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Polysaccharide hydrogels, which can mimic the natural extracellular matrix and possess appealing physicochemical and biological characteristics, have emerged as significant bioinks for 3D bioprinting. They are highly promising for applications in tissue engineering and regenerative medicine because of their ability to enhance cell adhesion, proliferation, and differentiation in a manner akin to the natural cellular environment. This review comprehensively examines the fabrication methods, characteristics, and applications of polysaccharide hydrogel-driven 3D bioprinting, underscoring its potential in tissue engineering, drug delivery, and regenerative medicine. To contribute pertinent knowledge for future research in this field, this review critically examines key aspects, including the chemistry of carbohydrates, manufacturing techniques, formulation of bioinks, and characterization of polysaccharide-based hydrogels. Furthermore, this review explores the primary advancements and applications of 3D-printed polysaccharide hydrogels, encompassing drug delivery systems with controlled release kinetics and targeted therapy, along with tissue-engineered constructs for bone, cartilage, skin, and vascular regeneration. The use of these 3D bioprinted hydrogels in innovative research fields, including disease modeling and drug screening, is also addressed. Despite notable progress, challenges, including modulating the chemistry and properties of polysaccharides, enhancing bioink printability and mechanical properties, and achieving long-term in vivo stability, have been highlighted., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Polymer microgels are swollen macromolecular networks with a typical size of hundred of nanometers to several microns that show an extraordinary open and responsive architecture to different external stimuli, being therefore important candidates for nanobiotechnology and nanomedical applications such as biocatalysis, sensing and drug delivery. It is therefore crucial to understand the delicate balance of physical-chemical interactions between the polymer backbone and solvent molecules that to a high extent determine their responsivity. In particular, the co-nonsolvency effect of poly(N-isopropylacrylamide) in aqueous alcohols is highly discussed, and there is a disagreement between molecular dynamics (MD) simulations (from literature) of the preferential adsorption of alcohol on the polymer chains and the values obtained by several empirical methods that mostly probe the bulk solvent properties. It is our contention that the most efficacious method for addressing this problem requires a nanoscopic method that can be combined with spectroscopy and record fluorescence spectra and super-resolved fluorescence lifetime images of microgels labeled covalently with the solvatochromic dye Nile Red. By employing this approach, we could simultaneously resolve the structure of sub-micron size objects in the swollen and in the collapsed state and estimate the solvent composition inside of them in - mixtures for two very different polymer architectures. We found an outstanding agreement between the MD simulations and our results that estimate a co-solvent molar fraction excess of approximately 3 with a very flat profile in the lateral direction of the microgel., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Precise deposition of metal-organic framework (MOF) materials is important for fabricating high-performing MOF-based devices. Electric-field assisted drop-casting of poly(3,4-ethylenedioxythiophene)-functionalized (PEDOT) MIL-101(Cr) nanoparticles onto interdigitated electrodes allowed their precise spatioselective deposition as percolating nanoparticle chains in the interelectrode gaps. The resulting aligned materials were investigated for resistive and capacitive humidity sensing and compared with unaligned samples prepared via regular drop-casting. The spatioselective deposition of MOFs resulted in up to over 500 times improved conductivity and approximately 6 times increased responsivity during resistive humidity sensing. The aligned samples also showed good capacitive humidity sensing performance, with up to 310 times capacitance gain at 10 versus 90 % relative humidity. In contrast, the resistive behavior of the unaligned samples rendered them unsuitable for capacitive sensing. This work demonstrates that applying an alternating potential during drop-casting is a simple yet effective method to control MOF deposition for greater efficiency, conductivity, and enhanced humidity sensing performance., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jia Min Chin reports financial support was provided by European Research Council. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Mercury (Hg) is a global pollutant with substantial risks to human and ecosystem health. By upward transport in tropical regions, mercury enters into the stratosphere, but the contribution of the stratosphere to global mercury dispersion and deposition remains unknown. We find that between 5 and 50% (passing through the 400-kelvin isentropic surface and tropopause, respectively) of the mercury mass deposited on Earth's surface is chemically processed in the lower stratosphere. Our results show the stratosphere as a unique chemical environment where elemental mercury is efficiently converted to long-lived oxidized species. Subsequent downward transport contributes substantially to the oxidized mercury burden in the troposphere. The results show that the stratosphere facilitates the global dispersion of large amounts of mercury from polluted source regions to Earth's remote environments. We find that stratospheric transport is as important as tropospheric transport in interhemispheric mercury dispersion. Future projections suggest that expected changes in atmospheric circulation will increase the transport of mercury into the stratosphere.

Photodetectors based on lead halide perovskites often show excellent performance but poor stability. Herein, we demonstrate a photodetector based on MAPbBr 3 single crystals passivated with an ultrathin layer of PbSO 4 , which shows superior detectivity and on/off ratios compared to the control device due to the combined effect of lower surface traps, reduced recombination and low dark current. In addition, the device retained ∼56% of its initial D * with an impressive on/off ratio of ∼801 after one year compared to ∼22% of D * and an on/off ratio of ∼6 of the control device.

Light induced release of cisplatin from Pt(IV) prodrugs is a promising tool for precise spatiotemporal control over the antiproliferative activity of Pt-based chemotherapeutic drugs. A combination of light-controlled chemotherapy (PACT) and photodynamic therapy (PDT) in one molecule has the potential to overcome crucial drawbacks of both Pt-based chemotherapy and PDT via a synergetic effect. Herein we report green-light-activated Pt(IV) prodrug GreenPt with BODIPY-based photosentitizer in the axial position with an incredible high light response and singlet oxygen generation ability. GreenPt demonstrated the ability to release cisplatin under low-dose green light irradiation up to 1 J/cm2. The investigation of the photoreduction mechanism of GreenPt prodrug using DFT modeling and ΔG0 PET estimation revealed that the anion-radical formation and substituent photoinduced electron transfer from the triplet excited state of the BODIPY axial ligand to the Pt(IV) center is the key step in the light-induced release of cisplatin. Green-light-activated BODIPY-based photosentitizers 5 and 8 demonstrated outstanding photosensitizing properties with an extraordinary phototoxicity index (PI) >1300. GreenPt prodrug demonstrated gradual intracellular accumulation and light-induced phototoxicity with PI > 100, thus demonstrating dual action through light-controlled release of both cisplatin and a potent BODIPY-based photosensitizer., (© 2025 Wiley‐VCH GmbH.)

