Organic Dispersion Research Articles

Preparation of new polymeric phases for thin-film liquid phase microextraction (TF-LPME) of selected organic pollutants

Thin films made of a polymer (cellulose triacetate, CTA) and a plasticizer have been studied as novel sorptive phases for chlorpyrifos, triclosan and tonalide. The preparation is reproducible and only requires the plasticizer to be added into an organic dispersion containing CTA. The evaporation of the solvent leaves an easy to manipulate continuous and homogeneous thin film, which has been investigated in terms of both composition and extraction efficiency for the different compounds. Six different plasticizers (namely dibutyl sebacate, bis(2-ethylhexyl) sebacate, bis(2-ethylhexyl) phthalate, bis(1-butylpentyl) adipate, 2-nitrophenyl octyl ether and 2-fluorophenyl 2- nitrophenyl ether) with different chemical structure and physical properties, such as lipophilicity, dielectric constant and viscosity, have been incorporated in the CTA matrix and the resulting polymeric membranes have been characterized by different techniques (scanning electron microscopy, thermal techniques, and contact angle). Preliminary tests were undertaken in 0.01 M NaCl solution enriched with 100 μg L-1 of each analyte to study the kinetics and efficiency of extraction. All analytes were effectively extracted after 6 h with all the polymeric phases, with different kinetics. Among the different elutants tested, ethyl acetate provided satisfactory recovery values. The membrane made of CTA and dibutyl sebacate has been selected and successfully applied for the microextraction of pollutants in simulated natural water, river water and a wastewater effluent with trace concentrations added (0.2–2 μg L-1) before GC–MS determination. The overall method is easy to perform and provides good reproducibility (RSD < 10%) and recoveries higher than 80%.

XPS study of silver and copper nanoparticles demonstrated selective anticancer, proapoptotic, and antibacterial properties

Silver and copper nanoparticles were produced by an ecologically safe metal vapor synthesis (MVS) method using acetone as an organic dispersion medium. Transmission electron microscopy (TEM) showed that the specimens are spherical and polydisperse, and their average size is 2.5 nm for silver nanoparticles (Ag NPs) and 2.6 nm for copper nanoparticles (Cu NPs). X‐ray photoelectron spectroscopy analyses showed that the state of silver in the nanoparticles is close to that of silver in the Ag0 state, whereas copper black contains two oxidized states of the metal—Cu+ and Cu2+. Biological in vitro studies demonstrated that the nanoparticles have antibacterial activity against Gram‐positive and Gram‐negative bacterial species. Cu NPs exhibited more prominent antibacterial effects and induced significant growth inhibition of Bacillus cereus and Escherichia coli. Both types of nanoparticles showed anticancer properties in vitro. Cu NPs induced intense cytotoxicity in cancer and normal fibroblasts in vitro cultures, but their inhibitory effect against noncancerous cells was milder compared with cancer cell lines. Ag NPs demonstrated selective cytotoxicity against human lung and cervical adenocarcinoma cell lines. Further in vitro studies indicated that the mechanism of Ag NPs and Cu NPs anticancer effects involves induction of apoptosis. The present study describes a green synthesis approach for production of biologically active silver and copper nanoparticles and highlights their potential for medical application.

Inclusion Complexes of Daidzein with Cyclodextrin-Based Metal-Organic Framework-1 Enhance Its Solubility and Antioxidant Capacity.

Daidzein, an aglycone-type isoflavone, is useful in the prevention of atherosclerotic cardiovascular diseases. However, the solubility of daidzein remains relatively low even with pharmaceutical interventions (e.g., γ-cyclodextrin inclusion complex). In the present study, daidzein-cyclodextrin-metal organic framework solid dispersion complexes were prepared by the solvent evaporation method. The physicochemical properties of the complex and its effect on the solubility of daidzein were evaluated. The enhancement effect of a cyclodextrin-metal organic framework on the antioxidant properties of daidzein was verified using a diphenyl-picrylhydrazyl radical scavenging test. Powder X-ray diffraction results showed that the characteristic diffraction peaks of daidzein and cyclodextrin-metal organic framework disappeared and new peaks (2θ = 7.1°, 16.5°) were observed. FT-IR measurements showed that the peak derived from the carbonyl group of daidzein shifted to the lower wavenumber. NOESY 1H-1H NMR showed cross peaks at the proton on the resorcinol side of daidzein and the proton (H-5, H-6) in a cyclodextrin-metal organic framework. Dissolution rate of daidzein at 5min in distilled water was 0.06% for daidzein alone while the daidzein inclusion complex was about 100%. When fasted state simulated intestinal fluid was used, the dissolution rate of the daidzein complex was about 71% compared with that of daidzein alone (~ 3.0%) at 5min. The daidzein inclusion complex improved the antioxidant capacity to ~ 1.3 times (17.8µg/mL) compared to the IC50 of daidzein alone (22.9µg/mL). Preparations of cyclodextrin-metal organic framework inclusion complexes will be a platform in developing pharmaceutical formulations to enhance the bioavailability and activity of drugs.

