Nanoscale Distribution Research Articles

Operando Decoding Ion-Conductive Switch in Stimuli-Responsive Hydrogel by Nanodiamond-Based Quantum Sensing.

Thermal-responsive hydrogels are developed as ion-conductive switchs for energy storage devices, however, the molecule mechanism of switch on/off remains unclear. Here, poly(N-isopropylacrylamide-co-acrylamide) hydrogel is synthesized as a model material and nanodiamond (ND) based quantum sensing for phase change study is developed. First, micro-scale phase separation with cross-linked mesh structure after sol-gel transition is visualized in situ and water molecules are trapped by polymer chains and on a chemically "frozen" state. Then, the nano-scale inhomogeneous distributions of viscosity, thermal conductivity and ionic mobility in hydrogel at high temperature are observed by measuring the rotation, translation and zero-field splitting of NDs. Besides, the ionic mobility of hydrogel is found to be dependent not only on temperature but also on polymer concentration. These observations suggested that the physical "wall" induced by inhomogeneous phase separation at microscopic scale blocked the ion conduction pathways, providing a potential intrinsic explanation for ion migration shut-down of ionic hydrogels at high temperature.

SUB-immunogold-SEM reveals nanoscale distribution of submembranous epitopes

Electron microscopy paired with immunogold labeling is the most precise tool for protein localization. However, these methods are either cumbersome, resulting in small sample numbers and restricted quantification, or limited to identifying protein epitopes external to the membrane. Here, we introduce SUB-immunogold-SEM, a scanning electron microscopy technique that detects intracellular protein epitopes proximal to the membrane. We identify four critical sample preparation factors contributing to the method’s sensitivity. We validate its efficacy through precise localization and high-powered quantification of cytoskeletal and transmembrane protein distribution. We evaluate the capabilities of SUB-immunogold-SEM on cells with highly differentiated apical surfaces: (i) auditory hair cells, revealing the presence of nanoscale MYO15A-L rings at the tip of stereocilia; and (ii) respiratory multiciliate cells, mapping the distribution of the SARS-CoV-2 receptor ACE2 along the motile cilia. SUB-immunogold-SEM extends the application of SEM-based nanoscale protein localization to the detection of intracellular epitopes on the exposed surfaces of any cell.

Nanoscale dosimetry for a radioisotope-labeled metal nanoparticle using MCNP6.2 and Geant4.

Metal nanoparticles (MNPs) labeled with radioisotopes (RIs) are utilized as radio-enhancers due to their ability to amplify the radiation dose in their immediate vicinity. A thorough understanding of nanoscale dosimetry around MNPs enables their effective application in radiotherapy. However, nanoscale dosimetry around MNPs still requires further investigation. This study aims to provide insight into the radio-enhancement effects of MNPs by elucidating nanoscale dosimetry surrounding MNPs labeled with Auger-emitting RIs. We particularly focus on distinguishing the respective dose contributions of photons and electrons emitted by Auger-emitting RIs in the context of dose enhancement. A 50nm diameter NP of silver (Ag) core and gold (Au) shell (Ag@Au NP) was assumed to emit mono-energetic electrons and photons (3, 5, 10, 20, and 30keV), or the energy spectrum corresponding to one of three Auger-emitting RIs (103Pd, 125I, and 131Cs) from the Ag core. Nanoscale radial dose distributions around a single radioactive Ag@Au NP were evaluated in spherical shells of water. Monte Carlo simulations were conducted using single-event and track structure transport methods implemented in MCNP6.2 and Geant4-DNA-Au physics, respectively. To evaluate the extent of radio-enhancement by the Ag@Au NP, two scenarios were considered: Ag@Au NPs (Au shell included) and Ag@water NPs (Au shell replaced by water). The radial doses of 10, 20, and 30keV electrons estimated by both codes were comparable. However, the radial doses of 3 and 5keV electrons by MCNP6.2 were much larger near the NP surface than those by Geant4. There was a dose enhancement of a few % to tens % by the Au shell in the region of the NP surface to 10µm, depending on the electron energy. The radial doses of photons with the Au shell were higher up to their secondary electron ranges than those without the Au shell. The maximum dose enhancement factor of photons occurred at 20keV and was 63.4 by MCNP6.2 and 50.5 by Geant4. The overall radial doses of electrons were 1-2 orders of magnitude larger than those of photons. As a result, in cases of RIs emitting both electrons and photons, the radial doses up to electron ranges were dominantly governed by electrons. The dose enhancement estimated by both codes for the RIs ranged from a few % except in the immediate vicinity of the NP surface. Given the dominant contribution of electrons to radial doses of MNP labeled with Auger-emitting RIs, physical dose enhancement expected by interactions with photons was hindered. Since there are no available RIs emitting exclusively photons, achieving enhanced physical doses within a cell through a combination of MNPs and RIs appears currently unattainable. The radial doses of photons near the NP surface exhibited considerable discrepancies between the codes, primarily attributed to low-energy electrons. The difference may arise from higher cross-sections of Au inelastic scattering in Geant4-DNA-Au compared to MCNP6.2.