Comparison of the reactivity of sialyl chlorides and bromides based on N -acetylneuraminic acid (Neu5Ac) and its deaminated analogue (KDN) in reactions with MeOH and i -PrOH without a promoter revealed that the acetoxy group at C-5 in a molecule of a sialic acid glycosyl donor can destabilize the corresponding glycosyl cation making the S N 1-like reaction pathway unfavorable. A change to the S N 2-like reaction pathway ensures preferential formation of the α-glycoside.

Electrolysis of o -alkynyl- N -(formyl)anilides and sodium sulfinates on graphite electrodes delivers biologically sound 3-(sulfonyl)quinol-4-ones with moderate to good yields. The reaction is carried out in an undivided cell in the presence of silver(I) oxide with potassium iodide or sodium tetrafluoroborate as the supporting electrolyte. The reaction tolerates variously substituted anilides as well as aryl and alkyl sulfinates. The transformation proceeds as a domino sequence of oxysulfonylation and cyclocondensation steps.

The recent discovery of frustrated Lewis pairs (FLPs) during the activation of small molecules has inspired extensive research across the full span of chemical science. Owing to the nature of weak interactions, it is experimentally challenging to directly observe and modulate FLP at the molecular scale. Here we design a boron cluster anion building block (B 10 H 8 2- ) and organic amine cations ([NR 4 ] + , R=-CH 3 , -C 2 ) as the FLP to prove the feasibility of controlling their interaction in the electric double layer (EDL) via an electrochemical strategy. In situ single-molecule electrical measurements and Raman monitoring of B 5 ) as the FLP to prove the feasibility of controlling their interaction in the electric double layer (EDL) via an electrochemical strategy. In situ single-molecule electrical measurements and Raman monitoring of B 10 H 8 2- -[NR 4 ] + near or below the potential of zero charge (PZC). Furthermore, this FLP chemistry leads to a shift in the local density of states of boron clusters towards the E 10 for enhancing electron transport, providing a new prototype of a reversible single-cluster switch that digitally switches upon controlling FLP chemistry in the electric double layer.8 2- near or below the potential of zero charge (PZC). Furthermore, this FLP chemistry leads to a shift in the local density of states of boron clusters towards the E F for enhancing electron transport, providing a new prototype of a reversible single-cluster switch that digitally switches upon controlling FLP chemistry in the electric double layer., (© 2024 Wiley-VCH GmbH.)

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 50 (light) varied from 27 to 358 nM (3.5 J/cm 2 , 660 nm) with IC 50 (dark)/IC 50 (light) ratios up to ∼3700. This is due to the intracellular disassembly of aggregated phthalocyanines with the formation of monomeric photoactive forms, as demonstrated by fluorescence microscopy. Indeed, the interaction of aggregated phthalocyanines with serum proteins in a buffer resulted in the disassembly of nonluminescent aggregate species with the release of photoactive monomers bound to protein macromolecules.

Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di( p -carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = p -tolyl (1), mesityl (2), p -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10 -6 -10 -3 M), ionic strengths (0-0.81 M), and pH values (4-12). Single-crystal X-ray diffraction studies of the diethyl phosphonates Pt6d and Pd6d revealed that π-π stacking of the aromatic macrocycles is sterically hindered in the crystals, providing a rationale for the low degree of solution aggregation observed for ethyl phosphonate M3d. Photophysical studies of M3m and M1d-M3d demonstrated that these compounds are phosphorescent and generate singlet oxygen in aqueous solutions. Pd(II) complex Pd3d is an excellent photocatalyst for the oxidation of sulfides using di-oxygen in a solvent mixture (MeCN/H 2 O, 4 : 1 v/v). Under these conditions, various alkyl and aryl sulfides were quantitatively converted into the desired sulfoxides. For the oxygenation of mixed alkyl-aryl sulfides, Pd3d outperforms Pd(II) meso -tetrakis( p -carboxyphenyl)porphyrin (PdTCPP). This photocatalyst can be recycled and reused to afford sulfoxides with no loss of product yield.

The design and development of particulate photocatalysts has been an attractive strategy to incorporate earth-abundant metal ions to water splitting devices. Herein, we synthesized CoFe-Prussian blue (PB) coated ZnO origami core-shell nanostructures (PB@ZnO) with different mass ratio of PB components and investigated their photocatalytic water oxidation activities in the presence of an electron scavenger. Photocatalytic experiments reveal that the integration of PB on ZnO boosts the oxygen evolution rate by a factor of ~2.4 compared to bare ZnO origami. We ascribe this increased photocatalytic rate to an improved charge carrier separation and transfer due to the formation of heterojunction at the interface between PB and ZnO. Long-term photocatalytic experiments indicate that the activity and stability of the catalyst was preserved up to 9 h. Our results indicate that the core-shell PB@ZnO particles possess a proper band energy alignment for the photocatalytic water oxidation process., (© 2025 Wiley‐VCH GmbH.)

Envenomation accidents are usually diagnosed at the hospital through signs and symptoms assessment such as short breath, dizziness and vomiting, numbness, swilling, bruising, or bleeding around the affected site. However, this traditional method provides inaccurate diagnosis given the interface between snakebites and scorpion stings symptoms. Therefore, early determination of bites/stings source would help healthcare professionals select the suitable treatment for patients, thus improving envenomation management. In this study, we developed an innovative multiplexing platform based on dual immunosensors for the simultaneous determination of snake and scorpion venoms using a label-free electrochemical platform. The dual immunosensor was fabricated on graphene/gold nanoparticle modified screen-printed electrodes. The electrodes were first modified with two chemical linkers (cysteamine/phenylene diisothiocyanate) to facilitate the immobilization of the antibodies (antivenoms) through covalent binding. The proposed immunosensor was tested with different venoms that specific to six snake species and two scorpion species. The detection was undergone by monitoring the reduction peak current variation after the venom binding using square wave voltammetry, in presence of ferro/ferricyanide redox system. The dual immunosensor enabled a sensitive and selective simultaneous detection of the snake and scorpion species venoms within wide linear ranges in the limits of detection ranging from 0.057 to 0.027 μg/mL. The applicability of the venoms immunosensor has also been evaluated for the detection of snake and scorpion venoms in human serum samples showing high recovery percentages. These achievements show the great potential of our multiplexing approach for the early detection of snake or scorpion envenomation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025. Published by Elsevier B.V.)

