Waste-to-energy storage: Bio-Waste derived activated carbon from wood apple shell for symmetric electrochemical supercapacitors

Solution-state two-dimensional (2D) 1H-13C HSQC NMR is a powerful tool for polysaccharide structure elucidation but often suffers from limited sensitivity and broad peaks due to the low natural abundance of 13C and poor digital resolution of the indirect dimension, respectively, as well as the typically low concentration and high viscosity of polysaccharide solutions. It is therefore pivotal to improve the resolution of 2D 1H-13C HSQC spectra for accurate peak picking and assignment, particularly in the indirect 13C dimension. In this study, we developed an algorithm that combines first derivative processing with a novel logarithmic cosine transformation (FDP-LCT) to convert 2D 1H-13C HSQC spectra into local-resolution-enhanced images resembling a dark forest of straight, densely standing trees. These images revealed sharpened spectral features and enabled extraction of precise 1H and 13C chemical shifts, as demonstrated using per-O-ethylated kappa- and iota-carrageenans, two sulfated galactans differing only by a single substitution at the O-2 position of anhydrogalactose. In conclusion, this approach provides an effective post-acquisition strategy for enhancing digital resolution in 2D HSQC spectra and improving the structural analysis of closely related complex polysaccharides.

While pulse crops are valued for their symbiotic nitrogen-fixing capacity, the dynamics of N fixation during crop development are not well quantified in cool-season pulses. Single-time measurements, typically at peak biomass, limit our understanding of how N source acquisition shifts with crop ontogeny. We aimed to quantify the temporal dynamics of N fixation, soil mineral N uptake and shoot dry matter accumulation in chickpea, faba bean, field pea and lentil grown under two seasons, with seasonal rainfall of 267 mm and 196 mm. We randomly sampled shoots weekly between late vegetative stage and physiological maturity. Samples were analysed for shoot N content and δ 15 N for both pulses and for a non-fixing reference crop (canola), and quantified N fixation using the 15 N natural abundance method. Sigmoid and logistic models characterised temporal growth patterns and allometric relationships between N source and shoot dry matter accumulation. Across species and seasons, peak N fixation occurred between 1000 and 1100 °C d after sowing—typically 100–200 °C d before flowering and 350–500 °C d before podding—but its synchrony with maximum growth rate varied among species. In faba bean, close temporal coupling between N fixation and growth was associated with the seasonal-dependent peak dry matter. Chickpea had pronounced asynchrony, with growth peaking 270–370 °C d after N fixation and a consistent reliance on soil N that accounted for 66–77 % of total N accumulation. In field pea, synchrony between N fixation and growth was stronger under drier conditions, while lentil maintained stable asynchrony across seasons. Allometric scaling between shoot dry matter and N sources were species-specific. Faba bean accumulated nitrogen from both N fixation and soil N proportionally with plant growth. Chickpea was more reliant on soil N relative to N fixation in meeting N requirements, while field pea and lentil had reduced N fixation with plant development. Interspecific variation in N fixation was associated with temporal synchronisation with growth rather than the absolute timing of N fixation. Consistent thermal timing of peak N fixation but species-specific synchrony with growth requires reconsidering species-specific: (i) sampling protocols for N fixation quantification, (ii) allometric models that account for distinct relationships between N source and growth, and (iii) N acquisition strategies with practical implications for nitrogen management. • We quantified temporal dynamics of N fixation, soil N uptake, and growth in pulses. • Across species, peak N fixation occurred at 350–500 ℃d before podding. • Faba bean N fixation synchronised with growth in favourable environment. • Chickpea relied on soil N (66–77 %) with asynchronous growth patterns. • Field pea improved synchrony under stress; lentil maintained asynchrony.