Encapsulation and release of tetrabromobisphenol A in microplastics: Trade-off in their individual toxicity to Xenopus tropicalis tadpoles

The toxicity of microplastics (MPs) to aquatic animals is closely related to the presence and release kinetics of contained additives, as most plastic products contain various additives. However, the relationship between the occurrence and release of additives from MPs, and their individual or combined toxicity remains unclear. In this study, the nanoscale distribution and release of tetrabromobisphenol A (TBBPA, a common flame retardant with endocrine-disrupting effect) in polystyrene (PS) MPs, and the long-term (60 days) toxicity of TBBPA and MPs containing TBBPA (at doses of 0 %, 1 %, 10 %, w/w) to Xenopus tropicalis tadpoles were investigated. Exposure to 10 μg/L TBBPA alone was the most toxics, while the encapsulation of TBBPA in MPs significantly delayed its lethal toxicity to tadpoles by inhibiting the rapid and extensive release of TBBPA. PS MPs alone and MPs containing 10 % TBBPA exhibited delayed survival toxicity compared to TBBPA alone, whereas PS MPs containing 1 % TBBPA did not show this effect but inhibited growth. These findings suggest that chronic toxicity assessments should be based on long-term (months or even years) exposure experiments due to the encapsulation-controlled slow release of toxic additives.

Automatic dendritic spine segmentation in widefield fluorescence images reveal synaptic nanostructures distribution with super-resolution imaging.

Dendritic spines are the main sites for synaptic communication in neurons, and alterations in their density, size, and shapes occur in many brain disorders. Current spine segmentation methods perform poorly in conditions with low signal-to-noise and resolution, particularly in the widefield images of thick (10 μm) brain slices. Here, we combined two open-source machine-learning models to achieve automatic 3D spine segmentation in widefield diffraction-limited fluorescence images of neurons in thick brain slices. We validated the performance by comparison with manually segmented super-resolution images of spines reconstructed from direct stochastic optical reconstruction microscopy (dSTORM). Lastly, we show an application of our approach by combining spine segmentation from diffraction-limited images with dSTORM of synaptic protein PSD-95 in the same field-of-view. This allowed us to automatically analyze and quantify the nanoscale distribution of PSD-95 inside the spine. Importantly, we found the numbers, but not the average sizes, of synaptic nanomodules and nanodomains increase with spine size.

Enhancing Anticancer Potential: Optimization of Allicin Extraction from Regular Garlic and Characterization of Allicin-Loaded Copper Oxide Nanoparticles