Bone tissue, with its complex structure, often necessitates decalcification of the hard tissue for ex vivo morphological studies. The choice of a suitable decalcification method plays a crucial role in preserving desired features and ensuring compatibility with diverse imaging techniques. The search for a universal decalcification method that is suitable for a range of biophotonic analyses remains an ongoing challenge. In this study, we systematically assessed five standard bone decalcification protocols, encompassing strong mineralic acids (3% and 5% nitric acid), a commercially available formulation of hydrochloric and formic acid), as well as weak organic acids (5% trichloroacetic acid and 8% formic acid), and a chelating agent (25% ethylenediamine-tetraacetic acid) with varying decalcification durations, using mouse long bones as our experimental model. Our imaging analysis panel included classical histological staining (Hematoxylin and Eosin, H&E), immunofluorescence staining, and label-free Raman microspectroscopic imaging. We used cryosections instead of paraffin sections since paraffin interferes with tissue Raman signals. This approach is not as commonly used as it is more prone to handling artifacts, but is the preferred method for subsequent Raman analysis. Decalcification efficacy was evaluated based on various qualitative and some quantitative imaging parameters by 2-3 independent observers. Our systematic approach revealed that the chelating agent, when used for 24 h, optimally preserved bone features and, thus, would be the ideal decalcifying agent for comprehensive subsequent analysis. However, the choice of decalcifier and the ideal decalcification duration may vary depending on the type and thickness of bone, necessitating tailored adjustments to meet specific experimental requirements., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

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. LEGO-1-4 permeabilized cytoplasmic membrane of Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, and Escherichia coli, LEGO-1 with the longest linker module being the most effective. Gram-positive bacteria were more sensitive to LEGO-LPPO action compared to Gram-negatives, which was manifested as a delayed membrane permeabilization, higher minimal inhibitory concentration and lower amount of LEGO-LPPO bound to the cells. Outer membrane permeability measurements and time-kill assay showed that presence of the intact outer membrane brought about reduced susceptibility of Gram-negatives. Using liposome leakage and in silico simulations, we showed that membranes with major content of phosphatidylethanolamine were more prone to LEGO-LPPO permeabilization. The proposed mechanism stems from an electrostatic repulsion between highly positively charged LEGO-1 molecules and positively charged amino groups of phosphatidylethanolamine which destabilizes the membrane. Collectively, these data suggest that LEGO-LPPO membrane activity is enhanced by presence of phosphatidylethanolamine but hindered by presence of intact outer membrane., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

In this study, the antioxidant and prooxidant potency of protocatechuic aldehyde (PCA) was evaluated using density functional theory (DFT). The potency of direct scavenging of hydroperoxyl (HOO • ) and lipid peroxyl radicals (modeled by vinyl peroxyl, H 2 C=CHOO • ) involved in lipid peroxidation was estimated. The repair of oxidative damage in biomolecules (lipids, proteins and nucleic acids) and the prooxidant ability of PCA phenoxyl radicals were considered. The repairing potency of PCA was investigated for damaged tryptophan, cysteine, leucine, DNA base guanine and linolenic acid. The thermodynamics and kinetics of the single electron transfer (SET) and formal hydrogen atom transfer (fHAT) mechanisms underlying the studied processes were investigated under physiological conditions in aqueous and lipid environments using the SMD/M06-2X/6-311++G(d,p) level of theory. Sequestration of catalytic Fe 2+ and Fe 3+ ions by PCA, which prevents HO • production via Fenton-like reactions, was modeled. Molecular docking was used to study the inhibitory capability of PCA against xanthine oxidase (XO), one of the enzymes producing reactive oxygen species. The attained results show that PCA has the capability to scavenge lipid peroxyl radicals, repair damaged tryptophan, leucine and guanine, chelate catalytic iron ions and inhibit XO. Thus, PCA could be considered a possible multifunctional antioxidant.

Control of individual spins at the atomic level holds great promise for miniaturized spintronics, quantum sensing, and quantum information processing. Both single atomic and molecular spin centers are prime candidates for these applications and are often individually addressed and manipulated using scanning tunneling microscopy (STM). In this work, we present a hybrid approach and demonstrate a robust method for self-assembly of magnetic organometallic complexes consisting of individual iron (Fe) atoms and molecules on a silver substrate using STM. We employ two types of molecules, bis(dibenzoylmethane) copper(II) [Cu(dbm) 2 ] and iron phthalocyanine (FePc). We show that in both cases, the Fe atoms preferentially attach underneath the benzene ring ligand of the molecules, effectively forming an organometallic half-sandwich arene complex, Fe(C 6 H 6 ), which is akin to the properties of metallocenes. In both situations, a molecule can be combined with up to two Fe atoms. In addition, we observe a change in the magnetic properties of the attached Fe atoms in scanning tunneling spectroscopy, revealing a distinct Kondo signature at the Fe sites. We explain the latter using density functional theory calculations and find that the bond formation between the Fe 3d-orbitals and the benzene π-molecular orbitals creates a favorable situation for Kondo screening of the d xz -like orbitals. Thus, this work establishes a reliable design principle for forming hybrid organometallic complexes and simultaneous tuning of their atomic spin states.d yz -like orbitals. Thus, this work establishes a reliable design principle for forming hybrid organometallic complexes and simultaneous tuning of their atomic spin states.

In this work, a series of DFT and DFT-D methods is combined with double-ζ basis sets to benchmark their performance in predicting the structures of five newly synthesized hexacarbonyl diiron complexes with a bridging ligand featuring a μ-S 2 C 3 motif in a ring-containing unit functionalized with aromatic groups. Such complexes have been considered as [FeFe] hydrogenase catalytic site models with potential for eco-friendly energetic applications. According to this assessment, r 2 SCAN is identified as the density functional recommended for the reliable description of the molecular and crystal structures of the herein studied models. However, the butterfly (μ-S) 2 Fe 2 core of the models demonstrates a minor deformation of its optimized geometry obtained from both molecular and periodic calculations. The FeFe bond length is slightly underestimated while the FeS bonds tend to be too long. Adding the D3(BJ) correction to r 2 SCAN does not lead to any improvement in the calculated structures., (© 2024 Wiley Periodicals LLC.)

