A Class of Accelerated Subspace Minimization Conjugate Gradient Methods

Journal of Optimization Theory and Applications - The subspace minimization conjugate gradient methods based on Barzilai–Borwein method (SMCG_BB) and regularization model (SMCG_PR), which...     

Development and validation of LC–MS/MS method for amlexanox in rat plasma and its application in preclinical pharmacokinetics

Amlexanox, an anti-inflammatory and anti-allergic agent, has been widely used clinically for the treatment of canker sores, asthma, and allergic rhinitis. Recently, amlexanox has received considerable attention in curing nonalcoholic fatty liver diseases and hepatitis virus infection. Herein, we first established a sensitive high-performance liquid chromatography-tandem mass spectrum (LC–MS/MS) method for the determination of amlexanox in rat plasma. Propranolol was used as the internal standard (IS). Using a simple protein precipitation method, the amlexanox and IS were separated with Capcell Pak C18 column (2.0 × 50 mm, 5 μm) and eluted with water and acetonitrile each containing 0.1% formic acid using gradient elution condition at a flow rate of 0.4 mL·min⁻¹. Amlexanox and IS were detected by a triple quadrupole mass in multiple reactive monitoring (MRM) under the transitions of m/z 299.2 → 281.2 and m/z 259.9 → 116.1 with positive electrospray ionization, respectively. The calibration curves of amlexanox were established with the range of 50 to 2000 ng·mL⁻¹ (r² > 0.99). The validation method consisted of selectivity, accuracy, precision, carryover effect, matrix effect, recovery, dilution effect, and stability. The fully validated method was successfully applied to the pharmacokinetic study of amlexanox in Wistar rats.     

Imposing accurate wall boundary conditions in corrective‐matrix‐based moving particle semi‐implicit method for free surface flow

Corrective matrix that is derived to restore consistency of discretization schemes can significantly enhance accuracy for the inside particles in the Moving Particle Semi‐implicit method. In this situation, the error due to free surface and wall boundaries becomes dominant. Based on the recent study on Neumann boundary condition (Matsunaga et al, CMAME, 2020), the corrective matrix schemes in MPS are generalized to straightforwardly and accurately impose Neumann boundary condition. However, the new schemes can still easily trigger instability at free surface because of the biased error caused by the incomplete/biased neighbor support. Therefore, the existing stable schemes based on virtual particles and conservative gradient models are applied to free surface and nearby particles to produce a stable transitional layer at free surface. The new corrective matrix schemes are only applied to the particles under the stable transitional layer for improving the wall boundary conditions. Three numerical examples of free surface flows demonstrate that the proposed method can help to reduce the pressure/velocity fluctuations and hence enhance accuracy further.     

Effect of phosphorus (P) on the structure and reactivity of biochars produced from the pyrolysis of acid-washed biomass loaded with P of various forms

This paper investigates the effect of phosphorus (P) on char structure and reactivity of char prepared from the fast pyrolysis of purposely-prepared P-loaded biomass samples at 1000 °C in absence of other inorganic species. Biomass was first acid-washed then loaded with P of three different occurrence forms (one organic P i.e. phytic acid, and two inorganic P i.e. orthophosphoric acid and polyphosphoric acid) at the same P content of 0.8 wt%. Experimental results show that both organic and inorganic P substantially increase char yields during pyrolysis from 6.2% for the biomass sample without P to 23.0–26.0% for P-loaded samples due to the enhanced crosslinking by P-containing structures in char, leading to increases in the char C and H contents and decrease in O content. The presence of P in biochars from fast pyrolysis of various P-loaded biomass samples plays important role in the evolution of char structure and intrinsic reactivity measured during low-temperature oxidation at 500 °C in air under chemical-reaction-controlled regime. After pyrolysis and subsequent char oxidation, all P in biomass either as organic or inorganic P are found to be present in forms of acid-insoluble organic structures. For char prepared from acid-washed wood, char reactivity increases with char conversion due to the increasing pore surface area at higher conversion. Comparatively, for char prepared from acid-washed wood loaded with various P at char conversion below 60%, the presence of P increases char intrinsic reactivity due to the enhanced crosslinking of reactive carbon structures and reduced condensation of char structures. However, at conversions above 60%, P-containing species in char lead to a significant decrease in char reactivity, due to the formation of abundant CO-P bonds, that is highly resistant to the oxidation in air, in the reacting chars.     

Dynamic mechanical relaxation and thermal creep of high-entropy La30Ce30Ni10Al20Co10 bulk metallic glass

Spatial frequency shift(SFS) microscopy with evanescent wave illumination shows intriguing advantages, including large field of view(FOV), high speed, and good modularity. However, a missing band in the spatial frequency domain hampers the SFS superresolution microscopy from achieving resolution better than 3 folds of the Abbe diffraction limit. Here, we propose a novel tunable large-SFS microscopy, making the resolution improvement of a linear system no longer restricted by the detection numerical aperture(NA). The complete wide-range detection in the spatial frequency domain is realized by tuning the illumination spatial frequency actively and broadly through an angle modulation between the azimuthal propagating directions of two evanescent waves. The vertical spatial frequency is tuned via a sectional saturation effect, and the reconstructed depth information can be added to the lateral superresolution mask for 3D imaging. A lateral resolution of λ/9, and a vertical localization precision of ~λ/200(detection objective NA = 0.9) are realized with a gallium phosphide(GaP) waveguide. Its unlimited resolution enhancing capability is demonstrated by introducing a designed metamaterial chip with an unusual large refractive index. Besides the great resolution enhancement, this method shows better anti-noise capability than classical structured illumination microscopy without SFS tunability. This method is chip-compatible and can potentially provide a massproducible illumination chip module achieving the fast, large-FOV, and deep-subwavelength 3D nanoscopy.     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.     

微生物燃料电池阴极脱氮

微生物燃料电池(MFC)阴极电子受体的多样性可实现其阴极脱氮,从而将产生的电能合理利用,因此阴极脱氮成为了MFC的一个研究方向,同时也为实际废水中氮素的去除提供了新的可能。然而在反应过程中有众多因素会导致NOx-N与其他电子受体竞争阳极电子的现象,影响阴极反硝化过程对于电子的利用率,从而造成脱氮效率低等现实问题。目前已有许多研究通过优化MFC自身结构弥补产电的缺陷,及将与其他工艺系统耦合实现同步硝化反硝化等方法,取长补短以增加脱氮效率,降低对碳源的需求,以此解决微生物燃料电池阴极脱氮出现的问题。本文从MFC不同的脱氮历程、MFC工艺条件(pH、C/N、DO)、极室分隔材料等影响MFC阴极脱氮的因素及影响其阴极反硝化微生物群落构成等方面,进行了综述并预测未来研究方向。     

Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe₁©SiC₂), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH₂ intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe₁©SiO₂ and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Electron-donating methoxy group enhances the stability and efficiency of indole-based fluorescent probe for detecting Cu2+

Research on Chemical Intermediates - Two novel Schiff-base fluorescent probes bearing different substituents were synthesized by the reaction of indole derivatives with 4-aminoantipyrine. The...