Observation of a chemical reaction in a levitating microdroplet cluster and droplet-generated music.

Ordered clusters of water droplets levitating over a heated water surface can be used as chemical microreactors and computational devices. Here we show that a chemical reaction between melamine and cyanuric acid can occur during coalescence of pairs of droplets containing these reagents and lead to the sedimentation of the product, crystals of melamine cyanurate. In rotating droplets, the crystals flash with frequencies dependent mostly on the rotational velocity of the droplets defined by the rotor of the velocity field of the air-vapor flow above the heated water surface. With the Machine Learning (ML) approach, we trace the brightness and frequencies of individual crystals and convert the frequencies into musical notes thus making a "micro-orchestra" of the levitation cluster.

Altering the structures of 3D supramolecular assemblies from melamine and cyanuric acid derivatives in water.

Herein, we obtained two supramolecular assemblies with layered structures from melamine, N-methylmelamine, and hexynyl-cyanuric acid in water. By combination of X-ray diffraction, electron microscopy, and molecular dynamics studies, we found that introducing one methyl group in melamine alters the arrangement of the layers in these structures.

Exploring the Frontiers of Heterometallic Systems: the {FeW5} Octahedral Cluster Complex.

This research presents the first examples of heterometallic octahedral cluster complexes incorporating both 5d and 3d metals, specifically, tungsten and iron. The key compound, (TBA)2[FeW5Br14] (TBA = tetrabutylammonium), exhibits selective ligand substitution reactions at the iron site when exposed to various solvents. Several {FeW5}-type anions, namely, [FeW5Br14]2-, [FeW5Br13(L)]- (L = H2O, DMSO, CH3CN), and [(FeW5Br13)2O]4-, were revealed and characterized by single-crystal X-ray diffraction analysis. The redox properties of [FeW5Br14]2- were studied and compared with those of [W6Br14]2-. Density functional theory calculations demonstrated that the bonding between Fe and W atoms is fundamentally different from the bonding between 4d (Mo-Mo) or 5d (W-W) metals in isotypic {M6} clusters.

Giant ultrafast dichroism and birefringence with active nonlocal metasurfaces.

Switching of light polarization on the sub-picosecond timescale is a crucial functionality for applications in a variety of contexts, including telecommunications, biology and chemistry. The ability to control polarization at ultrafast speed would pave the way for the development of unprecedented free-space optical links and of novel techniques for probing dynamical processes in complex systems, as chiral molecules. Such high switching speeds can only be reached with an all-optical paradigm, i.e., engineering active platforms capable of controlling light polarization via ultrashort laser pulses. Here we demonstrate giant modulation of dichroism and birefringence in an all-dielectric metasurface, achieved at low fluences of the optical control beam. This performance, which leverages the many degrees of freedom offered by all-dielectric active metasurfaces, is obtained by combining a high-quality factor nonlocal resonance with the giant third-order optical nonlinearity dictated by photogenerated hot carriers at the semiconductor band edge.

Introduction of Niobium in the Chemistry of Octahedral Chalcogenide Clusters: Synthesis and Detailed Study of Compounds Based on Condensed and Discrete {Re5NbQ8} (Q = S or Se) Cores.

It is known that niobium practically does not form cluster chalcogenide compounds of the {M6(µ3-Q8)} type, which are widespread in the chemistry of group 6 and 7 metals. This work reports the preparation of a series of polymeric and discrete niobium-containing heterometallic clusters based on the {Re5Nb(µ3-S8)} and {Re5Nb(µ3-Se8)} cores. The compounds were prepared by the high-temperature reaction between rhenium and niobium dichalcogenides in a KCN melt. The 1D polymers K5[Re5NbQ8(CN)5] (Q = S or Se), which were formed as a result of the reaction, crystallize in the structural type of K6[Mo6Se8(CN)5], similar to the previously reported heterometallic clusters K6[Re6-xMoxQ8(CN)5] (x = 2-3). The polymers were solubilized to form discrete anionic clusters [Re5NbQ8(CN)6]4-. The structure and properties of the new clusters were investigated using a combination of X-ray diffraction analysis, UV/vis spectroscopy, high-resolution electrospray mass spectrometry, cyclic voltammetry, and DFT calculations. Among other features, the compounds showed high electrochemical activity, being able to form three redox states in solution with reversible transitions. It was found that redox potentials of the isoelectronic octahedral clusters demonstrate a strong cathodic shift in the sequence [Re5OsSe8(CN)6]3- > [Re6Se8(CN)6]4- > [Re5MoSe8(CN)6]5- > [Re5NbSe8(CN)6]6-, illustrating the effect of systematic changes in the composition of octahedral cluster cores on their properties.

