Acidification-Induced Micronano Mechanical Properties and Microscopic Permeability Enhancement Mechanism of Coal.

An acid solution improves the pore-plugging problem in hydraulic fracturing, which in turn improves the permeability of the coal seam. The study aimed to investigate the effect of mixed acid on the micronano mechanical properties and permeability of the coal seam. The surface morphology of acidified coal was analyzed from the micronano scale using atomic force microscopy (AFM) and scanning electron microscopy. Additionally, the micronano scale mechanical characteristics of acidified coal were examined using the mechanical mode in an atomic force microscope. Furthermore, the complexity and connectivity of the micronano pores of samples were investigated using the low-temperature nitrogen adsorption and mercury intrusion porosimetry methods and the fractal theory. The results indicated that the surface minerals of acidified coal were dissolved, loosening the coal and increasing the complexity of the pore structure. Mineral deformation and pore deformation weakened the mechanical properties of coal at the micronano scale, and the mean elastic modulus of acidified coal (B# and E#) decreased by 28.78 and 25.66% compared to that of raw coal. The acid solution effectively enlarged the pore diameter, transitioning from micropores to mesopores and macropores, and the total pore volume of acidified coal increased by 1.88 times and 1.25 times, Kn increased from 0.064 to 0.581 and 0.37, respectively. The type of methane diffusion in the diffusion pores changed from Knudsen diffusion to transition-type diffusion. The tortuosity of the pore structure of acidified coal decreased, the fractal dimension of the tortuosity of the pore structure decreased, and the permeability increased by nearly three times. The research results indicate that the mechanical properties of coal decrease after acidification and that the microstructural changes can promote methane migration (diffusion-seepage), which can provide theoretical guidance for coalbed methane extraction in low-permeability coal reservoirs.

Enhanced coalbed methane well production prediction framework utilizing the CNN-BL-MHA approach.

As the mechanization of the CBM extraction process advances and geological conditions continuously evolve, the production data from CBM wells is deviating increasingly from linearity, thereby presenting a significant challenge in accurately predicting future gas production from these wells. When it comes to predicting the production of CBM, a single deep-learning model can face several drawbacks such as overfitting, gradient explosion, and gradient disappearance. These issues can ultimately result in insufficient prediction accuracy, making it important to carefully consider the limitations of any given model. It's impressive to see how advanced technology can enhance the prediction accuracy of CBM. In this paper, the use of a CNN model to extract features from CBM well data and combine it with Bi-LSTM and a Multi-Head Attention mechanism to construct a production prediction model for CBM wells-the CNN-BL-MHA model-is fascinating. It is even more exciting that predictions of gas production for experimental wells can be conducted using production data from Wells W1 and W2 as the model's database. We compared and analyzed the prediction results obtained from the CNN-BL-MHA model we constructed with those from single models like ARIMA, LSTM, MLP, and GRU. The results show that the CNN-BL-MHA model proposed in the study has shown promising results in improving the accuracy of gas production prediction for CBM wells. It's also impressive that this model demonstrated super stability, which is essential for reliable predictions. Compared to the single deep learning model used in this study, its prediction accuracy can be improved up to 35%, and the prediction results match the actual yield data with lower error.

Experimental research on the influence of acid on the chemical and pore structure evolution characteristics of Wenjiaba tectonic coal.

The chemical and pore structures of coal play a crucial role in determining the content of free gas in coal reservoirs. This study focuses on investigating the impact of acidification transformation on the micro-physical and chemical structure characteristics of coal samples collected from Wenjiaba No. 1 Mine in Guizhou. The research involves a semi-quantitative analysis of the chemical structure parameters and crystal structure of coal samples before and after acidification using Fourier Transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) experiments. Additionally, the evolution characteristics of the pore structure are characterized through high-pressure mercury injection (HP-MIP), low-temperature nitrogen adsorption (LT-N2A), and scanning electron microscopy (SEM). The experimental findings reveal that the acid solution modifies the structural features of coal samples, weakening certain vibrational structures and altering the chemical composition. Specifically, the asymmetric vibration structure of aliphatic CH2, the asymmetric vibration of aliphatic CH3, and the symmetric vibration of CH2 are affected. This leads to a decrease in the contents of -OH and -NH functional groups while increasing aromatic structures. The crystal structure of coal samples primarily dissolves transversely after acidification, affecting intergranular spacing and average height. Acid treatment corrodes mineral particles within coal sample cracks, augmenting porosity, average pore diameter, and the ratio of macro-pores to transitional pores. Moreover, acidification increases fracture width and texture, enhancing the connectivity of the fracture structure in coal samples. These findings provide theoretical insights for optimizing coalbed methane (CBM) extraction and gas control strategies.

