Search Results (1,695)

Understanding the intrinsic Li–H₂ interaction, decoupled from substrate effects, is essential to rationalize the performance of lithium-decorated hydrogen storage materials. To address the current lack of a clean theoretical baseline, we characterized the sequential H₂ adsorption on the gas-phase Li₆ superatomic cluster using high-level density functional theory (DFT), complemented by Energy Decomposition Analysis (EDA), QTAIM, and NICS(0) calculations. Li₆ acts as a structurally rigid platform (RMSD < 0.032 Å) where ligand-induced polarization progressively strengthens its σ-aromaticity (NICS(0) from −2.917 to −13.98 ppm) and increases the HOMO–LUMO gap up to 5.05 eV. EDA identifies the binding as field-activated physisorption, electrostatically dominated (65–67%) and mechanistically distinct from Kubas coordination, as confirmed by QTAIM closed-shell interaction parameters. Negative cooperativity governs an effective loading capacity of n = 2 molecules under cryogenic conditions (T_eq = 143.76 and 114.64 K), while an entropic bottleneck renders higher loading non-spontaneous at all temperatures. These results establish Li₆(H₂)_n as a foundational gas-phase reference, providing a systematic, contamination-free descriptor set for the intrinsic Li–H₂ interaction. This framework is essential for isolating the electronic role of the lithium superatom and unambiguously identifying substrate-induced modulations in supported hydrogen storage materials. Full article

The European Middle Pleistocene represents a critical spatiotemporal interval in human evolution, marked by increasing morphological variability and ongoing debate regarding the evolutionary processes leading to the emergence of Neandertals. In particular, it remains unclear whether this variability reflects the coexistence of multiple evolutionary lineages within Europe or structured variation within a single, evolving lineage. Within this context, the site of Bilzingsleben (Thuringia, Germany) provides a key contribution to discussions of European Middle Pleistocene population structure. This study presents a detailed morphological assessment of the Bilzingsleben E7 mandibular fragment, integrating qualitative anatomical observations with quantitative analyses of discrete characters. The Bilzingsleben mandible was examined directly and evaluated within a broad comparative framework including European Middle Pleistocene hominins, Neandertals, and selected African and Asian specimens. Multivariate analyses, including Principal Coordinates Analysis (PCoA) and neighbor-joining cluster analysis based on Gower distances, were used to explore patterns of morphological affinity. Qualitative analysis indicates that the Bilzingsleben mandible exhibits a mosaic combination of predominantly primitive features—such as multiple mental foramina, marked lateral relief of the corpus, and a weakly developed submandibular fossa—together with a limited number of incipiently derived traits, including posterior extension of the corpus and a downward orientation of the digastric fossae. Quantitative results consistently place Bilzingsleben within the morphological variability of European Middle Pleistocene hominins but outside the compact Neandertal cluster. In the PCoA, Bilzingsleben occupies an intermediate (PCo1) and peripheral position (PCo2), contrasting with more centrally positioned specimens such as Mauer. Taken together, these results support an interpretation of Bilzingsleben as part of a European Middle Pleistocene set of populations exhibiting mosaic morphology, rather than considering Bilzingsleben as evidence for a distinct evolutionary lineage. When integrated with evidence from other anatomical elements from Bilzingsleben, the mandibular morphology supports interpreting this population within the broader evolutionary context of the Neandertal lineage. Full article

We report a π-extended N-phenylphenothiazine dye bearing thiophene substituents, designed to address the practical compromise between long-wavelength near-infrared (NIR) absorption and the isolability of a stable radical cation state. The target compound was synthesized via Suzuki–Miyaura cross-coupling and exhibited good solubility in common organic solvents. Cyclic voltammetry in dichloromethane showed a reversible one-electron oxidation at E⁰ = 0.19 V vs. Fc/Fc⁺. Chemical oxidation afforded the corresponding radical cation, which showed an intense NIR absorption maximum at 910 nm. DFT calculations support thiophene-induced narrowing of the HOMO–SOMO gap and predict a pronounced bathochromic shift of the main absorption band. The radical cation was isolated as a stable PF₆⁻ salt and readily processed into spin-coated films, which retained strong NIR absorption and remained stable for months under ambient conditions. Full article

