The mechanisms and kinetics of atmospheric degradation for halogenated formyl and carboxylic acid compounds, denoted as HC(O)X and XC(O)OH (where X represents F, Cl, Br, and I), were thoroughly investigated through quantum chemical calculations and kinetic modeling, initiated by hydroxyl (OH) radicals. The potential energy surfaces of the hydrogen abstraction reaction pathways were analyzed at the CCSD(T)-MP2/CBS//M06-2X theoretical level, using the aug-cc-pVXZ (D, T, and Q) basis sets for systems with F, Cl, and Br substitutions. For iodine-containing compounds, the aug-cc-pVXZ-PP (D, T, and Q) basis sets were used. Our findings demonstrate that the OH attack on HC(O)X (X = F, Cl, Br, and I) is more favorable than on XC(O)OH, clearly indicating that hydrogen abstraction from the carbonyl position is the preferred pathway. Reaction enthalpies and Gibbs free energies were calculated at the M06-2X/aug-cc-pVTZ and aug-cc-pVTZ-PP levels, while kinetic calculations employed canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) corrections over a range of 250-500 K temperatures. The calculated rate coefficients were then used to evaluate the atmospheric implications of these systems by estimating their tropospheric lifetimes with respect to oxidation by the OH radical.

Mitochondrial transfer and transplantation (mitoTT) has emerged as an experimental and potentially transformative therapeutic strategy, drawing attention for its ability to modulate cellular bioenergetics, stress responses, and tissue repair. Endogenous mitochondrial transfer can occur through tunneling nanotubes, extracellular vesicles, cell fusion, gap junction-associated communication, and phagocytosis-like internalization. These routes differ substantially in distance, directionality, cargo integrity, regulatory control, and physiological relevance. Preclinical studies indicate that exogenous mitochondria may transiently improve bioenergetic function, attenuate oxidative stress, and support recovery in models of cardiac, skeletal muscle, and nervous system injury, whereas clinical evidence remains limited and heterogeneous. Broad clinical implementation remains constrained by unresolved biological and translational barriers. These include inefficient or poorly controlled uptake of extracellular mitochondria, uncertain long-term persistence, incomplete functional integration, donor-recipient incompatibility, mitochondrial-nuclear mismatch, heteroplasmy-related risks, immunogenicity, and the lack of standardized potency and delivery assays. Here, we critically synthesize the cellular mechanisms enabling mitoTT, emphasizing the checkpoints that determine whether transferred mitochondria are integrated, remodeled, immunologically sensed, or eliminated. We further discuss cristae biology and the mitochondrial contact site and cristae organizing system, mitochondrial nucleoid maintenance, mitochondrial DNA replication, organelle contact sites, and emerging bioengineering strategies required to move mitoTT from experimental rescue toward reproducible therapeutic application.

The use of probabilistic spintronic devices for infrared radiation detection has introduced a shift in the approach to thermal imaging. The integration of probabilistic magnetic tunnel junctions with infrared plasmonic nano-antennas yields digital-mode infrared sensors at room temperature. Here, we present a scalable approach towards multi-pixel plasmonic-spintronic bolometer array fabrication and readout. We fabricate proof-of-concept 2x2 row-column multiplexed probabilistic plasmonic-spintronic arrays and show their response to long-wave infrared radiation (8-14 μm) with high readout speeds (104-106 counts per second). These spintronic, ultrafast, nanoscale (SUN) bolometers can enable high-pixel density CMOS compatible infrared detection platforms. Our work provides a broadband (9 kHz to 3 GHz) readout platform for future digital probabilistic detector applications. Furthermore, our approach addresses a key challenge associated with scaling infrared pixel sizes that can drive progress towards high pixel density detector arrays for infrared sensing and microscopy applications.

