Equimolar Ratio Research Articles

A self-catalyzing strategy for co-immobilization of two distinct proteins at equimolar ratio: A case study of 3A and 2C to develop a chromatographic method for finding prospective dual-target compoundsfrom complex matrices

BackgroundImmobilized proteins hold promise as the basic units that have enabled a broad range of analytical applications within chemical measurement science. As yet, the co-immobilization of diverse proteins at precise ratio and whether they give rise to improved analytical performance remain challengeable. Herein, we utilized a circularly permuted HaloTag (cpHaloTag) to achieve the co-immobilization of two proteins at precise ratio, which was applied in developing a chromatographic method with improved specificity for pursuing dual-target compounds. ResultsThe methodology involved the fusion 3A and 2C at N- and C-terminuses of cpHaloTag, the immobilization of the fusion protein onto silica gel through bioorthogonal reaction, the morphological and functional characterization, the application in finding dual-target compounds. Expression of the fusion protein in E. coli system showed a yield of milligram level with the presence of 3A and 2C domains. Immobilization of the protein was achieved in 10 min with a reaction efficiency more than 88.5 %. Immobilized 3A-cpHalo-2C exhibited higher specificity and better retentions of canonical compounds of the two enzymes in comparison with the column containing immobilized 3A or 2C alone. In real sample application, screening analysis found that hyperoside, cymaroside, and baicalin were dual-target compounds in concert with 3A and 2C in Shuanghuanglian extract. SignificanceTaking 3A and 2C as probe, we proposed a simple method for direct co-immobilization of diverse proteins from cell lysates and demonstrated an affinity chromatographic-based dual-target compound screening platform. The implications of these methodology are possible to insight the de novo design of multi-target surface for fabricating new bioanalytical methods with improved performance.

Structural, optical, and electrical properties of multi-component P-type oxide-semiconductor Cu-Mn-Sn-O thin films

P-type oxide semiconductors have attracted significant attention as conducting channel layers due to their wide applications in electronic devices. In this study, multi-component oxide-semiconductor Cu1–2xMnxSnxO thin films with x = 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, and 0.33 were prepared on glass substrates using a solution process accompanied by a spin-coating technique. A phase transition between the cupric oxide monoclinic structure and the rock salt structure was observed with increasing concentrations of Mn and Sn, while the concentration of Cu simultaneously decreased in the precursors. The crystallite size decreased throughout the samples, reaching a minimum value of 9.8 nm at an equimolar ratio. Scanning electron microscopy further confirmed this downward trend and indicated an improvement in the quality of the film surfaces. According to the optical absorption measurements, the bandgap energy ranged from 2.68 to 3.44 eV. Interestingly, the sheet resistance of Cu1–2xMnxSnxO films dropped sharply from 5.24 kΩ/sq for CuO to 0.034 kΩ/sq for the film with a molar ratio of Cu:Mn:Sn being 34:33:33.

Evaluating Serum Copeptin as a Promising Biomarker for Predicting Acute Ischaemic Stroke Severity: A Hospital-Based Study on Strokes.