Nuclear magnetic resonance (NMR)-based 13C tracing is widely used in medicine, metabolomics, and environmental research. Here, we introduce a 2D 1H-1H (12C/13C) "in-phase/opposite-phase" (IP/OP) TOCSY experiment that uniquely generates 2D subspectra discriminating 13C-13C, 12C-13C, and 12C-12C connectivity. The sequence was demonstrated first on a standard mixture of 50/50 13C-phenylalanine and 1-13C-glucose, followed by an in vivo ethanol fermentation using brewer's yeast (Saccharomyces cerevisiae) with 1-13C-glucose. Finally, incorporation of 13C in marine copepods (Tigriopus californicus) was monitored ex vivo. Copepods were analyzed at natural abundance and again on 7 days of feeding >98% 13C-enriched green algae. The sequence successfully identified three carbon pools: intact fragments or molecules from the 13C diet (13C-13C), intact fragments from pre-existing biomass (12C-12C), and new bond formation between 12C and 13C molecules during metabolite turnover (12C-13C). Molecules involved in osmotic regulation, alanine, proline, glycine, choline, betaine, and TMAO, were particularly abundant in the 12C-13C pool, suggesting rapid turnover by combining 13C food with existing 12C biomass. This was supported by a quantitative 1D 1H-(12C/13C) IP/OP experiment, measuring average enrichment of the six osmolytes at 22.8 ± 0.1% 13C on day 7. A complementary "singlet-only" experiment quantified glycine at 27.4 ± 0.2% 13C and betaine at 3.7 ± 0.4% 13C, enabling detection of molecules without scalar couplings. In summary, the 2D 1H-1H IP/OP TOCSY simultaneously identified pre-existing and newly synthesized molecules, while 1D experiments provide quantitative support, offering a sensitive framework to study carbon dynamics, preservation, and transformation in complex in vivo and ex vivo processes.

Abstract Species of the genus Stylosanthes show great potential for use in mixed pastures and as green manure due to their symbiotic potential in symbiosis with diazotrophic bacteria, particularly Bradyrhizobium . These herbaceous legumes can improve pasture quality and contribute to sustainability. This study evaluated performance of Stylosanthes cv. Campo Grande when inoculated with Bradyrhizobium strains isolated from Oxisols in Roraima, Brazil, versus standard strains. A greenhouse experiment tested 18 new Bradyrhizobium strains isolated from soil alongside two recommended strains, including uninoculated and nitrogen‐fertilized controls. Also, two field experiments were conducted using the best‐performing greenhouse strain, the recommended strains, and absolute control and nitrogen fertilization (30 kg ha − 1 of N). Variables measured included nodule number and dry nodule mass, root and shoot biomass, and total nitrogen in shoot biomass. The proportion of nitrogen derived from biological nitrogen fixation (percentage of N derived from the atmosphere) was estimated by the 1 5 N natural abundance method, with Urochloa brizantha as the reference plant. In the greenhouse, strains ERR 917, ERR 922, ERR 942, ERR 1110, and ERR 1173 present great nodulation and dry matter production, identifying ERR 917 as optimal for field testing. Inoculation significantly increased both shoot and root biomass of cv. Campo Grande. Standard strain BR 446 T and ERR 917 enabled plants to obtain 38%–44% of their total nitrogen from biological nitrogen fixation, with inoculated plants accumulating about twice as much nitrogen and biomass versus the uninoculated control (averaging 1900 and 3900 kg ha − 1 of dry biomass for control and inoculated treatments, respectively).

Isoaspartate forms spontaneously from Asn deamidation or Asp isomerization, which can plague protein purification and storage processes. Indeed, it often comes with deleterious consequences, from a loss of function to a gain of toxic properties. IsoAsp detection is not straightforward, notably because it causes weak mass shifts, i.e., +1 or 0 from the native Asn or Asp, respectively. NMR spectroscopy might help in nontargeted detection of isoAsp, but information on isoAsp NMR fingerprint and sensitive detection methods were missing. Here, we report the NMR characterization of isoAsp in ten model, random coil hexapeptides, and release reference chemical shifts and scalar couplings of backbone nuclei from (i-1)-(i)-(i+1) residues (from 283 to 310 K). We show how isoAsp chemical shifts evolve with pH (from 2 to 8) and urea concentration (from 0 to 8 M). This led us to draw methods to identify isoAsp in 13C/15N-enriched and in natural abundance polypeptides. In the latter case, we use notably trypsinization, protein denaturation, and 1H-only NMR, enabling the detection of 10 nmol of isoAsp-containing protein in 1 h. We exemplify this approach on therapeutic products like insulin or the monoclonal antibody trastuzumab.