Porphyrins and their isomers possess high affinity towards the formation of complexes with metal cations, but their use for the determination of metal cations is rather limited, due to low selectivity. In this study, we have investigated the unsubstituted hemiporphycene, which shows a highly irregular shape of the inner cavity, and very different reactivity with various metal cations in methanol:water solutions. It was found that hemiporphycene can act as a pH-tunable specific probe for the determination of Zn 2+ at pH 8.6 and specific for Cu 2+ detection at pH 5.5., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Due to the industry's rapid growth, the presence of organic pollutants, especially antibiotics, in water and wastewater resources is the main concern for wildlife and human health. Therefore, these days, a significant challenge is developing an efficient, sustainable, and eco-friendly photocatalyst. Natural biological models have numerous advantages compared to artificial model materials. Biological models with unique multi-level structures and morphology can be used to create porous bio-templates to produce hierarchical materials. So, in this work, for the first time, this was achieved by using sorghum grain seeds as a bio-template (natural waste material) and urea as a precursor, through a simple and environmentally friendly method. We believed that natural waste materials with high carbon atom content could be used as both a carbon doping agent and a bio-template, thus improving the physical and optical properties of the resulting materials. In comparison to previous studies on the synthesis of C-doped g-C 3 N 4 , our work offers a greener and more cost-effective approach to synthesis, while also reducing waste material. We succeeded in the photo-degradation of a series of organic pollutants such as phenol, bisphenol A (BPA), and amoxicillin (AMX) in an aqueous solution under solar light illumination., Competing Interests: Declarations. Ethical approval: Not applicable. Consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

We report the synthesis, isolation, and comprehensive characterization of N-heterocyclic carbene gold xanthate (NHC-Au-X, X - xanthate) complexes. These easily accessible complexes demonstrate significant versatility as photocatalysts, facilitating [2+2]-cycloadditions, and as π-catalysts in the intramolecular hydroxylation of allenes and hydrohydrazination of alkynes.

Herein, we present a novel liquid crystal (LC)-based sensing platform utilizing microgel-stabilized Pickering LC droplets dispersed in water for simple and label-free detection of proteins in an aqueous environment. This could be achieved by tailoring the surface of 4-cyano-4'-pentylbiphenyl (5CB) LC droplets dispersed in aqueous medium through the interfacial adsorption of poly( N -isopropylacrylamide) (PNIPAM) microgel particles, followed by the introduction of model surfactants, such as anionic sodium dodecyl sulfate and cationic dodecyltrimethylammonium bromide. These surfactant/microgel complex-coated LC droplets underwent a configurational transition from radial-to-bipolar under a polarized optical microscope, upon exposure to model proteins, namely bovine serum albumin and lysozyme. This transition stemmed from the interfacial adsorption of proteins, which was facilitated by their strong interaction with the preadsorbed microgel particles and surfactant molecules. The adsorption of proteins led to the disruption of the interfacial packing density of surfactant molecules, inducing a switch from homeotropic-to-planar surface anchoring of LCs within the droplets. In addition to providing remarkable Pickering stability to the LC droplets, the microgel coating significantly enhanced the sensitivity of the resulting emulsions to proteins. The dose-response behavior and detection limit of these modified LC droplets were strongly influenced by the microgel concentration, surfactant charge, pH of the medium, and the types of proteins. Notably, the droplets exhibited heightened responsiveness under conditions that favor attractive interactions between the proteins and interfacial surfactant molecules. Thus, this study opens avenues for engineering Pickering LC-based biosensors to discern biomolecular interactions, thereby facilitating various interfacial and sensing applications.

Compositionally complex doping of spinel oxides toward high-entropy oxides is expected to enhance their electrochemical performance substantially. We successfully prepared high-entropy compounds, i.e. the oxide (Zn 0.25 Mg 0.25 Co 0.25 Cu 0.25 )Fe 2 O 4 (HEOFe), lithiated oxyfluoride Li 0.5 (Zn 0.25 Mg 0.25 Co 0.25 Cu 0.25 ) 0.5 Fe 2 O 3.5 F 0.5 (LiHEOFeF), and lithiated oxychloride Li 0.5 (Zn 0.25 Mg 0.25 Co 0.25 Cu 0.25 ) 0.5 Fe 2 O 3.5 Cl 0.5 (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. The average elemental composition of the samples is close to the nominal value. 57 Fe Mössbauer spectroscopy revealed that incorporating Li and F or Cl and forming oxygen defects do not influence the redistribution of Fe 3+ cations over the spinel lattice sites and result in their preferred octahedral coordination. Electrochemical measurements carried out using 2032-coin cells with a Li-metal anode have shown voltammetric charge capacities of 450, 694, and 593 mA h g -1 for HEOFe, LiHEOFeCl, and LiHEOFeF, respectively. The best electrochemical performance of LiHEOFeCl was ascribed to its smallest particle size. Galvanostatic chronopotentiometry at 1C rate confirmed high initial charge capacities for all the samples but galvanostatic curves exhibited capacity decay over 100 charging/discharging cycles. Raman spectroelectrochemical analysis conducted on the LiHEOFeF sample proved the reversibility of the electrochemical process for initial charging/discharging cycles. Electrochemical impedance spectroscopy revealed the lowest initial charge transfer resistance for LiHEOFeCl and its gradual decrease both for LiHEOFeCl and LiHEOFeF during galvanostatic cycling, whereas the charge transfer resistance of HEOFe slightly increases over 100 galvanostatic cycles due to the different mechanism of the electrochemical reduction.

Ion mobility spectrometry (IMS) (also including IMS-IMS measurements) as well as DFT calculations have been used to study isomer distributions and isomer interconversion in a range of electrospray-generated lanthanide chloride cluster anions, Ln x Cl 3 x +1 - (where x = 1-6, and Ln corresponds to the 15 lanthanide elements (except for radioactive Pm)). Where measurement and structural rearrangement timescales allow, we obtain almost quantitative agreement between experiment and theory thus confirming isomer predictions and reproducing isomer intensity ratios. Ln x Cl 3 x +1 - structures reflect strong ionic bonding with limited directionality. Ring and chain motifs dominate for smaller clusters while for larger clusters more compact three-dimensional structures become favourable. At cluster sizes with two or more closely lying isomers, the lanthanide contraction can lead to systematic variations in structure types across the series.