Polymer/C.I. Pigment Red 170 hybrid latexes prepared by RAFT-mediated surfactant-free emulsion polymerization

By using organic pigment-based ink-jet inks, the digital ink-jet printing of textiles is one kind of environmentally friendly technology for cleaner dyeing. Due to the shortcomings of easy agglomeration and poor water dispersion stability of organic nanoparticles, however, the encapsulation and dispersion of organic pigment nanoparticles are also hot and difficult research problems. In this work, we report the reversible addition-fragmentation chain transfer (RAFT) polymerization technology was used to synthesize random copolymer of 2-(dimethylamino) ethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate (PEGA), and methyl methacrylate (MMA) or butyl acrylate (BA) with a trithiocarbonate reactive end-group. These cationic macromolecular RAFT agents (macro-RAFT) with a pH of 5 were subsequently adsorbed at the surface of size-monodisperse colloidal Pigment Red 170 particles. The absorbed macro-RAFT agents were considered to be the living points to mediate the RAFT polymerization of monomers (MMA and BA) by starved feed emulsion polymerization. TEM results shown that the resulting hybrid latexes synthesized in presence of the tri-copolymer macro-RAFT agents resulted in the formation of individually encapsulated pigment particles. In addition, the dynamic light scattering (DLS), zeta potential and stability tests found that the macro-RAFT agent participated in the growing latex stabilization which is the key to obtaining the stable and uniform core-shell hybrid latex. More importantly, the preparation of film-forming copolymer/pigment hybrid latex in this study shown that the high potential of the P(DMAEMA- co -PEGA- co -MMA or BA) macro-RAFT agent for the development of polymer-pigment hybrid latexes which has good application properties. • Cationic and brush-type macro-RAFT agents were synthesized through RAFT polymerization. • Amphiphilic macro-RAFT agent has good adsorption and dispersion properties for the C.I. Pigment Red 170. • The film-forming polymers with lower T g are successfully encapsulated on the surface of pigment. • The encapsulated polymer/pigment hybrid latexes exhibit excellent dispersion stability with freeze-thaw, storage and pH.

Polymer-Assisted Dispersion of Boron Nitride/Graphene in a Thermoplastic Polyurethane Hybrid for Cooled Smart Clothes.

The avoidance and mitigation of energy wastage have attracted increasing attention in the context of global warming and climate change. With advances in materials science, diverse multifunctional materials with high thermal conductivity have shown excellent energy-saving potential. In this study, a hybrid film exhibiting high thermal conductivity with excellent stretchability and washability was prepared. First, a simple surface modification of boron nitride (BN) was performed to realize a modified boron nitride (BNOH) filler. Next, an organic dispersant was synthesized to enhance the dispersion of BNOH and graphene nanoplatelets (GNPs) in the proposed composite. Subsequently, a simple procedure was used to combine the dispersed GNPs and BNOH fillers with thermoplastic polyurethane (TPU) to fabricate a hybrid structure. The hybrid films composed of BNOH–GNP/TPU with a dispersant exhibited a high thermal conductivity of 12.62 W m–1 K–1 at a low filler loading of 20 wt.%. This hybrid film afforded excellent stretchability and washability, as indicated by the very small thermal-conductivity reduction to only 12.23 W m–1 K–1 after 100 cycles of fatigue testing and to 12.01 W m–1 K–1 after 10 washing cycles. Furthermore, the cooling and hydrophobicity properties of the hybrid film were enhanced when compared with neat TPU. Overall, our approach demonstrates a simple and novel strategy to break the passive effect of traditional commercial cooling clothing by combining a high-thermal-conductivity film with an active cooling source to amplify the cooling effect and develop wearable cooled smart clothes with great commercial potential.

