A SIFT Study of Reactions of Positive and Negative Ions With Polyfluoroalkyl (PFAS) Molecules in Dry and Humid Nitrogen at 393 K.

Rationale: Data are required for SIFT-MS analysis of perfluoroalkyl and polyfluoroalkyl substances (PFAS), which are persistent in the environment and cause adverse health effects. Specifically, the rate coefficients and product ion branching ratios of the reactions of HO, NO, O •, O•, OH, O •, NO and NO with PFAS vapours are needed.

Methods: The dual polarity SIFT-MS instrument (Voice200) was used to generate these eight reagent ions and inject them into the flow tube with N carrier gas at a temperature of 393 K.

Enamel surface roughness after orthodontic adhesive removal: an in vitro study comparing four clearance methods.

Purpose: Adhesive remnants removal is the last key step influencing orthodontic treatment outcomes. Four different clearance methods (CM) of orthodontic adhesive were evaluated to determine, which achieved the smoothest enamel surface in the shortest time.

Materials And Methods: 75 intact premolars extracted for orthodontic purposes were included, sixty had an orthodontic bracket bonded and subsequently removed, and fifteen served as the control group.

Radiation and DNA Origami Nanotechnology: Probing Structural Integrity at the Nanoscale.

DNA nanotechnology has emerged as a groundbreaking field, using DNA as a scaffold to create nanostructures with customizable properties. These DNA nanostructures hold potential across various domains, from biomedicine to studying ionizing radiation-matter interactions at the nanoscale. This review explores how the various types of radiation, covering a spectrum from electrons and photons at sub-excitation energies to ion beams with high-linear energy transfer influence the structural integrity of DNA origami nanostructures.

Selected ion flow tube studies of the reactions of HO, NO, O˙ and O˙ ions with alkanes in He and N carrier gases at different temperatures.

The kinetics of the reactions of HO, NO, O˙ and O˙ with -hexane, 3-methylpentane, 2,5-dimethylhexane and 2,3-dimethylheptane were studied experimentally under several selected ion flow tube (SIFT) conditions: in a Profile 3 instrument in He and N carrier gases at 300 K and in the Voice200 instrument in N carrier gas at 300 and 393 K - where the effect of the extraction lens voltage was also assessed. It was found that HO ions react differently than expected, with reaction rates slower than collisional. Instead of transferring a proton, they associate and form fragment product ions [M-H].

In(III) pyridinecarboxylate complexes: Composition, solution equilibria estimation, bioevaluation and interactions with HSA.

Two In(III) - pyridinecarboxylates ([In(Pic)(NO)(HO)] (InPic; HPic = picolinic acid), [In(HDpic)(Dpic)(HO)]·5HO (InDpic; HDpic = dipicolinic acid), have been synthesized by one-step procedure. The complexes composition was confirmed by physicochemical analyses and X-ray diffraction confirmed molecular structure of both complexes. Moreover, complex species speciation was described in both systems by potentiometry and H NMR spectroscopy and mononuclear complex species were determined; [In(Pic)] (logβ = 6.

Plasmon-driven chemical transformation of a secondary amide probed by surface enhanced Raman scattering.

Plasmon-driven chemical conversion is gaining burgeoning interest in the field of heterogeneous catalysis. Herein, we study the reactivity of N-methyl-4-sulfanylbenzamide (NMSB) at nanocavities of gold and silver nanoparticle aggregates under plasmonic excitation to gain understanding of the respective reaction mechanism. NMSB is a secondary amide, which is a frequent binding motive found in peptides and a common coupling product of organic molecules and biomolecules.

Addressing Individual Layers and Their Optical Properties in Artificial MoS Bilayers via Sulfur Isotope Labeling.

The physicochemical properties of van der Waals (vdW) heterostructures are driven by the delicate interactions between the individual layers in a multilayer stack. While addressing the monolayers of different compositions in the multilayer is feasible, exploring the intrinsic properties of the monolayers of the same composition within a multilayer is extremely challenging. This becomes of utmost importance in energy conversion and storage concepts based on layered vdW materials.

Watching a Single Enzyme at Work Using Single-Molecule Surface-Enhanced Raman Scattering and DNA Origami-Based Plasmonic Antennas.

