Ultra-thin and Mechanically Stable LiCoO2-Electrolyte Interphase Enabled by Mg2+ Involved Electrolyte.

LiCoO2 (LCO) cathode materials have attracted significant attention for its potential to provide higher energy density in current Lithium-ion batteries (LIBs). However, the structure and performance degradation are exacerbated by increasing voltage due to the catastrophic reaction between the applied electrolyte and delithiated LCO. The present study focuses on the construction of physically and chemically robust Mg-integrated cathode-electrolyte interface (MCEI) to address this issue, by incorporating Magnesium bis(trifluoromethanesulfonyl)imide (Mg[TFSI]2) as an electrolyte additive. During formation cycles, the strong MCEI is formed and maintained its 2 nm thickness throughout long-term cycling. Notably, Mg is detected not only in the robust MCEI, but also imbedded in the surface of the LCO lattice. As a result, the parasitic interfacial side reactions, surface phase reconstruction, particle cracking, Co dissolution and shuttling are considerably suppressed, resulting in long-term cycling stability of LCO up to 4.5 V. Therefore, benefit from the double protection of the strong MCEI, the Li||LCO coin cell and the Ah-level Graphite||LCO pouch cell exhibit high capacity retention by using Mg-electrolyte, which are 88.13% after 200 cycles and 90.4% after 300 cycles, respectively. This work provides a novel approach for the rational design of traditional electrolyte additives.

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries.

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next-generation high-density energy-storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structures. Types of fluorinated cosolvents used in LHCEs are investigated here in searching for the most suitable diluent for high-concentration electrolytes (HCEs). Nonsolvating solvents (including fluorinated ethers, fluorinated borate, and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low-solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through coparticipation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

Gray mold disease on bottle gourd caused by Cladosporium tenuissimum in China.

Bottle gourd [Lagenaria siceraria (Mol.) Stand] is a widely cultivated succulent crop species. In December 2022, a serious bottle gourd disease occurred in the protected vegetable planting base of Xingguo County, Ganzhou City, Jiangxi Province, China, with 85% of the 2,100 plants having gray mold disease-like symptoms, including gray spots on the infected fruit. They quickly expanded at suitable temperature and humidity, forming a gray mold layer with inward depressions, which spread to the fruit stem causing watery rot, and the flesh turned black and started to rot. To isolate the pathogen, fruits of the diseased plants were surface-disinfected with 75% ethanol for 30 s, immersed in 0.1% HgCl2 for 1 min, rinsed thrice with sterile water, and cultured on a potato-dextrose agar (PDA) medium at 28°C. Mycelia from the diseased tissue were subcultured on fresh PDA medium to obtain pure cultures. After incubation at 25°C for 7 days, olive-green colonies (~2.5 mm·d-1) developed. Cultures developed numerous elliptical and limoniform conidia measuring 2.69~9.79 µm to 2.10~5.92 µm (average 5.62×3.12 µm) (n=20). The morphological characteristics of the pathogen resembled those of Cladosporium spp. Fungal genomic DNA was extracted, and the internal transcribed spacer (ITS), partial translation elongation factor-1 alpha (TEF-1α), and actin (ACT) regions were amplified with primers ITS1/4, TEF-728F/986R, and ACT-512F/783R, respectively, and sequenced (Bensch et al. 2012; Jo et al. 2018). Basic Local Alignment Search Tool analysis (BLAST) revealed that the ITS (accession no. OQ186729), ACT (OQ240962), and TEF-1α (OQ240963) sequences of isolate hjt4 shared the highest similarity (99-100%) with those of Cladosporium tenuissimum (accessions no. OM232068, OM256530, OM256526) (Duccio et al. 2015). A phylogenetic tree of the isolate hjt4 and its close relatives within Cladosporium was constructed using the MEGA X neighbor-joining method. The pathogen was identified as C. tenuissimum based on morphological and molecular characteristics. A specimen (JXAU-H2022982) was deposited at the Herbarium of the College of Agronomy, Jiangxi Agricultural University. To confirm its pathogenicity, seven-day-old healthy bottle gourd fruits were disinfected with 75% ethanol, 1 mm-deep wounds were made with sterilized scalpels, and the plants were inoculated with PDA plugs (0.8 cm in diameter) containing actively growing mycelia of isolate hjt4. Plants inoculated with sterile PDA plugs served as controls. Each group contained three fruits, and the experiment was performed in triplicate. All fruits were incubated in a biochemical incubator at 28°C. After 3 days, the fruit surface shrank, and the flesh turned to a black colour and rotten, which rapidly spread to the branches. Control fruits did not develop any symptoms. Reisolated colonies showed the same morphological traits as those of the inoculation isolates, whereas no target colonies were isolated from the control fruits. The pathogen was previously reported to cause leaf blight disease in Coriandrum sativum (Zhou et al. 2022) and sooty spots on Cape gooseberry (Miyake et al. 2022), among others. To our knowledge, this is the first report of gray mold disease caused by C. tenuissimum on bottle gourd in China. The findings provide an important foundation for monitoring and controlling the spread of this disease.

