Spectroscopic Studies Research Articles

Unveiling Doppler effects and charge phenomena in the elastic scattering of keV electrons on polystyrene

Abstract Recoil energy is a phenomenon that is observed in various spectroscopy experiments. Elastic Peak Electron Spectroscopy (also known as electron Compton scattering) studies the shape of the elastic peak resulting from electron scattering from solid targets. As the atoms move around their equilibrium position, they scatter the distribution of recoil energies, re- sulting in a broadening of the elastic peak known as Doppler broadening. Since the hydrogen peak has the largest recoil energy shifts due to the low mass of hydrogen, Elastic Peak Electron Spectroscopy is ideal for the detection of hydrogen. The most important aspects of this method for the detection of hydrogen include electron-induced hydrogen desorption and, in dielectric materials, charging phenomena. This work focuses on the elastic peak spectra of keV electrons impinging on polystyrene, with particular interest in the changes in line shape due to the Doppler effect and surface charging during electron irradiation.

The Standardized Spectroscopic Mixture Model

The standardized spectral mixture model combines the specificity of a physically based representation of a spectrally mixed pixel with the generality and portability of a spectral index. Earlier studies have used spectrally and geographically diverse collections of broadband and spectroscopic imagery to show that the reflectance of the majority of ice-free landscapes on Earth can be represented as linear mixtures of rock and soil substrates (S), photosynthetic vegetation (V) and dark targets (D) composed of shadow and spectrally absorptive/transmissive materials. However, both broadband and spectroscopic studies of the topology of spectral mixing spaces raise questions about the completeness and generality of the Substrate, Vegetation, Dark (SVD) model for imaging spectrometer data. This study uses a spectrally diverse collection of 40 granules from the EMIT imaging spectrometer to verify the generality and stability of the spectroscopic SVD model and characterize the SVD topology and plane of substrates to assess linearity of spectral mixing. New endmembers for soil and non-photosynthetic vegetation (NPV; N) allow the planar SVD model to be extended to a tetrahedral SVDN model to better accommodate the 3D topology of the mixing space. The SVDN model achieves smaller misfit than the SVD, but does so at the expense of implausible fractions beyond [0, 1]. However, a refined spectroscopic SVD model still achieves small (<0.03) RMS misfit, negligible sensitivity to endmember variability and strongly linear scaling over more than an order of magnitude range of spatial resolution.

Atomically precise Cu32 nanoclusters with selenide doping: Synthesis, bonding, and catalysis

AbstractCopper nanoclusters with stable compositions and precise structures have long been sought after, as they possess properties that are absent in gold and silver counterparts. However, the creation of copper nanoclusters with novel compositions, structures, and functionalities remains largely unexplored in the literature. In this study, we demonstrate that selenide doping is an effective method for fabricating stable copper nanostructures through controlled synthesis and structure determination of a copper–selenide nanocluster. The nanocluster of [Cu32Se7(BnSe)18(PPh3)6]+ (denoted as Cu32Se7, Bn is benzyl) has been prepared by reducing copper salts in the presence of organic diselenides. The atomic structure of the Cu32Se7 cluster, accurately determined through single‐crystal X‐ray diffraction, reveals a core–shell arrangement of Cu20Se7@Cu12(BnSe)18(PPh3)6, where Se2− anions are well dispersed in the Cu20 framework. Notably, this cluster represents a rare example of copper–selenide semiconductor nanoclusters. Experimental and theoretical analysis shows strong interactions between Se ligands and metal atoms, resulting in high stability of the Cu32Se7 cluster. Furthermore, the cluster exhibits excellent catalytic performance in the hydroboration reaction of alkynes, producing a range of vinylboron compounds with adjustable structures and functions. Importantly, the cluster undergoes no structural or nuclearity changes during the reaction, as confirmed by extended X‐ray absorption fine structure and X‐ray photoelectron spectroscopy studies. This study not only presents a molecular cluster model highlighting the effectiveness of selenide dopants in fabricating new copper nanostructures but also paves the way for utilizing stable copper nanoclusters in diverse and exciting areas beyond catalysis.