A group of new zwitterion based ionic liquid crystals (ILCs) have been synthesized. Depending on the counter anion (mesylate or hydrogen sulfate) the phase behavior of the resulting ILCs is quite different. Mesylate based ILCs show complex phase behavior with multiple phases depending on the alkyl chain length. In contrast, hydrogen sulfate based systems always exhibit Col r phases irrespective of the alkyl chain length. The latter show much larger ILC mesophase windows and are thermally stable up to ca. 200 °C. All ILCs show reasonable ionic conductivities of up to 10 -4 S cm -1 at elevated temperatures, making these ILCs candidates for intermediate temperature ionic conductors.

Nucleoproteins (N) play an essential role in virus assembly and are less prone to mutation than other viral structural proteins, making them attractive targets for drug discovery. Using an NMR fragment-based drug discovery approach, we identified the 1,3-benzothiazol-2-amine (BZT) group as a scaffold to develop potential antivirals for SARS-CoV-2 nucleocapsid (N) protein. A thorough characterization of BZT derivatives using NMR, X-ray crystallography, antiviral activity assays, and intrinsic fluorescence measurements revealed their binding in the C-terminal domain (CTD) domain of the N protein, to residues Arg 259, Trp 330, and Lys 338, coinciding with the nucleotide binding site. Our most effective compound exhibits a slightly better affinity than GTP and the ALS drug riluzole, also identified during the screening, and displays notable viral inhibition activity. A virtual screening of 218 BZT-based compounds revealed a potential extended binding site that could be exploited for the future development of new SARS-CoV-2 antivirals., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Microorganisms assigned as Cronobacter are Gram-negative, facultatively anaerobic, bacteria widely distributed in nature, home environments, and hospitals. They can also be detected in foods, milk powder, and powdered infant formula (PIF). Additionally, as an opportunistic pathogen, Cronobacter may cause serious infections, sometimes leading to the death of neonates and infants. Thus, it is essential to test food products for the presence of Cronobacter spp. The currently used standard described in ISO 22964:2017 is a laborious method that could be easily replaced by surface-enhanced Raman scattering (SERS). Here, we demonstrate that SERS allows the identification of food-borne bacteria belonging to Cronobacter spp. based on their SERS spectra. For this purpose, twenty-six Cronobacter strains from different food samples were analyzed. Additionally, it was shown that it is possible to differentiate them from other closely related pathogens such as Salmonella enterica subsp. enterica, Escherichia coli, or Enterobacter spp. The SERS results were supported by principal component analysis (PCA), as well as and sequencing of 16S rRNA, rpoB and fusA genes. Last but not least, it was demonstrated that the cells of Cronobacter sakazakii may be easily separated from PIF using an appropriate filter, microfluidic chip, and dielectrophoresis (DEP) technique., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Agnieszka Kaminska reports financial support was provided by Foundation for Polish Science. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

To study the effect of a dye on the photoluminescence (PL) properties of metal complexes, a series of gold(I) complexes were synthesized, containing a 7-amino-4-methylcoumarin luminophore. The complexes are comprised of a coumarin moiety featuring different ancillary ligands, specifically N-heterocyclic carbenes, triphenylphosphine, and diphenyl-2-pyridylphosphine. The synthesized gold(I) complexes are luminescent both in solution and the solid state at room temperature and 77 K. Complexes of different nuclearity, i.e., mono-, di- and trinuclear compounds were synthesized. A clear trend between the nuclearity and the quantum yields can be seen. The coumarin dye not only improves the PL properties, but also enhances the luminescence of trinuclear clusters, which are otherwise known to be weak emitters in solution. The optical absorption properties were investigated in detail by quantum chemical calculations., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We study the conformational, conductometric and rheological properties of semiflexible polyelectrolyte carboxymethyl cellulose in mixtures of water and three non-solvents (ethanol, isopropanol and acetone). Small angle x-ray scattering measurements of the correlation length reveal that the local conformation of the carboxymethyl chain is unchanged by the presence of a non-solvent, even for solutions not far from the solubility boundary. Rheological measurements confirm the invariance of the correlation length upon non-solvent addition. Conductivity measurements show that as the non-solvent content is increased, the fraction of condensed counterions increases, presumably due to the lowering of the dielectric constant of the solvent media. These results therefore show that under room temperature and pressure, the conformation of polyelectrolyte chains is independent of the effective charge fraction of the backbone. We suggest this occurs because the bare Kuhn length (≃10nm) is much larger than electrostatic blob size (≃1-2nm)., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Endocytosis, apart from providing a mechanism for cells to take up nutrients, is the principal route of entry for many nanomedicines. The evaluation of therapeutic delivery efficiency without providing quantitative parameters, like the number of molecules entering the cell and the time of their entry, is very limited. Despite advances in single-molecule methods for in-cell quantitative measurements, they have not become widely used in the study of endocytosis. Their application, however, is challenging owing to the appropriate experimental design and applicable analysis methods. Here, by using an integrated approach based on the multidimensional time-correlated single-photon counting (TCSPC) technique, we demonstrate the quantitative method to measure the time- and concentration-dependent uptake of TRITC-transferrin into living cells with single-molecule sensitivity. The methodology opens possibilities for quantitatively assessing the delivery efficiency of fluorescent molecules into living cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The escalating use of antibiotics across diverse sectors, including human healthcare, agriculture, and livestock, has led to their pervasive presence in the environment, raising concerns about their impact on ecosystems and human health. Traditional detection methods, reliant on high-performance liquid chromatography and immuno-assays, face challenges of complexity, cross-reactivity, and limited specificity. Aptamer-based biosensors offer a promising alternative, leveraging the specificity, stability, and cost-effectiveness of aptamers. Herein, we present a novel dual-screen-printed carbon electrode (SPCE) biosensor, modified with a nanocomposite of gold nanoparticles (AuNPs) and carbon nanofibers (CNFs), for the label-free electrochemical detection of lincomycin and neomycin antibiotics. Lincomycin and neomycin, two antibiotics of environmental concern due to their widespread usage and potential ecological impact, were simultaneously detected using square wave voltammetry. The aptasensors showed high sensitivity with detection limits of 0.02 pg/mL and 0.035 pg/mL for lincomycin and neomycin, respectively. The developed biosensor exhibited high selectivity and reproducibility in detecting both antibiotics. This multiplex biosensing platform offers a promising strategy for efficient and cost-effective monitoring of antibiotic residues in environmental samples, addressing the critical need for robust detection methods in environmental monitoring and public health surveillance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Two In(III) - pyridinecarboxylates ([In(Pic) 2 (NO 3 )(H 2 O)] (InPic; HPic = picolinic acid), [In(HDpic)(Dpic)(H 2 O) 2 ]·5H 2 O (InDpic; H 2 Dpic = 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 1 H NMR spectroscopy and mononuclear complex species were determined; [In(Pic)] 2+ (logβ 011  = 6.94(4)), [In(Pic) 2 ] + (logβ 021  = 11.98(9)), [In(Dpic)] + (logβ 011  = 10.42(6)), [In(Dpic) 2 ] - (logβ 021  = 17.58(7)) and [In(Dpic) 2 (OH)] 2- (logβ - 121 H NMR spectra were measured (immediately after dissolution up to 96 h). Antimicrobial and anticancer assays indicate a more significant sensitivity of S. aureus bacteria and MDA-MB-231 cancer cells to the InPic complex (IC 1 H NMR spectra were measured (immediately after dissolution up to 96 h). Antimicrobial and anticancer assays indicate a more significant sensitivity of S. aureus bacteria and MDA-MB-231 cancer cells to the InPic complex (IC 50  = 50 and 975.4 μM). The interaction and binding mechanism of picolinic/dipicolinic acid and their indium(III) complexes with HSA (human serum albumin) were studied using fluorescence and CD spectroscopy. The results confirmed that the studied compounds had bound successfully to HSA, and the binding parameters and constants (K 50  = 50 and 975.4 μM). The interaction and binding mechanism of picolinic/dipicolinic acid and their indium(III) complexes with HSA (human serum albumin) were studied using fluorescence and CD spectroscopy. The results confirmed that the studied compounds had bound successfully to HSA, and the binding parameters and constants (K SV , K q ) were calculated together with the number of binding sites. The binding forces were identified based on calculated thermodynamic parameters (ΔG, ΔH, ΔS). Synchronous spectra were used to study the microenvironment of Tyr and Trp residues and displacement assays revealed that site I was the preferred binding site. After binding, conformational changes were found to have occurred in the HSA molecule and the % α-helical content had decreased.b ) were calculated together with the number of binding sites. The binding forces were identified based on calculated thermodynamic parameters (ΔG, ΔH, ΔS). Synchronous spectra were used to study the microenvironment of Tyr and Trp residues and displacement assays revealed that site I was the preferred binding site. After binding, conformational changes were found to have occurred in the HSA molecule and the % α-helical content had decreased., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