Reactivity-related characterization of dissolved organic matter (DOM) is crucial for mitigating undesirable byproduct formation during ozonation. However, the characterization of DOM remains challenging due to its molecular complexity, especially in distinguishing olefin- and phenol-type moieties, primary O3 reactive sites responsible for generating carbonyl-containing byproducts. Here, we present a novel approach based on stable oxygen isotope analysis of H2O2, a common byproduct of ozone reactions, to differentiate between these two moieties. The natural abundance oxygen isotopic signatures of residual H2O2 (δ18OH2O2) after ozonation with 13 model compounds (6 olefins and 7 phenols) at pH 3 and 7, and their pH-dependency, Δ18OH2O2 (δ18OH2O2 (pH 7) - δ18OH2O2 (pH 3)), enabled the distinction of olefins and phenols. Olefins exhibited near-zero or positive Δ18OH2O2 (0.4-9.0‰), whereas phenols showed negative Δ18OH2O2 (-14.2 - -1.6‰). These contrasting trends allowed derivation of an empirical correlation linking Δ18OH2O2 to olefinic-phenolic fractions in mixtures, resulting in estimation of molar fractions of the two moieties in DOM isolates. This stable-isotope based approach offers unique mechanistic insights into H2O2 formation mechanisms for widespread applications in H2O2-generating reactions, as well as for synergistic use with existing DOM characterization techniques.

Aqueous potassium-ion batteries have emerged as a promising energy storage technology by combining the intrinsic safety of aqueous electrolytes with the high natural abundance of potassium. However, the narrow electrochemical stability window of water and the limited availability of suitable cathode and anode materials impose critical challenges on achieving high energy density and long-term cycling stability. In recent years, substantial progress has been achieved through electrolyte engineering strategies, which effectively suppress water activity, expand the operational voltage window, and stabilize electrode-electrolyte interfaces. On the cathode side, advances in materials such as Prussian blue analogs, transition-metal oxides, and polyanionic compounds have significantly improved structural robustness and K diffusion kinetics. On the anode side, increasing attention has been devoted to interfacial regulation, kinetic compatibility, and mechanical stability under aqueous conditions. Importantly, emerging insights into electrolyte-material interactions reveal that interfacial chemistry plays a decisive role in governing the reversibility and durability of aqueous potassium-ion batteries. This review systematically summarizes recent progress in electrolytes, cathode materials, and anode materials for aqueous potassium-ion batteries. It highlights the remaining challenges and future perspectives toward high-energy-density, durable, and practically viable aqueous potassium-ion batteries.

The LowCOST-HSQC is a sensitivity-enhanced HSQC version that retains unused proton polarization for subsequent scans in correlations to low natural abundance nuclei like C or N. Together with fast polarization distribution via isotropic mixing, it allows the acquisition of fast-pulsing 2D experiments. We give a detailed introduction and comparison of three possible INEPT-type transfer elements for the LowCOST approach-the original LowCOST, the ZIP, and a specific TIG-BIRD element-and evaluate various variants of the LowCOST-HSQC.

Aqueous zinc-ion batteries (AZIBs) are promising alternatives to lithium-ion batteries due to the natural abundance of zinc and inherent safety, but dendrite growth on Zn anode and parasitic side reactions impair their lifespan and large-scale applications. Herein, we introduce vitamin C-derived, oxygen functionalized carbon dots (VC-CDs) as a novel modulator to aqueous electrolyte. Negatively charged VC-CDs preferentially adsorb on Zn anode, homogenizing electric fields and enabling uniform Zn2 + deposition, and their coordination with Zn2 + promotes ion migration, boosting full-cell capacity by 15% at 1 A g- 1. Accordingly, the Zn||Zn symmetric cells deliver a long-term stable cycling lifespan of 2000h, whereas the Zn||Cu asymmetric cells attain an exceptional Coulombic efficiency of 99% across 2000 cycles. Furthermore, the Zn||VO2 full cells exhibit remarkable cycling stability, retaining 80% of their initial capacity after 2000 cycles at a current density of 4 A g- 1. Notably, the practical feasibility of VC-CDs is further corroborated in both Zn||VO2 and Zn||I2 pouch cells, which highlights their great potential for advancing next-generation aqueous zinc-ion battery technologies.