Tetraarylpyrrolo[3,2-b]pyrrole-BODIPY dyad: a molecular rotor for FRET-based viscosity sensing

With the aim to develop a FRET-based viscosity sensor, two dyad molecules, 4 and 5, comprising tetraarylpyrrolo[3,2-b]pyrrole (TAPP) (donor) and naked boron-dipyrromethene (BODIPY) dyes (acceptor), were designed. Dyads were synthesized via acid-catalyzed multicomponent reactions followed by Sonogashira coupling. In both dyads, the BODIPY and TAPP moieties are linked through phenylethynyl groups, which allow free rotation of the BODIPY dyes; that is, they can act as molecular rotors. This was supported by X-ray crystallographic and DFT-optimized structures. Spectroscopic studies also confirmed the presence of both TAPP and BODIPY dyes in dyads with no electronic interactions that are suitable for fluorescence resonance energy transfer (FRET). Very high energy transfer efficiency (ETE >99%) from the donor TAPP moiety to the acceptor BODIPY moiety on excitation at the TAPP part was observed. However, due to the non-fluorescent nature of naked BODIPY dyes, no fluorescence emission was observed from the BODIPY moiety in both dyads. With increasing solvent viscosities, emission from the BODIPY moieties increases due to the restricted rotation of the BODIPY moieties. Plotting the logarithms of the fluorescent intensity of dyad 5 and the viscosity of the solution showed a good linear correlation obeying a Förster–Hoffmann equation. Non-fluorescent dyad 5 in methanol became greenish-yellow fluorescent in a methanol/glycerol (1:1) solvent. Furthermore, with an increase in the temperature of the methanol/glycerol (1:1) system, as the viscosity decreases, the fluorescence also starts decreasing. Thus, dyad 5 is capable of sensing the viscosity of the medium via a FRET-based “Off-On” mechanism. This type of viscosity sensor with a very large pseudo-Stokes shift and increased sensitivity will be useful for advancing chemo-bio sensing and imaging applications.

Impedance Spectroscopy for Bacterial Cell Monitoring, Analysis, and Antibiotic Susceptibility Testing.

Conventional approaches for bacterial cell analysis are hindered by lengthy processing times and tedious protocols that rely on gene amplification and cell culture. Impedance spectroscopy has emerged as a promising tool for efficient real-time bacterial monitoring, owing to its simple, label-free nature and cost-effectiveness. However, its limited practical applications in real-world scenarios pose a significant challenge. In this review, we provide a comprehensive study of impedance spectroscopy and its practical utilization in bacterial system measurements. We begin by outlining the fundamentals of impedance theory and modeling, specific to bacterial systems. We then offer insights into various strategies for bacterial cell detection and discuss the role of impedance spectroscopy in antimicrobial susceptibility testing (AST) and single-cell analysis. Additionally, we explore key aspects of impedance system design, including the influence of electrodes, media, and cell enrichment techniques on the sensitivity, specificity, detection speed, concentration accuracy, and cost-effectiveness of current impedance biosensors. By combining different biosensor design parameters, impedance theory, and detection principles, we propose that impedance applications can be expanded to point-of-care diagnostics, enhancing their practical utility. This Perspective focuses exclusively on ideally polarizable (fully capacitive) electrodes, excluding any consideration of charge transfer resulting from Faradaic reactions.

Design of PtSn Nanocatalysts for Fuel Cell Applications.

The challenges in the fuel cell industry lie in the cost, performance, and durability of the electrode components, especially the platinum-based catalysts. Alloying has been identified as an effective strategy to reduce the cost of the catalyst and increase its efficiency and durability. So far, most studies focused on the design of PtM bimetallic nanocatalyst, where M is a transition metal. The resulting PtM materials show higher catalytic activity, but their stability remained challenging. In addition, most of the transition metals M are expensive or low abundant. Tin (Sn) has gained attention as alloying element due to its versatility in manufacturing both anode and cathode electrodes. If used as anode catalyst, it is able to overcome poisoning from CO and related intermediates. As cathode catalyst, it improves the kinetics of the oxygen reduction reaction (ORR). Additionally, Sn is an abundant and cheap element. The current contribution outlines the state of the art on the alloy and shape effect on PtSn activity and stability, demonstrating its high potential to develop cheaper, more efficient and durable catalysts for fuel-cell electrodes. Additionally, in situ analytical and spectroscopic studies can shed light on the elementary steps involved in the use of PtSn catalytic systems. Finally, this intriguing material can be used as a parent system for the synthesis of high-entropy-alloys and intermetallics materials.