Cobalt-Catalyzed Asymmetric Aza-Nozaki-Hiyama-Kishi (NHK) Reaction of α-Imino Esters with Alkenyl Halides.

Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for the formation of chiral carbon-heteroatom bond. However, the construction of sterically encumbered tetrasubstituted stereocenter through NHK reaction still posts a significant challenge. Herein, we disclose a cobalt-catalyzed aza-NHK reaction of ketimine with alkenyl halide to provide a convenient synthetic approach for the manufacture of enantioenriched tetrasubstituted α-vinylic amino acid. This protocol exhibits excellent functional group tolerance with excellent 99 % ee in most cases. Additionally, this asymmetric reductive method is also applicable to the aldimine to access the trisubstituted stereogenic centers.

Nutrient Solution Flowing Environment Affects Metabolite Synthesis Inducing Root Thigmomorphogenesis of Lettuce (Lactuca sativa L.) in Hydroponics.

The principal difference between hydroponics and other substrate cultivation methods is the flowing liquid hydroponic cultivation substrate. Our previous studies have revealed that a suitable flowing environment of nutrient solution promoted root development and plant growth, while an excess flow environment was unfavorable for plants. To explain the thigmomorphogenetic response of excess flow-induced metabolic changes, six groups of lettuce (Lactuca sativa L.), including two flow conditions and three time periods, were grown. Compared with the plants without flow, the plants with flow showed decreased root fresh weight, total root length, root surface area, and root volume but increased average root diameter and root density. The roots with flow had more upregulated metabolites than those without flow, suggesting that the flow may trigger metabolic synthesis and activity. Seventy-nine common differential metabolites among six groups were screened, and enrichment analysis showed the most significant enrichment in the arginine biosynthesis pathway. Arginine was present in all the groups and exhibited greater concentrations in roots with flow than without flow. It can be speculated from the results that a high-flowing environment of nutrient solution promotes arginine synthesis, resulting in changes in root morphology. The findings provide insights on root thigmomorphogenesis affected by its growing conditions and help understand how plants respond to environmental mechanical forces.

First report of Phytophthora blight caused by Phytophthora nicotianae on Daphne odora in China.

The variegated leaves and fragrant flowers of Daphne odora var. marginata Mak. make it a popular garden plant. In May 2020, we found diseased D. odora plants in a greenhouse at the Ganzhou Vegetable and Flower Research Institute, in southeast China; 72% of 1800 plants had Phytophthora blight-like symptoms-shrunken stems, black withered branches, wilted and dropped leaves (Fig 1a), and rotted and dark green roots. The root and stem tissue surfaces were disinfected with 75% ethanol for 30 s followed by 0.1% HgCl2 for 1 min, rinsed thrice with sterile water, and cultured on potato-dextrose agar (PDA) medium at 25°C. Mycelia from the diseased tissue were subcultured on fresh PDA medium, providing three colonies. White colonies (~4.1 mm) were formed after 10 days at 25°C (Fig 1b). Sporangia and chlamydospores were induced by placing actively growing mycelia on PDA medium at 25°C for ~30 days and then at 45°C for ~3 days. Sporangia were ovoid to spherical and 19.33 × 20.99 µm in size (Fig 1c), whereas chlamydospores were spherical and 15.68 × 16.10 µm in size (Fig 1d). All three colonies resembled Phytophthora spp. Genomic DNA was extracted from isolates using the Ezup Column Fungi Genomic DNA Purification Kit (Sangon Biotech [Shanghai] Co. Ltd.), and rDNA-ITS and ß-tubulin were amplified and sequenced. BLAST analysis (GenBank) revealed that the ITS (Accession No. MZ676071) and ß-tubulin (MZ748503) sequences of isolates shared the highest similarity (99-100%) with those of Phytophthora nicotianae (Duccio et al. 2015). A phylogenetic tree of the relationship between our isolate hjt3 and its close relatives within the P. nicotianae species was constructed using the MEGA X neighbor-joining method (Fig 2). The pathogen was identified as P. nicotianae based on morphological and molecular characteristics. Sequencing results of the three samples were consistent, all indicating P. nicotianae. A specimen (JXAU-H2020245) was deposited in the Herbarium of the College of Agronomy, Jiangxi Agricultural University. To confirm pathogenicity, 9-month-old healthy D. odora plants were used for stem and soil inoculation. Stems were cut ~5 cm from the soil with sterilized scalpels and inoculated with 0.8 cm diameter PDA plugs containing actively growing mycelia of isolate hjt3. The soil was sterilized and 0.8 cm PDA plugs containing actively growing mycelia were buried in the soil at ~5 cm; the mycelia were in contact with the roots. Plants in both groups were treated equally; those inoculated with sterile PDA plugs served as controls. There were six plants in each group, with each experiment performed in triplicate. All plants were incubated in a greenhouse at 25-28°C. The stems shrank and began to rot rapidly after 7 days (Fig 3) and the branches turned black and withered within 2 weeks. After soil inoculation, the stems of the inoculated plants blackened and rotted in ~20 days (Fig 4) and the roots rotted and turned dark green (Fig 5). These symptoms rapidly spread to the branches. The control plants did not exhibit any symptoms. Reisolated colonies showed the same morphological traits as the isolates used for inoculation; no target colonies were isolated from the control plants. Phytophthora blight caused by P. nicotianae on D. odora has been reported in Italy (Garibaldi A, 2009) and Korea (Kwon et al. 2005). This is the first detection in China. Therefore, Phytophthora blight on D. odora caused by P. nicotianae should be monitored and controlled to promote the development of the D. odora industry.