Stroke is the second cause of mortality and the foremost leading cause of disability globally. Many potential biomarkers have been described to contribute to prognosticating the severity in the acute phase of stroke as well as help with risk stratification. Copeptin, an inactive peptide that is produced in an equimolar ratio to arginine vasopressin and adequately mirrors an individual's stress response to acute illnesses like acute ischaemic stroke as evidenced by elevated or increasing levels is being explored in this study to determine its relationship with acute stroke severity and infarct size on admission. This is a cross-sectional study of 80 neuroimaging-confirmed acute ischaemic patients who presented within seven days of symptom onset and 80 control subjects. The ischaemic stroke cases had stroke severity and infarct volume determined on admission by the National Institute of Health Stroke Scale (NIHSS) and neuroimaging (brain CT/MRI). A baseline serum copeptin level was measured in the study subjects. Spearman correlation and Kruskal Wallis test were used to determine the relationship between serum copeptin level with admission NIHSS and infarct size respectively. The receiver operating characteristic (ROC) curve was calculated to determine the sensitivity and specificity of copeptin to predict severity and outcome. The mean age of the study group was 61.3 ± 12.7 years with 55.0% males and 45.0% females. The serum level of copeptin was significantly higher in the stroke cases with a median of 28.6 pmol/L (interquartile range (IQR)- 15.4-31.6 pmol/L) versus 8.8 pmol/L (IQR- 3.2- 10.7 pmol/L) among the stroke-free controls (p= 0.001) at a statistically significant level. There was a weak correlation between copeptin and NIHSS calculated at admission to measure stroke severity (r- 0.02, p= 0.873). Patients with infarct sizes in the fourth quartile (infarct sizes greater than 18.78 cm3) had higher copeptin levels, though this was not statistically significant (H= 2.88; p= 0.410). Admission serum copeptin did not show a statistically significant prognostic value in predicting stroke severity and mortality in stroke patients who presented within seven days of symptomonset with an area under curve (AUC) of 0.51 (95% CI: 0.36-0.65; p= 0.982). In this study, copeptin was higher among the stroke cases compared with the stroke-free controls which suggests a significant prognostic value in risk stratification in the acute phase of stroke; however, this did not significantly correlate with stroke severity and thus warrants further study in this field to elucidate it's fascinating potential as a prognostic biomarker (especially in the acute period) as this may enable allocation of a better-focused therapy for stroke patients.

Penetration of oils into hair.

The objective of this work was to understand how triglyceride plant oils can deliver strength and softness benefits to hair by their penetration. These plant oils are complex mixtures of TAGs, so the initial studies performed were with pure TAGs and then these data compared to plant oils and their measured TAG compositions. LC-MS was used to identify the di and triglycerides in coconut oil, Camellia oleifera oil and safflower seed oil. Penetration of these plant oils and pure individual triglycerides was measured by a differential extraction method. Cross-sections of oils treated with 13C-labelled triolein were studied by NanoSIMS to visualize location of triglyceride inside hair. Fatigue strength was measured using constant stress to generate a survival distribution. Models of the lipid-rich cell membrane complex (CMC) were created with the equimolar ratio of 18-methyl-eicosanoic acid (MEAS), palmitic acid (C16:0) and oleic acid (C18:1). Penetration of the individual pure TAGs was confirmed for all chain lengths and degree of unsaturation tested with higher penetration for shorter chain lengths and unsaturated fatty acids. Detailed compositional analysis of selected plant oils showed a wide variety of TAGs and penetration was also demonstrated for these oils. NanoSIMS and modelling confirmed these TAGs are penetrating the lipid-rich CMC of hair and are interacting with the fatty acids that make up the CMC. All plant oils delivered a fatigue strength improvement by penetration into the CMC and it is proposed that these oils prevent formation and/or propagation of flaws in the CMC network that leads to breakage. Many plant oils with a wide range of triglyceride compositions can penetrate into hair and NanoSIMS data confirmed these oils partition into the lipid-rich cell membrane complex. Penetration studies of individual TAGs shown to be present in these oils confirmed TAGs of varying chain length can penetrate and there is a correlation between increased penetration efficacy and shorter chain lengths and presence of unsaturation in the fatty acid chains. All the oils studied delivered single fibre fatigue strength benefits.

Solid solution strengthening in single-phase Au-Cu-Ni-Pd-Pt-based high-entropy alloys

The Au-Cu-Ni-Pd-Pt system is an ideal benchmark system to investigate the composition-dependent effect on solid solution strengthening in multi-element alloys, in particular high-entropy alloys. It allows studying the strength for deliberately adjusted compositional variations without any phase transformations taking place. In this study, alloy series are produced, in which one element is gradually replaced by another while these two elements are additionally alloyed to an equimolar three-element solid solution. The variations in concentration x are as follows: AuxNi25-x(CuPdPt)75 and NixPt25-x(AuCuPd)75 (x = 0, 5, 10, 15, 20, 25 at%). A non-linear trend of strength vs. concentration x is observed with maximum values close to the equimolar ratio of the two interchanged elements. The observed behavior cannot be explained by the commonly accepted model for solid solution strengthening of Varvenne and co-workers [1]. Possible reasons for the discrepancy between model and experiment are critically discussed.

