Application of machine learning and deep learning methods for hydrated electron rate constant prediction.

Accurately determining the second-order rate constant with eaq- (keaq-) for organic compounds (OCs) is crucial in the eaq- induced advanced reduction processes (ARPs). In this study, we collected 867 keaq- values at different pHs from peer-reviewed publications and applied machine learning (ML) algorithm-XGBoost and deep learning (DL) algorithm-convolutional neural network (CNN) to predict keaq-. Our results demonstrated that the CNN model with transfer learning and data augmentation (CNN-TL&DA) greatly improved the prediction results and overcame over-fitting. Furthermore, we compared the ML/DL modeling methods and found that the CNN-TL&DA, which combined molecular images (MI), achieved the best overall performance (R2test = 0.896, RMSEtest = 0.362, MAEtest = 0.261) when compared to the XGBoost algorithm combined with Mordred descriptors (MD) (0.692, RMSEtest = 0.622, MAEtest = 0.399) and Morgan fingerprint (MF) (R2test = 0.512, RMSEtest = 0.783, MAEtest = 0.520). Moreover, the interpretation of the MD-XGBoost and MF-XGBoost models using the SHAP method revealed the significance of MDs (e.g., molecular size, branching, electron distribution, polarizability, and bond types), MFs (e.g, aromatic carbon, carbonyl oxygen, nitrogen, and halogen) and environmental conditions (e.g., pH) that effectively influence the keaq- prediction. The interpretation of the 2D molecular image-CNN (MI-CNN) models using the Grad-CAM method showed that they correctly identified key functional groups such as -CN, -NO2, and -X functional groups that can increase the keaq- values. Additionally, almost all electron-withdrawing groups and a small part of electron-donating groups for the MI-CNN model can be highlighted for estimating keaq-. Overall, our results suggest that the CNN approach has smaller errors when compared to ML algorithms, making it a promising candidate for predicting other rate constants.

Preparation of Biochar with Developed Mesoporous Structure from Poplar Leaf Activated by KHCO3 and Its Efficient Adsorption of Oxytetracycline Hydrochloride.

The effective removal of oxytetracycline hydrochloride (OTC) from the water environment is of great importance. Adsorption as a simple, stable, and cost-effective technology is regarded as an important method for removing OTC. Herein, a low-cost biochar with a developed mesoporous structure was synthesized via pyrolysis of poplar leaf with potassium bicarbonate (KHCO3) as the activator. KHCO3 can endow biochar with abundant mesopores, but excessive KHCO3 cannot continuously promote the formation of mesoporous structures. In comparison with all of the prepared biochars, PKC-4 (biochar with a poplar leaf to KHCO3 mass ratio of 5:4) shows the highest adsorption performance for OTC as it has the largest surface area and richest mesoporous structure. The pseudo-second-order kinetic model and the Freundlich equilibrium model are more consistent with the experimental data, which implies that the adsorption process is multi-mechanism and multi-layered. In addition, the maximum adsorption capacities of biochar are slightly affected by pH changes, different metal ions, and different water matrices. Moreover, the biochar can be regenerated by pyrolysis, and its adsorption capacity only decreases by approximately 6% after four cycles. The adsorption of biochar for OTC is mainly controlled by pore filling, though electrostatic interactions, hydrogen bonding, and π-π interaction are also involved. This study realizes biomass waste recycling and highlights the potential of poplar leaf-based biochar for the adsorption of antibiotics.

Simultaneous determination of amitraz, chlordimeform, formetanate and metabolites in human blood by liquid chromatography tandem mass spectrometry with phospholipid-removal pretreatment.

In this study, a reliable ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method coupled with an easy, fast and effective sample pretreatment procedure was developed for simultaneous determination of amitraz, chlordimeform, formetanate and their metabolites in human blood. With the procedures of protein precipitation and a phospholipid-removal step, the endogenous compound interference was significantly reduced, and matrix effects were significantly reduced. The linear ranges of matrix-matched standard curves were from 0.5 to 1000 ng/mL with coefficients of determination >0.996. Very low limits of detection (0.05-0.12 ng/mL) and limits of quantitation (0.15-0.4 ng/mL) were achieved. Reasonable recoveries ranging from 88.1 to 103.5% were obtained. The intra-day RSDs ranging from 3.2 to 8.6% and inter-day RSDs ranging from 4.8 to 9.2% indicated good precision. With the introduction of a phospholipid-removal step, the ME ranged from 90.1 to 98.5%. The established method was successfully applied to the analysis of a blood sample from a formetanate poisoning case. This method possesses the advantages of high sensitivity, reduced matrix effects and rapidity.

