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.

Self-assembly of defined core-shell ellipsoidal particles at liquid interfaces.

Hypothesis: Ellipsoidal particles confined at liquid interfaces exhibit complex self-assembly due to quadrupolar capillary interactions, favouring either tip-to-tip or side-to-side configurations. However, predicting and controlling which structure forms remains challenging. We hypothesize that introducing a polymer-based soft shell around the particles will modulate these capillary interactions, providing a means to tune the preferred self-assembly configuration based on particle geometry and shell properties.

"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.

Gingival Margin Damage During Supragingival Dental Polishing by Inexperienced Operator-Pilot Study.

Background: Supragingival polishing is a crucial part of nonsurgical periodontal therapy. In recent years, air polishing has been used for this purpose, introducing different polishing powders. The purpose of the following study was to investigate the damage to the gingival margin during air polishing by an inexperienced operator.

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).

Pivotal Role of the Intracellular Microenvironment in the High Photodynamic Activity of Cationic Phthalocyanines.

To investigate the influence of phthalocyanine aggregation on their photodynamic activity, a series of six cationic water-soluble zinc(II) phthalocyanines bearing from four to sixteen 4-((diethylmethylammonium)methyl)phenoxy substituents was synthesized. Depending on their structure, the phthalocyanines have different aggregation behaviors in phosphate buffer solutions ranging from fully assembled to monomeric states. Remarkably, independent of aggregation in buffer, very high photodynamic efficiencies against the tumor cell lines MCF-7 and MDA-MB-231 in the nanomolar range were found for all investigated phthalocyanine, and the IC(light) varied from 27 to 358 nM (3.

Uncertainty Quantification and Flagging of Unreliable Predictions in Predicting Mass Spectrometry-Related Properties of Small Molecules Using Machine Learning.

Mass spectral identification (in particular, in metabolomics) can be refined by comparing the observed and predicted properties of molecules, such as chromatographic retention. Significant advancements have been made in predicting these values using machine learning and deep learning. Usually, model predictions do not contain any indication of the possible error (uncertainty) or only one criterion is used for this purpose.

Viral-Porphyrin Combo: Photodynamic and Oncolytic Viral Therapy for Potent Glioblastoma Treatment.

Combined viral and photodynamic therapy for oncological diseases has great potential to treat aggressive tumors such as glioblastomas. A conjugate of vesicular stomatitis virus (VSV) with protoporphyrin IX was prepared, and its oncolytic effects were studied and compared to the effects of the individual components. The VSV showed an oncolytic effect on glioblastoma cell lines T98G and LN229 at a virus titer of 10 TCID/mL.

Short-time accuracy and intra-electron correlation for nonadiabatic quantum-classical mapping approaches.

Nonadiabatic quantum-classical mapping approaches have significantly gained in popularity over the past several decades because they have acceptable accuracy while remaining numerically tractable even for large system sizes. In the recent few years, several novel mapping approaches have been developed that display higher accuracy than the traditional Ehrenfest method, linearized semiclassical initial value representation (LSC-IVR), and Poisson bracket mapping equation (PBME) approaches. While various benchmarks have already demonstrated the advantages and limitations of those methods, unified theoretical justifications of their short-time accuracy are still demanded.

Systematic ab initio calculation of spectroscopic constants for A-reduced rotational effective Hamiltonians of asymmetric top molecules using normal ordering of cylindrical angular momentum operators.

This research paper presents a new fundamental approach for evaluating accurate ab initio quartic, sextic, and octic centrifugal distortion parameters of A-reduced rotational effective Hamiltonians of asymmetric top molecules. In this framework, the original Watson Hamiltonian, expanded up to sextic terms of kinetic and potential energies, is subjected to a series of vibrational and rotational operator unitary transformations, leading to reduced Watson effective Hamiltonians for the equilibrium configuration, ground state, and weakly perturbed vibrationally excited states. The proposed scheme is based on a numerical-analytic implementation of the sixth-order Van Vleck operator perturbation theory with the systematic normal ordering of vibrational rising and lowering operators (a†, a) and cylindrical angular momentum operators (Jz, J+, J-).

Antioxidant effect, DNA-binding, and transport of the flavonoid acacetin influenced by the presence of redox-active Cu(II) ion: Spectroscopic and in silico study.

Acacetin (AC) is a natural polyphenol from the group of flavonoids. It is well established that the behavior of flavonoids depends on the presence of redox-active substances; therefore, we aim to investigate their biological activity following the interaction with Cu(II) ion. Our study demonstrates that AC can effectively bind Cu(II) ions, as confirmed by UV-Vis and EPR spectroscopy as well as DFT calculations.

Coupled methyl internal rotations with intermediate and low torsional barriers in 2,5-dimethylanisole investigated by microwave spectroscopy.

