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Cluster ion beams have revolutionized the analysis of organic surfaces in time-of-flight secondary ion mass spectrometry and opened up new capabilities for organic depth profiling. Much effort has been devoted to understanding the capabilities and improving the performance of [SF.sub.5.sup.+] and [C.sub.60.sup.n+], which are successful for many, but not all, organic materials. Here, we explore the potential of organic depth profiling using novel argon cluster ions, [Ar.sub.500.sup.+] to [Ar.sub.1000.sup.+]. We present results for an organic delta layer reference sample, consisting of ultrathin 'delta' layers of lrganox 3114 (~2.4 nm) embedded between thick layers of Irganox 1010 (~46 or 91 nm). This indicates that, for the reference material, major benefits can be obtained with Ar cluster ions, including a constant high sputtering yield throughout a depth of ~390 nm, and an extremely low sputter-induced roughness of 10.1021/ac901045q

[C.sub.60.sup.n+] ions have been shown to be extremely successful for SIMS depth profiling of a wide range of organic materials, causing significantly less degradation of the molecular information than more traditional primary ions. This work focuses on examining the definition of the interface in a [C.sub.60.sup.n+] SIMS depth profile for an organic overlayer on a wafer substrate. First it investigates the optimum method to define the organic/ inorganic interface position. Variations of up to 8 nm in the interface position can arise from different definitions of the interface position in the samples investigated here. Second, it looks into the reasons behind large interfacial widths, i.e., poor depth resolution, seen in [C.sub.60.sup.n+] depth profiling. This work confirms that, for Irganox 1010 deposited on a wafer, the depth resolution at the Irganox 1010/substrate interface is directly correlated to the roughening of material.

The kinetic mechanism of dimethylglycine oxidase reveals typical flavoprotein 'oxidase' properties in that the formation of a reduced flavin-iminium charge-transfer intermediate in the reductive half-reaction is similar to those mediated by other oxidases. Data indicate that decay of the intermediate is rate-limiting for the enzyme's steady-state reactions.

Two new chlorine structures on the (111) face of silver are reported.

An organic delta-layered sample is constructed from Irganox1010 and Irganox3114 and is used for showing that the sputtering yield is a well behaved function of the [C.sub.60] ion energy and dose. The comparison of the secondary ion mass spectrometry (SIMS) response function with atomic force microscopy (AFM) data has shown that the depth resolution is dominated by the development of roughness.

A novel radio frequency (RF) biasing technique was used to control the energy of positive ions at a depositing substrate, independently of other parameters. Mass spectrometry, an ion flux probe, quartz crystal microbalance and X-ray photoelectron spectroscopy (XPS) were used to investigate plasmas of propionic and acrylic and under bias conditions which gave maximum and minimum ion energies.

Near edge X-ray absorption fine structure (NEXAFS) is employed to provide insight in toy the chemical nature of nitrogen in deposits formed from plasmas of allylamine and propylamine. The findings indicate that there is a substantial level of dehydrogenation during the plasma polymerization process resulting in the formation of imine groups and, at high power, nitrile groups in addition to sp(power 3) hybridized amines.

The contact of nanoparticles with biological fluids such as serum results in rapid adsorption of proteins at the nanoparticle surface in a layer known as the "protein corona". Protein coatings modify and control the behavior of the nanoparticles potentially altering the aggregation state and cellular response, which may influence their fate and hazard to human health. Cells are likely to interact with the protein interface rather than with bare surface; therefore it is important to study the protein layer and develop appropriate measurement tools. In this study we investigate how adsorbed proteins from serum affect the size and the surface charge of plain and aminated silica nanoparticles. Particle size and size distributions in buffer and serum-based biological media were studied using tunable resistive pulse sensing (TRPS), as well as differential centrifugal sedimentation (DCS) and dynamic light scattering (DLS). Average and single particle ζ-potentials (related to surface charge) were also measured by electrophoretic light scattering (ELS) and TRPS, respectively. Size measurements showed an increase in size of the nanoparticles upon acquisition of a protein layer, thus allowing an estimation of its thickness. DLS proved incapable of providing an accurate measurement of the nanoparticles' size in serum due to the presence of agglomerates. The ability of TRPS to measure sample agglomeration was investigated by comparison with the high resolution technique of DCS. Particle-by-particle ζ-potential measurements by TRPS were consistent with those performed with ELS and allowed a description of the ζ-potential distribution within the samples. rightslinkexcluded [ABSTRACT FROM AUTHOR]