The detection of a single-enzyme catalytic reaction by surfaced-enhanced Raman scattering (SERS) is presented by utilizing DNA origami-based plasmonic antennas. A single horseradish peroxidase (HRP) was accommodated on a DNA origami nanofork plasmonic antenna (DONA) containing gold nanoparticles, enabling the tracing of single-molecule SERS signals during the peroxide reduction reaction. This allows monitoring of the structure of a single enzymatic catalytic center and products under suitable liquid conditions.

Influence of proline and hydroxyproline as antimicrobial and anticancer peptide components on the silver(I) ion activity: structural and biological evaluation with a new theoretical and experimental SAR approach.

Silver(I) complexes with proline and hydroxyproline were synthesized and structurally characterized and crystal structure analysis shows that the formulas of the compounds are {[Ag(Pro)(NO)]NO} (AgPro) (Pro = L-proline) and {[Ag(Hyp)(NO)]NO} (AgHyp) (Hyp = -4-hydroxy-L-proline). Both complexes crystallize in the monoclinic lattice with space group 2 with a carboxylate bidentate-bridging coordination mode of the organic ligands Pro and Hyp (with NH and COO groups in zwitterionic form). Both complexes have a distorted seesaw (C) geometry around one silver(I) ion with values of 58% (AgPro) and 51% (AgHyp).

Ion beam processing of DNA origami nanostructures.

DNA origami nanostructures are emerging as a bottom-up nanopatterning approach. Direct combination of this approach with top-down nanotechnology, such as ion beams, has not been considered because of the soft nature of the DNA material. Here we demonstrate that the shape of 2D DNA origami nanostructures deposited on Si substrates is well preserved upon irradiation by ion beams, modeling ion implantation, lithography, and sputtering conditions.

Accurate selected ion flow tube mass spectrometry quantification of ethylene oxide contamination in the presence of acetaldehyde.

In September 2020, traces of ethylene oxide (a toxic substance used as a pesticide in developing countries but banned for use on food items within the European Union) were found in foodstuffs containing ingredients derived from imported sesame seed products. Vast numbers of foodstuffs were recalled across Europe due to this contamination, leading to expensive market losses and extensive trace exposure of ethylene oxide to consumers. Therefore, a rapid analysis method is needed to ensure food safety by high-throughput screening for ethylene oxide contamination.

Modulation of Anionic Lipid Bilayers by Specific Interplay of Protons and Calcium Ions.

Biomembranes, important building blocks of living organisms, are often exposed to large local fluctuations of pH and ionic strength. To capture changes in the membrane organization under such harsh conditions, we investigated the mobility and hydration of zwitterionic and anionic lipid bilayers upon elevated HO and Ca content by the time-dependent fluorescence shift (TDFS) technique. While the zwitterionic bilayers remain inert to lower pH and increased calcium concentrations, anionic membranes are responsive.

Composite TiO-based photocatalyst with enhanced performance.

TiO is the most studied photocatalyst because of its non-toxicity, chemical stability, and low cost. However, the problem of TiO is its low activity in the visible region of the spectrum. In this study, we focused on the preparation of composite photocatalytic materials with altered light absorption properties.

Comparison of mononuclear and dinuclear copper(II) biomimetic complexes: spectroelectrochemical mechanistic study of their catalytic pathways.

Two catecholase-like biomimetic catalysts, namely, two dinuclear copper complexes [Cu(L1)(OH)(HO)(EtOH)][ClO] (C1) and [CuAcO(L1)ClO] (C2) with the 2,6-bis(4-methyl piperazin-1-yl-methyl)-4-formyl-phenoxy ligand (L1) together with the mononuclear complex Cu(ClO)(L2) (C3) containing ligand 1,2-(CHN-6-OCH-2-CHN)CHCH (L2), were synthesized. Their catalytic pathways were investigated and compared. The evaluation of the catalytic activity of compound C1 (and C2, C3) using the Michaelis-Menten model was represented by values of = 272.

What Does Time-Dependent Fluorescence Shift (TDFS) in Biomembranes (and Proteins) Report on?

The organization of biomolecules and bioassemblies is highly governed by the nature and extent of their interactions with water. These interactions are of high intricacy and a broad range of methods based on various principles have been introduced to characterize them. As these methods view the hydration phenomena differently (e.

Removal of Ampicillin by Heterogeneous Photocatalysis: Combined Experimental and DFT Study.