Size‐Distribution Control of Exfoliated Nanosheets Assisted by Machine Learning: Small‐Data‐Driven Materials Science Using Sparse Modeling

Abstract2D materials exhibit emergent properties originating from their characteristic nanostructures. In general, monolayered and few‐layered nanosheets are obtained by exfoliation of the precursor layered materials. However, lateral‐size distribution of the nanosheets is not easily controlled through the exfoliation because of the unpredictable down‐sizing processes. The present work shows selective syntheses of transition‐metal‐oxide nanosheets with the monodisperse and polydisperse lateral sizes by the assistance of machine learning on small experimental data. The precursor layered composites of host transition‐metal oxides and interlayer organic guests are exfoliated into the surface‐modified nanosheets in organic dispersion media. A prediction model of the size distribution is constructed by sparse modeling, a method of machine learning, on the experimental data. The host‐guest‐medium combinations achieving the monodisperse and polydisperse lateral sizes are recommended by the prediction model. Therefore, the nanosheets with the controlled lateral‐size distribution are selectively obtained in a limited number of the experiments. Moreover, self‐assembly of the polydispersed nanosheets forms the homogeneous thin film exhibiting interference color. The prediction model and its construction method can be applied to the other 2D materials. Moreover, the present work implies that sparse modeling is an effective approach for small‐data‐driven materials science.

Effect of lignin-containing highly fibrillated cellulose on the adsorption behavior of an organic dye

The morphological properties and particle size characteristics of micro- and nanofibrillated cellulose (NFC) and lignin-containing NFC (LNFC) produced by a microfluidizer processor were investigated. The effects mechanism of lignin-containing on the adsorption of NFC and the stable properties of organic dyes suspension were also studied. The results showed that the preparation process and final performance of NFC were affected by the key factors including lignin, homogenization pressure, and number of homogenization cycles. The increase in the homogeneity of the fibrillated cellulose was minor for the NFC samples, while LNFC samples showed a larger increase in the homogeneity of the particle size distribution. The influence of lignin was reflected both in improved fibrillation efficiency and in the final organic dye dispersion properties achieved by LNFC addition, primarily observed as deceased particle sizes and fibril dimensions. This study indicated that pollution-free dispersion of organic dyes can be realized through the application of lignin-containing NFC.

APFoam 1.0: integrated computational fluid dynamics simulation of O&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt;–NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt;–volatile organic compound chemistry and pollutant dispersion in a typical street canyon

Abstract. Urban air quality issues are closely related to human health and economic development. In order to investigate street-scale flow and air quality, this study developed the atmospheric photolysis calculation framework (APFoam 1.0), an open-source computational fluid dynamics (CFD) code based on OpenFOAM, which can be used to examine microscale reactive pollutant formation and dispersion in an urban area. The chemistry module of APFoam has been modified by adding five new types of reactions, which can implement the atmospheric photochemical mechanism (full O3–NOx–volatile organic compound chemistry) coupled with a CFD model. Additionally, the model, including the photochemical mechanism (CS07A), air flow, and pollutant dispersion, has been validated and shows good agreement with SAPRC modeling and wind tunnel experimental data, indicating that APFoam has sufficient ability to study urban turbulence and pollutant dispersion characteristics. By applying APFoam, O3–NOx–volatile organic compound (VOC) formation processes and dispersion of the reactive pollutants were analyzed in an example of a typical street canyon (aspect ratio H/W=1). The comparison of chemistry mechanisms shows that O3 and NO2 are underestimated, while NO is overestimated if the VOC reactions are not considered in the simulation. Moreover, model sensitivity cases reveal that 82 %–98 % and 75 %–90 % of NO and NO2, respectively, are related to the local vehicle emissions, which is verified as the dominant contributor to local reactive pollutant concentration in contrast to background conditions. In addition, a large amount of NOx emissions, especially NO, is beneficial to the reduction of O3 concentrations since NO consumes O3. Background precursors (NOx/VOCs) from boundary conditions only contribute 2 %–16 % and 12 %–24 % of NO and NO2 concentrations and raise O3 concentrations by 5 %–9 %. Weaker ventilation conditions could lead to the accumulation of NOx and consequently a higher NOx concentration but lower O3 concentration due to the stronger NO titration effect, which would consume O3. Furthermore, in order to reduce the reactive pollutant concentrations under the odd–even license plate policy (reduce 50 % of the total vehicle emissions), vehicle VOC emissions should be reduced by at least another 30 % to effectively lower O3, NO, and NO2 concentrations at the same time. These results indicate that the examination of the precursors (NOx and VOCs) from both traffic emissions and background boundaries is the key point for understanding O3–NOx–VOCs chemistry mechanisms better in street canyons and providing effective guidelines for the control of local street air pollution.