This research aimed to optimize the extraction and purification processes of allicin from regular garlic (Allium sativum) and to evaluate the potential of allicin-loaded copper oxide (CuO) nanoparticles for anticancer applications. Initially, various solvents, including MilliQ water, 25% methanol, and phosphate buffer pH 2.5 in 60% methanol, were tested to determine the most effective conditions for extracting allicin. Among these, MilliQ water and 25% methanol demonstrated the highest extraction efficiencies, as evidenced by their absorbance values. The extracted allicin underwent purification and was subsequently characterized using fourier-transform infrared spectroscopy (FTIR) and high-performance liquid chromatography (HPLC). These techniques confirmed the identity and high purity of the allicin. Following purification, the allicin was encapsulated into copper oxide (CuO) nanoparticles using an optimized nanoprecipitation protocol. The physicochemical properties of the allicin-loaded nanoparticles were thoroughly characterized. Dynamic light scattering (DLS) analysis revealed a mean particle size of 123 nm, indicating a uniform and nanoscale particle distribution. Zeta potential measurements indicated a surface charge of -28.34 mV, suggesting good stability of the nanoparticles in suspension. Scanning electron microscopy (SEM) was employed to further analyze the particle size, surface charge, and morphology, providing detailed insights into the structural attributes of the nanoparticles. The successful encapsulation of allicin into CuO nanoparticles not only enhances the stability and bioavailability of allicin but also leverages the unique properties of CuO nanoparticles, which are known for their anticancer, antioxidant, and antimicrobial activities. This study underscores the potential of allicin-loaded CuO nanoparticles derived from regular garlic as a promising formulation for pharmaceutical applications, particularly in the field of oncology. These findings warrant further investigation into their clinical efficacy and safety to fully harness their therapeutic potential.

Uncovering the origin of unique elemental distribution behaviors of Vanadium in high entropy alloys

Owing to the unique elemental character, Vanadium (V) has recently gained growing interest in the field of high entropy alloys. It is known that V benefits in the mechanical strength in alloys, accompanying by the unique elemental distribution behaviors. In this work, we concentrate on the mechanism of V's distribution characters in VFeCoNi, which is similar to that of Cr in CrFeCoNi, by evaluating element inherent electronegativity, charge transfer, atomic volume, Voronoi volume and the atomic stress resulting from the combined effects of these factors. Another unique character of electronic interaction in the t2g and eg orbitals has been observed, which contributed to the fluctuation of atomic volume, thus enhancing solid solution strengthening. The tensile stress-strain tests show that the chemical ordering of V enhanced mechanical strength, especially for the grain boundary. Our work will provide new insights into the nanoscale distribution of V elements and the related macroscopic mechanical effects.

BIN1 knockdown rescues systolic dysfunction in aging male mouse hearts

Cardiac dysfunction is a hallmark of aging in humans and mice. Here we report that a two-week treatment to restore youthful Bridging Integrator 1 (BIN1) levels in the hearts of 24-month-old mice rejuvenates cardiac function and substantially reverses the aging phenotype. Our data indicate that age-associated overexpression of BIN1 occurs alongside dysregulated endosomal recycling and disrupted trafficking of cardiac CaV1.2 and type 2 ryanodine receptors. These deficiencies affect channel function at rest and their upregulation during acute stress. In vivo echocardiography reveals reduced systolic function in old mice. BIN1 knockdown using an adeno-associated virus serotype 9 packaged shRNA-mBIN1 restores the nanoscale distribution and clustering plasticity of ryanodine receptors and recovers Ca2+ transient amplitudes and cardiac systolic function toward youthful levels. Enhanced systolic function correlates with increased phosphorylation of the myofilament protein cardiac myosin binding protein-C. These results reveal BIN1 knockdown as a novel therapeutic strategy to rejuvenate the aging myocardium.

Uncovering the impact of UV radiation on mitochondria in dermal cells: a STED nanoscopy study

Mitochondria are essential organelles in cellular energy metabolism and other cellular functions. Mitochondrial dysfunction is closely linked to cellular damage and can potentially contribute to the aging process. The purpose of this study was to investigate the subcellular structure of mitochondria and their activities in various cellular environments using super-resolution stimulated emission depletion (STED) nanoscopy. We examined the morphological dispersion of mitochondria below the diffraction limit in sub-cultured human primary skin fibroblasts and mouse skin tissues. Confocal microscopy provides only the overall morphology of the mitochondrial membrane and an indiscerptible location of nucleoids within the diffraction limit. Conversely, super-resolution STED nanoscopy allowed us to resolve the nanoscale distribution of translocase clusters on the mitochondrial outer membrane and accurately quantify the number of nucleoids per cell in each sample. Comparable results were obtained by analyzing the translocase distribution in the mouse tissues. Furthermore, we precisely and quantitatively analyzed biomolecular distribution in nucleoids, such as the mitochondrial transcription factor A (TFAM), using STED nanoscopy. Our findings highlight the efficacy of super-resolution fluorescence imaging in quantifying aging-related changes on the mitochondrial sub-structure in cells and tissues.