A spectroscopic study on the Amyloid-βinteraction with clicked peptide-porphyrin conjugates: a vision toward the detection of Aβpeptides in aqueous solution.

Alzheimer's disease (AD) is a multifactorial form of dementia mainly affecting people in the elderly, but no effective cure is available. According to the amyloid hypothesis the aggregation of Amyloid-β (Aβ) into oligomeric toxic species is believed to concur with the onset and progression of the disease heavily. By using a click chemistry approach, we conjugated a suitable designed peptide sequence to a metalloporphyrin moiety to obtain three hybrid peptide systems to be studied for their interact ion with Amyloid-β peptides. The aim is to get new tools for the diagnosis and therapy in AD. The results described in this study, which were obtained through spectroscopic techniques (UV-Vis, CD, Bis-Ans and intrinsic porphyrin Fluorescence), Microfluidics (GCI) and cell biology (MTT, Live cell imaging and flow cytometry), reveal interesting features about the structure-activity relationships connecting these conjugates with the interaction with Aβ, as well as on their potential use as sensing systems. In our opinion the data reported in this paper make the porphyrin-peptide conjugates highly compelling for further exploration as spectroscopic probes to detect Aβ biomarkers in biological fluids.

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies.

Recent research and reviews on CO2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO2. The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO2 capture efficiency.

Structural characterization of a cell wall-associated polysaccharide of Nocardia rubra FIM-21 and its immunostimulatory activity

In this work, a neutral polysaccharide named NP-1 was obtained from the cell wall of Nocardia rubra FIM-21 by column chromatography. Its chemical structure was characterized by methylation analysis, 2D NMR spectroscopic study, and other techniques. It was shown that NP-1 contained five types of monosacchrides, including mannose (Man), glucose (Glc), N-acetylglucosamine (GlcpNAc), galactose (Gal) and arabinose (Ara) in a molar ratio of 7.7:3:2:1:1.5. According to linkage analysis and NMR spectra, the backbone contains 1,6-linked Manp, 1,4-linked Glcp, and 1,6-linked Galp, with branches substituted at the C-6 of 1,4-linked Glcp and the C-2 of 1,6-linked Galp by GlcpNAc, and at C-2 of 1,6-linked Manp by Araf, Araf-1,5-Araf or GlcpNAc. Biological activity research showed that NP-1 could stimulate the proliferation of RAW264.7 cells and enhance their phagocytosis and release of NO.

Solar driven highly efficient photocatalyst based on Dy2O3 nanorods deposited on reduced graphene oxide nanocomposite for methylene blue dye degradation.

In recent years, the demand for rare earth elements has surged due to their unique characteristics and diverse applications. This investigation focuses on utilizing the rare earth element dysprosium oxide (Dy2O3) for the photocatalytic oxidation of model pollutants under solar light irradiation. A novel RGO-Dy2O3 nanocomposite photocatalyst was developed using a solvothermal approach, Dy2O3 nanorods uniformly deposited onto reduced graphene oxide (RGO) nanosheets. Comprehensive characterization techniques, including Brunner-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR), Raman spectroscopy, high resolution - transmittance electron microscopy (HR-TEM), field emission-electron scanning microscopy (FE-SEM), atomic force microscopy (AFM), electron paramagnetic resonance spectroscopy (EPR), photoluminescence spectroscopy (PL), and electrochemical impedance spectroscopy EIS techniques. The UV-visible diffusive reflectance spectroscopy (UV-Vis-DRS) studies revealed a band gap energy of 3.18eV and a specific surface area of 114 m2/g for the fabricated RGO-Dy2O3 nanocomposite. The RGO-Dy2O3 nanocomposite demonstrated a high photocatalytic degradation efficiency of 98.1% at neutral pH for methylene blue (MB) dye for the dye concentration of 10ppm. The remarkable photocatalytic performance was achieved within 60min under solar light irradiation. Reusability tests demonstrated stability, maintaining over 90% photocatalytic efficiency after three cycles. The EPR spectra and quenching experiments confirmed that photogenerated hydroxyl radicals significantly influence the photodegradation processes. The RGO-Dy2O3 nanocomposite photocatalyst, with its green, easy preparation process and recycling capabilities, presents an ideal choice for various applications. It offers a viable alternative for the photocatalytic degradation of organic dyes in real wastewater, contributing to sustainable environmental remediation.