Red mud (RM), a highly alkaline by-product of alumina production, poses serious environmental risks, while its high-value utilization remains challenging. Although red mud-based cementitious materials have been widely investigated, simultaneously achieving high mechanical performance and effective heavy metal immobilization remains difficult because the coupling mechanism between hydration evolution and contaminant stabilization is still unclear. This study developed an optimized red mud-based cementitious material to simultaneously enhance compressive strength and heavy metal stabilization while elucidating the underlying mechanism. The final optimized formulation achieved a 28-day compressive strength of 9.02 MPa while maintaining acceptable flowability. At the final 56-day test point, the leaching concentrations of Pb, As, Cd, and Mn were more than 98% lower than those of the freshly prepared reference mixture. XRD and SEM observations were consistent with AFt formation, the development of poorly crystalline gel-like products, and progressive matrix densification. These structural changes were consistent with the observed decrease in heavy metal leaching. However, the chemical states and binding environments of the immobilized metals were not directly determined. These findings suggest a link between hydration-driven microstructural evolution, strength development, and contaminant stabilization, supporting the sustainable use of red mud in low-carbon cementitious materials.

The ulnar nerve runs at the level of the ulnar carpus through Guyon's canal. Due to the proximity to very rigid ligamentous and bony structures, space-occupying processes or fractures can easily cause compression of the ulnar nerve and its two distal branches. Pathologies of the adjacent ulnar artery can also irritate the nerve.

The utilization of tunnel dreg-based recycled sand (TDRS) concrete in high-altitude regions kills four birds with one stone by reducing carbon emissions, addressing raw material shortages, promoting the value-added utilization of building solid waste, and encouraging recycling in construction. Herein, concrete incorporating varying amounts of TDRS powder (4-12%) and sand ratios (37-43%) was prepared and real high-altitude environment exposure tests were carried out. The mechanical properties, drying shrinkage, microstructure, carbon footprint, and costs were systematically analyzed. Results show that compressive strength and drying shrinkage initially increase then decrease with rising TDRS contents, attributed to TDRS concrete's dense microstructure with ∼ 50 nm pore size. A modified drying shrinkage model for TDRS concrete achieved prediction errors within ± 10%. Replacing natural sand with TDRS reduces carbon emissions by 11.204 kgCO2/t, and shortens transport distances, yielding at least 13.7% reduction in costs. Future systematic research on the durability and long-term performance of TDRS concrete is essential for advancing its practical application.

Niemann-Pick disease type C (NPC) arises from failure of the NPC1 and/or NPC2 proteins to mobilize lysosomal cholesterol, yet the mechanism by which the complex drives sterol translocation lacks a thorough understanding. Here, we capture an NPC1-NPC2 complex conformation at lysosomal pH using a bis-sterol ligand (JM046), fortifying NPC2 engagement with NPC1 and enabling structural characterization of an alternative transport state. In this complex, the sterol moiety is absent from the NPC1 central tunnel, and the neck site adopts an expanded architecture that resembles a previously observed NPC1 conformation at neutral pH, indicating that the tunnel geometry may not be influenced by the pH alone. Instead, we provide evidence that cholesterol occupancy in the neck site is a key determinant of tunnel contraction. Supporting this notion, NPC1 purified from cholesterol-auxotrophic insect cells exhibits a similarly expanded neck conformation. Integrating these structures and molecular dynamics (MD) simulations exploring the directional cholesterol handoff from NPC2 to the NPC1 tunnel, we propose a substrate-induced gating cycle where luminal and membrane-facing openings of NPC1 switch states in a coordinated manner to transfer cholesterol across the hydrophilic glycocalyx, reminiscent of the alternating access mechanism of membrane transporters. This framework synthesizes NPC1 conformational states into a mechanistic basis that may be used to map pathogenic NPC variants to their relevant transport steps.

