Molecular Dynamics Simulations of Soft and Reactive Landing of Proteins Desorbed by Argon Cluster Bombardment.

Reactive molecular dynamics (MD) simulations were conducted to investigate the soft and reactive landing of hyperthermal velocity proteins transferred to a vacuum using large argon clusters. Experimentally, the interaction of argon cluster ion beams (Ar) with a target biofilm was previously used in such a manner to transfer lysozymes onto a collector with the retention of their bioactivity, paving the way to a new solvent-free method for complex biosurface nanofabrication. However, the experiments did not give access to a microscopic view of the interactions needed for their full understanding, which can be provided by the MD model.

Gas Cluster Ion Beam-Assisted Deposition for Fabricating Dry Multilayers Containing Enzyme and Substrate with On-Demand Release.

Gas cluster ion beam (GCIB)-assisted deposition is used to build multilayered protein-based structures. In this process, Ar clusters bombard and sputter molecules from a reservoir (target) to a collector, an operation that can be sequentially repeated with multiple targets. The process occurs under a vacuum, making it adequate for further sample conservation in the dry state, since many proteins do not have long-term storage stability in the aqueous state.

Unraveling the Molecular Dynamics of Glucose Oxidase Desorption Induced by Argon Cluster Collision.

The bombardment of a protein multilayer target by an energetic argon cluster ion beam enables protein transfer onto a collector in the vacuum while preserving their bioactivity (iBEAM method). In parallel to this new soft-landing variant, protein transfer in the gas phase is a prerequisite for their characterization by mass spectrometry. The successful transfer of bioactive lysozymes (14 kDa) by cluster-induced soft landing and its mechanistic explanation by molecular dynamics (MD) simulations have sparked an important inquiry: Can heavier biomolecules be desorbed while maintaining their tridimensional structure and hence their bioactivity? To address this question, we employed MD simulations using a reactive force field (ReaxFF).

Improvement of Lipid Detection in Mouse Brain and Human Uterine Tissue Sections Using In Situ Matrix Enhanced Secondary Ion Mass Spectrometry.

The potential of mass spectrometry imaging, and especially ToF-SIMS 2D and 3D imaging, for submicrometer-scale, label-free molecular localization in biological tissues is undisputable. Nevertheless, sensitivity issues remain, especially when one wants to achieve the best lateral and vertical (nanometer-scale) resolution. In this study, the interest of in situ matrix transfer for tissue analysis with cluster ion beams (Bi, Ar) is explored in detail, using a series of six low molecular weight acidic (MALDI) matrices.

Enhancing Ion Signals and Improving Matrix Selection in Time-of-Flight Secondary Ion Mass Spectrometry with Microvolume Expansion Using Large Argon Clusters.

The molecular environment has an important impact on the ionization mechanism in time-of-flight secondary ion mass spectrometry (ToF-SIMS). In complex samples, desorption/ionization, and thus the detection of a molecular signal, can be hampered by molecular entanglement, ionization-suppressive neighbors, or even an unfavorable sample substrate. Here, a method called microvolume expansion is developed to overcome these negative effects.

Topochemical Design of Cellulose-Based Carriers for Immobilization of Endoxylanase.

Xylooligosaccharides (XOSs) gained much attention for their use in food and animal feed, attributed to their prebiotic function. These short-chained carbohydrates can be enzymatically produced from xylan, one of the most prevalent forms of hemicellulose. In this work, endo-1,4-β-xylanase from was immobilized on cellulose-based beads with the goal of producing xylooligosaccharides with degrees of polymerization (DPs) in the range of 4-6 monomeric units.

Gas Cluster Ion Beams as a Versatile Soft-Landing Tool for the Controlled Construction of Thin (Bio)Films.

Surface biofunctionalization with proteins is the key to many biomedical applications. In this study, a solvent-free method for the controlled construction of protein thin films is reported. Using large argon gas cluster ion beams, proteins are sputtered from a target (a pool of pure proteins), and collected on a chosen substrate, being nearly any solid material.

Green Synthesis of Iron-Doped Cobalt Oxide Nanoparticles from Palm Kernel Oil via Co-Precipitation and Structural Characterization.