Nitrogen, Phosphorus, and Sulfur Co-Doped Hollow Carbon Shell as Superior Metal-Free Catalyst for Selective Oxidation of Aromatic Alkanes.

Metal-free heteroatom-doped carbocatalysts with a high surface area are desirable for catalytic reactions. In this study, we found an efficient strategy to prepare nitrogen, phosphorus, and sulfur co-doped hollow carbon shells (denote as NPS-HCS) with a surface area of 1020 m(2) g(-1). Using a poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) shell as carbon source and N, P, S-doping source, and the ZIF-67 core as structural template as well as extra N-doping source, NPS-HCS were obtained with a high surface area and superhydrophilicity. All these features render the prepared NPS-HCS a superior metal-free carbocatalyst for the selective oxidation of aromatic alkanes in aqueous solution. This study provides a reliable and facile route to prepare doped carbocatalysts with enhanced catalytic properties.

Nanoscale magnetic stirring bars for heterogeneous catalysis in microscopic systems.

Nanometer-sized magnetic stirring bars containing Pd nanoparticles (denoted as Fe3 O4 -NC-PZS-Pd) for heterogeneous catalysis in microscopic system were prepared through a facile two-step process. In the hydrogenation of styrene, Fe3 O4 -NC-PZS-Pd showed an activity similar to that of the commercial Pd/C catalyst, but much better stability. In microscopic catalytic systems, Fe3 O4 -NC-PZS-Pd can effectively stir the reaction solution within microdrops to accelerate mass transfer, and displays far better catalytic activity than the commercial Pd/C for the hydrogenation of methylene blue in an array of microdroplets. These results suggested that the Fe3 O4 -NC-PZS-Pd could be used as nanoscale stirring bars in nanoreactors.

Achieving Near-Infrared Phosphorescence Supramolecular Hydrogel Based on Amphiphilic Bromonaphthalimide Pyridinium Hierarchical Assembly.

Phosphorescent supramolecular hydrogels are currently a prevalent topic for their great promise in various photonic applications. Herein, an efficient near-infrared (NIR) phosphorescence supramolecular hydrogel is reported via the hierarchical assembly strategy in aqueous solution, which is fabricated from amphiphilic bromonaphthalimide pyridinium derivative (G), exfoliated Laponite (LP) nanosheets, and polymeric polyacrylamide (PAAm). Initially, G spontaneously self-aggregates into spherical nanoparticles covered with positively charged pyridinium units and emits single fluorescence at 410 nm. Driven by electrostatic interactions with negatively charged nanosheets, the nanoparticles subsequently function as the cross-linked binders and coassemble with LP into supramolecular hydrogels with an engendered red room-temperature phosphorescence (RTP) up to 620 nm. Benefiting from hydrogen-bonding interactions-mediated physical cross-linkage, the further introduction of PAAm not only significantly elevates the mechanical strength of the hydrogels showing fast self-healing capability, but also increases phosphorescence lifetime from 2.49 to 4.20 ms, especially generating phosphorescence at even higher temperature (τ 363 K = 2.46 ms). Additionally, efficient RTP energy transfer occurs after doping a small amount of organic dye heptamethine cyanine (IR780) as an acceptor into hydrogels, resulting in a long-lived NIR emission at 823 nm with a high donor/acceptor ratio, which is successfully applied for cell labeling in the NIR window.

Correction to "Multiplayer Reach-Avoid Differential Games in 3D Space Inspired by Harris' Hawks' Cooperative Hunting Tactics".

[This corrects the article DOI: 10.34133/research.0246.].

Multiplayer Reach-Avoid Differential Games in 3D Space Inspired by Harris' Hawks' Cooperative Hunting Tactics.

