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A novel tridentate ligand featuring an acridine core and pyrazole rings, namely 2,7- di-tert-butyl-4,5-di(pyrazol-1-yl)acridine, L, was designed and used to create two ruthenium(II) complexes: [RuL2](PF6)2 and [Ru(tpy)L](PF6)2. Surprisingly, the ligand adopted different coordination modes in the complexes: facial coordination for the homoleptic complex and meridional coordination for the heteroleptic complex. The electronic absorption and electrochemical properties were evaluated. Although both complexes exhibited favorable electronic properties for luminescence, neither emitted light at room temperature nor at 77 K. This study highlights the complex interplay between ligand design, coordination mode, and luminescence in ruthenium(II) complexes. [ABSTRACT FROM AUTHOR]

Total amount of creatine (Cr) and phosphocreatine, or total creatine (tCr), may have a significant impact on the performance of skeletal muscles. In sports such as bodybuilding, it is popular to take Cr supplements to maintain tCr level. However, no study has explored the quantitative relationship between exercise intensity and the induced change in muscle's tCr. In this well‐controlled study, straight‐leg plantar flexion with specific load and duration was performed by 10 healthy subjects inside an MRI scanner, immediately followed by 1H MR spectroscopy (MRS) for measuring tCr concentration in gastrocnemius. For repeatability assessment, the experiment was repeated for each subject on two different days. Across all the subjects, baseline tCr was 46.6 ± 2.4 mM, ranging from 40.6 to 50.1 mM; with exercise, tCr significantly decreased by 10.9% ± 1.0% with 6‐lb load and 21.0% ± 1.3% with 12‐lb load (p < 0.0001). Between two different days, baseline tCr, percentage decrease induced by exercise with a 6‐lb and 12‐lb load differed by 2.2% ± 2.3%, 11.7% ± 6.0% and 4.9% ± 3.2%, respectively. In conclusion, the proposed protocol of controlled exercise stimulation and MRS acquisition can reproducibly monitor tCr level and its exercise‐induced change in skeletal muscles. The measured tCr level is sensitive to exercise intensity, so can be used to quantitatively assess muscle performance or fatigue. [ABSTRACT FROM AUTHOR]

A strained triple nanohoop with a shared central benzene unit is synthesized using a threefold intramolecular ring‐closing approach. Among the five possible constitutional isomers, the isomer with the highest D3h symmetry is isolated, the structure of which contains three nanohoop blades and a central hexaphenylbenzene unit. The structure is elucidated using NMR spectroscopy and mass spectrometry. The optical and electrochemical properties are investigated, revealing a moderate fluorescence quantum yield of 40 %. A water‐soluble nanomaterial is prepared using a nanoparticle encapsulation method, and a fluorescence quantum yield of 10 % is retained, which demonstrates the potential of the nanomaterial in biological systems. [ABSTRACT FROM AUTHOR]

Objective: Although astrocytic pathology is a pathological hallmark of progressive supranuclear palsy (PSP), its pathophysiological role remains unclear. This study aimed to assess astrocyte reactivity in vivo in patients with PSP. Furthermore, we investigated alterations in brain lactate levels and their relationship with astrocyte reactivity. Methods: We included 30 patients with PSP‐Richardson syndrome and 30 healthy controls; in patients, tau deposition was confirmed through 18F‐florzolotau positron emission tomography. Myo‐inositol, an astroglial marker, and lactate were quantified in the anterior cingulate cortex through magnetic resonance spectroscopy. We measured plasma biomarkers, including glial fibrillary acidic protein as another astrocytic marker. The anterior cingulate cortex was histologically assessed in postmortem samples of another 3 patients with PSP with comparable disease durations. Results: The levels of myo‐inositol and plasma glial fibrillary acidic protein were significantly higher in patients than those in healthy controls (p < 0.05); these increases were significantly associated with PSP rating scale and cognitive function scores (p < 0.05). The lactate level was high in patients, and correlated significantly with high myo‐inositol levels. Histological analysis of the anterior cingulate cortex in patients revealed reactive astrocytes, despite mild tau deposition, and no marked synaptic loss. Interpretation: We discovered high levels of astrocyte biomarkers in patients with PSP, suggesting astrocyte reactivity. The association between myo‐inositol and lactate levels suggests a link between reactive astrocytes and brain energy metabolism changes. Our results indicate that astrocyte reactivity in the anterior cingulate cortex precedes pronounced tau pathology and neurodegenerative processes in that region, and affects brain function in PSP. ANN NEUROL 2024;96:247–261 [ABSTRACT FROM AUTHOR]

A novel diphenyl monomer, dimethyl 2,2'-(((ethane-1,2-diylbis(oxy))bis(4-acetyl-3,1-phenylene))bis(oxy))diacetate (EDPD), was synthesized from methyl 2-(4-acetyl-3-hydroxyphenoxy)acetate (MAHA), a 2,4-dihydroxyacetophenonederivative, and combined with 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or p-phenylenedimethanolto afford a series of biodegradable polyesters via melt polymerization. The polyesters were characterized by Fourier transform infrared and proton nuclear magnetic resonance spectroscopy, gel permeation chromatography, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The weight-average molecular weight (Mw) of the polyesters varied from 3.2–4.4 × 104 g/mol, the glass transition temperature (Tg) from 52 to 80 °C, and the 5% decomposition temperature (Td,5%) was in the 334–362 °C range. All the samples exhibited high yield strength (53–68 MPa) and elongation at break (230–330%) values, comparable with poly(ethylene terephthalate) (PET), owing to their aromatic character. Degradability testing of the polyesters in soil yielded mass losses reaching up to 7% after 32 weeks. In ecotoxicity testing, earthworms had a survival rate of more than 80% after 14 d of incubation, indicating relatively low toxicity. Overall, the good thermal and mechanical properties, biodegradability and low ecotoxicity of the polyesters make them promising materials for packaging applications, in replacement for PET, thereby promoting carbon neutrality and sustainable development. [ABSTRACT FROM AUTHOR]

BACKGROUND: The pickling process with NaCl is an essential step for pork preservation. This study aimed to investigate the effect of different ultrasonic intensities of tri‐frequency simultaneous ultrasound (TSIU) pickling on the NaCl content and quality of pork (longissimus dorsi). After 30 min pickling, the NaCl content, moisture content, pickling yield, cooking loss, textural properties, color, pH, moisture migration and distribution as well as microstructure of pork were assessed. RESULTS: Results showed that among all the ultrasonic treatment intensities (85–150 W L−1), the NaCl content of the sample pickled by an intensity of 101.3 W L−1 was higher than that of other intensities. TSIU 101.3 W L−1 showed 59.95% higher NaCl content than the control sample. In addition, the sample treated with TSIU of 101.3 W L−1 had higher pickling yield and moisture content, better textural properties of pork (including hardness and chewiness), and less cooking loss. The results of the low‐field nuclear magnetic resonance showed that, compared with the control group, the relaxation time T21 of the ultrasound‐assisted pickling samples increased, while the proportion of T22 (A22) reduction ranged from 175.0% to 379.9%. The microstructure designated that the ultrasonic treatment could facilitate changes in meat texture. CONCLUSION: Ultrasound marination of different intensities promoted the diffusion of NaCl and affected the quality of pork tenderloins. The TSIU at 101.3 W L−1 could better accelerate NaCl transport and homogeneous distribution on meat, thereby improving the sample quality. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