Screen-Printed Bimetallic Cobalt-Manganese Metal-Organic Framework Electrodes for Electrochemical Detection of Dichlorvos

Organophosphate pesticides are extremely hazardous to human health and the environment, discerning the development of sensitive and selective detection technologies. In this paper, we describe a novel technique for detecting dichlorvos (DDVP), an organophosphate pesticide, using a modified screen-printed electrode (SPE). The metal-organic framework (MOF) containing cobalt and manganese ions in an equimolar ratio was synthesised using a solvothermal method. The synthesized material was characterized using various techniques: FE-SEM, XRD, XPS, BET, Raman spectroscopy, and FTIR. The electro-catalytic behavior of the material was studied utilizing electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The insightful behaviour of the material towards dichlorvos had been investigated through differential pulse voltammetry (DPV) in the concentration range of 1–10 nM with a detection limit of 0.645 nM. Furthermore, we tested our proposed sensor’s selectivity and applicability using real-world samples. Our findings provide insight into the development of highly sensitive and selective detection systems for organophosphate pesticides, which might have implications for environmental monitoring and public health.

Elucidating the dynamics behavior of PFASs at the water and hydrophobic low-melting mixture solvents interphase

In this work, we studied the interphase dynamics of hydrophobic low-melting mixture solvents (LoMMSs) for the advanced remediation of per- and polyfluoroalkyl substances (PFASs) in wastewater systems by using classical molecular dynamics (MD) simulations. We showed the interaction between widely prevalent PFAS-specifically perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and an innovative LoMMS composed of cineole (CIN) and linoleic acid (LNA) at equimolar ratios. Our investigations reveal that the interphase diffusion of PFASs through the LoMMS is a multi-stage process involving diffusion, interface sorption, and subsequent migration into the bulk aqueous phase. The simulations underscore a robust affinity between the PFASs molecules and the LoMMS, with the displacement of PFASs from the water interface marked by the formation of complex hydrogen-bonded networks. This intricate interplay results in a significant reorganization of water molecules, leading to potential clustering at the interface and compression of the fluid phase. These findings not only substantiate the efficacy of LoMMSs in PFASs extraction but also highlight the need to account for competitive interactions at the water interface, which could impede the absorption kinetics. By providing a detailed molecular-level narrative of the interphase capture phenomena, this study paves the way for designing efficient, low-toxicity LoMMS-based systems for the targeted removal of PFASs from contaminated water sources.

Comments on “Investigations on growth, XRD, strain, FTIR, UV–Vis NIR, photoluminescence, SHG, and z-scan analyses of l-cysteine picrate single crystal for NLO and optical limiting applications”

Alexandar et al. (Inorg. Chem. Commun. 159 (2024) 111751) report to have grown “l-cysteine picrate” crystal (LCP) by evaporation of an aqueous solution containing equimolar ratios of l-cysteine and picric acid at 40 °C in a constant temperature bath. A critical analysis of the reported infrared spectral and X-ray powder data, reveals that the LCP crystal is, in fact, picric acid. Previously, Alexandar et al. has claimed to have grown a so-called “l-methioninium picrate” crystal (LMP) (J. Nonlinear Opt. Phys. Mater. 25 (2016) 1650052) which is also improperly characterized as it is devoid of any picrate and LMP is indeed l-methionine. Taking as examples LCP, LMP and the supposedly new crystals “l-methionine succinic acid” (Chem. Phys. Impact 6 (2023) 100203) and “(4-nitrophenyl) methionine” (Indian J. Phys. 97 (2023) 3835) which are, in fact, succinic acid and l-methionine, respectively, we highlight a combined use of infrared spectra and X-ray diffraction data for accurate characterization of known crystals.