The immunoglobulins (IG) or antibodies and the T cell receptors (TR) are the antigen receptors of the adaptive immune responses (AIR) of jawed vertebrates (Gnathostomata). IMGT^®, the international ImMunoGeneTics information system^®, was created in 1989 by Marie-Paule Lefranc (Laboratoire d’ImmunoGénétique Moléculaire (LIGM), Université de Montpellier and CNRS) to deal with and to manage the huge diversity of IG or antibodies and TR. The founding of IMGT^® marked the advent of immunoinformatics, a new science which emerged at the interface between immunogenetics and bioinformatics. For the first time, the IG and TR variable (V), diversity (D), joining (J) and constant (C) genes were officially recognized as ‘genes’, as were the conventional genes. The IMGT-ONTOLOGY CLASSIFICATION axiom and the concepts of classification have generated the IMGT nomenclature and the IMGT Scientific chart rules for assigning IMGT names to IG and TR genes and alleles of Homo sapiens and of any other jawed vertebrate species. The IMGT nomenclature is used for genes in locus, in sequences (genomic or rearranged, expressed or not) and in structures enabling comparative immunology, evolutionary immunogenetics, standardized analysis and comparison of IG and TR repertoires analysis in normal or pathologic situations. IMGT nomenclature is used in basic, veterinary, and medical research, in clinical applications (mutation analysis in leukemia and lymphoma), and in therapeutic antibody design, engineering and humanization. By providing consistent and high standard biocuration for the description of the IG and TR loci, genes and alleles, and for the analysis of the IG or antibody and TR-expressed rearranged sequences and proteins and structures, the IMGT nomenclature is the common language for immunoinformatics and artificial intelligence (AI). Full article

The precise determination of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels is critical for understanding the photophysical and photochemical properties of carbon dots (C-dots), which directly govern their performance in optoelectronic, catalytic, and sensing applications. However, the lack of distinct redox peaks in cyclic voltammetry (CV) curves of C-dots poses a major challenge to conventional energy level calculation methods. Herein, we propose a novel strategy to calculate the HOMO–LUMO energy levels of C-dots by combining electron transfer (ET) kinetics with Marcus theory. A series of quinones (electron acceptors, EAs) and ferrocene derivatives (electron donors, EDs) were employed to quench the fluorescence of C-dots, and the ET rate constants (K) were derived from fluorescence lifetime measurements. The CV curves of EAs and EDs provided their respective oxidation and reduction potentials, which were used as reference energy levels. The UV–Vis absorption spectra confirmed that the fluorescence quenching mechanism was dominated by ET rather than energy transfer. Based on Marcus theory, the free energy change (ΔG) of ET reactions was correlated with K, and the HOMO and LUMO energy levels of C-dots were calculated to be −1.84 V (vs. SCE) and +1.60 V (vs. SCE), respectively. This study not only provides a reliable method for determining the energy levels of C-dots without distinct redox peaks but also deepens the understanding of ET mechanisms between C-dots and small molecules. The proposed strategy is expected to be extended to other fluorescent nanomaterials with similar CV limitations. Full article

Humans, and most other late Homo species, are characterized by large brains and bodies. However, the discovery of two small-brained Homo species—H. floresiensis and Homo naledi—has cast doubts on large brain size as a defining feature of our genus. We reevaluated brain and body size scaling using data for 225 extant primates and 16 fossil hominid taxa, including one of the most diminutive species in genus Homo, H. floresiensis. Brain and body size are tightly correlated in genus Homo, varying along a positively allometric slope (R² = 0.84, F(1,5) = 33, p < 0.01) that is significantly different from the slope characterizing extant primates (R² = 0.94, F(1,222) = 3294, p < 0.001). Both small-bodied Homo floresiensis and Homo naledi have endocranial volumes (ECVs) that are consistent with their body size given the scaling relationship that characterizes genus Homo. Paired ECV and body mass estimates demonstrate considerable overlap of brain:body size proportions across fossil hominid taxa. Earlier hominids, Ardipithecus ramidus and Australopithecus anamensis, are characterized by ancestral brain:body size scaling; we discuss the hypothesis that a fundamental biological shift ca. 3 Ma altered the trajectory of encephalization—potentially linked to changes in fetal growth and gestation in Pleistocene fossil hominids—and may be directly implicated in the evolution of complex symbolic behavior in our lineage. Full article