In this study, a bio-derived precipitating agent/ligand, palm kernel oil, has been used as an alternative route for the green synthesis of nanoparticles of Fe-doped CoO via the co-precipitation reaction. The palm oil was extracted from dried palm kernel seeds by crushing, squeezing and filtration. The reaction of the palm kernel oil with potassium hydroxide, under reflux, yielded a solution containing a mixture of potassium carboxylate and excess hydroxide ions, irrespective of the length of saponification.

Investigating the relationship between the mechanical properties of plasma polymer-like thin films and their glass transition temperature.

This work aims at understanding the influence of the substrate temperature () on the viscoelastic properties of propanethiol plasma polymer films (PPFs). By means of state-of-the-art AFM characterization-based techniques including peak force quantitative nanomechanical mapping (PFQNM), nano dynamic mechanical analysis (nDMA) and "scratch" experiments, it has been demonstrated that the mechanical behaviour of PPFs is dramatically affected by the thermal conditions of the substrate. Indeed, the material behaves from a high viscous liquid ( viscosity ∼ 10 Pa s) to a viscoelastic solid (loss modulus ∼ 1.

Improvement of biomolecular analysis in thin films using matrix enhanced secondary ion mass spectrometry.

Sensitivity to molecular ions remains a limiting factor for high resolution imaging mass spectrometry of organic and biological materials. Here, we investigate a variant of matrix-enhanced secondary ion mass spectrometry in which the transfer of matrix molecules to the analyte sample is carried out ( ME-SIMS). This approach is therefore compatible with both 2D and 3D imaging by SIMS.

Deposition of Intact and Active Proteins In Vacuo Using Large Argon Cluster Ion Beams.

Providing inert materials with a biochemical function, for example using proteins, is a cornerstone technology underlying many applications. However, the controlled construction of protein thin films remains a major challenge. Here, an innovative solvent-free approach for protein deposition is reported, using lysozyme as a model.

Large cluster ions: soft local probes and tools for organic and bio surfaces.

Ionised cluster beams have been produced and employed for thin film deposition and surface processing for half a century. In the last two decades, kiloelectronvolt cluster ions have also proved to be outstanding for surface characterisation by secondary ion mass spectrometry (SIMS), because their sputter and ion yields are enhanced in a non-linear fashion with respect to monoatomic projectiles, with a resulting step change of sensitivity for analysis and imaging. In particular, large gas cluster ion beams, or GCIB, have now become a reference in organic surface and thin film analysis using SIMS and X-ray photoelectron spectroscopy (XPS).

Highly Efficient Wideband Microwave Absorbers Based on Zero-Valent Fe@-FeO and Fe/Co/Ni Carbon-Protected Alloy Nanoparticles Supported on Reduced Graphene Oxide.

Electronic systems and telecommunication devices based on low-power microwaves, ranging from 2 to 40 GHz, have massively developed in the last decades. Their extensive use has contributed to the emergence of diverse electromagnetic interference (EMI) phenomena. Consequently, EMI shielding has become a ubiquitous necessity and, in certain countries, a legal requirement.

Atmospheric Pressure Plasma Deposition of Hydrophilic/Phobic Patterns and Thin Film Laminates on Any Surface.

Patterned and layered hydrophilic/phobic coatings were deposited on multiple surfaces using nonfluorinated precursors (AA, acrylic acid; PMA, propargyl methacrylate) with an atmospheric pressure dielectric barrier discharge operating in open air. Water contact angles of the resulting films could be tuned from <5° (superhydrophilic) to >135° (very hydrophobic) by adjusting the AA/PMA feed ratio and/or via postdeposition exposure of films to an Ar/O plasma treatment. Coatings could be applied to any surface and were seen to be water stable, due in large part to cross-linking induced from the reactivity of the PMA pendant groups.

N-Doped TiO Photocatalyst Coatings Synthesized by a Cold Atmospheric Plasma.

This work presents a simple, fast (20 min treatment), inexpensive, and highly efficient method for synthesizing nitrogen-doped titanium dioxide (N-TiO) as an enhanced visible light photocatalyst. In this study, N-TiO coatings were fabricated by atmospheric pressure dielectric barrier discharge (DBD) at room temperature. The composition and the chemical bonds of the TiO and N-TiO coatings were characterized by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS).

Mixed Polymer Brushes for the Selective Capture and Release of Proteins.