The synthesis of the phosphorus‐capped heptaphenylsilsesquioxane T7Ph7P is reported. We show that, unlike previous examples, it readily forms Lewis acid‐base adducts with boranes of different steric demand and the FeCO4 fragment. All complexes were characterized by multinuclear NMR and IR spectroscopy in solution and the solid state. The molecular structures of the adducts with BPh3 and B(C6F5)3 were determined from XRD suitable single crystals. The relative conformation of the Ph and C6F5 rings in T7Ph7P−B(C6F5)3 suggests favorable π‐interactions, stabilizing the adducts to such a degree that attempts to activate H2 or CO2 were unsuccessful. [ABSTRACT FROM AUTHOR]

This study focuses on the synthesis of H‐ and MeO‐ functionalized alkali metal hypersilyl borates. Consequently, two distinct silanides were used as polysilane frameworks for our chemical manipulations. Tris(silyl)silanide (1) and tris(trimethoxysilyl)silanide (2) react in the same manner with the BH3 ⋅ SMe2 complex to obtain two new alkali metal hypersilyl borates [(R3Si)3SiBH3M (M=alkali metal; R=H, (3), R=MeO, (4 a–c))] in good to excellent yields. NMR spectroscopy for all compounds and single‐crystal X‐ray crystallography for 3 and 4 a, b enabled a clear structural characterization. Single crystal X‐ray analysis of 3 showed a dimeric structure, where two THF‐molecules and three hydrides from the BH3‐group contribute to the coordination sphere of the lithium atom. Interestingly, crystals suitable for X‐ray analysis of 4 a and 4 b showed a solvent‐free cluster formation, due to the coordination of the MeO groups. Both species form coordination polymers with different coordination modes depending on the nature of the alkali metal. Attempted hydride abstraction reactions of 3 and 4 with various reagents under the formation of the free boranes proceeded unselectively. [ABSTRACT FROM AUTHOR]

A series of organotin heterocycles of general formula [{Me2C(C6H3CH2)2O}SnR2] [R = methyl (Me, 4), n‐butyl (n‐Bu, 5), benzyl (Bn, 6) and phenyl (Ph, 7)] was easily synthesized by a Barbier‐type reaction assisted by the sonochemical activation of metallic magnesium. The 119Sn{1H} NMR data for all four compounds confirm the presence of a central Sn atom in a four‐coordinated environment in solution. Single‐crystal X‐ray diffraction studies for 17,17‐dimethyl‐7,7‐diphenyl‐15‐oxa‐7‐stannatetracyclo[11.3.1.05,16.09,14]heptadeca‐1,3,5(16),9(14),10,12‐hexaene, [Sn(C6H5)2(C17H16O)], 7, at 100 and 295 K confirmed the formation of a mononuclear eight‐membered heterocycle, with a conformation depicted as boat–chair, resulting in a weak Sn...O interaction. The Sn and O atoms are surrounded by hydrophobic C—H bonds. A Hirshfeld surface analysis of 7 showed that the eight‐membered heterocycles are linked by weak C—H...π, π–π and H...H noncovalent interactions. The pairwise interaction energies showed that the cohesion between the heterocycles are mainly due to dispersion forces. [ABSTRACT FROM AUTHOR]

The highly cytotoxic macrocyclic trichothecene Isororidin A (C29H40O9) was isolated from the fungus Myrothesium verrucaria endophytic on the wild medicinal plant 'Datura' (Datura stramonium L.) and was characterized by one‐ (1D) and two‐dimensional (2D) NMR spectroscopy. The three‐dimensional structure of Isororidin A has been confirmed by X‐ray crystallography at 0.81 Å resolution from crystals grown in the orthorhombic space group P212121, with one molecule per asymmetric unit. Isororidin A is the epimer of previously described (by X‐ray crystallography) Roridin A at position C‐13′ of the macrocyclic ring. [ABSTRACT FROM AUTHOR]

We evaluated the impacts of COVID‐19 on multi‐organ and metabolic function in patients following severe hospitalised infection compared to controls. Patients (n = 21) without previous diabetes, cardiovascular or cerebrovascular disease were recruited 5–7 months post‐discharge alongside controls (n = 10) with similar age, sex and body mass. Perceived fatigue was estimated (Fatigue Severity Scale) and the following were conducted: oral glucose tolerance (OGTT) alongside whole‐body fuel oxidation, validated magnetic resonance imaging and spectroscopy during resting and supine controlled exercise, dual‐energy X‐ray absorptiometry, short physical performance battery (SPPB), intra‐muscular electromyography, quadriceps strength and fatigability, and daily step‐count. There was a greater insulin response (incremental area under the curve, median (inter‐quartile range)) during the OGTT in patients [18,289 (12,497–27,448) mIU/min/L] versus controls [8655 (7948–11,040) mIU/min/L], P < 0.001. Blood glucose response and fasting and post‐prandial fuel oxidation rates were not different. This greater insulin resistance was not explained by differences in systemic inflammation or whole‐body/regional adiposity, but step‐count (P = 0.07) and SPPB scores (P = 0.004) were lower in patients. Liver volume was 28% greater in patients than controls, and fat fraction adjusted liver T1, a measure of inflammation, was raised in patients. Patients displayed greater perceived fatigue scores, though leg muscle volume, strength, force‐loss, motor unit properties and post‐exercise muscle phosphocreatine resynthesis were comparable. Further, cardiac and cerebral architecture and function (at rest and on exercise) were not different. In this cross‐sectional study, individuals without known previous morbidity who survived severe COVID‐19 exhibited greater insulin resistance, pointing to a need for physical function intervention in recovery. What is the central question of the study?What are the post‐COVID‐19 symptoms and associated metabolic and physiological sequelae in patients who contracted acute severe infection compared to healthy control volunteers?What is the main finding and its importance?Patients 5–7 months after hospital discharge for acute severe COVID‐19 compared to healthy control volunteers had (i) an increased insulin response to an oral glucose challenge, without demonstrating different whole‐body fuel oxidation rates, and (ii) greater perception of fatigue and worse functional mobility, though no abnormalities in muscle, heart or brain structure and function were identified. This provides novel targets for rehabilitation strategies in individuals recovering after severe COVID‐19. [ABSTRACT FROM AUTHOR]