Nanoscale mechanisms of carboxyl carbon preservation during Fe(II)-induced ferrihydrite transformation

The persistence of organic carbon (OC) in natural environments is widely attributed to OC associations with minerals such as iron (Fe) minerals. Carboxyl, a critical structure of OC, can form strong complexes with Fe minerals, but it is still largely unknown about the effects of carboxyl groups on the transformation of Fe oxides and the stabilization mechanisms of OC on Fe oxides at nanoscales. In this study, four carboxylic acids with varying numbers of carboxyl groups (2, 3, 4, and 27 carboxyls) and molecular weight (ranging from 100 to 2000 Da) were added during the coprecipitation of Fe oxides and OC. This approach was taken to systematically elucidate the nanoscale distribution and sequestration mechanisms of carboxyl-containing OC on Fe oxides over different aging periods. Results suggested that ferrihydrite transformed quickly into lepidocrocite, goethite, and magnetite with the presence of Fe(II). The transformation rate of lepidocrocite to goethite slowed with increasing carboxyl number in OC molecules for the low molecular weight carboxylic acids (100–300 Da), but the high molecular weight carboxylic acid (∼2000 Da) promoted ferrihydrite transformation into goethite. Meanwhile, the particle sizes of produced magnetite decreased with increasing carboxyl number in OC molecules. During the mineral transformation, the release of OC from Fe oxides to aqueous solution decreased with increasing numbers of carboxyl groups. Spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) coupled with electron-energy-loss spectroscopy (EELS) suggested that carboxyl-rich OC promoted the formation of abundant defective or porous structures in goethite, resulting in OC accumulation in the bulk areas of goethite, which provided an effective way to sequester OC. The aggregation of high molecular weight OC containing more carboxyl groups with magnetite nanoparticles also played an important role in the preservation of OC. Furthermore, Fourier-transform infrared spectroscopy (FTIR) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) indicated that OC may form bidentate binding with Fe oxides and the binding strength of Fe(III) and OC may change with varying numbers of carboxyl groups. Results in this study provided a comprehensive understanding of the dynamic interactions between OC with different numbers of carboxyl groups and Fe oxides, and shed insights into the nanoscale mechanisms of OC stabilization during Fe oxide transformation process.

Increased vesicular dynamics and nanoscale clustering of IL-2 after T cell activation

T cells coordinate intercellular communication through the meticulous regulation of cytokine secretion. Direct visualization of vesicular transport and intracellular distribution of cytokines provides valuable insights into the temporal and spatial mechanisms involved in regulation. Employing Jurkat E6-1 T cells and interleukin-2 (IL-2) as a model system, we investigated vesicular dynamics using single-particle tracking and the nanoscale distribution of intracellular IL-2 in fixed T cells using superresolution microscopy. Live-cell imaging revealed that in vitro activation resulted in increased vesicular dynamics. Direct stochastic optical reconstruction microscopy and 3D structured illumination microscopy revealed nanoscale clustering of IL-2. In vitro activation correlated with spatial accumulation of IL-2 nanoclusters into more pronounced and elongated clusters. These observations provide visual evidence that accelerated vesicular transport and spatial concatenation of IL-2 clusters at the nanoscale may constitute a potential mechanism for modulating cytokine release by Jurkat T cells.

Super-resolution imaging reveals the nanoscale distributions of dystroglycan and integrin ITG7A in zebrafish muscle fibers

Super-resolution imaging reveals the nanoscale distributions of dystroglycan and integrin ITG7A in zebrafish muscle fibers

Supramolecular Engineering of Ti3C2Tx MXene -Perylene Diimide Hybrid Electrodes for the Pseudocapacitive Electrochemical Storage of Calcium Ions.