A novel zwitterion incorporated Nano-crystalline ceramic and polymer for bacterial resistant dental CAD-CAM block

ObjectivesTo create bacteria-resistant dental CAD-CAM blocks with a biofilm-resistant effect by incorporating Nano-crystalline ceramic and polymer (NCP) with 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA) and at an equimolar ratio, referred to as MS. MethodsExperimental groups comprised NCP blocks containing zwitterions at 0.15wt% (MS015) and 0.45wt% (MS045). NCP blocks without MS served as control (CTRL). Flexural strength, surface hardness, water sorption and solubility, photometric properties, and cytotoxicity were assessed for all samples. Additionally, the resistance to single and multi-species bacterial adhesion was investigated. ResultsMS045 showed significant reduction in flexural strength (P < 0.01) compared to both CTRL and MS015. Both MS015 and MS045 showed significantly increased water sorption and significant reduction in water solubility compared to CTRL. Light transmission remained consistent across all MS content levels, but the irradiance value decreased by 12 % in the MS045 group compared to the MS015 group. Notably, compared to the CTRL group, the MS015 group exhibited enhanced resistance to adhesion by Porphyromonas gingivalis and a multi-species salivary biofilm, with biofilm thickness and biomass reduced by 45 % and 56 %, respectively. ConclusionsNCP containing 0.15 % MS can effectively reduce adhesion of multiple species of bacteria while maintaining physical and mechanical properties. Clinical SignificanceNCP integrating zwitterions is clinically advantageous in resisting bacterial adhesion at internal and external margins of milled indirect restoration.

Synergy between Fe-Co oxide catalysts supported over HZSM-5 for direct conversion of methane to methanol

The direct conversion of methane to methanol over iron and cobalt oxide based composite catalysts supported over HZSM-5 was carried out in a fixed-bed micro reactor under changing process parameters and catalyst compositions. The prepared catalysts were well characterized by various techniques including N2 adsorption desorption, X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), pyridine FTIR, X-ray photoelectron spectroscopy (XPS), UV–vis spectroscopy and temperature programmed reduction (H2-TPR). The characterization results revealed the presence of various reducible iron and cobalt oxide species depending on the Fe/Co molar ratio and total metal oxide loading. Moreover, the XPS and UV–vis spectroscopic results also confirmed the variation of Fe2+/Fe3+ and Co2+/Co3+ species depending on the Fe-Co molar ratio which had strong influence on the performance of the composite catalysts. It was found that the cobalt species favours the formaldehyde formation whereas the iron species promotes the formic acid formation in their respective pure supported oxide catalysts. However, the synergistic effect of iron and cobalt oxide in equimolar ratio in composite catalysts appeared as effective for achieving highest yield of methanol. The methanol selectivity was also influenced by the alteration of various studied process parameters. The higher reaction temperature favoured the overoxidation of methanol to CO2 whereas the methanol selectivity increased with increasing the methane to oxygen ratio. The lattice to adsorbed oxygen ratio also had strong influence on the activity of composite catalysts and methanol selectivity. The highest methanol yield of 1.87% was achieved at the methane conversion of 42.81 % with the 20Fe1Co1Z catalyst at 873 K reaction temperature with CH4/O2 ratio of 2:1 and WHSV of 1030 ml hr−1 gcat−1.

Repression of Acinetobacter baumannii DNA damage response requires DdrR-assisted binding of UmuDAb dimers to atypical SOS box.