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) interlaboratory study on the measurement of composition in organic depth profiling. Layered samples with known binary compositions of Irganox 1010 and either Irganox 1098 or Fmoc-pentafluoro-l-phenylalanine in each layer were manufactured in a single batch and distributed to more than 20 participating laboratories. The samples were analyzed using argon cluster ion sputtering and either X-ray photoelectron spectroscopy (XPS) or time-of-flight secondary ion mass spectrometry (ToF-SIMS) to generate depth profiles. Participants were asked to estimate the volume fractions in two of the layers and were provided with the compositions of all other layers. Participants using XPS provided volume fractions within 0.03 of the nominal values. Participants using ToF-SIMS either made no attempt, or used various methods that gave results ranging in error from 0.02 to over 0.10 in volume fraction, the latter representing a 50% relative error for a nominal volume fraction of 0.2. Error was predominantly caused by inadequacy in the ability to compensate for primary ion intensity variations and the matrix effect in SIMS. Matrix effects in these materials appear to be more pronounced as the number of atoms in both the primary analytical ion and the secondary ion increase. Using the participants' data we show that organic SIMS matrix effects can be measured and are remarkably consistent between instruments. We provide recommendations for identifying and compensating for matrix effects. Finally, we demonstrate, using a simple normalization method, that virtually all ToF-SIMS participants could have obtained estimates of volume fraction that were at least as accurate and consistent as XPS. [ABSTRACT FROM AUTHOR]

The depth profiling of organic materials with argon cluster ion sputtering has recently become widely available with several manufacturers of surface analytical instrumentation producing sources suitable for surface analysis. In this work, we assess the performance of argon cluster sources in an interlaboratory study under the auspices of VAMAS (Versailles Project on Advanced Materials and Standards). The results are compared to a previous study that focused on C60q+ cluster sources using similar reference materials. Four laboratories participated using time-of-flight secondary-ion mass spectrometry for analysis, three of them using argon cluster sputtering sources and one using a C60+ cluster source. The samples used for the study were organic multilayer reference materials consisting of a ~400-nm-thick Irganox 1010 matrix with ~1 nm marker layers of Irganox 3114 at depths of ~50, 100, 200, and 300 nm. In accordance with a previous report, argon cluster sputtering is shown to provide effectively constant sputtering yields through these reference materials. The work additionally demonstrates that molecular secondary ions may be used to monitor the depth profile and depth resolutions approaching a full width at half maximum (fwhm) of 5 nm can be achieved. The participants employed energies of 2.5 and 5 keV for the argon clusters, and both the sputtering yields and depth resolutions are similar to those extrapolated from C60+ cluster sputtering data. In contrast to C60+ cluster sputtering, however, a negligible variation in sputtering yield with depth was observed and the repeatability of the sputtering yields obtained by two participants was better than 1%. We observe that, with argon cluster sputtering, the position of the marker layers may change by up to 3 nm, depending on which secondary ion is used to monitor the material in these layers, which is an effect not previously visible with C60+ cluster sputtering. We also note that electron irradiation, used for charge compensation, can induce molecular damage to areas of the reference samples well beyond the analyzed region that significantly affects molecular secondary-ion intensities in the initial stages of a depth profile in these materials. [ABSTRACT FROM AUTHOR]