Electrical properties determine the liquid flow direction in plasma-liquid interactions.

During atmospheric pressure plasma impingement, plasma induced liquid flow will influence the transport and distribution of plasma generated charged and reactive species in liquids. We use particle image velocimetry and supplementary pH, conductivity and temperature measurements to investigate electrical properties of an AC kHz plasma jet interacting with water and electrolytes. We observe that the dominant driving mechanism in low conductive solutions are surface forces such as shear stresses and stagnation-pressure induced dimpling. These give upwards flows beneath the plasma-liquid interaction point. In highly conductive solutions, such as water with dissolved salts, the dominant driving mechanism is electro-hydrodynamic forces, with flows directed downwards underneath the plasma jet in our system. We therefore demonstrate that the direction of initial plasma induced liquid flows can be controlled through the addition of salt ions. In electrically grounded salt solutions, we also observe time resolved flow direction switching, possibly due to modification of salt solutions via electrolytic and plasma induced reactions changing the dominant flow mechanism over time.

Photoredox Activation of Fluorinated Organozinc Reagents: Hydrofluoroalkylation of Unactivated and Electron Deficient Alkenes.

Hydrofluoroalkylation of alkenes with organozinc reagents under photocatalytic conditions is described. The fluorinated alkyl radicals were generated from organozincs by the single electron oxidation of the carbon-zinc bond. The radical addition step is followed either by hydrogen atom transfer for unactivated olefins or by a reduction/protonation sequence for strongly accepting arylidenemalononitriles.

Detecting emergence of ruptures in individual layers of the stretched intestinal wall using optical coherence elastography: A pilot study.

We report a new application of compression optical coherence elastography (C-OCE) to monitor the emergence of ruptures in individual layers of longitudinally stretched small-intestine walls using tissue samples (n = 36) from nine minipigs. Before stretching, C-OCE successfully estimated stiffness for each intestine-wall layer: longitudinal muscular layer with serosa, circumferential muscular layer, submucosa and mucosa. In stretched samples, C-OCE clearly visualized initial stiffening in both muscular layers. By 25% elongation, a sharp stiffness decrease for the longitudinal muscular layer, indicated emergence of tears in all samples. With further stretching, for most samples, ruptures emerged in the circumferential muscular layer and submucosa, while mucosa remained undamaged. Histology confirmed the OCE-revealed damaging and absence of tissue damage for ~15% elongation. Thus, C-OCE has demonstrated a high potential for determining the safety tissue-stretching threshold which afterward may be used intraoperatively to prevent rupture risk in intestinal tissues stretched during various diagnostic/therapeutic procedures.

Catalyst- and solvent-free regiospecific SNHAr phosphinylation of pyridines with H-phosphinates mediated by benzoylphenylacetylene.

Pyridines undergo a facile SNHAr phosphinylation with H-phosphinates under catalyst- and solvent-free conditions (50-55 °C) in the presence of benzoylphenylacetylene to afford 4-phosphinylpyridines in up to 68% yield. In this reaction, benzoylphenylacetylene activates the pyridine ring by the formation of a 1,3(4)-dipolar complex, deprotonates H-phosphinates to generate P-centered anions and finally acts as an oxidizer, being eliminated from an intermediate ion pair. Terminal electron-deficient acetylenes (methyl propiolate and benzoylacetylene) are inefficient as mediators in the above SNHAr process.

Gold/cobalt ferrite nanocomposite as a potential agent for photothermal therapy.

The study encompasses an investigation of optical, photothermal and biocompatibility properties of a composite consisting of golden cores surrounded by superparamagnetic CoFe2O4 nanoparticles. Accompanied with the experiment, the computational modeling reveals that each adjusted magnetic nanoparticle redshifts the plasmon resonance frequency in gold and nonlinearly increases the extinction cross-section at ~800 nm. The concentration dependent photothermal study demonstrates a temperature increase of 8.2 K and the photothermal conversion efficiency of 51% for the 100 µg/mL aqueous solution of the composite nanoparticles, when subjected to a laser power of 0.5 W at 815 nm. During an in vitro photothermal therapy, a portion of the composite nanoparticles, initially seeded at this concentration, remained associated with the cells after washing. These retained nanoparticles effectively heated the cell culture medium, resulting in a 22% reduction in cell viability after 15 min of the treatment. The composite features a potential in multimodal magneto-plasmonic therapies.