We recorded and analyzed the microwave spectra of 2,5-dimethylanisole using a pulsed molecular jet Fourier transform microwave spectrometer and the newly developed Passage And Resonant-Impulse Synergy spectrometer across a frequency range of 2-26.5 GHz with support from quantum chemical calculations. Only one conformer was predicted and observed, where the methoxy group and its adjacent methyl group adopt anti-positions.

A remarkable match of optical response in the amorphous-crystalline and zinc blende-rock salt phase pairs of GeTe.

Despite a large amount of theoretical and experimental work performed so far, the search of phase change materials (PCMs) is done with use of numerical modeling. However, it is not fully clear how and why the phase change translates into the optical contrast. In this work, we argue that a key prerequisite for a material to have a pronounced difference in optical properties between crystalline and glassy phases of PCM is the similar contrast between the observed crystalline and (may be experimentally inaccessible) parent crystalline polymorph of the glassy phase.

Beneficial Soil Fungus Kills Predatory Nematodes with Dehydropeptides Translocating into the Animal Gut.

is a mold fungus that has gained attention for its positive correlation with soil health, plant growth, and applications as a crop biocontrol agent to suppress the threats of nematode pests. To date, the mechanisms underlying the protective traits of against these plant parasites have remained elusive. Here we report that abundantly produced peptidic biosurfactants, malpinin A-D, exhibit robust inhibitory activity against nematodes.

Effect of simple shear on knotted polymer coils and globules.

We explore the effect of Couette flow on knotted linear polymer chains with extensive molecular dynamics simulations. Hydrodynamic interactions are accounted for using multi-particle collision dynamics. The polymer chain, originally containing a simple trefoil knot at rest, is described by a coarse-grained bead-spring model in a coil or globular state.

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.

Experimental and Theoretical X-ray Absorption Near Edge Structure Study of UO Systems at the U L Edge.

Uranium forms a large number of oxides and its electronic state in them is of great fundamental interest. We employ X-ray absorption spectroscopy at the U L edge to differentiate between mixed oxide phases in uranium compounds. By combining experimental XANES spectra with theoretical modeling using the FEFF code, we analyze five uranium oxides: UO, UO, UO, UO, and UO.

Toward robust electronic coupling predictions in redox-active TEMPO/TEMPO+ systems.

This research elucidates the intricate nature of electronic coupling in the redox-active (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), commonly utilized in organic radical batteries. This study employs a combination of classical molecular dynamics and various electronic coupling calculation schemes. Within the context of the generalized Mulliken-Hush method, the electronic couplings are investigated via the complete active space self-consistent field approach, in combination with n-electron valence state perturbation theory, to provide an accurate description of both static and dynamic electron correlation as well as using (time-dependent) density functional theory simulations.

Cobalt(II) and Manganese(II) Complexes of Sodium Monensinate A Bearing Nitrate Co-Ligands.

Monensic acid is a natural polyether ionophore and is a therapeutic of first choice in veterinary medicine for the control of coccidiosis. Although known as a sodium-binding ligand, it can also form a variety of coordination species depending on experimental conditions applied. In this study, we present the crystal structures and properties of Co(II) and Mn(II) complexes of sodium monensinate (MonNa) derived from the reaction of MonNa with cobalt or manganese dinitrates.

Difference in the Catalytic Activity of Atoms in the Corners and at the Edges of Gold Nanoparticles: Hydrogen Isotope Exchange Reaction.

The goal of this work is to investigate the catalytic activities of low-coordination atoms located in gold nanoparticles. Gold nanoparticles with sizes from 0.7 to 40 nm deposited on γ-AlO were used as a catalyst.

Continuous Tuning of Intersystem Crossing Times in Rose Bengal Water/Methanol Solutions.

We use femtosecond transient broadband absorption spectroscopy (TAS) to characterize Rose Bengal in water/methanol solutions and reveal a continuous tunability of intersystem crossing (ISC) times by changing the mole fraction of the solvents. We find that the transients of excited state absorptions (ESAs) in Rose Bengal at ∼430 nm can be attributed to transitions from the singlet state S, with decay times of 74 ps via ISC in pure water and up to 405 ps in pure methanol. TA measurements at near-infrared wavelengths, on the other hand, reveal the rise of an ESA at ∼1080 nm from the triplet state T with time constants of 68 and 491 ps in pure water and methanol, respectively, strongly supporting the associated UV-vis TAS data.

Filling the gaps: Introducing plasticizers into π-conjugated OPE-NH Langmuir layers for defect-free anisotropic interfaces and membranes towards unidirectional mass, charge, or energy transfer.

The construction of ultrathin membranes from linearly aligned π-electron systems is advantageous for targeted energy, charge, or mass transfer. The Langmuir-Blodgett (LB) technique enables the creation of such membranes, especially with amphiphilic π-electron systems. However, these systems often aggregate, forming rigid Langmuir monolayers with defects or holes.