Study on the mechanism of methane "solid-liquid-gas" conversion controlled by the evolution of coal micro- and nanopore structure.

Currently, the utilization of coalbed methane resources in the Guizhou region faces challenges such as complex reservoir structure, high gas content, and microporous development. Based on these, the pore structure and adsorption capacity of Guizhou tectonic deformed coals (TDCs) were evaluated using a suite of integrated diagnostic techniques including low-temperature nitrogen adsorption (LT-N2A), mercury intrusion porosimetry (MIP), methane isothermal adsorption. Through the above methods, the pore structure and adsorption characteristics of the samples were characterized; The samples were divided into the range of joint pores by combining the results of MIP and LT-N2A; Using the molecular simulation software, the 2 nm, 4 nm, 10 nm pores affecting the methane endowment state were investigated respectively, and from the perspective of the heat of adsorption and energy, the concept of the three-phase transition of methane was proposed, and explore the change of the pore spacing affecting the endowment state of methane from the solid state pore to the gas state pore. The results provide new ideas for the in-depth study of gas storage in tectonic coal reservoirs in Guizhou Province.

Direct α-vinylidenation of aldehydes and subsequent cascade: gold and amine catalysts work synergistically.

Carbonyl-substituted allenes are highly important synthetic intermediates for a number of heterocycles and strained-ring systems. However, chemistry of allenyl aldehydes has not been explored as extensively as their ketone, ester, or amide analogues because of a lack of general synthetic methods. Described herein is the first direct α-vinylidenation of aldehydes and an α-vinylidenation/γ-functionalization cascade to access tri- and tetrasubstituted allenyl aldehydes using a combination of a gold catalyst and an secondary amine. The reactive enamine intermediate of an aldehyde reacts with the gold-activated hypervalent silylethynyl benziodoxolone to selectively generate the corresponding trisubstituted allenyl aldehyde. The allenyl aldehyde can further react with another equivalent of the alkynylation reagent or other electrophiles to afford tetrasubstituted allenes bearing an aldehyde group, an acetylene, and a halogen functionality. This method enables rapid access to polysubstituted furans from aldehydes.

Evolution of fissures and pressure discharge of gas caused by mining of the upper protective layer of a coal seam.

The evolution of fissures and permeability associated with mining of the upper protective layer of the coal seam is crucial for pressure relief gas drainage of the underlying seam. To understand the influence of mining the upper protective layer on gas drainage within the underlying coal seam, this study utilized the M16 and M18 seams in the Qinglong Coal Mine in Guizhou. Theoretical analysis, discrete element numerical simulation, and field tests were used to characterize the evolution of fractures associated with mining of the upper protective layer and the effects of pressure relief gas drainage within the protected coal seam. The results show that mining-related stress changes controlled the development of fractures, altering the permeability values of coals. An analysis of the crack development in the coal mass caused by mining of the upper protective layer shows that during the initial stage of mining, the produced cracks exhibited a butterfly shape network. Yet, with further development of the mining, these cracks and the stress changes gradually produced an inverted butterfly shape network. According to simulations, the areas of maximum deformation via expansion in the protected coal seam were located near the open cut and the mining end line of the working face. The maximum deformation values were 29.06 and 26.68 mm, respectively, and the corresponding deformation rates were 9.37‰ and 8.61‰, which are greater than the required 3‰. The findings of this study provide a new reference for gas control in pressure relief coal seams under similar working conditions.