Cancer fusion transcripts with human non-coding RNAs.

Cancer chimeric, or fusion, transcripts are thought to most frequently appear due to chromosomal aberrations that combine moieties of unrelated normal genes. When being expressed, this results in chimeric RNAs having upstream and downstream parts relatively to the breakpoint position for the 5'- and 3'-fusion components, respectively. As many other types of cancer mutations, fusion genes can be of either driver or passenger type. The driver fusions may have pivotal roles in malignisation by regulating survival, growth, and proliferation of tumor cells, whereas the passenger fusions most likely have no specific function in cancer. The majority of research on fusion gene formation events is concentrated on identifying fusion proteins through chimeric transcripts. However, contemporary studies evidence that fusion events involving non-coding RNA (ncRNA) genes may also have strong oncogenic potential. In this review we highlight most frequent classes of ncRNAs fusions and summarize current understanding of their functional roles. In many cases, cancer ncRNA fusion can result in altered concentration of the non-coding RNA itself, or it can promote protein expression from the protein-coding fusion moiety. Differential splicing, in turn, can enrich the repertoire of cancer chimeric transcripts, e.g. as observed for the fusions of circular RNAs and long non-coding RNAs. These and other ncRNA fusions are being increasingly recognized as cancer biomarkers and even potential therapeutic targets. Finally, we discuss the use of ncRNA fusion genes in the context of cancer detection and therapy.

Radiosensitizing effects of heparinized magnetic iron oxide nanoparticles in colon cancer.

The combination of radiation treatment and chemotherapy is currently the standard for management of cancer patients. However, safe doses do not often provide effective therapy, then pre-treated patients are forced to repeat treatment with often already increased tumor resistance to drugs and irradiation. One of the solutions we suggest is to improve primary course of radiation treatment via enhancing radiosensitivity of tumors by magnetic-guided iron oxide nanoparticles (magnetite). We obtained spherical heparinized iron oxide nanoparticles (hIONPs, ∼20 nm), characterized it by TEM, Infrared spectroscopy and DLS. Then hIONPs cytotoxicity was assessed for colon cancer cells (XTT assay) and cellular uptake of nanoparticles was analyzed with X-ray fluorescence. Combination of ionizing radiation (IR) and hIONPs in vitro caused an increase of G2/M arrest of cell cycle, mitotic errors and decrease in survival (compared with samples exposed to IR and hIONPs separately). The promising results were shown for magnetic-guided hIONPs in CT26-grafted BALB/C mice: the combination of intravenously administrated hIONPs and IR showed 20,8% T/C ratio (related to non-treated mice), while single radiation had no shown significant decrease in tumor growth (72,4%). Non-guided by magnets hIONPs with IR showed 57,9% of T/C. This indicates that ultra-small size and biocompatible molecule are not the key to successful nano-drug design, in each case, delivery technologies need to be improved when transferred to in vivo model.

Mutational dissection of a hole hopping route in a lytic polysaccharide monooxygenase (LPMO).

Oxidoreductases have evolved tyrosine/tryptophan pathways that channel highly oxidizing holes away from the active site to avoid damage. Here we dissect such a pathway in a bacterial LPMO, member of a widespread family of C-H bond activating enzymes with outstanding industrial potential. We show that a strictly conserved tryptophan is critical for radical formation and hole transference and that holes traverse the protein to reach a tyrosine-histidine pair in the protein's surface. Real-time monitoring of radical formation reveals a clear correlation between the efficiency of hole transference and enzyme performance under oxidative stress. Residues involved in this pathway vary considerably between natural LPMOs, which could reflect adaptation to different ecological niches. Importantly, we show that enzyme activity is increased in a variant with slower radical transference, providing experimental evidence for a previously postulated trade-off between activity and redox robustness.

Tissue Elasticity as a Diagnostic Marker of Molecular Mutations in Morphologically Heterogeneous Colorectal Cancer.