Rutin is a naturally occurring flavonoid with well-documented antioxidant and pharmacological properties. In this study, a manganese(II) complex with rutin (Mn(II)-Rut) was synthesized in a solid state and characterized using FT-IR, Raman spectroscopy, thermogravimetric and elemental analysis, confirming its composition as C₂₇H₂₇O₁₆Mn₂·5H₂O. The IR spectra indicated that rutin coordinates manganese ions through the carbonyl group at the C4 position and the hydroxyl group at the C5 atom, as well as the catecholic system. The antioxidant potential of both Mn(II)-Rut and rutin was evaluated using several spectrophotometric assays. The Mn(II)-Rut complex showed stronger activity in most spectrophotometric assays than rutin, i.e., in ABTS assay, 50.37 ± 2.64% vs. 41.49 ± 1.38%; in CUPRAC assay, 0.468 ± 0.006 mM Trolox vs. 0.379 ± 0.007 mM Trolox; and FRAP assay, 0.201 ± 0.002 µM vs. 0.189 ± 0.003 µM. However, the DPPH assay complex showed a diminished effect compared with ligand (IC₅₀ 2.78 ± 0.13 µM vs. 0.98 ± 0.04 µM for rutin). Quantum-chemical calculations were also performed using the Gaussian09 program to determine the optimized geometric structures, electron charge distribution, and the energies of the HOMOs and LUMOs in the analyzed molecules in order to discuss the antioxidant mechanism of the molecules. Enzymatic assays demonstrated that the Mn(II) complex with rutin exhibited a stronger α-amylase inhibitory effect compared to free rutin, which showed the potential antidiabetic activity of the compound. The results suggest that the Mn(II) complex of rutin possesses better antioxidant and α-amylase inhibitory activity than the ligand alone. Full article

This article examines contemporary forms of algorithmic governance through a biopolitical framework grounded in Michel Foucault’s analysis of security, risk, and governmentality. Rather than treating algorithmic systems as a rupture with earlier modes of power, the article argues that they intensify a security-based rationality already oriented toward probabilistic reasoning, anticipatory intervention, and the indirect regulation of conduct. Governance increasingly operates by organizing environments in advance, shaping the conditions under which action becomes possible rather than correcting behavior after the fact. Situating transhumanism within this framework, the article approaches enhancement-oriented projects not as speculative or external developments, but as an extension of biopolitical governance from the regulation of life toward its optimization and redesign. Human capacities become objects of assessment and intervention, shifting the biopolitical subject from a bearer of risk to an upgrade-eligible profile oriented toward projected futures. To conceptualize the form of subjectivity produced at the intersection of algorithmic prediction and transhumanist optimization, the article introduces the heuristic figure of Homo virtualis. This figure describes a form of subjectivity in which individuals are approached through predictive profiles rather than stable identities, and responsibility shifts toward managing expected outcomes rather than accounting for past actions. By examining these shifts, the article contributes to debates on algorithmic governance by clarifying how biopolitics, prediction, and subjectivity are reconfigured as futures become increasingly organized in advance. This article adopts a descriptive and analytical approach rather than a normative one. Full article

Conjugated organic polymers are the cornerstone of modern organic electronics, yet accurate prediction of their properties remains a challenging task due to their synthetic complexity and high computational cost of quantum-chemical methods. Here, we develop a graph neural network based on the DimeNet++ direct message passing architecture to predict HOMO, LUMO and energy gaps of conjugated polymers directly from their 3D monomer structure. The model was pre-trained on TD-DFT-extrapolated data and trained on a limited dataset of experimentally measured properties. As a result, pre-training had significantly improved model’s accuracy compared to direct training (MAEs ~0.3 eV vs. 0.074 eV, 0.141 and 0.172 for HOMO/LUMO and energy gap, respectively). Pre-training on monomer DFT data did not provide comparable gains. The results demonstrate that polymer-relevant pre-training is critical for capturing structure–property relationships and enables accurate predictions without delta-learning or prior quantum-chemical calculations, facilitating efficient screening and rational design of conjugated polymers for organic optoelectronics. Full article

Two series of N-hydroxyalkyl-1,8-naphthalimide derivatives were synthesized to investigate the influence of structural variables on their electrochemical and photophysical properties. The first series includes compounds containing N-hydroxyalkyl substituents of various chain lengths and branches. The second series includes derivatives functionalized in the naphthalene core with electron-donating or electron-withdrawing groups. Cyclic voltammetry, UV–Vis spectroscopy and fluorescence measurements were supported by theoretical DFT calculations. Branched hydroxyalkyl chains enhanced photoluminescence quantum yields by up to 19%, compared to less than 4% for linear chains. Functionalization of the naphthalene core at the C4 position strongly affected optical band gaps, electrochemical properties and photoluminescence quantum yields. DFT calculations revealed significant changes in the energies of the frontier orbits: the HOMO energy varied from −6.95 eV to −5.51 eV, while the LUMO energy varied from −3.24 eV to −1.94 eV. Preliminary tests have demonstrated the suitability of the selected derivatives as cathode materials in lithium-ion batteries, achieving an initial capacity of 47 mAh/g. Full article