The rare combination of metallic conductivity and surface redox activity enables 2D MXenes as versatile charge storage hosts for the design of high-rate electrochemical energy storage devices. However, high charge density metal ions including but not limited to Ca+2 and Mg+2 pose challenges such as sluggish solid-state diffusion and also inhibiting the charge transfer across electrode-electrolyte interfaces. In this work, free-standing hybrid electrode architectures based on 2D titanium carbide-cationic perylene diimide (Ti3C2Tx@cPDI) via supramolecular self-assembly are developed. Secondary bonding interactions such as dipole-dipole and hydrogen bonding between Ti3C2Tx and cPDI are investigated by zeta potential and Fourier-transformed infrared (FTIR) spectroscopy . Ti3C2Tx@cPDI free-standing electrodes show typical volumetric capacitance up to 260 F cm-3 in Mg2+ and Ca2+ aqueous electrolytes at charging times scales from 3minutes to a few seconds. Three-dimensional (3D) Bode maps are constructed to understand the charge storage dynamics of Ti3C2Tx@cPDI hybrid electrode in an aqueous Ca-ion electrolyte. ,Pseudocapacitance is solely contributed by the nanoscale distribution of redox-active cPDI supramolecular polymers across 2D Ti3C2Tx. This study opens avenues for the design of a wide variety of MXene@redox active organic charge hosts for high-rate pseudocapacitive energy storage devices.

Super-Resolution Analysis of the Origins of the Elementary Events of ER Calcium Release in Dorsal Root Ganglion Neurons.

Coordinated events of calcium (Ca2+) released from the endoplasmic reticulum (ER) are key second messengers in excitable cells. In pain-sensing dorsal root ganglion (DRG) neurons, these events can be observed as Ca2+ sparks, produced by a combination of ryanodine receptors (RyR) and inositol 1,4,5-triphosphate receptors (IP3R1). These microscopic signals offer the neuronal cells with a possible means of modulating the subplasmalemmal Ca2+ handling, initiating vesicular exocytosis. With super-resolution dSTORM and expansion microscopies, we visualised the nanoscale distributions of both RyR and IP3R1 that featured loosely organised clusters in the subplasmalemmal regions of cultured rat DRG somata. We adapted a novel correlative microscopy protocol to examine the nanoscale patterns of RyR and IP3R1 in the locality of each Ca2+ spark. We found that most subplasmalemmal sparks correlated with relatively small groups of RyR whilst larger sparks were often associated with larger groups of IP3R1. These data also showed spontaneous Ca2+ sparks in <30% of the subplasmalemmal cell area but consisted of both these channel species at a 3.8-5 times higher density than in nonactive regions of the cell. Taken together, these observations reveal distinct patterns and length scales of RyR and IP3R1 co-clustering at contact sites between the ER and the surface plasmalemma that encode the positions and the quantity of Ca2+ released at each Ca2+ spark.

Tau forms synaptic nano-biomolecular condensates controlling the dynamic clustering of recycling synaptic vesicles

Neuronal communication relies on the release of neurotransmitters from various populations of synaptic vesicles. Despite displaying vastly different release probabilities and mobilities, the reserve and recycling pool of vesicles co-exist within a single cluster suggesting that small synaptic biomolecular condensates could regulate their nanoscale distribution. Here, we performed a large-scale activity-dependent phosphoproteome analysis of hippocampal neurons in vitro and identified Tau as a highly phosphorylated and disordered candidate protein. Single-molecule super-resolution microscopy revealed that Tau undergoes liquid-liquid phase separation to generate presynaptic nanoclusters whose density and number are regulated by activity. This activity-dependent diffusion process allows Tau to translocate into the presynapse where it forms biomolecular condensates, to selectively control the mobility of recycling vesicles. Tau, therefore, forms presynaptic nano-biomolecular condensates that regulate the nanoscale organization of synaptic vesicles in an activity-dependent manner.