This paper investigates a multiplayer reach-avoid differential game in 3-dimensional (3D) space, which involves multiple pursuers, multiple evaders, and a designated target region. The evaders aim to reach the target region, while the pursuers attempt to guard the target region by capturing the evaders. This class of research holds significant practical value. However, the complexity of the problem escalates substantially with the growing number of players, rendering its solution extremely challenging. In this paper, the multiplayer game is divided into many subgames considering the cooperation among pursuers, reducing the computational burden, and obtaining numerically tractable strategies for players. First, the Apollonius sphere, a fundamental geometric tool for analyzing the 3D differential game, is formulated, and its properties are proved. Based on this, the optimal interception point for the pursuer to capture the evader is derived and the winning conditions for the pursuer and evader are established. Then, based on the Apollonius sphere, the optimal state feedback strategies of players are designed, and simultaneously, the optimal one-to-one pairings are obtained. Meanwhile, the Value function of the multiplayer reach-avoid differential game is explicitly given and is proved to satisfy Hamilton-Jacobi-Isaacs (HJI) equation. Moreover, the matching algorithm for the case with pursuers outnumbered evaders is provided through constructing a weighted bipartite graph, and the cooperative tactics for multiple pursuers are proposed, inspired by the Harris' Hawks intelligent cooperative hunting tactics. Finally, numerical simulations are conducted to illustrate the effectiveness of the theoretical results for both cases where the number of adversary players is equal and unequal between the 2 groups.

Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins.

The combination of photo and copper catalysts has emerged as a novel paradigm in organic catalysis, which provides access to the acceleration of chemical synthesis. Herein, we describe an aminoalkylation of amino-dependent olefins with maleimides through a cooperative photo/copper catalytic system. In this report, the strategy allows the generation of a broad complex of functionalized nitrogenous molecules including oxazolidinones, 2-pyrrolidones, imidazolidinones, thiazolidinones, pyridines, and piperidines in the absence of an external photosensitizer and base. The approach is achieved through a photoinduced Cu(I)/Cu(II)/Cu(III) complex species of nitrogen nucleophiles, intermolecular radical addition, and hydrogen atom transfer (HAT) processes. The plausible mechanism is investigated by a series of control experiments and theoretical tests, including radical scavenging experiments, deuterium labeling experiments, ultraviolet-visible absorption, and cyclic voltammetry (CV) tests.

Superelastic 3D Assembled Clay/Graphene Aerogels for Continuous Solar Desalination and Oil/Organic Solvent Absorption.

Superelastic, arbitrary-shaped, and 3D assembled clay/graphene aerogels (CGAs) are fabricated using commercial foam as sacrificial skeleton. The CGAs possess superelasticity under compressive strain of 95% and compressive stress of 0.09-0.23 MPa. The use of clay as skeletal support significantly reduces the use of graphene by 50%. The hydrophobic CGAs show high solvent absorption capacity of 186-519 times its own weight. Moreover, both the compression and combustion methods can be adopted for reusing the CGAs. In particular, it is demonstrated a design of 3D assembled hydrophilic CGA equipped with salt collection system for continuous solar desalination. Due to energy recovery and brine transport management promoted by this design, the 3D assembled CGA system exhibits an extremely high evaporation rate of 4.11 kg m-2  h-1 and excellent salt-resistant property without salt precipitation even in 20 wt% brine for continuous 36 h illumination (1 kW m-2 ), which is the best reported result from the solar desalination devices. More importantly, salts can be collected conveniently by squeezing and drying the solution out of the salt collection system. The work provides new insights into the design of 3D assembled CGAs and advances their applications in continuous solar desalination and efficient oil/organic solvent adsorption.

Visible-Light-Catalyzed Tandem Radical Addition/1,5-Hydrogen Atom Transfer/Cyclization of 2-Alkynylarylethers with Sulfonyl Chlorides.

A novel visible-light-catalyzed tandem radical addition/1,5-hydrogen atom transfer/cyclization cascade of 2-alkynylarylethers with sulfonyl chlorides in 2-methyltetrahydrofuran was developed under photocatalyst- and additive-free conditions. This reaction relies on unique energy transfer and solvent-radical relay strategies to generate sulfonyl radicals for the preparation of a series of sulfonyl-functionalized dihydrobenzofurans in moderate to high yields catalyzed by visible light or solar radiation.