Vacancy-ordered double halide perovskites have gained attention as a stable and environmentally friendly alternative to organic-inorganic hybrid halide perovskites. However, despite extensive optimization, their theoretical efficiency remains unattained, and the fundamental charge conduction mechanism is not well understood. This study investigates the conduction mechanism in Cs2RuX6 (X = Br- and Cl-) using temperature-dependent Electrochemical Impedance Spectroscopy (EIS) and Raman spectroscopy. Our findings reveal the presence of redox-mediated charge conduction in this material class, attributed to multiple valence states. Cs2RuBr6 demonstrates superior conductivity, with correlated barrier hopping identified as the dominant conduction mechanism. In contrast, Cs2RuCl6 exhibits the coexistence of two conduction mechanisms: correlated barrier hopping and non-overlapping small polaron tunneling. This fundamental insight provides a pathway for addressing existing challenges and unlocking the full potential of this material class for a wide range of optoelectronic and photoelectrochemical applications.

Using a photochromic spirooxazine ligand 1,3,3-trimethylindolinonaphthospirooxazine (TMI-NSO), two novel anionic coordination complexes with dysprosium(III) iodide and different counterions were synthesized: (TBA+){(TMI-NSO)2·DyIIII4}- (1) and (Cp*2Co+)2{(TMI-NSO)2·DyIIII4}-(I-)·4C6H4Cl2 (2). Both complexes have two short axial Dy-O bonds (2.17-2.26 Å) and four longer equatorial Dy-I bonds (3.05-3.08 Å). Both complexes exhibit slow magnetic relaxation in a zero magnetic field with high magnetization reversal barriers: Ueff = 750 ± 30 (1) and 680 ± 40 (2) cm-1. For both compounds, magnetic hysteresis and a divergence between zero-field- and field-cooling curves are observed at temperatures below 6 K, indicating a blocking temperature Tb = 6 K. Thus, compared to the previously studied DyIII complex with the photochromic ligand 1,3,3-trimethylindolino-β-naphthopyrylospiran, (TBA+){(TMI-NPS)2·DyIIII4}-·0.5C6H4Cl2 (3, Ueff = 470 ± 40 cm-1), the magnetization reversal barriers increased by about 210-280 cm-1, while the Tb decreased by 2 K. To suppress tunneling, magnetic relaxation was measured in a static magnetic field of 500 Oe; interestingly, this field slightly increased the magnetization reversal barriers only for compound 2. To gain a deeper understanding of the magnetic properties of the compounds under study, ab initio relativistic calculations were performed; analysis of the results confirms the very high anisotropy of the lowest Kramers doublets, as evidenced by the high value of Ueff, and convincingly points to Raman relaxation as the primary source of differences in the SIM properties of 1-3. The Dy complex in compound 1 exhibits an absorption band peaking at 614-623 nm; when excited by green light, it rapidly dissociates, and subsequent UV irradiation only partially restores the intensity of the original band.

Background US-guided hydrodissection is a minimally invasive treatment for nerve entrapment syndromes. However, its independent therapeutic efficacy remains unproven because most studies combine hydrodissection with corticosteroids or dextrose. Purpose To evaluate and compare the clinical and sonographic outcomes and complication rates of three US-guided hydrodissection techniques for the treatment of carpal tunnel syndrome (CTS) and to assess the relative efficacy of hydrodissection. Materials and Methods Adults with refractory CTS were included in this prospective randomized controlled trial (May 2019 to November 2020). Baseline assessment included the Boston Carpal Tunnel Questionnaire (BCTQ), Visual Analog Scale (VAS), and US measurement of median nerve cross-sectional area (CSA). Participants were randomized into three single-blinded groups: group 1, US-guided hydrodissection with normal saline (NS); group 2, perineural corticosteroid injection; and group 3, US-guided hydrodissection with NS plus corticosteroid. For hydrodissection, injectate was administered around the median nerve until complete nerve separation was achieved. Follow-up was performed at 4, 12, and 24 weeks. A linear mixed-effects model was used to evaluate within-group and between-group changes over time. Results Thirty-nine participants (mean age, 42.22 years ± 10.46 [SD]; 20 male; 63 wrists) were included. Persistent improvement in BCTQ and VAS scores was observed in groups 1 and 3. At 24 weeks, minimal clinically important difference for BCTQ Symptom Severity Scale was achieved in 85.7% and 90.5% of wrists in groups 1 and 3, respectively, with no significant intergroup difference (P = .979). Although group 2 demonstrated early clinical improvement, symptoms recurred and outcomes at 24 weeks were not significantly different from baseline. Percentage reduction in median nerve CSA was greater in groups 1 and 3 than in group 2 at 12 weeks (43% and 46%, respectively, vs 11%; P = .0001). No major complications were observed. Conclusion US-guided hydrodissection with NS alone resulted in sustained clinical and morphologic improvement in CTS, and the addition of corticosteroid provided no additional benefit. Clinical trial registration no. CTRI/2018/12/016604 © RSNA, 2026.