Cholesterol plays a pivotal role in defining the structure and signaling function of plasma membrane lipid rafts, yet direct nanoscale measurements of cholesterol-rich domains in intact cells that enable atomic scale analysis remains challenging. Here, we present AsymPol-Chol-AF647, a bimodal cholesterol-based probe that integrates a biradical (AsymPol) for Dynamic Nuclear Polarization (DNP) with a fluorescent dye (AF647), enabling correlative in-cell DNP solid-state NMR and confocal fluorescence microscopy of the plasma membrane. The cholesterol anchor ensures insertion into the plasma membrane, providing a spatially defined delivery of the polarizing agent. Confocal imaging in live cells confirms plasma membrane localization and reveals concentration-dependent perturbations to lipid raft integrity, with optimal conditions at 0.19 nmol/106 cells maintaining cell viability and discrete GM1-positive microdomains (associated with lipid rafts). Under these conditions, significant global enhancements of natural abundance 13C of ε ≈ 14 were achieved. Analysis of signal buildup kinetics unveiled evidence for more complex hyperpolarization dynamics than the simple spherical model indicated by the microscopy. These findings lay the groundwork for future studies utilizing bimodal polarizing agents for use not just for selective cellular enhancements but also as tools for the determination of the spatial organization of cellular structures at nanometer resolution.

Imidacloprid (IMI) is a widespread neonicotinoid insecticide of environmental concern because of its ecotoxicity and persistence. Tracing its commercial sources and environmental transformation is difficult with concentration-based approaches. We explored electrospray ionization Orbitrap isotope ratio mass spectrometry ((ESI) Orbitrap MS-Based Isotope Ratio Analysis) for compound- and fragment-specific stable isotope analysis of IMI at natural abundance. This approach enables direct measurement of 13C, 15N, 37Cl, and multiple substituted isotopologue ratios. Experimental parameters were optimized to control sources of bias in isotopologue ratios. A dual-inlet bracketing protocol enabled normalization and drift correction. IMI from seven different commercial sources could be distinguished by their isotopic fingerprints. We demonstrate that principal component analysis (PCA) can exploit the expanded set of isotopic variables. Two PCAs with distinct variable sets were performed: a fragment-only, nonoverlapping isotopologue subset for source material attribution, and a combined molecular-average and fragment-level subset to maximize manufacturer discrimination. Alkaline hydrolysis (pH ≈ 12, 30 °C) based on compound-average δ13C and δ15N values measured by (ESI) Orbitrap MS-Based Isotope Ratio Analysis revealed significant carbon isotope fractionation (εC = -4.3 ± 1.4 ‰) and a statistically negligible nitrogen fractionation (εN = 0.6 ± 1.6 ‰), consistent with initial OH- attack at the nitroimine carbon as the primary pathway. (ESI) Orbitrap MS-Based Isotope Ratio Analysis can elucidate transformation mechanisms in analytically challenging polar analytes. The chemometric approach of using MS1/MS2 data can be transferred to other (agro-)chemicals either to enhance isotopic discrimination or to discover patterns.

Rechargeable magnesium-sulfur (Mg-S) batteries are considered promising candidates for next-generation energy storage systems due to their intrinsic safety and natural abundance. However, their practical deployment is limited by the sluggish conversion of short-chain polysulfides, which contribute 75% of the theoretical capacity. Herein, cuprous tetrahydroxyquinone (Cu-THQ) is employed as an electrocatalyst anchored on a polypropylene interlayer to accelerate polysulfide conversion in Mg-S batteries. The restricted π-delocalization in the coordination framework and enhanced electron donation from oxygen atoms to Cu centers create the localized electron enrichment microenvironment and upshift the d-band center. This electronic modulation establishes an efficient charge-transfer pathway and strengthens Cu-S orbital hybridization, thereby facilitating the robust anchoring and accelerated reduction of MgS2 intermediates. Consequently, Mg-S batteries incorporating the Cu-THQ interlayer deliver a high reversible capacity of 470 mAh g-1 after 2000 cycles at 8.36 A g-1. Stable cycling performance is also maintained under -20 °C, demonstrating promising application potential. This work presents a π-conjugation-driven approach for accelerating polysulfide conversion and promotes the development of long-life Mg-S batteries.