Vacuolar sorting receptors (VSRs) and secretory carrier membrane proteins (SCAMPs) are essential for pollen tube growth.

Vacuolar sorting receptors (VSRs) are type-I integral membrane proteins that mediate biosynthetic protein traffic in the secretory pathway to the vacuole, whereas secretory carrier membrane proteins (SCAMPs) are type-IV membrane proteins localizing to the plasma membrane and early endosome (EE) or trans-Golgi network (TGN) in the plant endocytic pathway. As pollen tube growth is an extremely polarized and highly dynamic process, with intense anterograde and retrograde membrane trafficking, we have studied the dynamics and functional roles of VSR and SCAMP in pollen tube growth using lily (Lilium longiflorum) pollen as a model. Using newly cloned lily VSR and SCAMP cDNA (termed LIVSR and LISCAMP, respectively), as well as specific antibodies against VSR and SCAMP1 as tools, we have demonstrated that in growing lily pollen tubes: (i) transiently expressed GFP-VSR/GFP-LIVSR is located throughout the pollen tubes, excepting the apical clear-zone region, whereas GFP-LISCAMP is mainly concentrated in the tip region; (ii) VSRs are localized to the multivesicular body (MVB) and vacuole, whereas SCAMPs are localized to apical endocytic vesicles, TGN and vacuole; and (iii) microinjection of VSR or SCAMP antibodies and LlVSR small interfering RNAs (siRNAs) significantly reduced the growth rate of the lily pollen tubes. Taken together, both VSR and SCAMP are required for pollen tube growth, probably working together in regulating protein trafficking in the secretory and endocytic pathways, which need to be coordinated in order to support pollen tube elongation.

Culture of Escherichia coli in SOC medium improves the cloning efficiency of toxic protein genes.

In this paper, we report a useful protocol for cloning toxic protein genes. Use of the SOC medium, which is a glucose-containing rich medium, significantly improved the transformation efficiency of a recombinant plasmid containing a toxic plant subtilase SaSBT1 cDNA. Both glucose and rich nutrients present in the SOC medium prevented the unintended activation of the lac promoter carried on the cloning vector, and led to significantly improved transformation efficiency of recombinant plasmids containing toxic protein genes and an increased rate of transformant growth.

Using silica particles to isolate total RNA from plant tissues recalcitrant to extraction in guanidine thiocyanate.

The most commonly used protocol of the RNA isolation, the guanidine thiocyanate method, was unsuitable for recalcitrant plant tissues containing a large amount of storage proteins and secondary metabolites. We demonstrated that RNA could bind to the silica particles, which have been used successfully in DNA isolation from various sources, under a high concentration of NaCl in the presence of ethanol and sodium acetate. Based on this observation, an efficient, inexpensive, and highly reproducible technique, the acid phenol-silica method, was developed to isolate high-quality RNAs from various plant tissues recalcitrant to extraction in guanidine thiocyanate.

Spindle-shaped nanoscale yolk/shell magnetic stirring bars for heterogeneous catalysis in macro- and microscopic systems.

A new type of spindle-shaped nanoscale yolk/shell magnetic stirring bar containing noble metal nanoparticles was prepared. The as-synthesized Pd-Fe@meso-SiO2 not only showed impressive activity and stability as a heterogeneous catalyst in a macroscopic flask system, but also acted as an efficient nanoscale magnetic stir bar in a microscopic droplet system.

In situ encapsulation of Pd inside the MCM-41 channel.

Pd nanoparticles were successfully introduced into the channels of mesoporous silica MCM-41 with their dispersion well-tuned. We identified the dual role played by CTAB, which was critical for both the micelle template and Pd grafting, leading to the formation of a highly active Pd-MCM-41 nanocomposite for catalysing the Suzuki reaction.

C60 fullerenol as an active and stable catalyst for the synthesis of cyclic carbonates from CO2 and epoxides.

C60 fullerenol was found to be a highly active, selective and stable catalyst for cycloaddition between CO2 and epoxides to produce various cyclic carbonates with excellent yields (89-99%). A solid/liquid interfacial hydrogen-bond assisted mechanism was proposed to account for its high efficiency.