Performances of Nano-Structured Cu2O Thin Films Electrochemically Deposited on ITO Substrates in Lactate Bath as Liquid Petroleum Gas Sensors

The investigations are focused on structural and surface morphological features and their influence on electrical and wetting characteristics against liquid petroleum gas (LPG) sensing of synthesized nanostructured cuprous oxide (Cu2O) thin films grown by electrochemical deposition (ECD) on indium tin oxide (ITO) glass substrates in lactate bath (pH 10). p-Cu2O films revealed a cubical-tetrahedron nano-scale polycrystalline grain distribution (average grain size: 64.2 nm, inter planer spacing: 0.24 nm) that exhibited dominance in the crystallographic plane (111). LPG sensing evaluations of p-Cu2O/ITO done at 70 °C constant temperature with 100% LPG at 5 cc min−1 flow rate, showed excellent gas sensor response, recovery, and stability over time due to its moderate wetting behavior (average contact angle: ∼86°). AC impedance measurements carried out at room temperature demonstrated an ionic to electronic conduction variation from 100 Hz to 1 MHz, due to adsorption/desorption of LPG molecules (CnH2n+2) and oxygen species on the nano-particles surface. Cu2O/ITO flat band potential was found to be higher than its’ ambient state after exposure to LPG with an increment in acceptor density. Overall, this efficient LPG sensing could be attributed to the interfacial properties of Cu2O thin films and ITO substrates, that provide an optimized fabrication process of nano-structured Cu2O thin films.

Enhancing Benzene Combustion Activity through Preferential Platinum Atom Exposure via Strategic Pt-Cu Alloying.

Volatile organic compounds such as benzene are hazardous air pollutants that require effective elimination. Noble metal-based catalysts exhibit high benzene combustion activity, but their prohibitive cost necessitates strategies to enhance utilization efficiency. This study investigates a Pt-Cu alloy catalyst for improved benzene combustion by preferentially exposing Pt active sites through Cu alloying. Aberration-corrected scanning transmission electron microscopy and X-ray spectroscopy characterize the nanoscale distribution and enrichment of Pt on the alloy surface. Kinetic measurements demonstrate substantially enhanced activity compared with Pt catalysts, attributed to increased Pt metallic site exposure rather than alteration of the reaction mechanism. In situ Fourier transform infrared (FTIR) spectroscopy reveals a higher abundance of terrace-like Pt sites in the alloy, beneficial for benzene adsorption. Partial pressure dependence analyses indicate competitive adsorption of benzene and O2, following Langmuir-Hinshelwood kinetics. These findings provide conceptual insights into tuning surface composition in bimetallic catalysts to optimize noble metal efficiency, with broad applicability for sustainable catalytic process advancement.

Beyond the G protein α subunit: investigating the functional impact of other components of the Gαi3 heterotrimers

BackgroundSpecific interactions between G protein-coupled receptors (GPCRs) and G proteins play a key role in mediating signaling events. While there is little doubt regarding receptor preference for Gα subunits, the preferences for specific Gβ and Gγ subunits and the effects of different Gβγ dimer compositions on GPCR signaling are poorly understood. In this study, we aimed to investigate the subcellular localization and functional response of Gαi3-based heterotrimers with different combinations of Gβ and Gγ subunits.MethodsLive-cell imaging microscopy and colocalization analysis were used to investigate the subcellular localization of Gαi3 in combination with Gβ1 or Gβ2 heterotrimers, along with representative Gγ subunits. Furthermore, fluorescence lifetime imaging microscopy (FLIM-FRET) was used to investigate the nanoscale distribution of Gαi3-based heterotrimers in the plasma membrane, specifically with the dopamine D2 receptor (D2R). In addition, the functional response of the system was assessed by monitoring intracellular cAMP levels and conducting bioinformatics analysis to further characterize the heterotrimer complexes.ResultsOur results show that Gαi3 heterotrimers mainly localize to the plasma membrane, although the degree of colocalization is influenced by the accompanying Gβ and Gγ subunits. Heterotrimers containing Gβ2 showed slightly lower membrane localization compared to those containing Gβ1, but certain combinations, such as Gαi3β2γ8 and Gαi3β2γ10, deviated from this trend. Examination of the spatial arrangement of Gαi3 in relation to D2R and of changes in intracellular cAMP level showed that the strongest functional response is observed for those trimers for which the distance between the receptor and the Gα subunit is smallest, i.e. complexes containing Gβ1 and Gγ8 or Gγ10 subunit. Deprivation of Gαi3 lipid modifications resulted in a significant decrease in the amount of protein present in the cell membrane, but did not always affect intracellular cAMP levels.ConclusionOur studies show that the composition of G protein heterotrimers has a significant impact on the strength and specificity of GPCR-mediated signaling. Different heterotrimers may exhibit different conformations, which further affects the interactions of heterotrimers and GPCRs, as well as their interactions with membrane lipids. This study contributes to the understanding of the complex signaling mechanisms underlying GPCR-G-protein interactions and highlights the importance of the diversity of Gβ and Gγ subunits in G-protein signaling pathways.C8a11hmRuxdWs3DubYRKG2Video