Summary: Succinic semialdehyde dehydrogenase deficiency (SSADHD) is an inherited metabolic disorder of γ‐aminobutyrate (GABA) catabolism. Cerebral waste clearance along glymphatic perivascular spaces depends on aquaporin 4 (AQP4) water channels, the function of which was shown to be influenced by GABA. Sleep disturbances are associated independently with SSADHD and glymphatic dysfunction. This study aimed to determine whether indices of the hyperGABAergic state characteristic of SSADHD coincide with glymphatic dysfunction and sleep disturbances and to explicate the modulatory effect that GABA may have on the glymphatic system. The study included 42 individuals (21 with SSADHD; 21 healthy controls) who underwent brain MRIs and magnetic resonance spectroscopy (MRS) for assessment of glymphatic dysfunction and cortical GABA, plasma GABA measurements, and circadian clock gene expression. The SSADHD subjects responded to an additional Children's Sleep Habits Questionnaire (CSHQ). Compared with the control group, SSADHD subjects did not differ in sex and age but had a higher severity of enlarged perivascular spaces in the centrum semiovale (p < 0.001), basal ganglia (p = 0.01), and midbrain (p = 0.001), as well as a higher MRS‐derived GABA/NAA peak (p < 0.001). Within the SSADHD group, the severity of glymphatic dysfunction was specific for a lower MRS‐derived GABA/NAA (p = 0.04) and lower plasma GABA (p = 0.004). Additionally, the degree of their glymphatic dysfunction correlated with the CSHQ‐estimated sleep disturbances scores (R = 5.18, p = 0.03). In the control group, EPVS burden did not correlate with age or cerebral and plasma GABA values. The modulatory effect that GABA may exert on the glymphatic system has therapeutic implications for sleep‐related disorders and neurodegenerative conditions associated with glymphatic dysfunction. [ABSTRACT FROM AUTHOR]

In order to improve the PI resin's processability and thermal properties, a novel diamine monomer bis(p-aminophenylethynyl)dimethylsilane was designed and synthesized by introducing silicon and alkyne groups in this paper. And a new thermosetting polyimide resin SiOPI with silicon and alkynyl structures in the main chain was prepared using 4,4′-oxobis (phthalic anhydride) (ODPA) as the dianhydride monomer with this diamine monomer. The structures of the diamine monomer and the polyimide were characterized by H nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FT-IR), mass spectrometry (MS), and X-ray diffraction (XRD), respectively. The incorporation of silyl groups into the PI increases the flexibility of the resin and provides good solubility and processability. The SiOPI is well soluble in DMF, DMSO and THF. The resin has a viscosity of less than 200 Pa·s at 50–88°C and has a wide processability range. By virtue of the introduction of alkyne groups, the cured polyimide forms dense reticulated structures, analogous to the benzene ring, giving the resin excellent heat resistance and mechanical property. The glass transition temperature (Tg) of SiOPI reached 367°C, and the heat loss temperature at 5% (Td5) is 540.9°C, the heat loss temperature at 10% (Td10) is 592.2°C, and the residual carbon rate at 800°C (R800°C) is 65.76% in a nitrogen atmosphere. The tensile strength of c-SiOPI is 257.6 MPa at room temperature and 232.9 MPa with a retention rate of 90.41% at 300°C, respectively. [ABSTRACT FROM AUTHOR]

Alterations in the structure, function, and microcirculation of the thalamus, a key brain region involved in pain pathways, have previously been demonstrated in patients with painless and painful diabetic peripheral neuropathy (DPN). However, thalamic neurotransmitter levels including γ-aminobutyric acid (GABA) (inhibitory neurotransmitter) and glutamate (excitatory neurotransmitter) in different DPN phenotypes are not known. We performed a magnetic resonance spectroscopy study and quantified GABA and glutamate levels within the thalamus, in a carefully characterized cohort of participants with painless and painful DPN. Participants with DPN (painful and painless combined) had a significantly lower GABA:H2O ratio compared with those without DPN (healthy volunteers [HV] and participants with diabetes without DPN [no DPN]). Participants with painless DPN had the lowest GABA:H2O ratio, which reached significance compared with HV and no DPN, but not painful DPN. There was no difference in GABA:H2O in painful DPN compared with all other groups. A significant correlation with GABA:H2O and neuropathy severity was also seen. This study demonstrates that lower levels of thalamic GABA in participants with painless DPN may reflect neuroplasticity due to reduced afferent pain impulses, whereas partially preserved levels of GABA in painful DPN may indicate that central GABAergic pathways are involved in the mechanisms of neuropathic pain in diabetes. Article Highlights: The thalamus has been shown to play a key role in the cerebral mechanisms of diabetic peripheral neuropathy (DPN), but neurotransmitter levels have not been explored. We sought to determine the levels of excitatory (glutamate) and inhibitory (γ-aminobutyric acid [GABA]) neurotransmitter levels in the thalamus in participants with painful and painless DPN. Thalamic GABA levels were reduced in participants with painless DPN, with partially preserved levels seen in painful DPN. Alterations of thalamic GABAergic pathways could be involved in the central mechanisms of both painful and painless DPN. [ABSTRACT FROM AUTHOR]

The study represents new bioanalytical characterization of mainly organic components of the poorly investigated extracellular polymeric substances (EPS) of the enigmatic diatom Didymosphenia geminata, an invasive, worldwide expanding species endangering diverse ecosystems. This microalga attaches its siliceous cells to rocky substrates using fibrous stalks, which are made of an EPS-based matrix stabilized by crystalline calcite. The EPS were analyzed using selected methods, including microscopic, spectroscopic, and spectrometric techniques. We identified diverse types of biomolecules. The presence of lipids, condensed aromatics, and heteroaromatic compounds in the EPS has been confirmed using high-resolution mass spectrometry (HR-MS). Additionally, both sulfur-containing functionalities and carboxylic acids were determined too using infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. For the first time, lignin compounds have been detected as one of the components of the EPS of the D. geminata diatom, using HR-MS and fluorescence microscopy (FM) in combination with specific staining techniques. By increasing the understanding of the chemistry and structural features of the stalks, we aim to develop potential applications and methods for removing these stalks from affected regions in the future, or, alternatively, to use them as a large-scale source of sustainable biocomposite material. [ABSTRACT FROM AUTHOR]

Gellan gum prepared from the domestic raw materials of Kazakhstan is studied by methods of 1H NMR spectroscopy, FTIR, GPC, TGA, and compared with characteristics of commercial gellan gum. Fermentation on glucose‐fructose syrup of Zharkent and Burunday corn starch plants (Kazakhstan) by Sphingomonas paucimobilis ATCC 31461 produces a biomass containing a high acyl gellan gum (HAG). The average molecular weights, Mw, Mn, Mz, and polydispersity index (PDI) of HAG are determined by GPC. Low acyl gellan (LAG) is obtained by treatment of HAG with alkaline solution. It is shown that the spectral and thermal characteristics of HAG and LAG produced from the glucose‐fructose syrup and commercial gellan gum are similar. [ABSTRACT FROM AUTHOR]