Pyridine End-Capped Polymer to Stabilize Organic Nanoparticle Dispersions for Solar Cell Fabrication through Reversible Pyridinium Salt Formation.

Bulk-heterojunction nanoparticle dispersions in water or alcohol can be employed as eco-friendly inks for the fabrication of organic solar cells by printing or coating. However, one major drawback is the need for stabilizing surfactants, which facilitate nanoparticle formation but later hamper device performance. When surfactant-free dispersions are formulated, a strong limitation is imposed by the dispersion concentration due to the tendency of nanoparticles to aggregate. In this work, pyridine end-capped poly(3-hexylthiophene) (P3HT-Py) is synthesized and included as an additive for the stabilization of P3HT:indene-C60 bis-adduct (ICBA) nanoparticle dispersions. In the presence of acetic acid (AcOH), a surface-active pyridinium acetate end-capped P3HT ion pair, P3HT-PyH+AcO-, is formed which effectively stabilizes the dispersion and hence allows the formation of dispersions with smaller nanoparticle sizes and higher concentrations of up to 30 mg/mL in methanol. The dispersions exhibit an enhanced shelf-lifetime of at least 60 days at room temperature. After the deposition of light-harvesting layers from the nanoparticle dispersions, the ion-pair formation is reversed at elevated temperatures leading to regeneration of P3HT-Py and AcOH. The AcOH evaporates from the active layer, while the performance of the corresponding solar cells is not affected by the residual P3HT-Py in the devices. Enhanced nanoparticle stability is achieved with only 0.017 wt % pyridine in the P3HT/ICBA formulation.

Versatile Route toward Hydrophobically Polymer-Grafted Gold Nanoparticles from Aqueous Dispersions.

Stabilization of gold nanoparticles in organic solvents is a key challenge in making them available for a wider range of material applications. Polymers are often used as stabilizing ligands because they also allow for the introduction of new properties and functionalities. Many of the established synthesis protocols for gold nanoparticles are water-based. However, the insolubility of many synthetic polymers in water renders the direct functionalization of aqueous particle dispersions with these ligands difficult. Here, we report on an approach for the functionalization of gold nanoparticles, which were prepared by aqueous synthesis, with hydrophobic polymer ligands and their characterization in nonpolar, organic dispersions. Our method employs an auxiliary ligand to first transfer gold nanoparticles from an aqueous to an organic medium. In the organic phase, the auxiliary ligand is then displaced by thiolated polystyrene ligands to form a dense polymer brush on the particle surface. We characterize the structure of the ligand shell using electron microscopy, scattering techniques, and ultracentrifugation and analyze the influence of the molecular weight of the polystyrene ligands on the structure of the polymer brush. We further investigate the colloidal stability of polystyrene-functionalized gold nanoparticles in various organic solvents. Finally, we extend the use of our protocol from small, spherical gold nanoparticles to larger gold nanorods and nanocubes.

Self-Assembly of 2D Nematic and Random Arrays of Sterically Stabilized Nanoscale Rods with and without Evaporation.

The adequate manipulation of nanometer-scale building blocks using dispersion systems is regarded as a fundamental technique to fabricate elaborate microstructures. Although a liquid flow with evaporation is generally regarded as an essential factor for the self-assembly of floating blocks, experimental evidence has not been sufficient to clarify the importance of the flow in the dispersion systems. In the present study, 2D nematic layers of sterically stabilized nanoscale calcite rods were achieved in a millimeter-scale region on a solid substrate via the very slow recession of an organic dispersion with evaporation. 2D random arrays of the nanorods were obtained via recession of the liquid in the same system without evaporation. When the nanorods were not sterically stabilized, 3D random arrays were formed even with evaporation. We demonstrated that the evaporation-driven flow of sterically stabilized nanorods to a confined space at the air-liquid-solid interface is essential for the formation of 2D nematic structures on a substrate.