Nano-scale pore distribution characterisation of coal using small angle X-ray scattering

In the process of coal seam fracturing with liquid nitrogen (LN2), the change of coal pore structure has an important influence on the efficiency of coalbed methane (CBM) extraction. The nano-scale pore size distribution (PSD) in coal particles before and after freezing with LN2 are experimentally studied in this work. Coal samples are collected from four coal mines, where coal and gas outburst accidents have occurred. Small angle X-ray scattering technology (SAXS) and scanning electron microscopy (SEM) are used to study the pore structure changes of coal samples quantitatively and qualitatively. It is found that the scattering intensity of coal samples increases after freezing. The PSD of all samples significantly changes in the range of 0.8–7 nm, showing new pore spaces in 0.8–4 nm and fewer pores in the 4–7 nm range. Both the pore fractal dimension and the radius of gyration of coal samples increase after freezing and are mainly affected by the changes in pores and the anisotropy of the coal matrix. Crack expansion and pore connections are observed in the surface structure of the coal sample using SEM. This study provides a better understanding of the nano-scale mechanism of coal seam fracturing with LN2 for the prevention of coal and gas outbursts.

Profile and nano-scale distribution of soil organic carbon for upland and paddy soils from an alluvial plain in South China

Understanding the heterogeneous distribution of soil organic carbon (C) (SOC) in different soil environments is essential for predicting SOC preservation. However, SOC distribution differs in profile scales and molecular levels in various farmland soils, making it challenging to elucidate the environmental behaviors of SOC. In the present study, upland and paddy soil samples were both collected at different depths (0–100 cm) from an alluvial plain in the Pearl River Delta of South China. Wet chemistry experiments coupled with 13C-nuclear magnetic resonance (NMR) and spherical aberration correction scanning transmission electron microscopy (Cs-STEM) were used to determine the vertical distribution, chemical composition, and nano-scale sequestration mechanisms of SOC in upland and paddy soils. SOC content for upland soil, which was highest at the depth of 0–20 cm (6.98 ± 0.34 g·kg−1), decreased with increasing soil depth, while that of paddy soil had the highest content at a depth of 80–100 cm (86.66 ± 5.26 g·kg−1). Statistical analysis revealed that mineral-associated organic C (MAOC) in the upland soil and particulate organic C (POC) in the paddy soil were the major C fractions that were related to SOC content. Further analysis of NMR spectra showed that the molecular composition of upland SOC differs vertically, while the molecular composition and proportion of organic C in paddy soil varied with soil depth. Cs-STEM results revealed that the relative percentage of carboxyl C decreased from 0 to 20 cm (42.1%) to 80–100 cm (28.8%) with an increase in aromatic C from 7.7 to 27.2% for the upland soil, while the four C species showed similar abundance for paddy soil at different depths, consistent with the NMR results. Overall, the upland SOC was not as easily mineralized as that of paddy soil due to a lower percentage of easily oxidized carbon, higher percentage of MAOC, and higher decomposition degree. The results of this study would enrich our quantitative understanding of the profile distribution and chemical diversity of SOC from macro to micro scales in the alluvial plain from South China, and provide insights into C preservation in natural soils.