New voltammetric and flow amperometric methods for the determination of guaifenesin (GFE) using a perspective screen-printed sensor (SPE) with boron-doped diamond electrode (BDDE) were developed. The electrochemical oxidation of GFE was studied on the surface of the oxygen-terminated BDDE of the sensor. The GFE provided two irreversible anodic signals at a potential of 1.0 and 1.1 V (vs. Ag|AgCl|KCl sat.) in Britton-Robinson buffer (pH 2), which was chosen as the supporting electrolyte for all measurements. First, a voltammetric method based on differential pulse voltammetry was developed and a low detection limit (LOD = 41 nmol L -1 ), a wide linear dynamic range (LDR = 0.1-155 μmol L -1 ), and a good recovery in the analysis of model and pharmaceutical samples (RSD <3.0 %) were obtained. In addition, this sensor demonstrated excellent sensitivity and reproducibility in the analysis of biological samples (RSD <3.2 %), where the analysis took place in a drop of serum (50 μL) without pretreatment and additional electrolyte. Subsequently, SP/BDDE was incorporated into a flow-through 3D printed electrochemical cell and a flow injection analysis method with electrochemical detection (FIA-ED) was developed, resulting in excellent analytical parameters (LOD = 86 nmol L -1 , LDR = 0.1-50 μmol L -1 ). Moreover, the mechanism of electrochemical oxidation of GFE was proposed based on calculations of HOMO spatial distribution and spectroelectrochemical measurements focused on IR identification of intermediates and products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Depending on their aspect ratio, rod-shaped particles exhibit a much richer 2D and 3D phase behavior than their spherical counterparts, with additional nematic and smectic phases accompanied by defined orientational ordering. While the phase diagram of colloidal hard rods is extensively explored, little is known about the influence of softness in such systems, partly due to the absence of appropriate model systems. Additionally, investigating higher volume fractions for long rods is usually complicated because non-equilibrium dynamical arrest is likely to precede the formation of more defined states. This has motivated us to develop micrometric rod-like microgels with limited sedimentation that can respond to temperature and reversibly reorganize into defined phases via annealing and seeding procedures. A detailed procedure is presented for synthesizing rod-shaped hollow poly(N-isopropylacrylamide) microgels using micrometric silica rods as sacrificial templates. Their morphological characterization is conducted through a combination of microscopy and light scattering techniques, evidencing the unconstrained swelling of rod-shaped hollow microgels compared to core-shell microgel rods. Different aspects of their assembly in dispersion and at interfaces are further tested to illustrate the opportunities and challenges offered by such systems that combine softness, anisotropy, and thermoresponsivity., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Surfactants play an important role in modifying the properties of water-air interfaces. Here, we combine information from molecular dynamics simulations, surface tensiometry, and vibrational sum-frequency generation spectroscopy to study the interfacial behavior of photoswitchable arylazopyrazole (AAP) surfactants. This combination of the experimental techniques allows a direct relation between surface tension and surface concentration rather than just the bulk concentration. Specifically, we conducted a comparison between two derivatives, one with an octyl terminal group (O-AAP) and the other without this group (H-AAP), focusing on their respective E and Z isomers. From the simulations of these four systems, we see that those with a stronger cluster formation, likely resulting from higher intermolecular attractive interactions, display higher surface tensions for the intermediate surface excess. In some cases, even a small but noticeable maximum in the surface tension isotherm is observed for systems with strong cluster formation. Such a maximum is not observed in the experiments, although such an observation would be compatible with the general properties of the Frumkin isotherm. We exclude that the peak is due to the finite width of the simulation box. Apart from this effect, the general features of the surface tension are consistent between the experiment and simulation. Evidence is also provided that it is primarily the interaction of the aromatic rings that determines the strength of the surfactant interactions.