The geological factors affecting gas content and permeability of coal seam and reservoir characteristics in Wenjiaba block, Guizhou province.

The gas content and permeability of coal reservoirs are the main factors affecting the productivity of coalbed methane. To explore the law of gas content and permeability of coal reservoirs in the Zhijin area of Guizhou, taking No.16, No.27 and No.30 coal seams in Wenjiaba mining area of Guizhou as the engineering background, based on the relevant data of coalbed methane exploration in Wenjiaba block, the geological structure, coal seam thickness, coal quality characteristics,coal seam gas content and permeability of the area were studied utilizing geological exploration, analysis of coal components and methane adsorption test. The results show that the average thickness of coal seams in this area is between 1.32 and 1.85 m; the average buried depth of the coal seam is in the range of 301.3-384.2 m; the gas content of No.16 and No.27 coal seams is higher in the syncline core. The gas content of the No.30 coal seam forms a gas-rich center in the south of the mining area. The buried depth and gas content of coal seams in the study area show a strong positive correlation. Under the same pressure conditions, the adsorption capacity of dry ash-free basis is significantly higher than that of air-dried coal. The permeability decreases exponentially with the horizontal maximum principal stress and the horizontal minimum principal stress. The horizontal maximum primary stress and the flat minimum prominent stress increase with the increase of the buried depth of the coal seam. The permeability and coal seam burial depth decrease exponentially. This work can provide engineering reference and theoretical support for selecting high-yield target areas for CBM enrichment in the block.

Influences of Evolution of Pore Structures in Tectonic Coal under Acidization on Methane Desorption.

Experiments on corrosion reactions of pulverized coal with monomeric and polymeric (mixed) acid solutions reveal that monomeric acids are listed in a descending order as HF, HCl, and CH3COOH according to their corrosion effects on tectonic coal collected in Faer Coal Mine (Liupanshui City, Guizhou Province, China). In addition, the optimal mixing ratio of mixed acids is 6% HCl + 6% HF + 3% CH3COOH + 2% KCl. The mineral grains filled in pores in coal samples treated with mixed acid solutions are dissolved, so the porosity increases. The volumes of transition pores and mesopores are obviously affected by acidization, and some transition pores are transformed into mesopores and macropores to form dissolved pores. At the same time, inkbottle-shaped pores reduce, while slit pores or open pores increase. The coal samples after acidization show a higher aromatization degree and an increased relative content of oxygen-containing functional groups, with a generally lower hydroxyl content, so the methane (CH4) adsorption capacity of coal declines, which promotes CH4 desorption. The control effect of pore structures after acidization reactions on CH4 desorption was revealed from perspectives of the diffusion coefficient (Kn), adsorption volume (ω), average pore-throat ratio (PT), and average sinuosity (τav). That is, CH4 molecules in tectonic coal after acidization turn from Knudsen diffusion to transitional diffusion, the adsorption volume of CH4 molecules shrinks, the average pore-throat ratio decreases, and the average sinuosity reduces, which promotes CH4 desorption from tectonic coal.

Modeling Dynamic Gas Desorption in Coal Reservoir Rehabilitation: Molecular Simulation and Neural Network Approach.

A thorough understanding of the control mechanisms of coal reservoir modification on methane adsorption and desorption is essential as this is a key technique for increasing the effectiveness of gas extraction. In this study, molecular dynamics simulations and neural networks were used to evaluate the effects of several coal reservoir alteration factors on gas desorption, from both microscopic and macroscopic perspectives. The findings demonstrated a direct correlation between coal pore size and the amount of methane adsorbed, as well as an inverse relationship between coal pore size and methane adsorption capacity and energy. The different methane-repelling properties of CO2, N2, and H2O, which are frequently used in coal reservoir reforming, are primarily due to the different diffusion capabilities of these three gases. The best reservoir reforming effect can be obtained by setting the pressure ratio of CO2 to N2 to 3.4:6.6. The thickness, depth, gas content, height, advance speed, rate of extraction, and daily production of coal are all closely interrelated, enabling a more accurate assessment of gas gushing.