The DNA damage response of the multi-drug-resistant nosocomial pathogen Acinetobacter baumannii possesses multiple features that distinguish it from the commonly used LexA repression system. These include the absence of LexA in this genus, the evolution of a UmuD polymerase manager into the UmuDAb repressor of error-prone polymerases, the use of a corepressor unique to Acinetobacter (DdrR), and an unusually large UmuDAb binding site. We defined cis- and trans-acting factors required for UmuDAb DNA binding and gene repression, and tested whether DdrR directly enhances its DNA binding. We used DNA binding assays to characterize UmuDAb's binding to its proposed operator present upstream of the six co-repressed umuDC or umuC genes. UmuDAb bound tightly and cooperatively to this site with ~10-fold less affinity than LexA. DdrR enhanced the binding of both native and dimerization-deficient UmuDAb forms, but only in greater than equimolar ratios relative to UmuDAb. UmuDAb mutants unable to dimerize or effect gene repression showed impaired DNA binding, and a strain expressing the G124D dimerization mutant could not repress transcription of the UmuDAb-DdrR regulon. Competition electrophoretic mobility shift assays conducted with mutated operator probes showed that, unlike typical SOS boxes, the UmuDAb operator possessed a five-base pair central core whose sequence was more crucial for binding than the flanking palindrome. The presence of only one of the two flanking arms of the palindrome was necessary for UmuDAb binding. Overall, the data supported a model of an operator with two UmuDAb binding sites. The distinct characteristics of UmuDAb and its regulated promoters differ from the typical LexA repression model, demonstrating a novel method of repression.IMPORTANCEAcinetobacter baumannii is a gram-negative bacterium responsible for hospital-acquired infections. Its unique DNA damage response can activate multiple error-prone polymerase genes, allowing it to gain mutations that can increase its virulence and antibiotic resistance. The emergence of infectious strains carrying multiple antibiotic resistance genes, including carbapenem resistance, lends urgency to discovering and developing ways to combat infections resistant to treatment with known antibiotics. Deciphering how the regulators UmuDAb and DdrR repress the error-prone polymerases could lead to developing complementary treatments to halt this mechanism of generating resistance.

Natural lipopeptide surfactin inhibits insulin aggregation and prevents amyloid-induced cytotoxicity and inflammation

Despite the centennial of the pioneering discovery of insulin, challenges regarding insulin aggregation at the site of repeated injection, as well as during industrial production, storage, and transportation, have cast a gloom over this remarkable success story. Aggregation substantially impacts the quality, potency, and effectiveness of insulin formulation, decreasing bioavailability, intensifying the risk of immunogenicity, and endangering patient health. Herein, the suitability of Bacillus-derived amphiphilic biosurfactant surfactin was demonstrated to evade temperature-induced fibrillation of insulin. Fluorometric assessment employing thioflavin-T and intrinsic tyrosine fluorescence indicated the dose-dependent reduction in insulin unfolding and subsequent formation of fibrils. Decreased thioflavin fluorescence at the plateau stage and about a 79% increase in fibrillation lag time was observed for samples containing an equimolar ratio of insulin to surfactin. Circular dichroism analysis further indicated about a 30% increase in α-helix content in samples containing an equimolar ratio of insulin and surfactin, as compared to controls. The findings were further bolstered by dynamic light scattering, electron microscopic analysis, and native polyacrylamide gel electrophoresis. Molecular docking and simulation studies did not indicate any structural destabilization of insulin with surfactin, having major interactions at the hydrophobic and potential amyloidogenic regions of insulin B-chain: B12-B19 (VEALYLVC) and B23-B27 (GFFYT) through hydrophobic and hydrogen bonds. Notably, an almost 22% increase in cell viability was observed for cells incubated with aggregated insulin containing equimolar concentrations of SFN. Surfactin also subdued insulin amyloid-induced upregulation of the pro-inflammatory genes. Thus, surfactin may be contemplated as an additive in biopharmaceutical formulations to imbue stability and may also be evaluated as anti-amyloid therapeutics for other pathological proteinopathies.

Limited miscibility in hydrated DPPC – Lyso-PPC systems

Hydrated dipalmitoylphosphatidylcholine (DPPC) and lyso-palmitoylphosphatidylcholine (Lyso-PPC, abbreviated as LPC) mixtures form vesicles composed from periodically or randomly arranged layers and micelle-like nanoparticles, as revealed by a wide range of thermodynamical, structural, and morphological characterization methods. Based on five different experimental methods, we have reconstructed the phase diagram of the system. The micelle-like objects are strongly anisotropic and are identified as bicelles. Even a small amount of LPC induces drastic changes in the thermotropic phase behaviour of DPPC. Here, an interdigitated gel (LβI) structure, coexisting with the other gel phases, forms at moderate LPC concentration. Bicelles and LβI structured vesicles appear in the equimolar LPC ratio range (0.4 ≤ XLPC ≤ 0.6). Two complex phase transition regimes are detectable. Between 36–40 °C, bicelles are pre-melted while domains of LβI structure are “crystallized” through local endothermic and exothermic transitions, respectively. Then, around 42 °C the chains of both the LβI and bicelles melt completely. Above the equimolar LPC ratio range (XLPC > 0.6) the chain melting in the LβI structure vanishes, while this transition still exists in the chain region of bicelles. This wealth of structural forms, due to the weak first order transition characteristics, is highly sensitive for perturbations and interactions induced by e.g. the presence of membrane proteins.