Heme is involved in many critical processes in pathogenic bacteria as iron acquisition by these microorganisms is achieved by either direct uptake of heme or use of heme-binding proteins called hemophores. Exploring the underlying mechanisms on a molecular level can open new avenues in understanding the host-pathogen interactions. Any imbalance of the heme concentration has a direct impact on the bacterial growth and survival. Thus, heme-regulated proteins that are involved in heme homeostasis poise to be promising targets for research. Similarly, naturally occurring compounds, including cysteine-rich peptides from either plant secondary metabolites or venom toxins from vertebrates and invertebrates, have been studied for their therapeutic potential. NCR247 is such a cysteine-rich peptide, known to be crucial for nitrogenase activity in M. truncatula and its symbiotic relation with S. meliloti. NCR247-derived peptides were suggested to serve as high-affinity heme-binding molecules with remarkable heme-capturing properties. A comprehensive biochemical and computational analysis of NCR247-derived peptides, however, redefines their heme-binding capacity and consequently their potential therapeutic role., (© 2024 Wiley‐VCH GmbH.)

Electrochemical polymerization of 3,4-ethylenedioxythiophene in the presence of water-soluble fullerene derivatives was investigated. The electronic structure, morphology, spectroelectrochemical, electrochemical properties and near-IR photoconductivity of composite films of poly(3,4-ethylenedioxythiophene) with fullerenes were studied for the first time. It was shown that fullerene with hydroxyl groups creates favorable conditions for the formation of PEDOT chains and more effectively compensates for the positive charges on the PEDOT chains. The near-IR photoconductivity results from the generation of charge carriers due to electron transfer from the photoexcited PEDOT molecule to the fullerene acceptor.

Colloidal semiconductor nanocrystals are promising materials for classical and quantum light sources due to their efficient photoluminescence (PL) and versatile chemistry. While visible emitters are well-established, excellent (near-infrared) sources are still being pursued. We present the first comprehensive analysis of low-temperature PL from two-dimensional (2D) PbS nanoplatelets (NPLs). Ultrathin 2D PbS NPLs exhibit high crystallinity confirmed by scanning transmission electron microscopy, revealing Moiré patterns in overlapping NPLs. At 4 K, unique PL features are observed in single PbS NPLs, including narrow zero-phonon lines with line widths down to 0.6 meV and a linear degree of polarization up to 90%. Time-resolved measurements identify trions as the dominant emission source with a 2.3 ns decay time. Sub-meV spectral diffusion and no inherent blinking over minutes are observed, as well as discrete spectral jumps without memory effects. These findings advance the understanding and underscore the potential of colloidal PbS NPLs for optical and quantum technologies.

A domino approach towards β-carboline natural product taraxacine A and its analogues was developed. The main step relies on a silver(I) and base co-catalysed imidate-alkyne cyclization. The reaction tolerates primary and secondary alcohols, and various substitutions in the indole are possible.

The adsorption of ellipsoidal colloidal particles on liquid interfaces induces interfacial deformation, resulting in anisotropic interface-mediated interactions and the formation of superstructures. Soft prolate-shaped microgels at the air-water interface offer an ideal model for studying spontaneous capillary-driven self-assembly due to their tunable aspect ratio, controlled functionality, and softness. These microgels consist of a polystyrene core surrounded by a cross-linked, fluorescently labeled poly([Formula: see text]-isopropylmethylacrylamide) shell. By uniaxially stretching the particles embedded in polyvinyl alcohol films, the aspect ratio [Formula: see text] can be finely adjusted. [Formula: see text] was found to vary from 1 to 8.8 as estimated in their swollen conformation at 20 ° C from confocal laser scanning microscopy. The spontaneous interfacial self-assembly at the air-water interface is investigated through fluorescence microscopy, theoretical calculations, and computer simulations. A structural transition occurs from a seemingly random assembly for small aspect ratios to compact clusters, which transform into a side-to-side assembly forming long chains for high aspect ratios. The influence of the poly([Formula: see text]-isopropylmethacrylamide) shell on the assembly indicates a significant [Formula: see text]-dependent microgel deformation. This deformation, in turn, determines the average distance between the particles. Consequently, capillary-driven self-assembly of soft anisotropic colloids becomes a powerful mechanism for structuring interfaces and designing microstructured materials., Competing Interests: Competing interests statement:The authors declare no competing interest.

This paper presents the results of microbial corrosion tests on M0-grade copper under conditions simulating a geological repository for radioactive waste at the Yeniseisky site (Krasnoyarsk Krai, Russia). The work used a microbial community sampled from a depth of 450 m and stimulated with glucose, hydrogen and sulfate under anaerobic conditions. It was shown that the maximum corrosion rate, reaching 9.8 µm/y, was achieved with the addition of sulfate (1 g/L) with the participation of microorganisms from the families Desulfomicrobiaceae , Desulfovibrionaceae and Desulfuromonadaceae . It was noted that the most important factor leading to copper corrosion was the accumulation of hydrogen sulfide during the activation of sulfate-reducing microorganisms of the genera Desulfomicrobium , Desulfovibrio and Desulfuromonas. During the development of the microbial community under these conditions, the content of copper can have a significant toxic effect at a concentration of more than 250 mg/L.

Surface-enhanced Raman spectroscopy (SERS) has evolved significantly over fifty years into a powerful analytical technique. This review aims to achieve five main goals. (1) Providing a comprehensive history of SERS's discovery, its experimental and theoretical foundations, its connections to advances in nanoscience and plasmonics, and highlighting collective contributions of key pioneers. (2) Classifying four pivotal phases from the view of innovative methodologies in the fifty-year progression: initial development (mid-1970s to mid-1980s), downturn (mid-1980s to mid-1990s), nano-driven transformation (mid-1990s to mid-2010s), and recent boom (mid-2010s onwards). (3) Illuminating the entire journey and framework of SERS and its family members such as tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and highlighting the trajectory. (4) Emphasizing the importance of innovative methods to overcome developmental bottlenecks, thereby expanding the material, morphology, and molecule generalities to leverage SERS as a versatile technique for broad applications. (5) Extracting the invaluable spirit of groundbreaking discovery and perseverant innovations from the pioneers and trailblazers. These key inspirations include proactively embracing and leveraging emerging scientific technologies, fostering interdisciplinary cooperation to transform the impossible into reality, and persistently searching to break bottlenecks even during low-tide periods, as luck is what happens when preparation meets opportunity.