Translating sensory inputs to perceptual decisions relies on building internal representations of features critical for solving complex tasks. Yet, we still lack a mechanistic account of how the brain forms these mental templates of task-relevant features to optimize decision-making. Here, we provide evidence for recurrent inhibition: an experience-dependent plasticity mechanism that refines mental templates by enhancing A-aminobutyric acid (GABA)-mediated (GABAergic) inhibition and recurrent processing in superficial visual cortex layers. We combine ultrahigh-field (7 T) functional magnetic resonance imaging at submillimeter resolution with magnetic resonance spectroscopy to investigate the fine-scale functional and neurochemical plasticity mechanisms for optimized perceptual decisions. We demonstrate that GABAergic inhibition increases following training on a visual (i.e., fine orientation) discrimination task, enhancing the discriminability of orientation representations in superficial visual cortex layers that are known to support recurrent processing. Modeling functional and neurochemical plasticity interactions reveals that recurrent inhibitory processing optimizes brain computations for perpetual decisions and adaptive behavior. [ABSTRACT FROM AUTHOR]

Four new tirucallane-type triterpenoids, polystanins H–K (1–4), were obtained from the stems and leaves of Aphanamixis polystachya. Their structures were elucidated by analysis of the spectroscopic data and comparison with literature data. Compounds 1 and 2 showed week inhibitory effects against NO production in LPS-stimulated RAW264.7 cells. All the isolates were investigated for their antifungal activities against drug-resistant Candida albicans. [ABSTRACT FROM AUTHOR]

Nine jatrophane diterpenoids were isolated from the whole plant Euphorbia helioscopia, including two new ones, helioscopnins A (1) and B (2). Comprehensive spectroscopic data analysis and ECD calculations elucidated their structures, including absolute configurations. All compounds were evaluated for bioactivity towards autophagic flux by flow cytometry using HM mCherry-GFP-LC3 cells. Compounds 1, 3, 4, 5, 8, and 9 significantly increased autophagic flux. [ABSTRACT FROM AUTHOR]

Two new triterpene fatty acid esters, 3β-palmityloxy-12,27-cyclofriedoolean-14-en-11α-ol (1) and 3β-palmityloxy-19α-hydroxyursane (2), together with 3β-hydroxy-11-oxo-olean-12-enyl palmitate (3) were isolated from the potent anti-inflammatory active fraction of the petroleum ether-soluble part of Cirsium setosum ethanol extract. Compound 1 was found to be a rare 12,27-cyclopropane triterpenoid. Their structures were determined through spectral data analysis combined with literature reports. Furthermore, in vitro experiment, compounds 1-3 exhibited significant inhibitory effects on nitric oxide production in lipopolysaccharide-activated mouse RAW264.7 macrophages. [ABSTRACT FROM AUTHOR]

A new 14-membered resorcylic acid lactone (RAL14), chaetolactone A (1), along with three known ones (2−4), was obtained from the fermentation of the soil-derived fungus Chaetosphaeronema sp. SSJZ001. Their structures were established based on extensive spectroscopic data analyses (UV, IR, HRESIMS, 1D, and 2D NMR),13C NMR chemical shifts calculations coupled with the DP4+ probability method, theoretical calculations of ECD spectra, as well as X-ray diffraction analysis. All compounds were evaluated for their cytotoxic effects against A549, HO-8910, and MCF-7 cell lines. [ABSTRACT FROM AUTHOR]

Many 1,2,4-triazole derivatives have high biological activity. They are of interest for scientific and practical human activity as potential drugs and pesticides. In this work, we report a synthesis of a series of new 3-amino-1,2,4-triazole derivatives containing an alkylamide moiety. It was found that the amidoalkylation of 3-amino-1,2,4-triazole N-(1,2,2,2-tetrachloroethyl)carboxamides in the presence of triethylamine occurred selectively at the endocyclic nitrogen atom N-1 with the formation of the corresponding N-(1-(5-amino-1H-1,2,4-triazol-1-yl)-2,2,2-trichloroethyl)carboxamides. The reaction products were isolated in 79–85% yields and characterized by 1H NMR and 13C NMR spectroscopy. To unambiguously establish the structure of the obtained compounds, we carried out X-ray diffraction analysis for N-(1-(5-amino-1H-1,2,4-triazol-1-yl)-2,2,2-trichloroethyl)-3-methylbutanamide. [ABSTRACT FROM AUTHOR]

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Maternal obesity and hyperglycemia are linked to an elevated risk for obesity, diabetes, and steatotic liver disease in the adult offspring. To establish and validate a noninvasive workflow for perinatal metabolic phenotyping, fixed neonates of common mouse strains were analyzed postmortem via magnetic resonance imaging (MRI)/magnetic resonance spectroscopy (MRS) to assess liver volume and hepatic lipid (HL) content. The key advantage of nondestructive MRI/MRS analysis is the possibility of further tissue analyses, such as immunohistochemistry, RNA extraction, and even proteomics, maximizing the data that can be gained per individual and therefore facilitating comprehensive correlation analyses. This study employed an MRI and 1H‐MRS workflow to measure liver volume and HL content in 65 paraformaldehyde‐fixed murine neonates at 11.7 T. Liver volume was obtained using semiautomatic segmentation of MRI acquired by a RARE sequence with 0.5‐mm slice thickness. HL content was measured by a STEAM sequence, applied with and without water suppression. T1 and T2 relaxation times of lipids and water were measured for respective correction of signal intensity. The HL content, given as CH2/(CH2 + H2O), was calculated, and the intrasession repeatability of the method was tested. The established workflow yielded robust results with a variation of ~3% in repeated measurements for HL content determination. HL content measurements were further validated by correlation analysis with biochemically assessed triglyceride contents (R2 = 0.795) that were measured in littermates. In addition, image quality also allowed quantification of subcutaneous adipose tissue and stomach diameter. The highest HL content was measured in C57Bl/6N (4.2%) and the largest liver volume and stomach diameter in CBA (53.1 mm3 and 6.73 mm) and NMRI (51.4 mm3 and 5.96 mm) neonates, which also had the most subcutaneous adipose tissue. The observed effects were independent of sex and litter size. In conclusion, we have successfully tested and validated a robust MRI/MRS workflow that allows assessment of morphology and HL content and further enables paraformaldehyde‐fixed tissue‐compatible subsequent analyses in murine neonates. [ABSTRACT FROM AUTHOR]

INADEQUATE (Incredible Natural Abundance DoublE QUAntum Transfer Experiment) is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy. Nevertheless, its use for structural analysis is quite limited due to the low natural abundance of 13Ce13C connectivity (0.01%) and thus low sensitivity. Particularly, in semi-solids like rubbers, the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to 13C due to molecular motions induced averaging of 1He13C dipolar couplings. Herein, in this study, we demonstrate that transient nuclear Overhauser effect (NOE) can be used to efficiently enhance 13C signals, and thus enable rapid acquisition of two-dimensional (2D) 13C INADEQUATE spectra of rubbers. Using chlorobutyl rubber as the model system, it is found that an overall signalto- noise ratio (SNR) enhancement about 22% can be achieved, leading to significant timesaving by about 33% as compared to the direct polarization-based INADEQUATE experiment. Further experimental results on natural rubber and ethylene propylene diene monomer (EPDM) rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment. [ABSTRACT FROM AUTHOR]

Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base (RPSB). Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics. Numerous microbial rhodopsins have been discovered, contributing to diverse functions and colors. Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins. This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field. We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Aqueous film-forming foams (AFFFs) are the primary source of toxic perfluoroalkyl and polyfluoroalkyl substances (PFAS) in wastewater. Thus, it is urgent to develop a facile and fast method for identifying fluorosurfactants in commercially available AFFFs. In this work, fluorine nuclear magnetic resonance (19F NMR) spectroscopy was optimized to measure AFFFs directly with the extra addition of 5% D2O as the locking reagent, and high-quality spectra could be acquired within 4 min (0.1% fluorosurfactant content). Recovery experiments demonstrated that the use of different AFFFs had no marked influence on the quantitative analysis of fluorosurfactants. Such method works with low-field NMR spectroscopy (1.4 T) as well. Two-dimensional (2D) 19F COSY NMR was used to make signal assignments for different fluorosurfactant derivatives. The optimized 19F NMR could quantify the commercially available fluorosurfactants in different AFFFs, identify them being in either the perfluorooctane sulfonate (PFOS) or fluorotelomer sulfonic acid (FTS) categories, and distinguish the head-group of PFOS and FTS derivatives, which exhibits great potentials in the developments of relevant commercial detections. [ABSTRACT FROM AUTHOR]

In order to improve the crystallinity of covalent organic frameworks (COFs) materials and improve their application in the field of gas adsorption, 2,5 dimethyl terephthalic hydrazide (Th-(Me)2) and 2,4,6-tri(4-aldehyde phenylphenyl)-1,3,5-triazine (TFPT) were used as building blocks, leading to the successful synthesis of novel methyl functionalized COF (COF-Th-Me) through the solvothermal method. Powder X-ray diffraction, fourier transform infrared spectroscopy, solid-state carbon nuclear magnetic resonance spectroscopy and nitrogen adsorption-desorption methods were employed to study its structural properties. The results show that compared with non-methyl functionalized COF (COF-Th), the crystallinity of COF-Th-Me is significantly improved, and the structure in AA stacked mode (Rwp =2.00%, Rp = 1.53%) according to simulation results. The thermogravimetric analysis show that COF-Th-Me has high thermal stability. Under the conditions of 273 K and 0.1 MPa, COF-Th-Me exhibits an adsorption capacity of 27.6 cm³/g for CO2, demonstrating its potential application in the field of gas adsorption. [ABSTRACT FROM AUTHOR]

The diversity of O-polysaccharides (O-antigens) among 28 Aeromonas salmonicida strains isolated from ill fish has been determined by using high-resolution magic angle spinning (HR MAS) NMR spectroscopy. The new O-polysaccharide has been identified in two isolates. This new structure was investigated by 1H and 13C NMR spectroscopy and matrix-assisted laser-desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The following structure of the linear hexasaccharide repeating unit of A. salmonicida O-antigen has been established: →3)-α-L-Rhap-(1→3)-α-D-ManpNAc-(1→2)-β-D-Glcp-(1→3)-α-L-Rhap2OAc4OAc-(1→3)-β-D-ManpNAc-(1→3)-α-D-Glcp-(1→. This new A. salmonicida O-polysaccharide was detected among two isolates collected from trout and turbot fish in 2010 and 2011, respectively. Further investigations should be conducted to evaluate the distribution of this new O-polysaccharide among a larger collection of isolates, depending on their geographic origin, the species of fish, and the health status of the fish. [ABSTRACT FROM AUTHOR]

Glioblastoma (GBM) is a malignant Grade VI cancer type with a median survival duration of only 8–16 months. Earlier detection of GBM could enable more effective treatment. Hyperpolarized magnetic resonance spectroscopy (HPMRS) could detect GBM earlier than conventional anatomical MRI in glioblastoma murine models. We further investigated whether artificial intelligence (A.I.) could detect GBM earlier than HPMRS. We developed a deep learning model that combines multiple modalities of cancer data to predict tumor progression, assess treatment effects, and to reconstruct in vivo metabolomic information from ex vivo data. Our model can detect GBM progression two weeks earlier than conventional MRIs and a week earlier than HPMRS alone. Our model accurately predicted in vivo biomarkers from HPMRS, and the results inferred biological relevance. Additionally, the model showed potential for examining treatment effects. Our model successfully detected tumor progression two weeks earlier than conventional MRIs and accurately predicted in vivo biomarkers using ex vivo information such as conventional MRIs, HPMRS, and tumor size data. The accuracy of these predictions is consistent with biological relevance. [ABSTRACT FROM AUTHOR]

Sexual dimorphism influences cardiovascular outcomes in type 1 diabetes (T1D), with women facing a higher relative risk of macrovascular events compared to men, especially after menopause. This study hypothesizes that abnormalities in intermediate metabolism may be associated with cardiac autonomic neuropathy (CAN) in T1D. We aim to assess low molecular weight metabolites (LMWM) as markers of CAN in T1D, considering the effects of sexual dimorphism and age. In this cross-sectional study, we included 323 subjects with T1D (147 women and 176 men), with a mean age of 41 ± 13 years. A total of 44 women and 41 men were over 50 years old. CAN was assessed using Ewing's tests, and serum metabolites were analyzed by proton nuclear magnetic resonance spectroscopy (1H-NMR). Patients with CAN had lower levels of valine, isoleucine, and threonine, and higher levels of lactate, compared to those without CAN. These differences persisted after adjusting for BMI and estimated glucose disposal rate (eGDR). In a logistic regression model (R² = 0.178, p < 0.001), the main determinants of CAN included isoleucine [Exp(β) = 0.972 (95% CI 0.952; 0.003)], age [Exp(β) = 1.031 (95% CI 1.010; 1.053)], A1c [Exp(β) = 1.361 (95% CI 1.058; 1.752)], and microangiopathy [Exp(β) = 2.560 (95% CI 1.372; 4.778)]. Sex influenced LMWM profiles, with over half of the metabolites differing between men and women. However, no interactions were found between CAN and sex, or between sex, age, and CAN, on metabolomics profiles. Our findings suggest an association between CAN and LMWM levels in T1D. The sexual dimorphism observed in amino acid metabolites was unaffected by the presence of CAN. [ABSTRACT FROM AUTHOR]

Cancer is a complex disease that can also affect the younger population; however, it is responsible for a relatively high mortality rate of children and youth, especially in low- and middle-income countries (LMICs). Besides that, lipidomic studies in this age range are scarce. Therefore, we analyzed blood serum samples from young patients (12 to 35 years) with bone sarcoma (osteosarcoma) and compared their lipidomics to the ones from the control group of samples, named healthy control (HC group), using NMR and LC-MS techniques. Furthermore, differences in the lipidomic profiles between OS patients with and without metastasis indicate higher glycerophosphocholine (GPC) and glycerophospholipid (GPL) levels in osteosarcoma and increased cholesterol, choline, polyunsaturated fatty acids (PUFAs), and glycerols during the metastasis. These differences, detected in the peripheral blood, could be used as biomarkers for liquid biopsy. [ABSTRACT FROM AUTHOR]