Dose-dependent effects of transcranial photobiomodulation on brain temperature in patients with major depressive disorder: a spectroscopy study.

This study aimed to evaluate the dose-dependent brain temperature effects of transcranial photobiomodulation (t-PBM). Thirty adult subjects with major depressive disorder were randomized to three t-PBM sessions with different doses (low: 50 mW/cm2, medium: 300 mW/cm2, high: 850 mW/cm2) and a sham treatment. The low and medium doses were administered in continuous wave mode, while the high dose was administered in pulsed wave mode. A 3T MRI scanner was used to perform proton magnetic resonance spectroscopy (1H-MRS). A voxel with a volume of 30 × 30 × 15 mm3 was placed on the left prefrontal region. Brain temperature (°C) was derived by analyzing 1H-MRS spectrum chemical shift differences between the water (~ 4.7 ppm) and N-acetyl aspartate (NAA) (~ 2.01 ppm) peaks. After quality control of the data, the following group numbers were available for both pre- and post-temperature estimations: sham (n = 10), low (n = 11), medium (n = 10), and high (n = 8). We did not detect significant temperature differences for any t-PBM-active or sham groups post-irradiation (p-value range = 0.105 and 0.781). We also tested for potential differences in the pre-post variability of brain temperature in each group. As for t-PBM active groups, the lowest fluctuation (variance) was observed for the medium dose (σ2 = 0.29), followed by the low dose (σ2 = 0.47), and the highest fluctuation was for the high dose (σ2 = 0.67). t-PBM sham condition showed the overall lowest fluctuation (σ2 = 0.11). Our 1H-MRS thermometry results showed no significant brain temperature elevations during t-PBM administration.

Consolidated Curium Reprocessing Procedure Inspires Molecular Design for Sensitized Curium Circularly Polarized Luminescence.

Curium's stable redox chemistry and ability to emit strong metal-based luminescence make it uniquely suitable for spectroscopic studies among the actinide series. Targeted ligand and coordination compound design can support both fundamental electronic structure studies and industrial safeguards with the identification of unique spectroscopic signatures. However, limited availability, inherent radioactive hazards, and arduous purifications have long inhibited such investigations of this element. A consolidated reprocessing procedure for curium has been developed for the milligram scale. The recovery of not only standard legacy curium samples but also hazardous legacy perchlorate containing curium samples was achieved, culminating in column chromatography utilizing the extraction resin DGA (N,N,N',N'-tetra-2-ethylhexyldiglycolamide, branched). Surprisingly, controlled elution of the Cm band from the extraction resin was followed through bright pink luminescence triggered by an inexpensive hand-held UV-vis lamp (380-400 nm). This observation inspired the design of an enantiopure, C2-symmetrical ligand bearing a chiral (trans-1,2-diaminocyclohexane) backbone with achiral DGA moieties (N,N,N',N'-tetra-n-octylacetamide), that enabled rarely observed curium circularly polarized luminescence upon metal chelation. These combined achievements should unlock more luminescence and circularly polarized luminescence studies of curium, and enable the recovery of many curium and other trivalent actinide samples.

Excitation energy transfer based naphthalimide-boron-dipyrromethene dyads as two-photon fluorescent probes for palladium(0) detection and live cell imaging

Increasing industrial demand has accelerated the consumption and contamination of palladium (Pd) worldwide. The implementation of fluorescent probes, especially with two-photon excitation, holds great promise for Pd detection in environmental and biological analysis. In this work, two naphthalimide (NPI)-boron-dipyrromethene (BDP) dyads (named NBH and NBN) were developed as two-photon fluorescent probes for Pd(0) detection based on an excitation energy transfer (EET) strategy, employing NPI as the energy donor and BDP as the acceptor. Spectroscopic studies revealed that both probes exhibited a fast response to Pd(0) in a pronounced fluorescence "ON-OFF" manner. The Pd-catalyzed Tsuji-Trost reaction activated an intramolecular photoinduced electron transfer (PET) process between the aniline and BDP moieties, resulting in the fluorescence quenching of the BDP fluorophore. The reaction-based probes exhibited excellent sensitivity and selectivity for Pd(0) species with a detection limit as low as 2.4 nM. These probes were successfully applied to the determination of Pd residues in drug, soil, and water samples. A simple smartphone-based platform was also constructed to determine Pd(0) via an RGB reader. With negligible cytotoxicity, confocal imaging study validated their feasibility of monitoring Pd(0) in living cells through multiple excitation channels.