For H-bonded (HCO3)2(2-) dimers in the kalicinite crystal, KHCO3, the anharmonic coupling between the high-frequency νOH and low-frequency νσOO modes was studied by calculating the double-well potentials of the multiple (collective) intradimer double proton transfers at fixed and relaxed O⋯O interatomic distances using five different one-electron Hamiltonians, viz., Hartree-Fock, gradient-corrected PW91 and PBE, hybrid B3LYP(-D*), and Möller-Plesset with the second-order contribution to the correlation energy based on localized orbitals (LMP2). The strongly anharmonic shape of the resulting double-well potential, governing the energy spacings between vibrational levels, is shown to be very sensitive to the chosen combination of the one-electron and vibrational Hamiltonians. Numerical solutions of the one- and two-dimensional vibrational problem for the OH oscillators allowed us to evaluate transitions between tunnel-split doublets of the ground and the first excited vibrational levels. The best agreement with the low-temperature inelastic neutron scattering data for KHCO3 is achieved by using the B3LYP-D* Hamiltonian for the collective proton transfer pathway, which is decoupled from the KHCO3 crystal lattice. The influence of the chosen one-electron Hamiltonian on the accuracy of the calculation of the weakly anharmonic δOH, γOH, and νσOO modes is shown to be less dramatic. The shape of the νOH vs ROO dependence, calculated for KHCO3, semi-quantitatively captures the experimentally observed trend for OHO bonds in hydroxyl-bearing solids: a non-linear red shift of the νOH band with the O⋯O distance shortening; in addition, a reversal of the trend is predicted for extremely short O⋯O contacts: νOH rises again, indicating potential well narrowing when oxygens are pushed closer than ∼2.35 Å.

π-Extended porphyrinoids are versatile platforms for the emerging field of π-electron magnetism in conjugated systems. However, achieving controlled bond-selective transformations that enable tuning of their electronic ground states remains a major challenge. Here, we propose a protocol for covalent bond dissociation in π-extended porphyrinoids at carbonitrile-Au substituents. By applying bias pulses with an STM tip positioned close to the molecule, the ligand can be selectively cleaved, resulting in chemisorption of the porphyrinoid onto the Au(111) surface. BR-STM provides structural insights into the bonding configurations before and after the scission, while STS in combination with DFT+CASCI calculations reveals the impact of the cleavage on the molecule's electronic properties. Whereas the intact molecule exhibits a closed-shell electronic structure, removal of the ligands induces a change in its electronic ground state, leading to the emergence of a Kondo resonance upon cleavage of the CN─Au ligands. In addition, DFT + vdW simulations show that carbonitrile─Au coordination weakens the carbon─carbon bond connecting the ligand to the molecular core, thereby facilitating its cleavage through tip-induced manipulation. Overall, these results provide insights into the bonding nature of the carbonitrile─Au interaction and demonstrate how the bond scission induces a transition from closed-shell to open-shell states.