excess electrons in the bulk and at the surface of rutile and anatase TiO₂ focusing on their localization, spatial distribution, energy levels, and dynamical properties. We examine specific features of the electronic states for photoexcited TiO₂, for intrinsic oxygen vacancy and Ti interstitial defects, and for surface hydroxyls. We discuss similarities and differences in the behaviors of excess electrons in the rutile and anatase phases. Finally, we consider the effect of excess electrons on the reactivity, focusing on the interaction between excess electrons and adsorbates.     

Role of the Carbohydrate Moiety and of α-L-Fucose in the Stabilization and the Dynamics of the Lens culinaris Agglutinin–Glycoprotein Complex. A Fluorescence Study

Interaction between the fluorescent Lens culinaris agglutinin–fluorescein complex (LCA-FITC) and two glycoproteins, lactotransferrin (LTF) and serotransferrin (STF), was studied. The two glycoproteins have the same glycan structures, with one difference: the lactotransferrin glycans contain a fucose residue -1,6-linked to the N-acetylglucosamine residue involved in the N-glycosylamine linkage. Fluorescence intensity quenching of the LCA-FITC complex shows that affinity between LCA and lactotransferrin is 50 times higher than that between LCA and serotransferrin, the fucose playing a major role in this high affinity (K _a is equal to 9.66 and 0.188 M ^–1 for the LCA–LTF complex and LCA–STF complex, respectively). Time-resolved anisotropy decay indicates that the rotational correlation time of LCA (20 ns) does not change to a large extent whether the glycoproteins are bound to LCA or not. This suggests that there is no extended physical contact between LCA and the glycoproteins. The interaction between LCA and the glycoproteins occurs likely only via the carbohydrate chains, the STF and the LTF rotating almost-freely in the vicinity of LCA, with the glycans as an anchor.     

Kinetics and Thermodynamics of Glycans and Glycoproteins Binding to Holothuria scabra Lectin: A Fluorescence and Surface Plasmon Resonance Spectroscopic Study

Holothuria scabra produces a monomeric lectin (HSL) of 182 kDa. HSL showed strong antibacterial activity and induced bacterial agglutination under in vitro conditions, indicating its role in animals’ innate immune responses. Very few lectins have been reported from echinoderms and none of these lectins have been explored in detail for their sugar-binding kinetics. Affinity, kinetics and thermodynamic analysis of glycans and glycoproteins binding to HSL were studied by fluorescence and surface plasmon resonance spectroscopy. Lectin binds with higher affinity to O-linked than N-linked asialo glycans, and the affinities were relatively higher than that for sialated glycans and glycoproteins. T-antigen α-methyl glycoside was the most potent ligand having the highest affinity (Ka 8.32 ×10⁷ M^?1). Thermodynamic and kinetic analysis indicated that the binding of galactosyl Tn-antigen and asialo glycans is accompanied by an enthalpic contribution in addition to higher association rate coupled by low activation energy for the association process. Presence of sialic acid or protein matrix inhibits binding. Higher affinity of HSL for O-glycans than N-glycans had biological implications; since HSL specifically recognizes bacteria, which have mucin or O-glycan cognate on their cell surfaces and play a major role in animal innate immunity. Since, HSL had higher affinity to T-antigen, makes it a useful tool for cancer diagnostic purpose.     

Photoluminescence Properties of Nanoporous Nanocrystalline Carbonate-Substituted Hydroxyapatite

Luminescence characteristics of an analogue of the mineral component of dental enamel—nanocrystalline B-type carbonate-substituted calcium hydroxyapatite (CHAP)—with defects (nanopores ～2?5 nm in size) on the surface of nanocrystals are studied. It is shown that laser-induced luminescence of CHAP samples synthesized by us occurs in the region of ～515 nm (～2.4 eV) and is related to the existence of CO₃ groups substituting PO₄ groups in the CHAP lattice. It is determined that the luminescence intensity of the CHAP samples depends on the amount of structurally bound CO₃ groups and decreases with decreasing concentration of these intracenter defects in the apatite structure. The results obtained in this work are of potential importance for developing the fundamentals of precision and early detection of caries in human hard dental tissue.     

Theory of GaAsoxide interface states

The discrete GaAsoxide interface states observed by Lagowski et al. can be explained by defects in the GaAs surface: The deep levels are in agreement with our predictions for surface antisite defects, and the shallow levels (observed for thick oxides) agree with our predictions for surface oxygen impurities on anion and cation sites.     