Protein adsorption at solid surfaces is central to many phenomena of medical and technological interest. The determination of the amount of protein attached to the surface is a critical measurement performed by using a wide range of methods. X-ray photoelectron spectroscopy (XPS) is able to provide a straightforward quantitative analysis of the amount of protein adsorbed as an overlayer on a material surface. While XPS is commonly employed to assess qualitatively the amount of adsorbed protein, this is usually expressed in terms of the elemental fraction (or at. %) of nitrogen calculated using an assumption of depth homogeneity despite the fact that this does not linearly scale with the amount of protein. In this paper, we have shown that thicknesses derived from XPS data linearly correlated with spectroscopic ellipsometry data on the same samples with a scatter of 10%. A straightforward equation to convert the concentration of nitrogen from XPS into an equivalent thickness of a protein film is presented. We highlight some discrepancies in the absolute thicknesses determined by XPS and ellipsometry on dried films and quartz crystal microbalance on wet films, which appear likely to result from the inclusion of a contribution from water in the latter two techniques. [ABSTRACT FROM AUTHOR]

C60n+ ions have been shown to be extremely successful for SIMS depth profiling of a wide range of organic materials, causing significantly less degradation of the molecular information than more traditional primary ions. This work focuses on examining the definition of the interface in a C60n+ SIMS depth profile for an organic overlayer on a wafer substrate. First it investigates the optimum method to define the organic/inorganic interface position. Variations of up to 8 nm in the interface position can arise from different definitions of the interface position in the samples investigated here. Second, it looks into the reasons behind large interfacial widths, i.e., poor depth resolution, seen in C60n+ depth profiling. This work confirms that, for Irganox 1010 deposited on a wafer, the depth resolution at the Irganox 1010/substrate interface is directly correlated to the roughening of material. [ABSTRACT FROM AUTHOR]

C60n+ ions have been shown to be extremely successful for SIMS depth profiling of a wide range of organic materials, causing significantly less degradation of the molecular information than more traditional primary ions. This work focuses on examining the definition of the interface in a C60n+ SIMS depth profile for an organic overlayer on a wafer substrate. First it investigates the optimum method to define the organic inorganic interface position. Variations of up to 8 nm in the interface position can arise from different definitions of the interface position in the samples investigated here. Second, it looks into the reasons behind large interfacial widths, i.e., poor depth resolution, seen in C60n+ depth profiling. This work confirms that, for Irganox 1010 deposited on a wafer, the depth resolution at the Irganox 1010/substrate interface is directly correlated to the roughening of material. [ABSTRACT FROM AUTHOR]

Alternating layers of two different organic materials, Irganox1010 and Irganox3114, have been created using vapor deposition. The layers of Irganox3114 were very thin (∼2.5 nm) in comparison to the layers of Irganox1010 (∼55 or ∼90 nm) to create an organic equivalent of the inorganic ‘delta-layers' commonly employed as reference materials in dynamic secondary ion mass spectrometry. Both materials have identical sputtering yields, and we show that organic delta layers may be used to determine some of the important metrological parameters for cluster ion beam depth profiling. We demonstrate, using a C60ion source, that the sputtering yield, S, diminishes with ion dose and that the depth resolution also degrades. By comparison with atomic force microscopy data for films of pure Irganox1010, we show that the degradation in depth resolution is caused by the development of topography. Secondary ion intensities are a well-behaved function of sputtering yield and may be employed to obtain useful analytical information. Fragments characteristic of highly damaged material have intensity proportional to S, and those fragments with minimal molecular rearrangment exhibit intensities proportional to S2. We demonstrate quantitative analysis of the amount of substance in buried layers of a few nanometer thickness with an accuracy of ∼10%. Organic delta layers are valuable reference materials for comparing the capabilities of different cluster ion sources and experimental arrangements for the depth profiling of organic materials. [ABSTRACT FROM AUTHOR]

