The nominal slit width is not equivalent to molecular accessibility. The reservoir-fed molecular dynamics of Lennard-Jones argon at 100 K in rigid five-layer graphene slits (w = 0.396-3.40 nm) separate three quantities that confined-fluid descriptions routinely merge: energetic accessibility of the slit interior, observed molecular admission, and stationary post-admission capacity. Cutoff-consistent lattice summation over the production carbon coordinates places the laterally averaged one-body zero crossing at , registry extrema 0.5700 and 0.5859 nm. No entry occurs at w = 0.575 nm over 35.38 ns or at 0.580 nm over 406.98 ns, whereas 0.590 nm admits argon after 7.595 ns and remains occupied for 99.92% of its post-entry record, giving an observation-dependent sustained-admission bracket 0.580 < wobsadm ≤ 0.590 nm. Near this admission boundary, loading remains nonstationary after approximately 1 µs, and the terminal-window attained accessibilities of Kterm50 = 0.0475, 0.2007, and 0.5282 at w = 0.590, 0.592, and 0.594 nm, respectively. Where loading is stationary, packing governs capacity: layer splitting near wflip = 0.773 nm produces a statistically resolved accessibility minimum (pooled K = 0.540 over w = 0.745-0.808 nm), and wide slits follow a capacity envelope Γ = a(w - δdead), a = 20.85 ± 0.48 atoms nm-3, and δdead = 0.328 ± 0.029 nm. Under a fixed-displacement-rate drive, the apparent conductance decreased 23.7-fold toward admission. Therefore, accessibility, admission, stationary loading, and capacity are distinct conditions, not one geometric threshold.

In this work, a versatile and efficient synthetic strategy for the selective N-1 alkylation of nitro-substituted 3-haloindazoles was developed using a complex base of NaH/t-BuOK. Various alkylating agents were employed under an argon atmosphere in DMF. This method successfully yielded several N-1-alkylated indazole derivatives, including 1-benzyl-3-chloro-6-nitro-1H-indazole, 1-benzyl-3-bromo-6-nitro-1H-indazole, and related analogs, with good to excellent yields (62%-100%). Subsequent amination reactions of the 3-bromoindazole intermediates with anilines provided N-arylindazoles at the C-3 position in moderate yields (11%-70%). In parallel, Suzuki-Miyaura cross-coupling reactions with boronic acids provided direct access to arylindazoles at the C-3 position with yields ranging from 54% to 92%. Of the compounds evaluated biologically, 16 and 18c stand out, having shown high inhibition of CDK2 (100% at 10 μM), while 13e and 16 showed maximum inhibition of ERK2 (100% at 10 μM), both proteins implicated in cancer.

Sonodynamic therapy is hindered by the insufficient catalytic activity of nanomaterials, the robust antioxidant capacity of the tumor microenvironment, and the limited targeting efficiency of conventional drug delivery systems. In this study, CuSn(OH)6 nanorods were synthesized via coprecipitation. These were then transformed into microspheres through zinc doping and calcination at 500°C under argon, yielding ZnSnO3/Cu0.97Zn0.03 (CZ) nanocomposites. They exhibit excellent piezoelectric catalysis, sonodynamic activity, peroxidase-like activity, and glutathione degradation capacity. These enable the generation of substantial reactive oxygen species under ultrasound (US), which disrupts the redox balance in tumors. Subsequently, FCZ composite drug-loaded microneedles (FCZ-MN) loaded with CZ and 5-fluorouracil (5-Fu) were fabricated. Matrix optimization endowed FCZ-MN with superior mechanical strength and skin biocompatibility, enabling targeted transdermal delivery with pH-responsive and US-controllable drug release. In vitro and in vivo studies have demonstrated that FCZ‑MN combined with US effectively induces ferroptosis, cuproptosis, and apoptosis through multiple pathways, leading to significant tumor suppression without apparent systemic toxicity. This integrated strategy offers a promising alternative to conventional treatment modalities, providing an efficient and well-tolerated platform for localized transdermal tumor therapy.