High entropy (HfTiZrVNb)B2 ceramic particulate reinforced Al matrix composites: Synthesis, mechanical, microstructural and thermal characterization

This study aims to introduce a novel type of particulate reinforced Al matrix composite. High entropy (HfTiZrVNb)B2 ceramic particulate reinforced Al matrix composites were produced via a combined process of different powder metallurgy methods. Firstly, boride compounds (HfB2, TiB2, ZrB2, VB2, NbB2) were synthesized in the laboratory scale using the related metal oxide, boron oxide, and magnesium by mechanochemical synthesis (MCS) and leaching processes under optimum conditions. Secondly, the synthesized and purified boride powders were mixed in equimolar ratios using a planetary ball mill for 72 h, and they were sintered at 2000 °C under 30 MPa via spark plasma sintering (SPS). Thirdly, equimolar high entropy (HfTiZrVNb)B2 bulks were crushed, converted into powder forms, and added into Al powders at different amounts as 1, 2, 5, 10, and 15 wt %. Lastly, these powder blends were mechanically alloyed in a vibratory ball mill for 6 h, cold pressed and pressureless sintered at 630 °C for 2 h. For characterization techniques, X-ray diffractometry (XRD), thermal analysis, scanning electron microscopy/energy dispersive spectrometry (SEM/EDS), density measurements using pycnometer and Archimedes' methods, microhardness and dry sliding wear tests were conducted on the sintered composites. The highest hardness (∼1.5 GPa) and the lowest wear rate (∼0.0012 mm3/Nm) were obtained in the Al-15 wt % (HfTiZrVNb)B2 sample.

High entropy alloys (FeCoNi)0.75Cr0.25-xCux – thermal stability and physical properties

The paper reports on the phase stability of the (FeCoNi)0.75Cr0.25-xCux HEA system with equimolar ratio of Fe, Co and Ni by differential scanning calorimetry (DSC) and measurements of physicochemical properties: density, electrical resistivity, Seebeck coefficient, thermal conductivity, and magnetic behaviour in a broad temperature region as well as hardness and elastic modulus at room temperature as a function of the gradual substitution of chromium by copper in a series of (FeCoNi)0.75Cr0.25-xCux alloys with different mole fraction of Cu (x = 0, 0.05, 0.1, 0.15 and 0.2). DSC measurements showed that all alloys are thermally stable. Increasing content of Cu was found (i) to increase the formation of a fcc Cu-rich phase, (ii) to strengthen ferromagnetic interactions, resulting in rising ordered magnetic moments, as well as in growing ferromagnetic transition temperatures, and (iii) to distinctly change physical properties like electrical resistivity, thermal expansion, and mechanical properties. Experimental data regarding the phase stability are supported by CALPHAD calculations.

Study of head and neck squamous cell carcinoma transcriptome after proton therapy