Selective protein adsorption is a key challenge for the development of biosensors, separation technologies, and smart materials for medicine and biotechnologies. In this work, a strategy was developed for selective protein adsorption, based on the use of mixed polymer brushes composed of poly(ethylene oxide) (PEO), a protein-repellent polymer, and poly(acrylic acid) (PAA), a weak polyacid whose conformation changes according to the pH and ionic strength of the surrounding medium. A mixture of lysozyme (Lyz), human serum albumin (HSA), and human fibrinogen (Fb) was used to demonstrate the success of this strategy.

Structural characterization and magnetic properties of undoped and copper-doped cobalt ferrite nanoparticles prepared by the octanoate coprecipitation route at very low dopant concentrations.

Nanoparticles of undoped and copper-doped cobalt ferrite Co Cu FeO at very low dopant concentrations ( = 0; 0.02; 0.04; 0.

Temperature Dependence of Ar Cluster Backscattering from Polymer Surfaces: a New Method to Determine the Surface Glass Transition Temperature.

In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to study the intensity variations of the backscattered Ar clusters as a function of temperature for several amorphous polymer surfaces (polyolefins, polystyrene, and polymethyl methacrylate). For all these investigated polymers, our results show a transition of the ratio Ar/(Ar + Ar) when the temperature is scanned from -120 °C to +125 °C (the exact limits depend on the studied polymer). This transition generally spans over a few tens of degrees and the temperature of the inflection point of each curve is always lower than the bulk glass transition temperature (T) reported for the considered polymer.

Ejection-ionization of molecules from free standing graphene.

We present the first data on emission of C60- stimulated by single impacts of 50 keV C602+ on the self-assembled molecular layer of C deposited on free standing 2 layer graphene. The yield, Y, of C60- emitted in the transmission direction is 1.7%.

Single impacts of keV fullerene ions on free standing graphene: Emission of ions and electrons from confined volume.

We present the first data from individual C60 impacting one to four layer graphene at 25 and 50 keV. Negative secondary ions and electrons emitted in transmission were recorded separately from each impact. The yields for C(n)(-) clusters are above 10% for n ≤ 4, they oscillate with electron affinities and decrease exponentially with n.

Heterometal nanoparticles from Ru-based molecular clusters covalently anchored onto functionalized carbon nanotubes and nanofibers.

Heterometal clusters containing Ru and Au, Co and/or Pt are anchored onto carbon nanotubes and nanofibers functionalized with chelating phosphine groups. The cluster anchoring yield is related to the amount of phosphine groups available on the nanocarbon surface. The ligands of the anchored molecular species are then removed by gentle thermal treatment in order to form nanoparticles.

Comparison of fullerene and large argon clusters for the molecular depth profiling of amino acid multilayers.

A major challenge regarding the characterization of multilayer films is to perform high-resolution molecular depth profiling of, in particular, organic materials. This experimental work compares the performance of C60(+) and Ar1700(+) for the depth profiling of model multilayer organic films. In particular, the conditions under which the original interface widths (depth resolution) were preserved were investigated as a function of the sputtering energy.

Molecular depth profiling of organic photovoltaic heterojunction layers by ToF-SIMS: comparative evaluation of three sputtering beams.

With the recent developments in secondary ion mass spectrometry (SIMS), it is now possible to obtain molecular depth profiles and 3D molecular images of organic thin films, i.e. SIMS depth profiles where the molecular information of the mass spectrum is retained through the sputtering of the sample.

Computer simulations of cluster impacts: effects of the atomic masses of the projectile and target.

Cluster secondary ion mass spectrometry is now widely used for the characterization of nanostructures. In order to gain a better understanding of the physics of keV cluster bombardment of surfaces and nanoparticles (NPs), the effects of the atomic masses of the projectile and of the target on the energy deposition and induced sputtering have been studied by means of molecular dynamics simulations. 10 keV C60 was used as a model projectile and impacts on both a flat polymer surface and a metal NP were analyzed.

Improving secondary ion mass spectrometry C60(n+) sputter depth profiling of challenging polymers with nitric oxide gas dosing.

Organic depth profiling using secondary ion mass spectrometry (SIMS) provides valuable information about the three-dimensional distribution of organic molecules. However, for a range of materials, commonly used cluster ion beams such as C60(n+) do not yield useful depth profiles. A promising solution to this problem is offered by the use of nitric oxide (NO) gas dosing during sputtering to reduce molecular cross-linking.