Central airway obstruction (CAO) is a life-threatening condition caused by malignant or benign processes involving the trachea and main bronchi. Bronchoscopic airway stenting is an established intervention to restore airway patency, relieve symptoms, and stabilize patients, particularly in urgent or critical settings. However, its clinical role varies according to underlying etiology and disease context. We report a single-center case series of seven adult patients with symptomatic CAO who underwent bronchoscopic airway stenting. Six cases were associated with malignant disease, and one involved benign obstruction due to endobronchial tuberculosis. Interventions included rigid and/or flexible bronchoscopy, with adjunctive techniques such as balloon dilatation, cryotherapy, and argon plasma coagulation. Stent selection was individualized based on anatomical and etiological considerations. Airway stenting led to immediate improvement in respiratory status in all cases. In benign obstruction, stenting achieved sustained airway patency without significant complications. In malignant CAO, stenting served primarily as a palliative or bridging intervention, providing temporary stabilization and enabling further oncologic or supportive therapy. In critically ill patients, including those with impending airway collapse or post-cardiac arrest, stenting functioned as a lifesaving or salvage procedure. Complications included tumor ingrowth, mucus retention, and infection; no fatal stent-related procedural events occurred. Airway stenting is a versatile and effective modality for managing CAO. Its role differs by etiology, offering durable benefit in benign disease, palliative or stabilizing effects in malignancy, and potential life-saving intervention in selected critically ill patients. Individualized decision-making and multidisciplinary management remain essential to optimize outcomes.

Flexible metal-organic frameworks (MOFs) exhibit coupled adsorption-deformation behavior that cannot be captured in molecular detail by conventional rigid-framework simulations. We present an iterative hybrid GCMC/MD methodology that explicitly couples grand canonical Monte Carlo sampling of adsorbate configurations with isothermal-isobaric molecular dynamics relaxation of the framework structure, using a Metropolis acceptance criterion in the osmotic ensemble to ensure thermodynamic consistency. Applied to argon adsorption on ZIF-8 at 87.3 K, the method quantitatively reproduces the experimental stepped isotherm characteristic of the gate-opening transition between low pressure (LP) and high pressure (HP) conformations and predicts nonmonotonic strain isotherm with initial contraction (∼0.5%) at low loadings followed by expansion (∼0.7%) during gate-opening. In addition, the elastic modulus variation upon loading is calculated from the volume fluctuations. The simulations reveal and quantify the molecular mechanism of gate-opening through cooperative linker reorientation from a unimodal swing angle distribution centered at 0° to a bimodal distribution peaked at ± 23°. The proposed approach is computationally efficient, yielding converged strain and compressibility isotherms within an accessible number of iterations, and provides a general framework for predicting adsorption-induced structural transitions in flexible porous materials without a priori knowledge of end point structures.

Garnet-phase Li7La3Zr2O12 (LLZO) is a promising solid-state electrolyte in lithium metal batteries but suffers from contaminant formation upon exposure to ambient conditions. We use a suite of analytical methods to quantify this contamination and the resulting protonation of Ta-doped LLZO's (LLZTO) crystal structure and their removal via heat treatment under argon. We quantify contaminant removal in 3 unique temperature regimes: one where LiOH is removed at lower temperatures (<350 °C) and two where Li2CO3 is removed at intermediate (350-550 °C) and high (>550 °C) temperatures. Removal of LiOH and Li2CO3 in the intermediate regime proceeds through a mechanism involving beneficial H+/Li+ exchange with the LLZTO lattice, whereas high-temperature Li2CO3 removal proceeds through the thermal decomposition mechanism of Li2CO3 to evolve CO2 and deposit solid Li2O. Through these quantification methods, we show that most, but not all, contaminants are removed upon heating to 800 °C, with 97% of Li2CO3 and 85% of LiOH present in the as-given materials being removed. We show that heat treatment in a stagnant atmosphere is less effective than treatment under active gas flow. Re-lithiation of the LLZTO lattice is also found to improve Li+ transport across the LLZTO particle interface when immersed in a Li+-bearing organic electrolyte, and the protonation of LLZTO contributes more to slowing interfacial Li+ transport than the presence of interfacial contaminants.