Protective effects of Polygonatum kingianum polysaccharides and aqueous extract on uranium-induced toxicity in human kidney (HK-2) cells.

The current detoxification options of uranium, a toxic radioactive heavy metal, have obvious side effects. Polygonatum kingianum (PK), a natural product with the function of antioxidant, may be effective in detoxification and prevention of uranium-induced nephrotoxicity. Here, we studied the protective effects of PK polysaccharides (PKP) and aqueous extract (PKAE) on uranium-induced toxicity in human kidney (HK-2) cells. First, the physicochemical properties of PKP and PKAE were characterized. Assays on cultured cells demonstrated that pretreatment with PKP and PKAE significantly increased metabolic activity, relieved morphological impairments, and alleviated apoptosis. The impairments caused by uranium exposure were ameliorated (mitochondrial membrane potential and ATP level increased while reactive oxygen species decreased). Molecular mechanistic studies revealed that PKP and PKAE alleviated uranium-induced cytotoxicity by regulating mitochondria-mediated apoptosis and the GSK-3ß/Fyn/Nrf2 pathway. Collectively, our data support the preventive and therapeutic applications of PKP and PKAE for uranium poisoning.

Thorium inhibits human respiratory chain complex IV (cytochrome c oxidase).

Thorium is a radioactive heavy metal and an emerging environmental pollutant. Ecological and human health risks from thorium exposure are growing with the excavation of rare earth metals and implementation of thorium-based nuclear reactors. Thorium poisoning is associated with carcinogenesis, liver impairments, and congenital anomalies. To date, the biomolecular targets that underlie thorium-induced toxicity remain unknown. Here, we used in vitro enzymatic activity assays to comprehensively evaluate the effects of thorium on the mitochondrial respiration process. Thorium was found to inhibit respiratory chain complex IV (cytochrome c oxidase) at sub-micromolar concentrations (IC50 ~ 0.4 µM, 90 µg/L). This is lower than the thorium level limit (246 µg/L) in drinking water specified by the World Health Organization. The inhibitory effects were further verified in mitochondria from human bone and liver cells (thorium mainly deposits in these organs). The inhibition of cytochrome c oxidase can readily rationalize well-documented cellular toxicities of thorium, such as alteration of mitochondrial membrane potential and production of reactive oxygen species. Therefore, cytochrome c oxidase is potentially a key molecular target underlying thorium-induced toxicological effect.

Fractal characteristics of shale pore structure and its influence on seepage flow.

The migration law of shale gas has a significant influence on the seepage characteristics of shale, and the flow of the gas is closely related to the pore structure. To explore the influence of shale pore parameters on permeability in different diffusion zones, the pore structure of the shale in the Niutitang Formation in Guizhou, China, was analysed based on liquid nitrogen adsorption experiments and nuclear magnetic resonance experiments. The relationship among fractal dimension, organic carbon content (TOC) and BET-specific surface area was analysed based on the fractal dimension of shale pores calculated using the Frenkel-Halsey-Hill model. Shale permeability was calculated using the Knudsen number (Kn) and permeability equation, and the influence of the fractal dimension and porosity in different diffusion zones on shale permeability was analysed. Previous studies have shown that: (i) the pores of shale in the Niutitang Formation, Guizhou are mainly distributed within 1-100 nm, with a small total pore volume per unit mass, average pore diameter, large BET specific surface area and porosity; (ii) fractal dimension has a negative correlation with average pore diameter and TOC content and a quadratic relationship with BET specific surface area; and (iii) permeability has a positive correlation with Kn, porosity and fractal dimension. In the transitional diffusion zone, fractal dimension and porosity have a significant impact on permeability. In the Knudsen diffusion zone, porosity has no obvious effect on permeability. The methodologies and results presented will enable more accurate characterization of the complexity of pore structures of porous media and allow further understanding of the seepage law of shale gas.

Uranium inhibits mammalian mitochondrial cytochrome c oxidase and ATP synthase.