The presence of molecular mutations in colorectal cancer (CRC) is a decisive factor in selecting the most effective first-line therapy. However, molecular analysis is routinely performed only in a limited number of patients with remote metastases. We propose to use tissue stiffness as a marker of the presence of molecular mutations in CRC samples. For this purpose, we applied compression optical coherence elastography (C-OCE) to calculate stiffness values in regions corresponding to specific CRC morphological patterns (n = 54). In parallel to estimating stiffness, molecular analysis from the same zones was performed to establish their relationships. As a result, a high correlation between the presence of KRAS/NRAS/BRAF driver mutations and high stiffness values was revealed regardless of CRC morphological pattern type. Further, we proposed threshold stiffness values for label-free targeted detection of molecular alterations in CRC tissues: for KRAS, NRAS, or BRAF driver mutation-above 803 kPa (sensitivity-91%; specificity-80%; diagnostic accuracy-85%), and only for KRAS driver mutation-above 850 kPa (sensitivity-90%; specificity-88%; diagnostic accuracy-89%). To conclude, C-OCE estimation of tissue stiffness can be used as a clinical diagnostic tool for preliminary screening of genetic burden in CRC tissues.

Clinical and genetic factors involved in Porto-sinusoidal vascular disorder after oxaliplatin exposure.

BACKGROUND AND AIMS: Oxaliplatin (OX) has been described as a potential etiologic agent for porto-sinusoidal vascular disorder (PSVD). Our aim was to describe the natural history of PSVD due to OX in colon cancer (CRC) and identify risk factors for its development. METHODS: We made a multicenter retrospective case-control (ratio 1:3) study with patients diagnosed of PSVD-OX. Baseline data, end of treatment, years of follow-up and diagnosis of PSVD were collected and compared to controls (without PSVD). Besides, 16 different SNPs were selected from bibliography and analyzed by genotyping in the case group to identify potential genetic risk factors. RESULTS: 41 cases were identified, with a median time to PSVD diagnosis after the end of OX of 34 months. Spleen diameter was the strongest predictor of PSVD during treatment (OR 43.94 (14.48-133.336); p < 0.0001). Additionally, thrombocytopenia (<150 × 10^9) at one year was a significant disease risk marker (OR 9.35; 95% CI: 3.71-23.58; p = 0.001). We could not establish any significant association between the selected SNPs and PSVD diagnosis. CONCLUSION: The increase of spleen diameter is the strongest predictor of PSVD in patients treated with OX for CRC. These patients could be candidates for a specific follow-up of portal hypertension-related complications.

Tungsten Oxide Dispersed on Silica as Robust and Readily Available Oxo/Imido Heterometathesis Catalyst.

Continuing our investigation of catalytic oxo/imido heterometathesis as novel water-free method for C=N bond construction, we report here the application of classical transition metal oxides dispersed on silica (MOx/SiO2, M=V, Mo, W) as cheap, robust and readily available alternative to the catalysts prepared via Surface Organometallic Chemistry (SOMC). The oxide materials demonstrated activity in heterometathetical imidation of ketones, WO3/SiO2 being the most efficient. We also describe a new well-defined supported W imido complex (≡SiO)W(=NMes)2(Me2Pyr) (Mes=2,4,6-Me3C6H2, Me2Pyr=2,5-dimethylpyrrolyl) and characterize it with SOMC protocols, which allowed us to identify the position of W on the oxo/imido heterometathesis activity scale (Mo

Exploration of Vitamin B6-Based Redox-Active Pyridinium Salts Towards the Application in Aqueous Organic Flow Batteries.

Pyridoxal hydrochloride, a vitamin B6 vitamer, was synthetically converted to a series of diverse redox-active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory-scale flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery was charged completely, corresponding to the transfer of two electrons to the electrolyte, but no discharge was observed. Both CV analysis and electrochemical simulations confirmed that the redox wave observed in the experimental voltammograms corresponds to a two-electron process. To explain the irreversibility in the battery tests, we conducted bulk electrolysis with the benzoyl pyridinium salts, affording the corresponding benzylic secondary alcohols. Computational studies suggest that the reduction proceeds in three consecutive steps: first electron transfer (ET), then proton-coupled electron transfer (PCET) and finally proton transfer (PT) to give the secondary alcohol. 1H NMR deuterium exchange studies indicated that the last PT step is not reversible in 0.1 M NaOH, rendering the entire redox process irreversible. The apparent reversibility observed in CV at the basic media likely arises from the slow rate of the PT step at the timescale of the measurement.