Deciphering electrocatalytic hydrogen production in water through a bioinspired water-stable copper(II) complex adorned with (N2S2)-donor sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H2 generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-LN2S2]ClO4, featuring the N,S-type ligand, LN2S2 (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by H2O during electrochemical conditions yielding [H2O-Cu-LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s-1 for hydrogen generation. Controlled potential electrolysis at -1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2%. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post-CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton-electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.

First naturally occurring homoacridone-flavanone dimers from Glycosmis parviflora

The structures of flavacitropones A (1)-B (2), which are new homoacridone-flavanone dimers from Glycosmis parviflora (Sims) Kurz. (Rutaceae), were elucidated by spectroscopic studies. Flavacitropone A (1) was evaluated for its biological effects on cytotoxicity and release of histamine and TNF-α in 2,4-dinitrophenyl-human serum albumin-stimulated RBL-2H3 cells (rat basophilic cell line). The compound downregulated TNF-α release, but not histamine release.

Synthesis, Characterization and Identification of Mononuclear Transition Metals Complexes 1, 3-Bis-((5-methyl-1H-Imidazol-4-yl) Methyleneamino) Propan-2-ol Ligand

The ligand 1,3-bis-((5-methyl-1H-imidazol-4-yl)methyleneamino)propan-2-ol (H3L) derived from 1,3-diaminopropan-2-ol and 5-methyl-1H-imidazole-4-carbaldehyde has been synthetized and used to prepare five complexes in which the ligand acts in tetradentate fashion. Complexes formulated as [Mn(H3L)(H2O)2].2SCN (1), [(Co(H3L)].2SCN (2), [(Ni(H3L)].2SCN (3), [(Cu(H3L)(NO3)].(NO3).2H2O (4), and [(Zn(H3L)].2SCN (5) were synthesized by mixing an equimolar amount of an methanol solution containing the appropriate nitrate salt and KSCN, in 1:2 ratio, in the case of 1, 2, 3 and 5 and an ethanol solution containing the appropriate ligand H3L. The complex 4 has been synthetized in the absence of KSCN. In all the complexes the ligand acts in its neutral form and in tetradentate fashion, its hydroxy group remaining free and non-deprotonated. The ligand is coordinated to metal ion through two azomethine nitrogen atoms and two pyrazole sp2 nitrogen atoms. The complexes are characterized by elemental analysis, conductance and room temperature magnetic moments measurements, UV–Vis and IR spectroscopic studies. The structure of the copper(II) complex 4 is confirmed by X-ray diffraction. 4 crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 8.5459 (3) Å, b = 10.9177 (3) Å, c = 22.4562 (6) Å, b = 96.954 (3)°, V = 2079.79 (11) Å3, Z = 4, R1 = 0.050 and wR2 = 0.131. The CuII cation in N4O inner is situated in a distorted square pyramidal environment.

Photoelectron Spectroscopy and Theoretical Studies on the Structures and Properties of Ge4C- and Ge4CH- Clusters.

We investigate the structures and properties of Ge4C-/0 and Ge4CH-/0 clusters using anion photoelectron spectroscopy and theoretical calculations. Our calculations show that the first two low-lying isomers coexist in the experiments of Ge4C- and Ge4CH-. The first two low-lying isomers of Ge4C- have trigonal bipyramidal structures with the C atom on the equatorial plane and the top vertex, respectively. It is found that the first two low-lying isomers of Ge4CH- can be obtained by adding an H atom to the top and equatorial C atoms of Ge4C-, respectively. The AdNDP analyses reveal that the C atom in Ge4C forms one 4c-2e σ bond, two 4c-2e π bonds, and one 5c-2e σ bond with Ge atoms. The C atom in Ge4C interacts with an H- forming a C-H σ bond in Ge4CH-. AIMD simulation results indicate high dynamic stabilities of Ge4C and Ge4CH- at 300 and 500 K. Our results show that the structures and chemical bonding of Ge4B- and Ge4N+ are similar to those of Ge4C, while those of Ge4BH2- and Ge4NH resemble those of Ge4CH-.