Alzheimer’s disease (AD) remains a significant global health challenge, highlighting the need for novel dual inhibitors targeting acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). This study investigated the trunk bark of Terminalia triptera Stapf. as a potential source of bioactive secondary metabolites for AD management. Bioassay-guided isolation led to the identification of two flavan-3-ol derivatives, epicatechin-(4β→8)-ent-catechin (1) and (−)-catechin (2), reported here for the first time from this species. In vitro assays demonstrated that the dimeric compound 1 exhibited stronger dual inhibitory activity against AChE and BChE, with IC₅₀ values of 4.41 × 10⁻⁴ and 4.75 × 10⁻⁴ mol/L, respectively, surpassing the reference compound berberine chloride. Molecular docking analysis revealed that compound 1 formed extensive interactions within both catalytic and peripheral anionic sites of the enzymes. Density Functional Theory (DFT) calculations indicated high kinetic stability, reflected by large HOMO–LUMO energy gaps (6.66–6.97 eV), while global reactivity descriptors suggested lower electrophilicity (ω = 2.19–2.34 eV), supporting a potentially favorable safety profile. Furthermore, 100 ns molecular dynamics simulations confirmed stable ligand–protein complexes stabilized by hydrogen-bond networks and deep binding within catalytic pockets. Overall, these findings highlight T. triptera and its dimeric proanthocyanidins as promising multi-target candidates for anti-Alzheimer drug development. Full article

This study explored the electronic and structural tunability of fullerene (C₆₀) derivatives via functionalization with heteroatoms (O, S, Se) in mono-, di-, and tri-bridged configurations, including covalently modeled dimers. Calculations were performed using density functional theory (DFT) at the B3LYP/6-31G(d,p) level. Electronic descriptors such as total dipole moments (TDMs), HOMO–LUMO energy gaps (ΔE), global reactivity descriptors, total density of states (TDOS), molecular electrostatic potential (MESP) and non-covalent interactions (NCIs) were analyzed to elucidate how functionalization alters reactivity and stability. Key findings indicate that TDM increases and ΔE decreases in all functionalized C₆₀; for example, the TDM increased from 0 Debye for C₆₀ to 2.156 Debye for C₆₀–O–S–Se, and ΔE decreased from 2.762 eV (C₆₀) to 2.532 eV (C₆₀–Se), indicating enhanced reactivity. This aligns with global reactivity descriptors such as reduced ionization energy and hardness. Mapped MESP surfaces showed activation around heteroatom sites. Quantum theory of atoms in molecules (QTAIM) and NCI analyses revealed that while mono-bridged structures retain covalent linkages, dimeric systems such as C₆₀–O–C₆₀ and C₆₀–S–C₆₀ relax into weak, van der Waals-type interactions. OPDOS (overlap population density of states) highlighted antibonding character between the fragments in the conduction region. These results demonstrate that heteroatom functionalization enhances the electronic properties of C₆₀, making it a promising candidate for optoelectronic, organic photovoltaic, and sensor applications. Full article

The inorganic proton acid-doped polyaniline (H-PANI-X) is synthesized directly on a graphite carbon paper electrode. The polyaniline doped with hydrochloric acid (yielding H-PANI-Cl), sulfuric acid (yielding H-PANI-HSO₄), and nitric acid (yielding H-PANI-NO₃) is employed to construct both finite molecule and periodic molecule computational models. Theoretical calculation and experimental measurement of a polyaniline/graphite carbon paper electrode are adopted to reveal the doping effect of inorganic acid radical ions (Cl⁻, HSO₄⁻, NO₃⁻) on electrical and electrochemical properties of H-PANI-X. H-PANI-X shows a lower electronic band gap structure, indicating more feasible electron transfer than PANI. H-PANI-X shows a lower HOMO-LUMO orbital energy gap, indicating lower excitation energy than PANI. H-PANI-X also shows a higher electronic density of states level, indicating higher electrical conductivity than PANI. The charge density difference of H-PANI-X reveals a more delocalized electrostatic potential distribution, indicating an enhanced electrostatic interaction between protonated PANI and charge-balancing anions. Furthermore, H-PANI-HSO₄ and H-PANI-NO₃ exhibit hydrogen bonding between the protonated PANI and charge-balancing anions, resulting in reduced electronic band gaps and enhanced electronic density of states compared with H-PANI-Cl. H-PANI-NO₃ with higher electronic states at the Fermi level and higher anionic electronegativity exhibits higher electrical conductivity than H-PANI-Cl and H-PANI-HSO₄. The experimental measurement is conducted to investigate the electrochemical properties of H-PANI-X. The electrochemical impedance spectroscopy measurement indicates H-PANI-NO₃ maintains lower charge transfer resistance (0.357 Ω) than H-PANI-HSO₄ (3.003 Ω) and H-PANI-Cl (10.571 Ω). The cyclic voltammetry measurement indicates that H-PANI-NO₃ has much higher redox current and mean current density responses, accordingly exhibiting superior capacitance (208.0 mF cm⁻²) performance in comparison with H-PANI-Cl (129.5 mF cm⁻²) and H-PANI-HSO₄ (157.9 mF cm⁻²). Theoretical calculation and experimental investigation confirm H-PANI-NO₃ presents superior electroactivity to H-PANI-Cl and H-PANI-HSO₄ for promoting its electrochemical capacitance performance. Full article