The goal of this analysis is to evaluate factors associated with PERT consultation and to determine if PERT consultation was associated with differences in outcomes for patients with intermediate-high and high-risk PE. All intermediate-high or high-risk PE cases at a single institution from 2016 to 2019 were reviewed. Outcomes were in-hospital mortality, length of stay (LOS), and moderate/severe bleeding. Clinical characteristics, imaging findings, and outcomes were compared between cases with and without PERT consultation. 335 cases were included, with PERT consulted in 52%. PERT was consulted more in cases with increased right ventricle (RV) size and depressed RV function (both p < 0.0001). PERT was consulted more for saddle (85.5%, p < 0.0001) and less for segmental (39.0%, p < 0.0001) PE. Use of catheter-based therapies, such as catheter-directed thrombolysis (23.0% vs. 1.9%, p < 0.001), was higher within the PERT group. Cases with PERT involvement had a shorter mean LOS (13 vs. 24 days), lower in-hospital mortality (8.1% vs. 21.0%), and less bleeding (9.8% vs. 21%) (all p < 0.004); there was no difference in PE-related mortality (p = 0.51). In multivariate analyses, PERT consultation was a predictor of lower in-hospital mortality (OR 0.30, CI 0.15-0.64, p = 0.002), bleeding (OR 0.43, CI 0.22-0.85, p = 0.01), and LOS (OR 0.38, CI 0.22-0.67, p = 0.0007). PERT was consulted more in cases of central PE and cases with greater signs of RV strain. PERT was associated with increased use of catheter-based therapies, lower in-hospital mortality and bleeding, and a shorter LOS.

Matrix isolation is an experimental technique which allows spectroscopists to observe highly reactive or weakly bound systems by trapping them in frozen noble gas matrices. In this work, we studied the viability of using ab initio molecular dynamics (AIMD) to simulate several H2S·amine complexes isolated in solid argon crystals, comparing the results with conventional density functional theory (DFT) harmonic and anharmonic calculations to assess the most practical and accurate method to calculate the vibrational spectrum of such systems. While AIMD accurately predicted the intensity ratios of certain peaks, the frequencies themselves were no more accurate than conventional harmonic DFT calculations. Modeling an explicit argon matrix did not improve the results. Based on the computational cost of each method, a gas phase anharmonic or scaled harmonic frequency calculation at an appropriate level of theory was determined to be the most accurate and efficient way to simulate matrix isolation spectra.

Magnetic fields exert a strong influence on plasma behavior, highlighting the need for diagnostic techniques that can measure magnetic fields with high accuracy while minimizing plasma perturbation. Quantum Beat Spectroscopy (QBS), recently demonstrated by Gilbert et al. [Plasma Sources Sci. Technol. 34 025020 (2025)] in a laboratory plasma, is a laser-based optical diagnostic that provides Doppler-free measurements of magnetic field strength. In this study, a femtosecond laser is employed in an argon plasma to investigate the dependence of the QBS signal on the polarization of the incident laser. The experiments are conducted in a tabletop six-way cross vacuum chamber. A pair of Helmholtz coils is mounted on a rotational stage such that the chamber remains centered between the coils, enabling precise control over the orientation of the applied magnetic field. The present study shows that the quantum beat amplitude strongly depends on the polarization of the injected laser. It is also demonstrated that excitation from a single initial state into a coherent superposition of two excited magnetic sublevels is a necessary condition for the observation of quantum beats. Furthermore, it is shown that the magnetic field orientation can be determined by rotating the polarization of the injected laser.