Neocryptotanshinone (NCTS), a rare diterpene quinone bioactive compound isolated from Salvia miltiorrhiza, was first reported in 1941 and structurally characterized in 1987. The phenanthraquinone core has been extensively characterized in terms of structural confirmation and synthesis. Due to its low natural abundance, NCTS is challenging to extract but can be obtained through semisynthesis. Mechanistically, NCTS was identified in 2015 as an inhibitor of the nuclear factor kappa-B (NF-κB) pathway, inducing a cascade of downstream effects. Its low cytotoxicity, minimal induction of cyclooxygenase-2 (COX-2) expression, and other favorable pharmacological properties suggest therapeutic potential. Recent research has focused on NCTS's therapeutic applications. By modulating multiple pathways, it exerts beneficial effects on heart failure, myocardial ischemia/ reperfusion injury, cerebral ischemia, and type 2 diabetes mellitus. Pharmacokinetic studies are progressing; its promising bioavailability and absorption kinetics require validation. This review summarizes research progress on NCTS and its derivative 16-Ooleoylneocryptotanshinone, covering structural characterization, synthetic routes, structural modifications, pharmacological activities, traditional Chinese medicine applications, and pharmacokinetics. Our goal is to provide a reference for further development of NCTS, which remains in its nascent research phase.

Abstract: The global escalation of Multidrug-Resistant (MDR) bacterial infections poses a serious and growing threat to public health, contributing to increased morbidity, mortality, and substantial economic burden worldwide. The widespread and often indiscriminate use of antibiotics in clinical and agricultural settings has accelerated the emergence of resistance, significantly diminishing the efficacy of conventional antimicrobial therapies. This pressing challenge necessitates the exploration of alternative sources for novel antibiotics. Marine ecosystems-renowned for their immense biodiversity and ecological complexity-have gained attention as a rich and largely untapped reservoir of bioactive natural products with potent antimicrobial activity. Marine organisms, such as sponges, tunicates, algae, and bacteria and fungi derived from marine sources, produce structurally diverse and pharmacologically active metabolites, including peptides, polyketides, alkaloids, terpenoids, sterols, lactones, and halogenated compounds. Many of these marine-derived molecules possess unique chemical scaffolds and novel mechanisms of action, offering the potential to circumvent existing resistance pathways. Some compounds have shown promising activity against MDR pathogens, including Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii. However, challenges such as low natural abundance, difficulty in cultivation, and structural complexity have limited their clinical translation. Recent advancements in marine biotechnology, genomics, metagenomics, and synthetic biology have opened new avenues for the discovery, biosynthesis, and structural optimization of these compounds. These innovative approaches not only facilitate sustainable production but also enhance the pharmacological properties.

All-solid-state potassium metal batteries (PMBs) emerge as promising alternatives to lithium batteries owing to their natural abundance and high theoretical energy density. Nevertheless, the advancement of efficient PMBs is still hindered by the lack of suitable electrolytes. Therefore, exploring solid-state electrolytes (SSEs) for PMBs is critical. Compared with inorganic SSEs, research on developing pristine organic potassium salt-based SSEs remains extremely sparse. Herein, a "Heteroaromatic-Assisted Migration" approach was employed to design crystalline organic potassium salts (i.e., potassium pyridonates) as SSEs by incorporating a nitrogen atom into the phenoxide ring. Specifically, through tuning the position of N, the isomer of "K-deficient" meta-KOC5H4N achieves an ionic conductivity of 0.22 mS cm-1 at 90 °C with an ion transference number (ti) higher than 0.99, ranking among the highest conductivity reported. Meanwhile, it demonstrates outstanding thermal stability (>240 °C), air tolerance, and low Young's modulus, which enable high stability, scalable synthesis, and ease of molding. The crystal structure of meta-KOC5H4N is determined as a monoclinic lattice with the space group of P21/m (no. 11), where unsaturated K-ion coordination and flexible layered structure are observed. We successfully demonstrated the first all-solid-state PMB prototype using this organic salt. Both experimental and first-principles calculations reveal that ion diffusion occurs via defect-mediated mechanisms within the layered flexible lattice. Compared with the inorganic SSEs, the present study opens up a new avenue for fabricating safe and facile organic electrolyte materials.