Background/Objectives: Ferroptosis, an iron-dependent form of regulated cell death defined by lipid peroxidation, has been extensively studied in cancer and neurodegeneration, but its contribution to erythropoiesis remains poorly understood. Methods: In this study, we investigated the expression of ferroptosis-related genes during HMBA-induced differentiation of murine erythroleukemia (MEL) cells and further assessed the effects of the ferroptosis inducer erastin in this model system. Results: HMBA treatment was accompanied by upregulation of ferroptosis-inducing genes (Atf3, Por, Tfrc, Slc11a2) and downregulation of inhibitory genes (Dhfr, Aifm2, Flvcr1, Nfe2l2, Slc3a2, Slc7a11), while Gpx4 levels increased. Erastin exposure identified 5 μM as the optimal concentration, which resulted in a significant reduction of Steap3 transcripts, an increase in Hbb expression, and an increased accumulation of differentiated cells in culture, along with mild cytotoxicity. To be noted that at the protein level, erastin induced a ~10% decrease in STEAP3 and a 1.5-fold increase in β-globin homo- or hetero-dimers. Ferroptosis markers confirmed erastin activity, with Fsp1 to be downregulated and Slc7a11, ferroportin, and the transferrin receptor upregulated. Importantly, erastin also enhanced apoptotic responses, as indicated by increased levels of active caspase-3 (~40%) and reduced cellular proliferation rate (Ki-67, ~35%), suggesting overlap between ferroptotic and apoptotic pathways. Conclusions: Collectively, these findings indicate that erastin modulates erythroid maturation by repressing Steap3 (Six-transmembrane epithelial antigen of prostate 3) and enhancing Hbb expression, yet its differentiation inducing potential is counterbalanced by concurrent apoptosis activation. Overall, our results support a role of ferroptosis in erythroid maturation by linking iron metabolism, regulated cell death, and erythropoiesis, a fact of pharmacological and therapeutic relevance too. Full article

Background: Point mutations to the androgen receptor (AR) ligand-binding domain (LBD) are becoming increasingly recognized as a mechanism of therapeutic resistance in castration resistant prostate cancer (CRPC). The present review explores how point mutations induce molecular changes that contribute to the eventual treatment failure of androgen receptor pathway inhibitors (ARPIs) in CRPC. Methods: The PubMed database was searched for structural studies on the AR LBD. Eligible articles included molecular docking analysis and emphasized changes in ligand–receptor interactions after point mutation. Structural data were obtained from the Protein Data Bank (PDB) using the search parameters “Androgen receptor ligand binding domain”, “Homo sapiens”, and “X-ray diffraction”. PDB files of wild-type and point mutant AR LBDs were accumulated for analysis. Results: A functional shift from inhibiting to activating AR has been documented for multiple ARPIs. Crystallography data and in silico evaluation have deciphered how changes in steric hindrance of the AF-2 domain contribute to ARPI loss of function. To combat therapeutic resistance, discovery efforts have begun to consider combination approaches of orthosteric and allosteric inhibitors, as well as compounds that target other AR domains. Although lead compounds have been identified, none have progressed into the clinic. Conclusions: Questions remain regarding the best approach for rationally designing new AR targeting therapeutics. Understanding how structural changes to the AR LBD lead to the failure of clinical therapeutics is a necessary step that should precede drug discovery campaigns. Moreover, computational modeling is a powerful tool that should be leveraged to streamline therapeutic development. Full article