Organic Nanocrystal Fabrication Using the Process of Resonant Second-Harmonic Generation of Light.

Laser ablation with the use of ultra-short laser pulses is a widely used technique for the fabrication of nanoparticles of metals, inorganic and hybrid materials. However, fabrication of fragile organic nanocrystals via laser ablation is rarely used due to easy photodegradation of molecules. The method employing laser irradiation of the target material is beneficial as no other chemicals are used in the production of nanoparticles, except for a given material and a solvent. In this work, we test the concept of formation of nonlinear optical (NLO) organic nanocrystals dispersion in water by irradiation of the microcrystals of the NLO material with nonabsorbed infrared nanosecond light pulses. These pulses, due to a nonlinear optical process active in a noncentrosymmetric organic crystal, such as those studied in this work, DCNP dye (3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole), produce nanosecond pulses of second-harmonic (SH) light. Due to doubling of photon energy, they are reabsorbed in the volume of DCNP microcrystals and thermal shocks fracture them into nanometer size crystals. To the best of our knowledge, such process and its interpretation have not been described yet in the literature.

In Ukrainian

Man-caused load on sources of industrial and domestic water supply, which causes the discharge of insufficiently treated wastewater, is one of the great environmental problems in Ukraine. The traditional way of solving this problem, associated with the disposal of such waters by adsorption, membrane or catalytic technologies, has a number of disadvantages associated with large volumes and a wide range of pollutants, traditional methods often require preparatory measures, time-consuming, scarce materials and expensive equipment. It would be ideal to create waste-free circulating water supply technologies, but these options are still far from being mass-produced. A promising way to solve these problems is to organize such production cycles, where the disposal of toxic wastewater will be combined with recovery technologies. Industrial and domestic wastewater often contains a significant proportion of the organic component. These are oil products, by-products of organic synthesis, spent lubricating and cooling suspensions, waste from the food, alcohol and pulp and paper industries, dyes and pigments, etc. All this waste is energy saturated and can be separated and used as fuel. However, due to low concentrations in most wastewater, their separation is economically unprofitable. A method is proposed for neutralizing toxic organic wastewater by using it as a dispersion medium for composite coal-aqueous fuel (CAF). The possibility of priming carbon microparticles obtained by preliminary plasma-chemical treatment of an organic dispersion medium to stabilize composite coal-water fuel were investigated. Waste cutting fluid (JCL) was used as an organic dispersion medium; anthracite served as the dispersed phase. A CAF sample was obtained based on anthracite from Ukrainian deposits with a solid phase (W) content of 70 mass. %, and studied its electrokinetic and rheological properties. It has been found that the preliminary plasma-chemical conversion of organic wastewater used as a dispersion medium for composite water-coal fuel significantly improves the operational properties of CAF. The growth of sedimentation stability and the optimization of the effective viscosity are achieved mainly through the implementation of the structural and mechanical factor by increasing the number of contacts with the introduction of a highly dispersed fraction of carbon microparticles and increasing the electrostatic repulsion of the elements of the suspension structure. Thus, the sedimentation stability of the obtained CAF is significantly improved in comparison with conventional anthracite suspensions in organic wastewater and reaches 2 days without the addition of stabilizers. In the future, it is planned to further improve the properties of CAF by introducing stabilizing reagents and dispersants into its composition.

Preparation and sintering characteristics of nanosilver-tin core–shell paste

Nanosilver paste, an interconnect solder, is a common choice in the electronic packaging industry; however, higher sintering temperatures and lower sintering strength limit its application. At present, core–shell nanoslurry has been studied and applied to chip interconnection. Based on the mechanism of heterogeneous flocculation, we have developed a new nanosilver wrapped tin paste (Sn@Ag paste), and according to the decomposition temperature of the organic dispersant in the slurry, a corresponding sintering process with a temperature of 300 °C was developed. The Sn@Ag core–shell structure makes Sn have good dispersibility and oxidation resistance, and the sintered product of the slurry is a mixture of a solid solution of Ag and an Ag3Sn phase. Among them, the hard and brittle phase Ag3Sn acts as a dispersion strengthening effect in the Ag matrix phase, and the solid solution of Ag acts as a replacement solid solution strengthening. With the increase of doping Sn content, the sintering strength is significantly improved. When the Sn content is 5%, the joint shear strength reaches the highest value of 55 Mpa, which is higher than the pure nanosilver paste by 10 Mpa. This new nanosilver wrapped tin paste technology has the characteristics of low-temperature sintering and high-temperature service.