Aim. To evaluate changes in the transcriptome of head and neck squamous cell carcinoma (HNSCC) tissue cells in patients after proton therapy.Materials and methods. Biopsy material obtained from 3 HNSCC patients before and after proton therapy at a total dose of 10 isoGy was homogenized, purified, and concentrated. Then total RNA was isolated with further purification and concentration with the RNA Clean &amp; Concentrator kit (Zymo Research). Library quantitation was assessed using the Qubit 2.0 instrument (Invitrogen, Life Technologies). After isolation of 1 μg total RNA for sequencing, libraries were prepared on the Illumina platform using the TruSeq RNA Sample Prep Kit v2 with a 10-cycle enrichment step according to the manufacturer’s recommendations. The quality of RNA and the resulting libraries was checked using the Agilent 2100 Bioanalyzer system (Agilent Tec. Inc., USA). The RIN parameter for RNA was at least 7. The library concentration was assessed by real-time PCR on the CFX96 Touch Real-Time PCR Detection System (Bio-Rad, USA). Final libraries were pooled in equimolar ratios before sequencing on the Illumina HiSeq 2500 platform using 50 base-pair paired-end reads. The Q20 parameter for all samples was &gt; 97%, and the number of reads averaged 60.2 million per sample. Raw reads were processed using the RTA 1.17.21.3 and Casava 1.8.2 (Illumina). The enrichment analysis was performed using the PANTHER 17.0 software.Results. The transcriptome analysis of HNSCC after proton radiation therapy (5 x 2 isoGy) at a total dose of 10 isoGy revealed 1,414 significantly differentially expressed genes. The 10 most and least expressed genes and their associated signaling pathways were identified. A number of signaling pathways associated with the underexpressed genes were detected in HNSCC after proton therapy, such as: STAT5; PD-1 signaling pathway; marked MET-mediated activation of PTK2 signaling pathway, PDGF signaling; CD22-mediated regulation of BCR; and FCERI-mediated MAPK activation. In addition to the above signaling pathways, activation of collagen degradation, FCGR3A-mediated phagocytosis, and FCGR3A-mediated interleukin (IL)-10 synthesis are of interest. In the enrichment analysis among highly expressed genes, keratinization and biological oxidation processes were activated in HNSCC tissues after proton therapy.Conclusion. Proton therapy in HNSCC leads to overexpression of genes involved in the regulation of keratinization and biological oxidation processes as well as to underexpression of genes associated with suppression of signaling pathways: STAT5, PD-1, MET-mediated activation of PTK2 signaling pathway, PDGF signaling; CD22-mediated regulation of BCR; FCERI-mediated MAPK activation, collagen degradation, FCGR3A-mediated phagocytosis activation, and FCGR3A-mediated IL-10 synthesis. All signaling pathways of underexpressed genes function in HNSCC cells if there is no negative influence on the tumor from outside (irradiation or delivery of antitumor drugs). The predominance of suppressed signaling pathways over activated ones most likely indicates a decrease in the functional potential of cells after proton therapy. The dose-dependence of PT effects necessitates further study of changes in cellular and molecular-genetic signatures of HNSCC after proton irradiation with different doses.

The Synthesis and Structure of Scandium Dichloride of Sterically Demanding Aminopyridinato Ligands

The reaction of the potassium salt of (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)-pyridine-2-yl]-amine (Ap*H) with the equimolar ratio of [ScCl3] in tetrahydrofuran (thf) resulted in the mononuclear mono(aminopyridinato) scandium dichloride complex [Ap*ScCl2(thf)2]. An X-ray analysis showed the title compound to be monomeric. The compound [C40H59Cl2N2O2Sc] crystallized in the monoclinic space group, P21/n, and possessed the following cell parameters: a = 12.4441(8) b = 22.9975(10) c = 13.9971(8) Å, β = 92.297(5)°, V = 4002.5(4) A3, and Z = 4. Hirshfeld analyses show that H…H (91.1%), H…C/C…H (5.0%), and H…Cl/Cl…H (3.9%) are the contributing interactions in the solid-state structure. The compound was further characterized by NMR spectroscopy, and its purity was confirmed by elemental analysis.

Does a “glycine magnesium chloride” crystal exist?

The authors of a recently published paper (J Mol Struct 1277 (2023) 134,839) report to have newly grown seeds of “glycine magnesium chloride” (GMC) crystal by slow evaporation of an aqueous solution containing equimolar ratios of glycine and magnesium chloride. A critical analysis of the unit cell data and infrared spectrum of the so-called GMC crystal reveals the total absence of magnesium chloride, as these correspond to the γ-modification of glycine. In this letter to the Editor, we prove that all papers reporting on so-called GMC, “coumarin doped GMC” CDGMC, and “methylene blue dye doped GMC” MDGMC crystals, are erroneous as the material studied in all cases is γ-glycine. Hence, the quantum mechanical studies on the non-existent GMC, CDGMC and MDCMG crystals have no scientific value.