Two-year retest reliability and predictive validity of the Self- and Informant-Personality Inventory for ICD-11 in older adults.

The International Classification of Diseases, 11th edition (ICD-11) adopted a fully dimensional model of personality disorder. The Personality Inventory for ICD-11 (PiCD) and Informant-Personality Inventory for ICD-11 (IPiC) were developed to assess the ICD-11 trait model, and the PiCD has since received significant validation support. However, there has only been one prior study of longitudinal predictive validity of the PiCD, two relatively short test-retest reliability studies of the PiCD, and no prior longitudinal tests of the IPiC. Longitudinal psychometric support for psychological assessment measures is essential. The present study provides a longer, larger, 2-year psychometric validation test of the PiCD and IPiC. Participants (N = 711) and their informants (N = 569) were recruited in the St. Louis Personality and Aging Network. The results demonstrated strong 2-year retest reliability for the PiCD and IPiC, as well as mean-level stability. Additionally, we explored the relationships between the PiCD and IPiC and important life outcome measures (depressive symptoms, satisfaction with life, and health status). The analysis revealed several significant associations between PiCD and IPiC scales and the outcome variables across time. Further, the PiCD Negative Affectivity and IPiC Detachment scales demonstrated incremental validity over each other and the outcome variables at Wave 1 in the prediction of depressive symptoms and satisfaction with life, respectively. The findings provide essential longitudinal test-retest reliability and predictive validity support for the PiCD and IPiC. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Perineuronal Net Microscopy: From Brain Pathology to Artificial Intelligence.

Perineuronal nets (PNN) are a special highly structured type of extracellular matrix encapsulating synapses on large populations of CNS neurons. PNN undergo structural changes in schizophrenia, epilepsy, Alzheimer's disease, stroke, post-traumatic conditions, and some other brain disorders. The functional role of the PNN microstructure in brain pathologies has remained largely unstudied until recently. Here, we review recent research implicating PNN microstructural changes in schizophrenia and other disorders. We further concentrate on high-resolution studies of the PNN mesh units surrounding synaptic boutons to elucidate fine structural details behind the mutual functional regulation between the ECM and the synaptic terminal. We also review some updates regarding PNN as a potential pharmacological target. Artificial intelligence (AI)-based methods are now arriving as a new tool that may have the potential to grasp the brain's complexity through a wide range of organization levels-from synaptic molecular events to large scale tissue rearrangements and the whole-brain connectome function. This scope matches exactly the complex role of PNN in brain physiology and pathology processes, and the first AI-assisted PNN microscopy studies have been reported. To that end, we report here on a machine learning-assisted tool for PNN mesh contour tracing.

Ankle arthrodesis through minimally-invasive transfibular approach: a new surgical technique.

PURPOSE: The purpose of our work was to demonstrate the surgical technique of ankle arthrodesis using the minimally-invasive transfibular (MITF) approach, which minimizes soft tissue damage and is advantageous for high-risk patients. METHODS: In this prospective study, a total of 12 patients with end-stage varus ankle osteoarthritis, including high-risk individuals, underwent ankle arthrodesis using the MITF approach. The technique involves a unique osteotomy at the joint space level, minimizing soft tissue detachment from the fibula. The primary outcomes assessed included bony union, time to weight-bearing, correction of varus deformity, and functional outcomes measured by the American Orthopedic Foot and Ankle Society (AOFAS) hindfoot scale. However, the study's limitations encompass a small sample size and the absence of a control group. RESULTS: At 6 months post-operation, all patients achieved bony union, with a mean time to union of 13.7 ± 5.2 weeks. The average time to initiate weight-bearing without additional support was 11.2 ± 3.8 weeks. Preoperative varus deformity (17.08 ± 8.36 degrees) and talar tilt (8.75 ± 4.33 degrees) were successfully corrected, with postoperative alignment within 0-5 degrees of valgus. Functional outcomes showed a significant improvement in AOFAS scores from 37.83 ± 7.79 points preoperatively to 77.42 ± 5.63 points one year after surgery (p = 0.002). Minor complications occurred in two patients, both effectively treated with local therapy and antibiotics. CONCLUSIONS: The MITF approach for ankle arthrodesis demonstrates promising results in addressing end-stage varus ankle osteoarthritis, even in high-risk patients. However, the study's limitations highlight the need for a prospective comparative clinical trial with a larger sample size to ascertain the technique's effectiveness and safety definitively.