High Concentration of Ti3C2Tx MXene in Organic Solvent

MXenes are currently one of the most widely studied two-dimensional materials due to their properties. However, obtaining highly dispersed MXene materials in organic solvent remains a significant challenge for current research. Here, we have developed a method called the tuned microenvironment method (TMM) to prepare a highly concentrated Ti3C2Tx organic solvent dispersion by tuning the microenvironment of Ti3C2Tx. The as-proposed TMM is a simple and efficient approach, as Ti3C2Tx can be dispersed in N,N-dimethylformamide and other solvents by stirring and shaking for a short time, without the need for a sonication step. The delaminated single-layer MXene yield can reach 90% or greater, and a large-scale synthesis has also been demonstrated with TMM by delaminating 30 g of multilayer Ti3C2Tx raw powder in a one-pot synthesis. The synthesized Ti3C2Tx nanosheets dispersed in an organic solvent possess a clean surface, uniform thickness, and large size. The Ti3C2Tx dispersed in an organic solvent exhibits excellent oxidation resistance even under aerobic conditions at room temperature. Through the experimental investigation, the successful preparation of a highly concentrated Ti3C2Tx organic solvent dispersion via TMM can be attributed to the following factors: (1) the intercalation of the cation can lead to the change in the hydrophobicity and surface functionalization of the material; (2) proper solvent properties are required in order to disperse MXene nanosheets well. To demonstrate the applicability of the highly concentrated Ti3C2Tx organic solvent dispersion, a composite fiber with excellent electrical conductivity is prepared via the wet-spinning of a Ti3C2Tx (dispersed in DMF) and polyacrylonitrile mixture. Finally, various types of MXenes, such as Nb2CTx, Nb4C3Tx, and Mo2Ti2C3Tx, can also be prepared as highly concentrated MXene organic solvent dispersions via TMM, which proves the universality of this method. Thus, it is expected that this work demonstrates promising potential in the research of the MXene material family.

Enhanced mechanical properties of carbon nanotube-reinforced magnesium composites with zirconia fabricated by spark plasma sintering

This study aims to enhance carbon nanotube (CNT)-reinforced magnesium (Mg) matrix composites fabricated by spark plasma sintering (SPS). Ultrasonic treatment with organic solvent (DMAc) and dispersant (K2CO3) were used for the processes to make each CNT apart. Nano-order ceramic powders of zirconia (ZrO2) were found to be effective to keep uniform dispersion of CNT in Mg matrix. Low melting point metals such as Sn were added to fill voids and cracks in the composites. Post-SPS rolling was also employed aiming to improve the microstructures. The fabricated CNT-reinforced Mg composites were investigated on mechanical properties such as hardness and three-point bending strength to be related to the microstructures.

Enhanced rate performance of the mortar-like LiFePO4/C composites combined with the evenly coated of carbon aerogel

Mortar-like LiFePO4/C composites are synthesized by a ball milling-spray drying-carbothermal reduction method using polyethylene glycol (PEG) as the organic carbon source, dispersant, and reductive agent, while the carbon aerogel as the excellent conductive network. PEG enables the carbon aerogel to uniformly coat the primary particles, which restricts the overgrowth of primary particles' during the synthesis process. While the carbon aerogel provides a three-dimensional conductive network, and its porous structure can absorb more electrolyte. Moreover, the mortar-like secondary particles could further increase the specific surface of LiFePO4/C composites. The high speed of electron transfer and lithium-ion transportation can be achieved simultaneously for the Mortar-like LiFePO4/C composites. All these factors contribute to the outstanding rate performance (163.4 mAh g-1 at 0.2 C and 115.4 mAh g-1 at 15 C) and considerable cycling stability (99.3% of capacity retention after 300 cycles at 5 C/5 C). The Mortar-like LiFePO4/C composites combined with the evenly coated carbon aerogel are promising cathode materials for rechargeable lithium-ion power batteries.

Lateral-size control of exfoliated transition-metal-oxide 2D materials by machine learning on small data.