Electrosurgical argon plasma sources have recently shown promising clinical results for the treatment of cervical intraepithelial neoplasia (CIN) without causing significant thermal tissue damage. Despite these findings, the underlying plasma-chemical mechanisms responsible for the therapeutic effects are still insufficiently understood, and quantitative data on key excited species under clinically relevant operating conditions remain scarce. In particular, argon metastable states are expected to play an important role in energy transfer and reactive species formation. In this work, tunable diode laser absorption spectroscopy (TDLAS) is employed to determine the temporal evolution of the argon metastable state densities Ar(1s5) and Ar(1s3) in a clinically applied electrosurgical argon plasma with sub-microsecond temporal resolution. Metastable densities in the order of 10[20]m[-3]for Ar(1s5) and 10[19]m[-3]for Ar(1s3) are observed. Both states exhibit pronounced temporal modulations within the discharge pulse, indicating the importance of stepwise excitation and de-excitation processes in the discharge kinetics. The measured densities are in good agreement with those reported in previous studies of similar systems. In addition, pressure-broadened absorption profiles are used to estimate characteristic electron densities and gas temperatures from Stark and van der Waals broadening, respectively. The results provide quantitative insight into the transient plasma chemistry of electrosurgical argon plasmas and support future modelling of reactive species generation relevant for biomedical applications.

At the DIII-D tokamak, the Charge Exchange Recombination (CER) spectroscopy diagnostic routinely measures impurity temperature, rotation, and density. The ability to make these measurements in real time within DIII-D's Plasma Control System (PCS) has recently been expanded and improved. High-speed network connections send raw data from 24 tangential CER views to the PCS, so spectral analysis can be performed. These views make measurements on the outboard midplane of DIII-D from the magnetic axis to the scrape off layer. Spectral analysis is completed quickly by a simplified least-squares fitting routine. Results are typically available within a millisecond of when the raw data become available and new raw data for all 24 views are typically sent to the PCS every 5 ms (for the most common CER sampling frequency). Fully ionized carbon is the most common impurity used for analysis, and analysis can also be performed for other highly charged impurities with relatively simple spectra such as boron, neon, and argon. The large majority of the real-time temperature and rotation measurements are within 20% of the most accurate automatic analysis available. As DIII-D discharges are typically separated by 10-15 min, the more rapid availability of the real-time analysis can be a major aid for control room analysis during an experiment. The real-time analysis can also be used in the PCS for control purposes (e.g., plasma profile feedback).

Estimating transport properties such as viscosity and thermal conductivity is crucial for a wide range of applications. No theory has yet been presented that is capable of predicting these properties accurately across the entire fluid region. With transfer lengths determined from intermolecular potentials, Revised Enskog Theory (RET) has been shown to yield accurate predictions from dilute gas to the liquid-solid transition at high temperatures. We present a methodology coupling RET with residual entropy scaling (RES), called REST, where the residual entropy scaling is derived from the high-temperature limit of RET. With equilibrium properties from thermodynamic perturbation theory, REST is fully predictive for transport properties of multicomponent mixtures under conditions ranging from dilute gas to dense liquid. It has an average absolute relative deviation (AARD) of 5.30%, 7.07%, and 2.97% for the viscosity of argon, neon, and air, respectively, across the full fluid range. The AARD is 1.3%-4.3% for the viscosity of several binary mixtures containing CH4, CO2, H2, and N2 at temperatures down to 100 K and pressures up to 792 bars. For the CH4/H2 mixture, REST significantly outperforms the present industry standard, which combines empirical correlations for the pure components with extended corresponding states theory. For a range of binary mixtures containing CO2, CH4, O2, and N2, the thermal conductivity is predicted with AARDs of 2.9%-6.3% at pressures up to 200 bars and temperatures ranging from 104 to 425 K, which is within the experimental accuracy. REST combined with the SAFT-VR Sum equation of state predicts the transport properties of argon and neon throughout the entire fluid region using an interaction potential derived from ab initio calculations as the sole input.