As an emerging pollutant, uranium poses serious concerns to ecological and human health. The kidney has been established as a major deposition site and the most sensitive target organ for uranium poisoning, and the underlying toxicological mechanisms have been associated with oxidative stress and mitochondrial respiration. However, the identities of key molecular targets in uranium-induced toxicity remain elusive. In this study, we comprehensively evaluated the in vitro effects of uranium on ten critical enzymes in the mitochondrial respiration pathway and discovered that respiratory chain complex IV (cytochrome c oxidase) and complex V (ATP synthase) were strongly inhibited. The inhibitory effects were validated with mitochondria from human renal proximal tubule cells-the most affected renal site in uranium poisoning. The IC50 values (around 1 mg/L) are physiologically relevant, as they are comparable to known kidney accumulation levels in uranium poisoning. In addition, these inhibitory effects could explain the well-documented uranium-induced reactive oxygen species generation and mitochondrial alterations. In conclusion, cytochrome c oxidase and ATP synthase are possibly key molecular targets underlying the toxic effects of uranium.

A responsive pure DNA hydrogel for label-free detection of lead ion.

It is of great significance to develop facile and economical strategies for on-site detection and treatment of toxic metal ions. Stimulus-responsive DNA hydrogel materials have been increasingly used for convenient detection of metal ions due to their advantages such as simplicity, portability, and ease of storage. However, these methods still require encapsulation of signal tags by labeling or embedding. In this paper, a one-step preparation of Pb2+-responsive pure DNA hydrogel material was designed to realize a new label-free strategy for Pb2+ biosensing. The Pb2+-dependent DNAzyme strand and substrate strand were introduced to fabricate the DNA hydrogel. The presence of Pb2+ in the sample activates the enzyme strand in the hydrogel skeleton and triggers the cleavage of the substrate, thereby destroy the hydrogel structure. DNA fragments released by the collapsed hydrogel were readily measured as signal output for quantifying Pb2+ concentrations with a minimum detection limit of 7.7 nM. We successfully eliminated the need for embedding or labeling of signal molecules by using the DNA molecules that construct hydrogels as the signal output. And the newly developed method for label-free detection of Pb2+ based on pure DNA hydrogel is simple, easy readout, and cost-effective. By adjusting the DNAzyme and substrate sequences, label-free analysis of other metal ions can also be achieved. We expect that our strategy can be applied to the field detection of toxic metal ions.

Structure-Based Drug Design and Identification of H2O-Soluble and Low Toxic Hexacyclic Camptothecin Derivatives with Improved Efficacy in Cancer and Lethal Inflammation Models in Vivo.

Camptothecin (CPT) has been shown to block disassembly of the topoisomerase I (Topo I)/DNA cleavable complex. However, the poor aqueous solubility, intrinsic instability, and severe toxicity of CPTs have limited their clinical applications. Herein, we report the design and synthesis of H2O-soluble and orally bioavailable hexacyclic CPT derivatives. By analysis of a virtual chemical library and cytotoxicity screening in vitro, 9 and 11 were identified as potential prodrugs and chosen for further characterization in vivo. Both compounds exhibited remarkable anticancer and anti-inflammation efficacies in animals and improved drug-like profiles.

Synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes and chemistry beyond Diels-Alder reactions.

Electron-rich dienes have revolutionized the synthesis of complex compounds since the discovery of the legendary Diels-Alder cycloaddition reaction. This highly efficient bond-forming process has served as a fundamental strategy to assemble many structurally formidable molecules. Amino silyloxy butadienes are arguably the most reactive diene species that are isolable and bottleable. Since the pioneering discovery by Rawal, 1-amino-3-silyloxybutadienes have been found to undergo cycloaddition reactions with unparalleled mildness, leading to significant advances in both asymmetric catalysis and total synthesis of biologically active natural products. In sharp contrast, this class of highly electron-rich conjugated olefins has not been studied in non-cycloaddition reactions. Here we report a simple synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes, a complementarily substituted Rawal's diene. This family of molecules is found to undergo a series of intriguing chemical transformations orthogonal to cycloaddition reactions. Structurally diverse polysubstituted ring architectures are established in one step from these dienes.