Three hybrid compounds based on decavanadates, i.e., (NH4)2[Co(H2O)5(β-HAla)]2[V10O28]·4H2O (1), (NH4)2[Ni(H2O)5(β-HAla)]2[V10O28]·4H2O (2), and (NH4)2[Cd(H2O)5(β-HAla)]2[V10O28]·2H2O (3), (where β-Hala = zwitterionic form of β-alanine) were prepared by reactions in mildly acidic conditions (pH ~ 4) at room temperature. These compounds crystallise in two structure types, both crystallising in monoclinic P21/n space group but with dissimilar cell packing, i.e., as tetrahydrates (1 and 2) and as a dihydrate (3). An influence of crystal radii and spin state of the central atom in [M(H2O)5(β-HAla)]2+ complex cations on the crystal packing leading to the formation of different crystallohydrate forms was investigated together with previously prepared (NH4)2[Zn(H2O)5(β-HAla)]2[V10O28]·4H2O (4) and (NH4)2[Mn(H2O)5(β-HAla)]2[V10O28]·2H2O (5) and spin states of [M(H2O)5(β-HAla)]2+ (M = Co2+, Ni2+, and Mn2+) cations in solution were confirmed by 1H-NMR paramagnetic effects. FT-IR and FT-Raman spectra for 1–5 are in agreement with the X-ray structure analysis results. [ABSTRACT FROM AUTHOR]

Background/Objectives: Myalgic encephalomyelitis/chronic fatigue syndrome (ME/CFS) is a neurological disorder characterized by post-exertional malaise. Despite its clinical relevance, the disease mechanisms of ME/CFS are not fully understood. The previous studies targeting brain function or metabolites have been inconclusive in understanding ME/CFS complexity. We combined single-voxel magnetic resonance spectroscopy (SV-MRS) and functional magnetic resonance imaging (fMRI). Our objectives were to examine the feasibility of the multimodal MRI protocol, identify possible differences between ME/CFS and healthy controls (HCs), and relate MRI findings with clinical symptoms. Methods: We enrolled 18 female ME/CFS participants (mean age: 39.7 ± 12.0 years) and five HCs (mean age: 45.6 ± 14.5 years). SV-MRS spectra were acquired from three voxels of interest: the anterior cingulate gyrus (ACC), brainstem (BS), and left dorsolateral prefrontal cortex (L-DLPFC). Whole-brain fMRI used n-back task testing working memory and executive function. The feasibility was assessed as protocol completion rate and time. Group differences in brain metabolites and fMRI activation between ME/CFS and HCs were compared and correlated with behavioral and symptom severity measurements. Results: The completion rate was 100% regardless of participant group without causing immediate fatigue. ME/CFS appeared to show a higher N-Acetylaspartate in L-DLPFC compared to HCs (OR = 8.49, p = 0.040), correlating with poorer fatigue, pain, and sleep quality scores (p's = 0.001–0.015). An increase in brain activation involving the frontal lobe and the brainstem was observed in ME/CFS compared to HCs (Z > 3.4, p's < 0.010). Conclusions: The study demonstrates the feasibility of combining MRS and fMRI to capture neurochemical and neurophysiological features of ME/CFS in female participants. Further research with larger cohorts of more representative sampling and follow-ups is needed to validate these apparent differences between ME/CFS and HCs. [ABSTRACT FROM AUTHOR]

Objective: Rare disease. Background: Leigh disease (LD) is a rare progressive mitochondrial neurodegenerative disorder characterized by subacute necrotizing encephalopathy and symmetrical spongiform lesions in the brain. Cytochrome C oxidase deficiencies due to SURF1 Cytochrome C Oxidase Assembly Factor (SURF1) gene mutations are seen only in 15% of LD cases. Consideration of these genetic mutations in young patients is crucial for early diagnosis, intervention, and further genetic counseling. Although only a few cases of the SURF1 mutation have been reported, there are anecdotal case reports describing imaging features. Case report: We report a case of a 2-year-old boy with developmental delay, hypotonia, involuntary movements, shortness of breath, and reduced activity since age 6 months. On blood examination there was mildly elevated lactate levels and increased lactate to pyruvate ratio and cerebrospinal fluid lactate levels. Magnetic resonance imaging findings showed symmetrical lesions in the dentate nucleus, subthalamic nucleus, midbrain (substantia nigra, periaqueductal gray matter), posterolateral pons, and olivary nucleus of the medulla extending into the cervical spinal cord, with mild elevation of the lactate peak on magnetic resonance spectroscopy. Conclusions: These findings prompted further genetic analysis, which indicated a mitochondrial type IV deficiency with the SURF1 gene defect, an intranuclear type 1 mutation (MC4DN1) (OMIM 220110). Treatment is usually supportive with vitamins supplementation and physiotherapy, and genetic counseling of the parents is mandatory. [ABSTRACT FROM AUTHOR]

The bio-depolymerization of coal is a promising technology for converting coal into low-molecular-weight industrial chemicals. In this study, we investigated the characteristics of biodepolymerized coal (BDC) and the associated depolymerization pathway. We analyzed the extracellular enzyme activities of Hypocrea lixii AH in the biodepolymerization system, performed Fourier transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance spectroscopy (NMR) of BDC, and performed gas chromatography and mass spectrometry (GC/MS) of the BDC methanol extract. Results showed that the activities of peroxidase (POD), polyphenol oxidase (PPO), laccase (Lac), and lignin peroxidase (LiP) were 1377, 162, 10, and 1.919 U, respectively. Following biodepolymerization by Hypocrea lixii AH, 20 organic compounds were identified. Benzaldehyde 4-hydroxy-3,5-dimethoxy was the most dominant at 33.16%, followed by (Z)-9-octadecenamide, accounting for 14.73%. The aromaticity (fa) decreased from 54.3% to 23.7%, suggesting ring-opening reactions catalyzed by LiP and Lac. The ratio of carbonyl carbon (faC) increased from 8.3% to 16.2%, suggesting oxidation reactions catalyzed by POD. By comparing the structure of the Fushun oxidized coal model and BDC, a biodepolymerization pathway was elucidated. Biodepolymerization of Fushun oxidized coal is an oxidation–depolymerization process catalyzed by a series of enzymes, which breaks the aromatic rings and oxidizes side chains. Altogether, our findings provide a theoretical support for the chemical application of BDC. [ABSTRACT FROM AUTHOR]

Our ability to study and valorize the lignin fraction of biomass is hampered by the fundamental and still unmet challenge of precisely quantifying native lignin's structural features. Here, we developed a rapid elevated‐temperature 1H−13C Heteronuclear Single‐Quantum Coherence Zero (HSQC0) NMR method that enables this precise quantification of native lignin structural characteristics even with whole plant cell wall (WPCW) NMR spectroscopy, overcoming fast spin relaxation in the gel phase. We also formulated a Gaussian fitting algorithm to perform automatic and reliable spectral integration. By combining HSQC0 measurements with yield measurements following depolymerisation, we can confirm the combinatorial nature of radical coupling reactions during biosynthesis leading to a random sequential organization of linkages within a largely linear lignin chain. Such analyses illustrate how this analytical method can greatly facilitate the study of native lignin structure, which can then be used for fundamental studies or to understand lignin depolymerization methods like reductive catalytic fractionation or aldehyde‐assisted fractionation. [ABSTRACT FROM AUTHOR]