Association of Exercise with Better Olfactory Performance and Higher Functional Connectivity Between the Olfactory Cortex and the Prefrontal Cortex: A Resting-State Functional Near-Infrared Spectroscopy Study.

Background: Olfactory deterioration is suggested to be a predictor of some neurodegenerative diseases. Recent studies indicate that physical exercise has a positive relationship with olfactory performance, and a subregion in the prefrontal cortex (PFC) may play an important role in olfactory processing. The PFC is not only related to olfactory function but it also engages in complex functions such as cognition and emotional processing. Methodology: Our study compared the functional connectivity between the olfactory cortex and the PFC in healthy individuals who exercised regularly and healthy persons who did not. Those who exercised more than three times/week for at least 30 min each time were considered the exercise group, and those who did not meet this exercise criteria were considered the nonexercise group. We also assessed their odor threshold. Participants were aged 55 years or older, and the two groups were balanced for age, sex, body mass index, and educational level. Results: We found that compared with individuals who did not exercise, exercisers had a significantly lower threshold for detecting odors. In addition, the olfactory cortex had stronger connectivity with the PFC in exercisers than in nonexercisers. More specifically, when the PFC was grouped into three subregions, namely, the ventrolateral prefrontal cortex (VLPFC), dorsolateral prefrontal cortex (DLPFC), and frontopolar cortex (FPA), Pearson correlation analysis revealed stronger connectivity between the VLPFC and the orbitofrontal cortex (OFC), between the OFC and the FPA, and between the left and right OFC hemispheres in the exercisers. In addition, Granger causality indicated higher directional connectivity from the DLPFC to the OFC in exercisers than in nonexercisers. Conclusion: Our findings indicated that the exercise group not only had better olfactory performance but also had stronger functional connectivity between the olfactory cortex and the PFC than nonexercise group.

Bioinorganic Chemistry Meets Microbiology: Copper(II) and Zinc(II) Complexes Doing the Cha-Cha with the C-t-CCL-28 Peptide, Dancing till the End of Microbes.

The necessity to move away from conventional antibiotic therapy has sparked interest in antimicrobial peptides (AMPs). One fascinating example is human CCL-28 chemokine produced by acinar epithelial cells in the salivary glands. It can also be released into the oral cavity with saliva, playing a crucial role in oral protection. The C-terminal domain of CCL-28 possesses antifungal and antibacterial properties, which are likely linked to membrane disruption and enzyme leakage. Studies suggest that AMPs can become more potent after they have bound Cu(II) or Zn(II). In many cases, these ions are essential for maximizing effectiveness by altering the peptides' physicochemical properties, such as their local charge or structure. The examined peptide binds Cu(II) and Zn(II) ions very effectively, forming equimolar complexes. Metal ion binding affinity, coordination mode, and antimicrobial activity strongly depend on the pH of the environment. Coordination modes have been proposed based on the results of potentiometric titrations, spectroscopic studies (UV-visible, electron paramagnetic resonance and circular dichroism at different path lengths), and mass spectrometry. The antimicrobial properties of the Cu(II) and Zn(II) complexes with the C-terminal fragment of CCL-28 chemokine have been assessed against fungal and bacterial strains, demonstrating exceptional activity against Candida albicans at pH 5.4. Moreover, the complex with Zn(II) ions shows the same activity against theStreptococcus mutans bacterium as chloramphenicol, a commonly used antibiotic. Cyclic voltammetry proposed a probable antimicrobial mechanism of the studied Cu(II) complex through the formation of reactive oxygen species, which was also confirmed by tests with ascorbic acid in UV-vis and fluorescence spectroscopic studies.

Spectroscopic ellipsometry study of linear and nonlinear optical properties of NaBi(Mo0.5W0.5O4)2 crystal

Spectroscopic ellipsometry study of linear and nonlinear optical properties of NaBi(Mo0.5W0.5O4)2 crystal