Unusual variability of isomers in copper(II) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam.

Copper isotopes and their complexes are intensively studied due to their high potential for applications in radiodiagnosis and radiotherapy. Here, we study the Cu complex of 1,8-bis(2-hydroxybenzyl)-cyclam (HL), which forms an unexpected variety of isomers differing in the mutual orientation of the substituents on the cyclam nitrogen atoms, the protonation of the phenolate pendant, and the ligand denticity. The interconversion of the isomers is rather slow, which made the isolation, identification and investigation of some of the individual species possible.

Optimized molecule detection in localization microscopy with selected false positive probability.

Single-molecule localization microscopy (SMLM) allows imaging beyond the diffraction limit. Detection of molecules is a crucial initial step in SMLM. False positive detections, which are not quantitatively controlled in current methods, are a source of artifacts that affect the entire SMLM analysis pipeline.

Correction: Radical ligand transfer: mechanism and reactivity governed by three-component thermodynamics.

[This corrects the article DOI: 10.1039/D4SC01507J.].

LEGO-Lipophosphonoxin membrane activity is enhanced by presence of phosphatidylethanolamine but hindered by outer membrane.

Finding effective antibiotics against multi-resistant strains of bacteria has been a challenging race. Linker-Evolved-Group-Optimized-Lipophosphonoxins (LEGO-LPPOs) are small modular synthetic antibacterial compounds targeting the cytoplasmic membrane. Here we focused on understanding the reasons for the variable efficacy of selected LEGO-LPPOs (LEGO-1, LEGO-2, LEGO-3, and LEGO-4) differing in hydrophobic and linker module structure and length.

Preparation of novel lithiated high-entropy spinel-type oxyhalides and their electrochemical performance in Li-ion batteries.

Compositionally complex doping of spinel oxides toward high-entropy oxides is expected to enhance their electrochemical performance substantially. We successfully prepared high-entropy compounds, the oxide (ZnMgCoCu)FeO (HEOFe), lithiated oxyfluoride Li(ZnMgCoCu)FeOF (LiHEOFeF), and lithiated oxychloride Li(ZnMgCoCu)FeOCl (LiHEOFeCl) with a spinel-based cubic structure by ball milling and subsequent heat treatment. The products exhibit particles with sizes from 50 to 200 nm with a homogeneous atomic distribution.

"Head-to-Toe" Lipid Properties Govern the Binding and Cargo Transfer of High-Density Lipoprotein.

The viscoelastic properties of biological membranes are crucial in controlling cellular functions and are determined primarily by the lipids' composition and structure. This work studies these properties by varying the structure of the constituting lipids in order to influence their interaction with high-density lipoprotein (HDL) particles. Various fluorescence-based techniques were applied to study lipid domains, membrane order, and the overall lateral as well as the molecule-internal glycerol region mobility in HDL-membrane interactions (i.

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.

Efficient Degradation of Recalcitrant Pharmaceuticals in Greywater Using Treatment of MBR and Immobilized TiO Porous Layers.

Traditional wastewater treatment often fails to remove pharmaceuticals, necessitating advanced solutions, such as TiO photocatalysis, for post-treatment. However, conventionally applied powder TiO can be cumbersome to separate from treated water. To solve this issue, this study immobilized three TiO photocatalysts (Anatase 16, Anatase 5, and P25) into porous layers and evaluated their efficacy for the degradation of three pharmaceuticals (naproxen, NPX; sulfamethoxazole, SMX; metformin, MTF) in standard solutions and greywater pretreated in a membrane bioreactor (MBR).

Generation of Ammonia in a Pulsed Hollow Cathode Discharge Operated in an Ar/H/N Gas Mixture Detected by Fourier Transform Infrared.

A hollow cathode discharge with a copper nickel cathode (Cu50Ni50) was operated in an Ar/H/N gas mixture. Optical emission spectroscopy revealed the formation of NH radicals, which serve as precursors for NH formation. Ion mass spectrometry showed the formation of NH and NH ions indicating NH formation.

The Importance of Catalytic Effects in Hot-Electron-Driven Chemical Reactions.

Hot electrons (HEs) represent out-of-equilibrium carriers that are capable of facilitating reactions which are inaccessible under conventional conditions. Despite the similarity of the HE process to catalysis, optimization strategies such as orbital alignment and adsorption kinetics have not received significant attention in enhancing the HE-driven reaction yield. Here, we investigate catalytic effects in HE-driven reactions using a compositional catalyst modification (CCM) approach.

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.

Importance of Electron Correlation on the Geometry and Electronic Structure of [2Fe-2S] Systems: A Benchmark Study of the [FeS(SCH)], [FeS(SCys)], [FeS(S--tol)], and [FeS(S--xyl)] Complexes.

Iron-sulfur clusters are crucial for biological electron transport and catalysis. Obtaining accurate geometries, energetics, manifolds of their excited electronic states, and reduction energies is important to understand their role in these processes. Using a [2Fe-2S] model complex with Fe and Fe oxidation states, which leads to different charges, i.

Autodetachment of Diatomic Carbon Anions from Long-Lived High-Rotation Quartet States.