Ensifentrine (ENSE) is a bifunctional dual phosphodiesterase 3/4 inhibitor that has both anti-inflammatory and bronchodilatory activities and is considered a new option for the therapy of chronic obstructive pulmonary disease (COPD) and various other respiratory inflammatory diseases for which it is currently undergoing clinical trials. This study presents a groundbreaking effort to evaluate the impact of ENSE polymorphs (forms I, II, and III) on ENSE solubility and chemical stability—both of which are critical factors for drug formulation. Different procedures for the induced crystallisation of ENSE were adopted, and the obtained polymorphic forms were investigated. All the newly obtained solid forms were characterized via single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), nuclear magnetic resonance (1H & 13C NMR), solid-state UV-visible spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC)). Interestingly, altering various crystallisation processes with varied solvent polarity in the solution affects the crystal structure and polymorphic forms. Form I (parent form) was converted into forms II and III using the reactive crystallization method with combinations of formic acid : H2O (1 : 1) and formic acid : ethyl acetate (1 : 1), respectively. The reverse transformation was accomplished through gradual evaporation using different solvents. Similarly, variable-temperature PXRD (VT-PXRD) experiments revealed that form II converted into form I at 204 °C, whereas form III remained unaltered. In addition, the physicochemical properties of these three polymorphs were thoroughly discussed, and their solubility was tested in pH 1.2 and pH 7 media. A comprehensive examination of the residue that was recovered after solubility tests verified that form II and form III were converted into form I at both pH levels and that form I did not exhibit any phase change or dissociation at pH 7, whereas at pH 1.2, form I was converted into a new stable form and a thorough analysis verified that it was transformed into ENSE.Cl salt. To the best of our knowledge, this is the first study on the investigation of multiple forms of ENSE with varying physicochemical properties, and we hope that the current data will offer some valuable perspective prior to the development of ENSE as a medication. [ABSTRACT FROM AUTHOR]

The reactions of the frustrated Lewis pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetrachloro-ortho-benzoquinone (o-chloranil) gave (F5C2)2Sb(CH2)(μ-E)P(tBu)2·CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, and Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2·2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms. [ABSTRACT FROM AUTHOR]

Flexible poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Hydrosilylation of 4b,8b,12b-triallyltribenzotriquinacene and subsequent exchange of the chlorine substituents with weaker coordinating triflate groups afforded a novel triple silyl-functionalised PLA. By regioselective hydroboration of triallyl–TBTQ with various organoboranes, PLAs with different Lewis acidities were obtained. The synthesised PLAs were combined with neutral bases in host–guest experiments. DOSY NMR spectroscopy was performed to elucidate the complexation process in solution. These experiments revealed a highly dynamic interaction between the boron-functionalised PLA and triazine. However, the addition of one equivalent of tris(dimethylphosphino(methyl))phenylsilane led to the formation of a 1 : 1 adduct, which was confirmed by diffusion experiments. [ABSTRACT FROM AUTHOR]

Quinazoline (Qz)‐linked covalent organic frameworks (COFs) have been constructed via a three‐component reaction of ortho‐acylanilines, benzaldehydes and NH4OAc. The structure of Qz‐COFs has been confirmed by solid‐state nuclear magnetic resonance spectroscopy, Fourier transform infrared and powder X‐ray diffraction patterns. The Qz‐COFs possess high chemical stability, showing good endurance to strong acid, strong base, oxidant, reductant and other conditions. Particularly, Qz‐COF‐3 can catalyze the aerobic photooxidation of toluene and other compounds containing C(sp3)−H bonds. [ABSTRACT FROM AUTHOR]

The aim of this study was to provide insight into high-energy phosphate compound concentration dynamics under realistic clinical cold-storage conditions using the Celsior solution in seven heart grafts discarded from transplantation. The hearts of seven local donors (three males, four females, age 37 ± 17 years, height 175 ± 5 cm, weight 75 ± 9 kg) initially considered for transplantation and eventually discarded were submitted to a Magnetic Resonance Spectroscopy observation in a clinical Magnetic Resonance Imaging scanner over at least 9 h. The grafts remained in their sterile container at 4°C during the entire examination. Hence, Phosphocreatine (PCr), adenosine triphosphate (ATP), inorganic phosphate (Pi) and intracellular pH were recorded non-destructively at a 30-minute interval. With the ischemic time Ti, the concentration ratios decreased at PCr/ATP = 1.68−0.0028·Tis, Pi/ATP = 1.38 + 0.0029·Tis, and intracellular pH at 7.43–0.0012·Tis. ATP concentration remained stable for at least 9 h and did not decrease as long as phosphocreatine was detectable. Acidosis remained moderate. In addition to the standard parameters assessed at the time of retrieval, Magnetic Resonance Spectroscopy can provide an assesment of the metabolic status of heart grafts before transplantation. These results show how HEPC metabolites deplete during cold storage. Although many parameters determine graft quality during cold storage, the dynamics of HEPC and intracellular pH may be helpful in the development of strategies aiming at extending the ischemic time. [ABSTRACT FROM AUTHOR]

Natural membrane receptors are proteins that can report on changes in the concentration of external chemical messengers. Messenger binding to a receptor produces conformational changes that are relayed through the membrane into the cell; this information allows cells to adapt to changes in their environment. Artificial membrane receptors (R)‐1 and (S)‐1 are helical α‐aminoisobutyric acid (Aib) foldamers that replicate key parts of this information relay. Solution‐phase 19F NMR spectroscopy of zinc(II)‐capped receptor 1, either in organic solvent or in membrane‐mimetic micelles, showed messenger binding produced an enrichment of either left‐ or right‐handed screw‐sense; the chirality of the bound messenger was relayed to the other receptor terminus. Furthermore, in situ production of a chemical messenger in the external aqueous environment could be detected in real‐time by a racemic mixture of receptor 1 in micelles. The hydrolysis of insoluble anhydrides produced carboxylate in the aqueous phase, which bound to the receptors and gave a distinct 19F NMR output from inside the hydrophobic region of the micelles. [ABSTRACT FROM AUTHOR]

The development of improved solid electrolytes (SEs) plays a crucial role in the advancement of bulk‐type solid‐state battery (SSB) technologies. In recent years, multicomponent or high‐entropy SEs are gaining increased attention for their advantageous charge‐transport and (electro)chemical properties. However, a comprehensive understanding of how configurational entropy affects ionic conductivity is largely lacking. Herein we investigate a series of multication‐substituted lithium argyrodites with the general formula Li6+x[M1aM2bM3cM4d]S5I, with M being P, Si, Ge, and Sb. Structure‐property relationships related to ion mobility are probed using a combination of diffraction techniques, solid‐state nuclear magnetic resonance spectroscopy, and charge‐transport measurements. We present, to the best of our knowledge, the first experimental evidence of a direct correlation between occupational disorder in the cationic host lattice and lithium transport. By controlling the configurational entropy through compositional design, high bulk ionic conductivities up to 18 mS cm−1 at room temperature are achieved for optimized lithium argyrodites. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors via entropy engineering, overcoming compositional limitations for the design of advanced electrolytes and opening up new avenues in the field. [ABSTRACT FROM AUTHOR]