Electron flood guns used for charge compensation in secondary ion mass spectrometry (SIMS) cause chemical degradation. In this study, the effect of electron flood gun damage on argon cluster depth profiling is evaluated for poly(vinylcarbazole), 1,4-bis((1-naphthylphenyl)amino)biphenyl and Irganox 3114. Thin films of these three materials are irradiated with a range of doses from a focused beam of 20 eV electrons used for charge neutralization. SIMS chemical images of the irradiated surfaces show an ellipsoidal damaged area, approximately 3 mm in length, created by the electron beam. In depth profiles obtained with 5 keV Ar sputtering from the vicinity of the damaged area, the characteristic ion signal intensity rises from a low level to a steady state. For the damaged thin films, the ion dose required to sputter through the thin film to the substrate is higher than for undamaged areas. It is shown that a damaged layer is formed and this has a sputtering yield that is reduced by up to an order of magnitude and that the thickness of the damaged layer, which increases with the electron dose, can be as much as 20 nm for Irganox 3114. The study emphasizes the importance of minimizing the neutralizing electron dose prior to the analysis. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is a debilitating disorder characterized by age-related dementia, which has no effective treatment to date. β-Amyloid depositions and hyperphosphorylated tau proteins are the main pathological hallmarks, along with oxidative stress, N -methyl-d-aspartate (NMDA) receptor-mediated excitotoxicity, and low levels of acetylcholine. Current pharmacotherapy for AD only provides symptomatic relief and limited improvement in cognitive functions. Many molecules have been explored that show promising outcomes in AD therapy and can regulate cellular survival through different pathways. To have a vivid approach to strategize the treatment regimen, AD physiopathology should be better explained considering diverse etiological factors in conjunction with biochemical disturbances. This Review attempts to discuss different disease modification approaches and address the novel therapeutic targets of AD that might pave the way for new drug discovery using the well-defined targets for therapy of the disease., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

We assessed two approaches for determining shell thicknesses of core-shell nanoparticles (NPs) by X-ray photoelectron spectroscopy (XPS). These assessments were based on simulations of photoelectron peak intensities for Au-core/C-shell, C-core/Au-shell, Cu-core/Al-shell, and Al-core/Cu-shell NPs with a wide range of core diameters and shell thicknesses. First, we demonstrated the validity of an empirical equation developed by Shard for determinations of shell thicknesses. Values of shell thicknesses from the Shard equation typically agreed with actual shell thicknesses to better than 10 %. Second, we investigated the magnitudes of elastic-scattering effects on photoelectron peak intensities by performing a similar series of simulations with elastic scattering switched off in our simulation software. Our ratios of the C-shell 1s intensity to the Au-core 4f 7/2 intensity with elastic scattering switched off were qualitatively similar to those obtained by Torelli et al. from a model that neglected elastic scattering. With elastic scattering switched on, the C 1s/Au 4f 7/2 intensity ratios generally changed by less than 10 %, thereby justifying the neglect of elastic scattering in XPS models that are applied to organic ligands on Au-core NPs. Nevertheless, elastic-scattering effects on peak-intensity ratios were generally much stronger for C-core/Au-shell, Al-core/Cu-shell, and Cu-core/Al-shell NPs, and there were second-order dependences on core diameter and shell thickness., Competing Interests: Notes The authors declare no competing financial interest.

We evaluated two methods for determining shell thicknesses of core-shell nanoparticles (NPs) by X-ray photoelectron spectroscopy (XPS). One of these methods had been developed for determining thicknesses of films on a planar substrate while the other was developed specifically for NPs. Our evaluations were based on simulated Cu 2p 3/2 spectra from Cu-core/Cu-shell NPs with a wide range of core diameters and shell thicknesses. Copper was chosen for our tests because elastic-scattering effects for Cu 2p 3/2 photoelectrons excited by Al Kα X-rays are known to be strong. Elastic scattering could also be switched off in our simulations so that the two methods could be evaluated in the limit of no elastic scattering. We found that the first method, based on both core and shell photoelectron intensities, was unsatisfactory for all conditions. The second method, based on an empirical equation for NPs developed by Shard, also utilized both core and shell photoelectron intensities and was found to be satisfactory for all conditions. The average deviation between shell thicknesses derived from the Shard equation and the true values was -4.1 % when elastic scattering was switched on and -2.2 % when elastic scattering was switched off. If elastic scattering was switched on, the effective attenuation length for a Cu film on a planar substrate was the appropriate length parameter while the inelastic mean free path was the appropriate parameter when elastic scattering was switched off.