We show that strong molecular rotation drastically modifies the autodetachment of C_{2}^{-} ions in the lowest quartet electronic state a^{4}Σ_{u}^{+}. In the strong-rotation regime, levels of this state only decay by a process termed "rotationally assisted" autodetachment, whose theoretical description is worked out based on the nonlocal resonance model. For autodetachment linked with the exchange of six rotational quanta, the results reproduce a prominent, hitherto unexplained electron emission signal with a mean decay time near 3 ms, observed on stored C_{2}^{-} ions from a hot ion source.

Photodesorption of CO ices: Rotational and translational energy distributions.

This study investigates the translational and rovibrational energy of vacuum-ultraviolet (VUV) photodesorbed CO molecules from a CO polycrystalline ice (15 K) at ∼8 eV. The electronic excitation was produced by a pulsed VUV laser, and the photodesorption of CO molecules in their ground and first vibrational states was observed using resonance enhanced multiphoton ionization. Time-of-flight and rotationally resolved spectra were measured, and the kinetic and internal energy distribution were obtained.

On the similar spectral manifestations of protonic and hydridic hydrogen bonds despite their different origin.

Previously studied complexes with protonic and hydridic hydrogen bonds exhibit significant similarities. The present study provides a detailed investigation of the structure, stabilization, electronic properties, and spectral characteristics of protonic and hydridic hydrogen bonds using low-temperature infrared (IR) spectroscopy and computational methods. Complexes of pentafluorobenzene with ammonia (C₆F₅H⋯NH₃) and triethylgermane with trifluoroiodomethane (Et₃GeH⋯ICF₃) were analyzed using both experimental and computational tools.

Ion Chemistry in Dielectric Barrier Discharge Ionization: Recent Advances in Direct Gas Phase Analyses.

Dielectric barrier discharge ionization (DBDI) sources, employing low-temperature plasma, have emerged as sensitive and efficient ionization tools with various atmospheric pressure ionization processes. In this review, we summarize a historical overview of the development of DBDI, highlighting key principles of gas-phase ion chemistry and the mechanisms underlying the ionization processes within the DBDI source. These processes start with the formation of reagent ions or metastable atoms from the discharge gas, which depends on the nature of the gas (helium, nitrogen, air) and on the presence of water vapor or other compounds or dopants.

Basicity of Mn-Hydroxo Complexes Controls the Thermodynamics of Proton-Coupled Electron Transfer Reactions.

Several manganese-dependent enzymes utilize Mn-hydroxo units in concerted proton-electron transfer (CPET) reactions. We recently demonstrated that hydrogen bonding to the hydroxo ligand in the synthetic [Mn(OH)(PaPyN)] complex increased rates of CPET reactions compared to the [Mn(OH)(PaPyQ)] complex that lacks a hydrogen bond. In this work, we determine the effect of hydrogen bonding on the basicity of the hydroxo ligand and evaluate the corresponding effect on CPET reactions.

Cell surface morphology mimicking nano-bio platform for immune cell stimulation.

Studying the complex realm of cellular communication and interactions by fluorescence microscopy requires sample fixation on a transparent substrate. To activate T cells, which are pivotal in controlling the immune system, it is important to present the activating antigen in a spatial arrangement similar to the nature of the antigen-presenting cell, including the presence of ligands on microvilli. Similar arrangement is predicted for some other immune cells.

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.

Nanoplasmonic sensing to study CO and oxygen adsorption and CO oxidation on size-selected Pt clusters.

The adsorption of CO and oxygen and CO oxidation on size-selected Pt clusters were studied by indirect nanoplasmonic sensing (INPS) in the pressure range of 1-100 Pa at = 418 K. CO adsorption was reversible, inducing a blue-shift in the localised surface plasmon resonance (LSPR) response, regardless of the initial CO pressure. We observe a plateau at approximately Δ = -0.

Experimental Characterization of the Isomer-Selective Generation of the Astrochemically Relevant Hydroxymethylene Radical Cation (HCOH/DCOH).

Interest in the observation and characterization of organic isomers in astronomical environments has grown rapidly with an increase in the sensitivity of detection techniques. Accurate modeling and interpretation of these environments require experimental isomer-specific reactivity and spectroscopic measurements. Given the abundance of formaldehyde (HCO) in various astrophysical objects, the properties and reactivities of its cation isomers HCO and HCOH are of significant interest.

Naphthylated LEGO-lipophosphonoxin antibiotics used as a fluorescent tool for the observation of target membrane perturbations preceding its disruption.

Linker-Evolved-Group-Optimized-Lipophosphonoxins (LEGO-LPPO) are small synthetic modular peptidomimetics with promising antimicrobial activity. The LEGO-LPPO mechanism of antibacterial action has been determined to be the depolarization and disruption of bacterial membranes. Their modular nature is advantageous for fine tuning their biological properties.

Polaritonic Chemistry Using the Density Matrix Renormalization Group Method.

The emerging field of polaritonic chemistry explores the behavior of molecules under strong coupling with cavity modes. Despite recent developments in polaritonic methods for simulating polaritonic chemistry under electronic strong coupling, their capabilities are limited, especially in cases where the molecule also features strong electronic correlation. To bridge this gap, we have developed a novel method for cavity QED calculations utilizing the Density Matrix Renormalization Group (DMRG) algorithm in conjunction with the Pauli-Fierz Hamiltonian.