Ginsenoside Rd, a protopanaxadiol (PPD)-type tetracyclic triterpenoid saponin, has emerged as a promising bioactive constituent for multitarget therapeutic interventions. However, its natural abundance in the source plant is extremely low, making direct extraction both costly and inefficient. This review systematically summarizes the latest research progress on regioselective biotransformation strategies for Rd production since 2022. Furthermore, it comprehensively reviews recent advances in the diverse pharmacological activities of Rd. Beyond its well-recognized neuroprotective effects against neurological disorders including Alzheimer's disease and Parkinson's disease, we also highlight its antitumor activity and multitarget protective effects in liver diseases. This review provides a theoretical basis for developing Rd as a high-value nutraceutical and therapeutic candidate for systemic health.

The broadband microwave spectrum of perfluorophenol (C6F5OH) was recorded over the 7.5-17.5 GHz and 26-40 GHz frequency ranges under jet-cooled conditions in the gas phase. 895 lines were assigned to the 12C6F6OH parent molecule. We also detect torsion-rotation transitions of the singly 13C and 18O-substituted isotopologues in natural abundance and fit a total of 405 transitions of the isotopologues. Tunneling due to OH internal rotation in a V2 potential leads to a 0+/0- tunneling splitting of ΔE = 24.826 MHz that appears on the a-type transitions. Using a properly symmetrized relaxed potential energy curve, we carry out discrete-variable reference (DVR) calculations to predict both the tunneling splitting and the Coriolis-like coupling term Fab[JaJb + JbJa] to an accuracy of 3% from first principles. We compare calculated transition frequencies using the best-fit Fab to those with Fab = 0 to identify sets of rotational levels in the 0+ and 0- tunneling levels that are shifted significantly by Coriolis-like mixing between them, which is maximized for Kc = 1,2 in this oblate symmetric top limit. Finally, in the singly substituted isotopologues of PFP (13C or 18OH), the potential energy surface for tunneling is still symmetric, but asymmetry in the kinetic terms of the Hamiltonian that are introduced by asymmetric 13C-substitution at the positions ortho and meta to the OH group quench the OH tunneling. While the v = 0+ and 0- torsional wave functions for these levels are completely localized in ortho-13C PFP, we predict partial delocalization in v = 0+ and 0- torsional substates of meta-13C PFP. However, the predicted transitions between tunneling levels in meta-13CC5F5OH could not be assigned experimentally.

This study examines the determinants of Foreign Direct Investment (FDI) inflows into 24 economies in the Middle East and North Africa (MENA) region from 1980 to 2023. Utilizing Dunning’s Eclectic Paradigm (OLI framework), institutional theory, and transaction cost economics, this research investigates how ownership, location, and internalization advantages influence FDI decisions in a region characterized by significant resource dependence and institutional heterogeneity. To ensure the robustness of our findings, we employ second-generation panel data techniques, including Fully Modified Ordinary Least Squares (FMOLS), Dynamic Ordinary Least Squares (DOLS), Common Correlated Effects Mean Group (CCEMG) and Augmented Mean Group (AMG). These methodologies effectively address issues such as Cross-Sectional Dependence (CSD) and Slope Heterogeneity (SH). Our results indicate that institutional quality, particularly in relation to control of corruption and government effectiveness, exerts a strong positive impact on FDI inflows. Conversely, natural resource abundance demonstrates a negative relationship with overall FDI, thus corroborating the “resource curse” hypothesis within the MENA context. Market size significantly positively influences FDI attraction. Notably indicators of political stability and regulatory quality do not consistently show statistical significance across the model, implying that broader stability metrics may inadequately capture investor sentiment. In contrast, control of corruption and government effectiveness emerge as more salient institutional mediators of FDI decisions. These findings contribute to the existing literature by providing a context-specific analysis of FDI dynamics in the MENA region, employing advanced econometric estimators that have been underutilized in prior studies, and enhancing methodological transparency through the construction of composite variables. The results furnish actionable insights for policymakers seeking to attract sustainable foreign investment through institutional reform and macroeconomic stabilization.

Efficient hydrazide-mediated total synthesis of Möbius cyclotides from Viola japonica and elucidation of the antibacterial mechanism of Vija 31.