A long-term exposition of antibiotics represents a serious problem for the environment, especially for human health. Heterogeneous photocatalysis opens a green way for their removal. Here, we correlated the structural-textural properties of TiO photocatalysts with their photocatalytic performance in ampicillin abatement.

Folding DNA into origami nanostructures enhances resistance to ionizing radiation.

We report experimental results on damage induced by ionizing radiation to DNA origami triangles which are commonly used prototypes for scaffolded DNA origami nanostructures. We demonstrate extreme stability of DNA origami upon irradiation, which is caused by (i) the multi-row design holding the shape of the origami even after severe damage to the scaffold DNA and (ii) the reduction of damage to the scaffold DNA due to the protective effect of the folded structure. With respect to damage induced by ionizing radiation, the protective effect of the structure is superior to that of a naturally paired DNA double helix.

Gold(I) and Silver(I) π-Complexes with Unsaturated Hydrocarbons.

Gold π-complexes have been studied largely in the past 2 decades because of their role in gold-catalyzed reactions. We report an experimental and theoretical investigation of the interaction between a wide range of unsaturated hydrocarbons (alkanes, alkynes, alkadienes, and allenes) and triphenylphosphine-gold(I), triphenylphosphine-silver(I), and acetonitrile-silver(I) cations. The bond dissociation energies of these complexes were determined by mass spectrometry collision-induced dissociations and their structures were studied by density functional theory calculations and infrared photodissociation spectroscopy.

Dioxygen splitting at room temperature over distant binuclear transition metal centers in zeolites for direct oxidation of methane to methanol.

Here we demonstrate for the first time the splitting of dioxygen at RT over distant binuclear transition metal (M = Ni, Mn, and Co) centers stabilized in ferrierite zeolite. Cleaved dioxygen directly oxidized methane to methanol, which can be released without the aid of an effluent to the gas phase at RT.

Ion chemistry of phthalates in selected ion flow tube mass spectrometry: isomeric effects and secondary reactions with water vapour.

Phthalates are widely industrially used and their toxicity is of serious environmental and public health concern. Chemical ionization (CI) analytical techniques offer the potential to detect and monitor traces of phthalate vapours in air or sample headspace in real time. Promising techniques include selected ion flow tube mass spectrometry (SIFT-MS), proton transfer reaction mass spectrometry (PTR-MS) and ion mobility spectrometry (IMS).

Chemical ionization of glyoxal and formaldehyde with HO ions using SIFT-MS under variable system humidity.

Glyoxal (C2H2O2) is a highly reactive molecule present at trace levels in specific gaseous environments. For analyses by chemical ionization mass spectrometry, it is important to understand the gas-phase chemistry initiated by reactions of H3O+ ions with C2H2O2 molecules in the presence of water vapour. This chemistry was studied at variable humidity using a selected ion flow tube, SIFT.

The proximity of aluminium atoms influences the reaction pathway of ethanol transformation over zeolite ZSM-5.

The organization of aluminium atoms in zeolites affects their catalytic properties. Here we demonstrate that the aluminium distribution is a key parameter controlling the reaction pathway of acid catalysed reactions over ZSM-5 zeolites. We study ethanol transformation over two ZSM-5 samples with similar Si/Al ratios of ~15, and with aluminium atoms located mainly at the channel intersections but differently distributed in the framework.

Solvation of Silver Ions in Noble Gases He, Ne, Ar, Kr, and Xe.

We use a novel technique to solvate silver cations in small clusters of noble gases. The technique involves the formation of large, superfluid helium nanodroplets that are subsequently electron ionized, mass-selected by deflection in an electric field, and doped with silver atoms and noble gases (Ng) in pickup cells. Excess helium is then stripped from the doped nanodroplets by multiple collisions with helium gas at room temperature, producing cluster ions that contain no more than a few dozen noble gas atoms and just a few (or no) silver atoms.

Strong and efficient doping of monolayer MoS by a graphene electrode.

The efficient manipulation of the optoelectronic properties of layered semiconductors is essential for future applications of these unique materials. Here, we demonstrate that single-layer, large-area graphene can serve as a conductive spacer between an electrolyte solution and single-layer MoS2. In situ Raman and photoluminescence (PL) spectroscopies were employed to monitor the charge transfer from graphene to MoS2.