Using single‐crystal to single‐crystal solid/gas reactivity the gold(I) acetylene complex [Au(L1)(η2‐HC≡CH)][BArF4] is cleanly synthesized by addition of acetylene gas to single crystals of [Au(L1)(CO)][BArF4] [L1=tris‐2‐(4,4′‐di‐tert‐butylbiphenyl)phosphine, ArF=3,5‐(CF3)2C6H3]. This simplest gold‐alkyne complex has been characterized by single crystal X‐ray diffraction, solution and solid‐state NMR spectroscopy and periodic DFT. Bonding of HC≡CH with [Au(L1)]+ comprises both σ‐donation and π‐backdonation with additional dispersion interactions within the cavity‐shaped phosphine. [ABSTRACT FROM AUTHOR]

Helicobacter pylori, a leading human pathogen associated with duodenal ulcer and gastric cancer, presents a significant threat to human health due to increasing antibiotic resistance rates. This study investigates G‐quadruplexes (G4s), which are non‐canonical secondary structures form in G‐rich regions within the H. pylori genome. Extensive research on G4s in eukaryotes has revealed their role in epigenetically regulating cellular processes like gene transcription, DNA replication, and oncogene expression. However, understanding of G4‐mediated gene regulation in other organisms, especially bacterial pathogens, remains limited. Although G4 motifs have been extensively studied in a few bacterial species such as Mycobacterium, Streptococci, and Helicobacter, research on G4 motifs in other bacterial species is still sparse. Like in other organisms such as archaea, mammals, and viruses, G4s in H. pylori display a non‐random distribution primarily situated within open reading frames of various protein‐coding genes. The occurrence of G4s in functional regions of the genome and their conservation across different species indicates that their placement is not random, suggesting an evolutionary pressure to maintain these sequences at specific genomic sites. Moreover, G‐quadruplexes show enrichment in specific gene classes, suggesting their potential involvement in regulating the expression of genes related to cell wall/membrane/envelope biogenesis, amino acid transport, and metabolism. This indicates a probable regulatory role for G4s in controlling the expression of genes essential for H. pylori survival and virulence. Biophysical techniques such as Circular Dichroism spectroscopy and Nuclear Magnetic Resonance were used to characterize G4 motifs within selected H. pylori genes. The study revealed that G‐quadruplex ligand inhibited the growth of H. pylori, with minimal inhibitory concentrations in the low micromolar range. This suggests that targeting G4 structures could offer a promising approach for developing novel anti‐H. pylori drugs. [ABSTRACT FROM AUTHOR]

Background Objective Materials and methods Results Discussion and conclusion Sperm‐borne microRNAs play a pivotal role in influencing essential cellular processes during fertilization, impacting the quality of embryo development. Dysregulated microRNA profiles have been associated with compromised embryonic development and increased incidences of pregnancy loss.This study aimed to investigate the potential associations between the abundance of miR‐34c‐5p and miR‐191‐3p in human spermatozoa with sperm quality, as well as with embryo quality and metabolic performance during in vitro development.Thirteen couples who underwent a total of 13 cycles participated in this study. The sperm quality was assessed using conventional methods following World Health Organization guidelines. Quantitative polymerase chain reaction was employed to measure microRNA abundance in spermatozoa. Embryos were categorized as good, lagging, or bad based on morphokinetic evaluation. Evaluation of embryo metabolic performance involved tracking changes in specific metabolites within the cultured media using nuclear magnetic resonance spectroscopy. Statistical analysis was conducted to explore the correlation between microRNA abundance in human spermatozoa and all other collected data.Our findings revealed a negative correlation between the abundance of miR‐34c‐5p (but not miR‐191‐3p) and total sperm motility, potentially mediated by the modulation of key signaling pathways. Additionally, higher levels of miR‐34c‐5p in spermatozoa were strongly associated with the consumption or release of key metabolites by developing embryos, particularly those linked with lipid and glucose metabolism, suggesting enhanced metabolic performance, while miR‐191‐3p was mostly associated with glucose consumption. Concurrently, only miR‐34c‐5p content in spermatozoa correlated with higher embryo quality.This study provides evidence suggesting that the abundance of miR‐34c‐5p in spermatozoa is correlated not only with total sperm motility but also with markers of embryo developmental competence, highlighting the potential significance of this sperm microRNA content as a biomarker in assisted reproduction. [ABSTRACT FROM AUTHOR]

The characteristics and heterogeneity of coal pores are crucial for understanding the production mechanism of coalbed methane (CBM). In this study, coal samples with varying degrees of metamorphism (0.58% ≤ RO, max ≤ 3.44%) were collected. The characteristics of pore development and the heterogeneous properties of pores were revealed through low-temperature nitrogen adsorption (LTNA) and low-field nuclear magnetic resonance (NMR) experiments. The results indicate that pores with varying diameters exhibit favorable development in low-rank coals, along with favorable pores connectivity. The micropores composition of middle-rank coals was found to be 73.56%, however, the connectivity among transitional, meso, and macropores was observed to be poor. In high-rank coals, the proportion of micropores was 92.74%, with numerous micropores being closed or semi-closed. This resulted in inferior connectivity between micropores and transitional pores. As coal metamorphism progressed, the DL1 (characterizing the roughness of adsorption pores (AP) surface, ranging from 2.13 to 2.45) and DL2 (characterizing the complexity of AP structure, ranging from 2.56 to 2.77) initially decreased and then increased, whereas the DN (characterizing the heterogeneity of seepage pores (SP), ranging from 2.92 to 2.95) consistently improved. Furthermore, the roughness of pore surface and the complexity of pore structure in AP increased as the specific surface area and volume of pores increased. On the contrary, as the SP content increased, the uniformity of the pore structure improved. When the volume of SP remained constant, the complexity of the pore structure decreased due to increased pore connectivity. [ABSTRACT FROM AUTHOR]

Quadruplex-Duplex (Q–D) junctions are unique structural motifs garnering increasing interest as drug targets, due to their frequent occurrence in genomic sequences. The viral HIV LTR-III sequence was chosen as a Q–D junction model to study the affinity of the selected compounds BMH-21, namitecan (ST-1968), and doxorubicin (DOXO), all containing a planar polycyclic aromatic moiety, linked to either one short aminoalkyl or an aminoglycosyl group. A multidisciplinary approach that combines NMR spectroscopy, molecular modelling, circular dichroism (CD) and fluorescence spectroscopy was employed. The studied ligands induced moderate but clear stabilization to the Q–D junction by interacting with the interfacial tetrad. DOXO was found to be the best Q–D junction binder. Interestingly, the removal of the aminoglycosyl group significantly changed the pattern of the interactions, indicating that highly polar substituents have a stronger affinity with the exposed regions of the Q–D junction, particularly at the level of the interfacial tetrad. [ABSTRACT FROM AUTHOR]