The introduction of 4,5-dihydroazuleno[2,1,8-ija]azulene as a central core between two 1,4-dithiafulvene (DTF) units provides a novel class of extended tetrathiafulvalene (TTF) electron donors. Herein we present the synthesis of such compounds with the azulenoazulene further expanded by annulation to benzene, naphthalene, or thiophene rings. Moreover, unsymmetrical donor-acceptor chromophores with one DTF and one carbonyl at the central core are presented. The effect of the odd-membered rings of the polycyclic aromatic hydrocarbon cores on the geometrical features and the extent of bond conjugation in these systems were investigated by UV/Vis absorption spectroscopy, (spectro)electrochemical studies, X-ray and electron diffraction, and computational studies. Altogether these studies reveal that, upon oxidation, the non-planar core of the bis(benzo)-fused dihydro-azulenoazulene-extended TTF generates a large 22π-aromatic system (together with two 6π-aromatic 1,3-dithiolium appendages) characterized by significant bond length equalizations. The dication formed by oxidation is EPR silent, indicating a singlet ground state. Computations reveal that the closed-shell singlet species and its open-shell singlet counterpart are nearly degenerate and of lower energy than a triplet species. According to cyclic voltammetry, the compounds can be oxidized further and present multi-redox systems., (© 2024 Wiley-VCH GmbH.)

Highly concentrated salt solutions are promising electrolytes for battery applications due to their low flammability, their high thermal stability, and their good compatibility with electrode materials. Understanding transport processes in highly concentrated electrolytes is a challenging task, since strong ion-ion and ion-solvent interactions lead to highly correlated movements on the microscopic scale. Here, we use an experimental overdetermination method to obtain accurate Onsager transport coefficients for concentrated binary electrolytes composed of either sulfolane (SL) or dimethyl carbonate (DMC) as solvent and either LiTFSI or LiFSI as salt. NMR-based electrophoretic mobilities demonstrate that volume conservation applies as a governing constraint for the transport. This fact allows to calculate the Onsager coefficients σ +0 , σ -0 is then defined, which is a measure for the relevance of a vehicular Li σ -solvent transport mechanism. We analyze the influence of the salt anion and of the solvent on dynamic correlations and transport mechanisms. In the case of the sulfolane-based electrolytes, the 00 related to the solvent. A parameter γ is then defined, which is a measure for the relevance of a vehicular Li + -solvent transport mechanism. We analyze the influence of the salt anion and of the solvent on dynamic correlations and transport mechanisms. In the case of the sulfolane-based electrolytes, the γ -sulfolane transport plays a significant role. In the case of DMC-based electrolytes, the + -sulfolane interactions are stronger than Li + -anion interactions and that vehicular Li + -sulfolane transport plays a significant role. In the case of DMC-based electrolytes, the γ -anion interactions and virtually uncorrelated movements of Li + -DMC vs. Li + -anion interactions and virtually uncorrelated movements of Li + ions and DMC molecules.

The spectra of internal friction and temperature dependencies of the frequency of a free-damped oscillation process excited in the specimens of an amorphous-crystalline copolymer of polyoxymethylene with the co-monomer trioxane (POM-C) with a degree of crystallinity ~60% in the temperature range from -150 °C to +170 °C has been studied. It has been established that the spectra of internal friction show five local dissipative processes of varying intensity, manifested in different temperature ranges of the spectrum. An anomalous decrease in the frequency of the oscillatory process was detected in the temperature ranges where the most intense dissipative losses appear on the spectrum of internal friction. Based on phenomenological model representations of a standard linear solid, the physical-mechanical (shear modulus defect, temperature position of local regions of inelasticity) and physical-chemical (activation energy, discrete relaxation time, intensities of detected dissipative processes) characteristics of each local dissipative process were calculated. It was found that the intensities of dissipative processes remain virtually unchanged for both annealed and non-annealed samples. The maximum variation in the shear modulus defect is 0.06%. Additionally, according to computational data, small changes are also characteristic of the following parameters: the activation energy varies from 0.5 to 1.4 kJ/mol and the relaxation time changes from 0.002 to 0.007 s, depending on the presence or absence of annealing. As a result of annealing, there is a significant increase in the relaxation microinheterogenity of the polymer system across the entire temperature range (250% for the low-temperature region and 115% for the high-temperature region).

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., Experiments: We fabricate core-shell ellipsoidal particles with defined aspect ratios and shell thickness through thermo-mechanical stretching. Using interfacial self-assembly experiments, we systematically explore how aspect ratio and shell thickness affect the self-assembly configurations. Monte Carlo simulations and theoretical calculations complement the experiments by mapping the phase diagram of thermodynamically preferred structures as a function of core-shell properties., Findings: Pure ellipsoidal particles without a shell consistently form side-to-side "chain-like" assemblies, regardless of aspect ratio. In contrast, core-shell ellipsoidal particles exhibit a transition from tip-to-tip "flower-like" arrangements to side-to-side structures as aspect ratio increases. The critical aspect ratio for this transition shifts with increasing shell thickness. Our results highlight how we can engineer the self-assembly of anisotropic particles at liquid interfaces by tuning their physicochemical properties such as aspect ratio and shell thickness, allowing the deterministic realization of distinct structural configurations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

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. In this article, we systematically examine the intra-electron correlation, as a statistical measure of electronic phase space, which has been first formally proposed for mapping approaches in the context of the generalized discrete truncated Wigner approximation and which is a key ingredient for the improvement in short-time accuracy of such mapping approaches. We rigorously establish the connection between short-time accuracy and intra-electron correlation for various widely used models. We find that LSC-IVR, PBME, and Ehrenfest methods fail to correctly reproduce the intra-electron correlation. While some of the traceless Meyer-Miller-Stock-Thoss (MMST) approaches, partially linearized density matrix (PLDM) approach, and spin partially linearized density matrix (spin-PLDM) approach are able to sample the intra-electron correlation correctly, the spin linearized semiclassical (spin-LSC) approach, which is a specific example of the classical mapping model, and the other traceless MMST approaches sample the intra-correlation faithfully only for two-level systems. Our theoretical analysis provides insights into the short-time accuracy of semiclassical methods and presents mathematical justifications for previous numerical benchmarks., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

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-). The efficiency of the developed theoretical model is demonstrated by the juxtaposition of predicted centrifugal distortion parameters for several three to eight atomic molecules, including H2S, CH2O, C2H4, CH2D2, CH2F2, CH2Cl2, and B2H6, using the coupled-cluster single double triple/quadruple-ζ level of quantum chemistry. In comparison with the values derived using the customary analytic expressions, the calculated quartic and sextic parameters may improve by an order of magnitude in the fourth and sixth orders, respectively, reaching an accuracy of about 1%. Predicted octic constants can serve as an excellent starting point for fitting to experimental spectra., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)