Observation of regular defects formed on the surface of PbTe thin films grown by molecular beam epitaxy

Regular shape defects on the surface of PbTe thin films grown by molecular beam epitaxy (MBE) were studied by scanning electron microscope (SEM). Two types of regular shape defects were observed on Te-rich PbTe films grown at substrate temperature T ≥ 235 °C with a beam flux ratio of Te to PbTe (R_f) to be 0.5 and at 280 °C with a R_f ≥ 0.4, which include cuboids and triangular pyramids. The formation mechanism of the observed regular shape defects is interpreted as following: They are the outcome of fast growth rate along {1 0 0} crystal planes that have the lowest surface energy and the enclosure of the {1 0 0} crystal planes. The formation of the regular shape defects in the growth of PbTe needs appropriate substrate temperature and Te-rich ambience. However, when R_f is decreased low enough to make the films slightly Pb-rich, triangular pits that originate from the insufficient glide of the threading dislocations along the main 〈1 1 0〉 {1 0 0} glide system of PbTe in Cottrell atmosphere, will be the main feature on the film surface.     

Structural defects on a 1T-TiSe2 surface: Experiment and model calculation of photoelectron diffraction

A 1T-TiSe₂ surface is studied by means of scanning tunneling microscopy (SMT) and X-ray photoelectron diffraction (XPD). The diffraction patterns were modeled in the multiple electron scattering approximation using the EDAC code. Variants of the point and structural defects on the 1T-TiSe₂ surface are considered. The experimental and theoretical XPD patterns are compared on the basis of a convergence analysis of their R factors.     

Nonequilibrium energy of Rayleigh waves in half-limited crystals with hot electrons close to the defect surface

Nonequilibrium energies of surface (Rayleigh) lattice oscillations in half-limited crystals with static defects and a two-dimensional layer of hot Fermi and Boltzmann electrons close to the stress free surface were calculated. Substances with electrons heated by an external field retaining their intrinsic temperature for a certain time, T _e ? T, where T is the temperature of the lattice, were considered. As shown earlier, the thermodynamic characteristics of thin films can then be determined by nonequilibrium energy of Rayleigh waves (R-phonons) caused by their interaction with hot electrons. This energy decreases as the widths of the energy spectrum of R-phonons increase. In this work, the earlier calculated spectrum widths are used. These widths are caused by the scattering of R-phonons by electrons and static defects close to the surface (point and extended surface defects, edge dislocations perpendicular to the surface and emerging to it, and random lattice grooves in the lattice plane). In all the calculations, the Keldysh diagram technique transformed for half-limited media was used.     

Photoemission spectroscopy and microscopy of n-, p-GaAs(110) homostructures

Zinc-blend III–V semiconductors being cleaved along nonpolar (110) planes yield atomically clean surfaces due to their charge neutrality, which can be employed as mirror planes for optical resonators. As a result of the Ga3d core level photoemission measurements after the n-, p-GaAs (110) plane cleavage in situ of doped semiconductors with 14 nominally identical p-n homojunctions having optically flat cleaved surface under the optical microscope inspection, the estimate of the Fermilevel positions on energy scale were acquired for p- and n-epilayers. The two-dimentional photoemission image for p-n homojunction was studied as well, using the focused synchrotron radiation beam (diameter 0.7 μm, 95 eV, ～10¹⁰ phot./s) at the scanning photoemission microscope. The average value of surface band bending for p-epilayer measured from the energy position of ideal flat-band conditions, was equal to 0.12 ± 0.05 eV, and that for n-epilayer—0.16 ± 0.08 eV, the spectrometer energy resolution being <0.15 eV. The detailed analysis of the experimental data was carried out in order to clarify the deviation fsrom ideal flat band conditions characteristic for absence of surface cleavage defects. Comparison was done with the well-known literature data on theoretical and experimental investigations of cleavage defects. The experimental results leading to different deviations from ideal flat-band conditions for each cleavage are explained by extrinsic local microscopic defects of cleavage which can appear accidentally and unpredictably, since the system dynamics during cleavage is a highly nonlinear many-body process with many degrees of freedom.     

EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

Rotational states of physisorbed hydrogen on graphite

We present an electron-energy-loss spectroscopy study of molecular hydrogen physisorbed on graphite at T ≃ 10 K. Rotational and rotational-vibrational excitations are observed, with frequencies close to the free rotor gas phase values. Moreover, only para-hydrogen is seen on the surface; it is probable that ortho-para conversion occurs rapidly at paramagnetic surface defects, the conversion rate being sensitive to the surface mobility of the H₂ molecules.     