Development of poly(safranine-co-phenosafranine)/GNPs/MWCNTs nanocomposites for quartz crystal microbalance sensor detection of arsenic (III) ions

Contamination of drinking water by heavy metals is extremely dangerous to human health. The formation of a quartz crystal microbalance (QCM) sensor for the rapid and portable detection of harmful heavy metals such as arsenic (As) ions in water samples is detailed in this work. Equimolar ratios of safranine (SF) and phenosafranine (Ph) copolymers (PSF-Ph) were synthesized via a chemical oxidative polymerization approach. The copolymer was modified with multi-wall carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) at different percentages (1, 3, 5, and 10%) to form nanocomposites of PSF-Ph/MWCNTs/GNPs. Thermal analysis of the nanocomposites revealed that the final polymer decomposition temperature (PDTfinal) values fell between 619 and 630 °C, and the nanocomposite with 10% loading exhibited the highest decomposition temperatures for T10, T30, and T50. The nanohybrid QCM sensor detected As(III) down to parts-per-billion levels based on the change in the oscillation frequency. The sensor was tested on water samples spiked with different concentrations of As(III) (0–20 ppb). A strong linear correlation (R2 ≈ 0.99) between the frequency shift and concentration with a low detection limit (0.1 ppb) validated the quantitative detection capability of the sensor. This QCM platform with an optimal recognition ligand is a promising field-deployable tool for on-site arsenic analysis in water.

The Antimicrobial Effects of Myrosinase Hydrolysis Products Derived from Glucosinolates Isolated from Lepidium draba.

Lepidium draba (hoary cress) is a perennial plant belonging to the Brassicaceae family that produces two dominant glucosinolates (GLSs): glucoraphanin (GRN) and sinalbin (SBN). They represent the stored form, which is converted upon the myrosinase (Myr) hydrolysis activity to active compounds, mainly isothiocyanates (ITCs) such as sulforaphane (SFN) or p-hydroxybenzyl isothiocyanate (pHBITC). Research on ITCs that have proven anticancer, antimicrobial, and chemoprotective properties is usually conducted with pure commercially available compounds. However, these are chemically reactive, making it difficult to use them directly for preventive purposes in dietary supplements. Efforts are currently being made to prepare dietary supplements enriched with GLS and/or Myr. In this study, we report a simple but efficient chromatographic procedure for the isolation and purification of GLSs from MeOH extract from hoary cress based on a combination of ion exchange and gel permeation chromatography on DEAE-Sephadex A-25 and Sephadex LH-20. To obtain the Myr required for efficient hydrolysis of GLSs into antibacterial ITCs, we developed a rapid method for its extraction from the seeds of Lepidium sativum (garden cress). The yields of GLSs were 22.9 ± 1.2 mg GRN (purity 96%) and 10.4 ± 1.1 mg SBN (purity 92%) from 1 g of dry plant material. Both purified GLSs were used as substrates for the Myr. Analysis of the composition of hydrolysis products (HPs) revealed differences in their hydrolysis rates and in the degree of conversion from GLSs to individual ITCs catalyzed by Myr. When GRNs were cleaved, SFNs were formed in an equimolar ratio, but the formation of pHBITCs was only half that of cleaved SBNs. The decrease in pHBITC content is due to its instability compared to SFN. While SFN is stable in aqueous media during the measurement, pHBITC undergoes non-enzymatic hydrolysis to p-hydroxybenzyl alcohol and thiocyanate ions. Testing of the antimicrobial effects of the HPs formed from GRN by Myr under premix or in situ conditions showed inhibition of the growth of model prokaryotic and eukaryotic microorganisms. This observation could serve as the jumping-off point for the design of a two-component mixture, based on purified GLSs and Myr that is, usable in food or the pharmaceutical industry in the future.