The sputtering yield volumes of binary mixtures of Irganox 1010 with either Irganox 1098 or Fmoc-pentafluoro-L-phenylalanine (FMOC) have been measured for 5 keV Ar2000(+) ions incident at 45° to the surface normal. The sputtering yields are determined from the doses to sputter through various compositions of 100 nm thick, intimately mixed, layers. Because of matrix effects, the profiles for secondary ions are distorted, and profile shifts in depth of 15 nm are observed leading to errors above 20% in the deduced sputtering yield. Secondary ions are selected to avoid this. The sputtering yield volumes for the mixtures are shown to be lower than those deduced from a linear interpolation from the pure materials. This is shown to be consistent with a simple model involving the changing energy absorbed for the sputtering of intimate mixtures. Evidence to support this comes from the secondary ion data for pairs of the different molecules. Both binary mixtures behave similarly, but matrix effects are stronger for the Irganox 1010/FMOC system.

The functionality of a new version of the National Institute of Standards and Technology database Simulation of Electron Spectra for Surface Analysis (SESSA) has been extended by implementing a new geometry engine. The engine enables users to simulate Auger-electron spectra and X-ray photoelectron spectra for different predefined morphologies (planar, islands, spheres, multi-layer core-shell particles). We compared shell thicknesses of core-shell nanoparticles derived from core-shell XPS peak intensities using Shard's method, which allows one to estimate shell thicknesses of core-shell nanoparticles, and a series of SESSA simulations for a wide range of nanoparticle dimensions. We obtained very good agreement of the shell thicknesses for cases where elastic scattering within the shell can be neglected, a result that is in accordance with the underlying assumptions of the Shard model. If elastic-scattering effects are important, there can be thickness uncertainties of up to 25 %. Experimental spectra of functionalized gold nanoparticles obtained by Techane et al . were analyzed with SESSA 2.0 both with respect to the relevant peak intensities as well as the spectral shape. Good agreement between experiment and theory was found for both cases. These results show that the single-sphere model for core-shell nanoparticles is valid when just using peak intensities, but more detailed modeling is needed to describe the inelastic background.

The first angle-dependent measurements of the sputtering yield of an organic material using argon gas cluster ions under a wide range of conditions are reported in order to develop an analytical description of the behavior important for the development of the application of secondary ion mass spectrometry to organic and biological systems. Data are presented for Irganox 1010 using argon gas cluster ion beams of 5 and 10 keV energy, E, with cluster sizes, n, from 1000 to 5000. The measurements are conducted in an X-ray photoelectron spectrometer for a range of angles from 0 to 80° from the surface normal. The results support the Universal Equation for argon gas cluster sputtering yields with the angle dependence incorporated into the equation via a simple angle dependence of the parameter A. This explains how and why the angular dependence of the sputtering yield changes significantly with increasing E/n. These results are also accurately confirmed using the published measurements for polystyrene by Rading et al.

Novel stilbene-chalcone (S-C) hybrids were synthesized via a sequential Claisen-Schmidt-Knoevenagel-Heck approach and evaluated for antiplasmodial activity in in vitro red cell culture using SYBR Green I assay. The most potent hybrid (11) showed IC(50) of 2.2, 1.4, and 6.4 μM against 3D7 (chloroquine sensitive), Indo, and Dd2 (chloroquine resistant) strains of Plasmodium falciparum, respectively. Interestingly, the respective individual stilbene (IC(50) > 100 μM), chalcone (IC(50) = 11.5 μM), or an equimolar mixture of stilbene and chalcone (IC(50) = 32.5 μM) were less potent than 11. Studies done using specific stage enriched cultures and parasite in continuous culture indicate that 11 and 18 spare the schizont but block the progression of the parasite life cycle at the ring or the trophozoite stages. Further, 11 and 18 caused chromatin condensation, DNA fragmentation, and loss of mitochondrial membrane potential in Plasmodium falciparum, thereby suggesting their ability to cause apoptosis in malaria parasite.