Adsorption ability comparison of plasma proteins on amorphous carbon surface

To understand why amorphous carbon (a-C:H) film shows antithrombogenicity, an adsorption ability of plasma proteins on a-C:H surface was investigated. Protein adsorption is the initial process of clot formation. The protein adsorption ability on a-C:H film surface was compared by the detection using the surface plasmon resonance (SPR) phenomenon to estimate the protein adsorption. The protein adsorption abilities of a fibrinogen (Fib) and a human γ-globulin (HGG) were estimated by the SPR method using a multilayer structure of a-C:H/Au/Cr/glass. Although the adsorption of HGG for a-C:H was saturated at 32 μM in HGG concentration, the adsorption of Fib was not saturated under the detection limit of this method. These results indicated that the adsorption ability to the a-C:H film surface of Fib was higher than HGG.     

Concepts,instruments, and model systems that enabled the rapid evolution of surface science

Over the past forty years, surface science has evolved to become both an atomic scale and a molecular scale science. Gerhard Ertl’s group has made major contributions in the field of molecular scale surface science, focusing on vacuum studies of adsorption chemistry on single crystal surfaces. In this review, we outline three important aspects which have led to recent advances in surface chemistry: the development of new concepts, in situ instruments for molecular scale surface studies at buried interfaces (solid–gas and solid–liquid), and new model nanoparticle surface systems, in addition to single crystals. Combined molecular beam surface scattering and low energy electron diffraction (LEED)- surface structure studies on metal single crystal surfaces revealed concepts, including adsorbate-induced surface restructuring and the unique activity of defects, atomic steps, and kinks on metal surfaces. We have combined high pressure catalytic reaction studies with ultra high vacuum (UHV) surface characterization techniques using a UHV chamber equipped with a high pressure reaction cell. New instruments, such as high pressure sum frequency generation (SFG) vibrational spectroscopy and scanning tunneling microscopy (STM) which permit molecular-level surface studies have been developed. Tools that access broad ranges of pressures can be used for both the in situ characterization of solid–gas and solid–liquid buried interfaces and the study of catalytic reaction intermediates. The model systems for the study of molecular surface chemistry have evolved from single crystals to nanoparticles in the 1–10 nm size range, which are currently the preferred media in catalytic reaction studies.     

Wetting of Heterogeneous Surfaces at the Mesoscopic Scale

We consider the problem of wetting on a heterogeneous wall with mesoscopic defects: i.e., defects of order L ^ε , 0<ε<1, where L is some typical length-scale of the system. In this framework, we extend several former rigorous results which were shown for walls with microscopic defects.^{(10, 11)} Namely, using statistical techniques applied to a suitably defined semi-infinite Ising-model, we derive a generalization of Young's law for rough and heterogeneous surfaces, which is known as the generalized Cassie–Wenzel's equation. In the homogeneous case, we also show that for a particular geometry of the wall, the model can exhibit a surface phase transition between two regimes which are either governed by Wenzel's or by Cassie's law.     

Noninvasive ultrasound image guided surface wave method for measuring the wave speed and estimating the elasticity of lungs: A feasibility study

Lung diseases, such as acute respiratory distress syndrome (ARDS) and idiopathic pulmonary fibrosis (IPF), are closely associated with altered lung elastic properties. Pulmonary function testing and imaging are routinely performed for evaluating lung diseases. However, lung compliance, a measure of lung elastic properties, is rarely used in clinic, because it is invasive and provides only a global and arguably biased estimate of lung elastic properties. Current ultrasound methods also cannot be used for imaging lungs because ultrasound cannot penetrate the lung tissue. In this paper, an ultrasound image guided and surface wave based method is proposed to measure regional lung surface wave speed and estimate lung elasticity noninvasively. The method described here was not explored before to the best knowledge of the authors. Experiments in an ex vivo pig lung and an in vivo human lung pilot study are reported. The surface wave speed is measured to be 1.83 ± 0.02 m/s at 100 Hz by ultrasound for the ex vivo pig lung at 3 mmHg pressure, which is validated by an optical measurement. An in vivo human lung pilot experiment measures the surface wave speed to be 2.41 ± 0.33 m/s for the 100 Hz sinusoidal wave at total lung capacity (TLC) and 0.99 ± 0.09 m/s at functional residual capacity (FRC). These values of wave speed fall well within the range of available literature.     

Photoemission study of oxygen adsorbed on coldly deposited silver films

UPS spectra of coldly deposited silver films differ from those of films deposited at room temperature by electronic states localized at surface defects with an energy about 4.2 eV below E_F. Changes after exposure at 140 K to oxygen only occur in the presence of these defects, demonstrating that oxygen is only adsorbed at defects. Raman vibrational spectroscopy shows that oxygen is adsorbed nominally as O₂^? and O₂^2?. Possible assignments of the oxygen related UPS structures are discussed.