A wide variety of nanosheets including monolayers and few-layers have attracted much interest as two-dimensional (2D) materials for the unique anisotropic structures and properties. On the other hand, one of the significant remaining and challenging issues is the lateral-size control. Since 2D materials are generally synthesized by the exfoliation of layered materials, the lateral size is not easily controlled in the breaking-down processes. The experimental factors have not been found for the control and prediction. In the present work, lateral sizes of the exfoliated transition-metal-oxide nanosheets were predicted and controlled by the assistance of machine learning. Layered composites of host inorganic layers and guest organic molecules were exfoliated into nanosheets in organic dispersion media. The lateral size of the nanosheets was estimated by dynamic light scattering (DLS), instead of microscopy methods, to achieve high-throughput analyses. Factors governing the lateral size are explored on the small experimental data by the assistance of sparse modeling, a method of machine learning. The eight physicochemical parameters of the organic guests and dispersion media were extracted by sparse modeling for the construction of the size-prediction model. The size-prediction model accelerated the selective syntheses of the nanosheets with large and small lateral sizes in a limited number of experiments. The results indicate that the prediction model is a guideline to find suitable exfoliation conditions for size control. Size-selective syntheses of a variety of 2D materials can be achieved by similar methods using sparse modeling on small experimental data. Moreover, sparse modeling is applicable to control the design and exploration of other materials and their processing based on small data.

Identification of Organic Matter Dispersions Based on Light Scattering Matrices Focusing on Soil Organic Matter Management.

The origin of organic matter, its spread, scattering, and functioning are influenced by the physical structure of liquid or dispersed media of organic matter. Refractive indices of fodder yeast grown on paraffin oil (paprin) and natural gas (gaprin) as well as Lycoperdon spore and organelles were measured by laser phase microscopy. The scattering matrices of aqueous suspensions of paprin, gaprin, and Lycoperdon spores were measured using a laser polarimeter with the scattering angle ranging from 20 to 150°. The experimentally measured scattering matrices have been approximated by the weighted sum of theoretically calculated scattering matrices using the T-matrix code developed by Mishchenko. Most of the particle radii in the filtered fraction of paprin and gaprin were within the range of about 0.05–0.12 μm. Particle radii of the Lycoperdon spore suspension were within the range of 0.4–2.4 μm, which corresponded to both whole spores and their separate organelles. A possibility of identifying a suspension by its scattering matrices was shown for a small difference in the real parts of the refractive index in the example of paprin and gaprin. The measurements of the light scattering matrix showed that for a small size parameter of about 1, the identification of paprin and gaprin can be based only on a difference in the particle shape. Refractive index difference is manifested for the size parameter values higher than 3. An example of a suspension consisting of micron-sized spores and their submicron organelles shows high sensitivity of the scattering matrix to the composition of the dispersed material. The presented data and models help to extrapolate the results of the light scattering matrix study to a vast spectrum of media of organic matter origin and functioning. This study focused on the Biogeosystem Technique (BGT*) transcendental methodology to manage soil as an arena of biodegradation and organic synthesis. A BGT*-based robotic system for intra-soil pulse continuous–discrete water and matter supply directly into the dispersed–aggregated physical structure of the soil media was developed. The system enables transformation of soil into a stable highly productive organic chemical bioreactor for better controlled nanoparticle biomolecular interactions and adsorption by biological and mineral media. The scattering matrix measurement unit is supposed to be used in the robotic system as a diagnostic tool for the dispersion composition of soil organic components.

Clay behavior following macroaggregate breakdown in Ferralsols

An increase in organic matter content is one of the most important factors favoring stabilization of macroaggregates in soils. However, organic matter is also known to inhibit the flocculation of suspended clay, which implies that flocculation is unlikely to happen after clay is released by the breakdown of water-stable macroaggregates. The aim of this study was to investigate whether clay flocculation is possible following the mechanical breakdown of water-stable macroaggregates in Ferralsols. Profiles of three soils weathered from igneous rocks were studied to create a natural gradient of organic matter, macroaggregation, clay dispersion, and flocculation. Macroaggregates stabilized mainly by inorganic bonds showed high water re-flocculable clay content following breakdown. Organic bonds increased the proportion of water-stable macroaggregates, but, following breakdown, the released clay showed a high imbalance in charges, thereby inhibiting its flocculation. Flocculation can still prevail over dispersion in clay saturated with organic matter when the base saturation is low and Al3+ concentration is high, but the charges in surface horizons are too imbalanced to allow flocculation. Highly stable microaggregates (pseudo-silt and pseudo-sand) are favored under both very low and very high organic matter contents.