Electron Beam Irradiation-Induced Formation of Defect-Rich Zeolites under Ambient Condition within Minutes.

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.

Electron Beam Irradiation as a General Approach for the Rapid Synthesis of Covalent Organic Frameworks under Ambient Conditions.

Crystalline porous materials such as covalent organic frameworks (COFs) are advanced materials to tackle challenges of catalysis and separation in industrial processes. Their synthetic routes often require elevated temperatures, closed systems with high pressure, and long reaction times, hampering their industrial applications. Here we use a traditionally unperceived strategy to assemble highly crystalline COFs by electron beam irradiation with controlled received dosage, contrasting sharply with the previous observation that radiation damages the crystallinity of solids. Such synthesis by electron beam irradiation can be achieved under ambient conditions within minutes, and the process is amendable for large-scale production. The intense and targeted energy input to the reactants leads to new reaction pathways that favor COF formation in nearly quantitative yield. This strategy is applicable not only to known COFs but also to new series of flexible COFs that are difficult to obtain using traditional methods.

A Long-Day Photoperiod and 6-Benzyladenine Promote Runner Formation through Upregulation of Soluble Sugar Content in Strawberry.

Commercial strawberries are mainly propagated using daughter plants produced on aerial runners because asexual propagation is faster than seed propagation, and daughter plants retain the characteristics of the mother plant. This study was conducted to investigate the effective factors for runner induction, as well as the molecular mechanisms behind the runner induction. An orthogonal test with 4 factors (photoperiod, temperature, gibberellin, and 6-benzyladenine), each with 3 levels was performed. Proteins were also extracted from the crowns with or without runners and separated by two-dimensional electrophoresis. The results of the orthogonal test showed that a long-day (LD) environment was the most influential factor for the runner formation, and 50 mg·L-1 of 6-BA significantly increased the number of runners. A proteomic analysis revealed that 32 proteins were differentially expressed (2-fold, p < 0.05) in the strawberry crowns with and without runners. A total of 16 spots were up-regulated in the crowns with runners induced by LD treatment. Identified proteins were classified into seven groups according to their biological roles. The most prominent groups were carbohydrate metabolism and photosynthesis, which indicated that the carbohydrate content may increase during runner formation. A further analysis demonstrated that the soluble sugar content was positively correlated with the number of runners. Thus, it is suggested that the photoperiod and 6-BA break the dormancy of the axillary buds and produce runners by increasing the soluble sugar content in strawberry.

Controlling crystal polymorphism of isotactic poly(1-butene) by incorporating long chain branches.

Isotactic poly(1-butene) (iPB-1) is a high performance plastic with outstanding properties, such as flexibility, superior creep, environmental stress cracking and abrasive resistance. However, it exhibits a complex crystal polymorphism and polymorphic transformation behavior, which has limited its commercial development. In this paper, the incorporation of long chain branches (LCBs) causes coil contraction in the melt, which favors the direct melt-crystallization of form III that was generally crystallized from solutions and made of unconventional highly twined lamellae. Consequently, low-to-moderately branched iPB-1 samples as-crystallize from the melt into mixtures of form II and form III by compression-molding and fast cooling of the melt to room temperature, and the fraction of crystals of form III (fIII) increases with increasing concentration of LCBs, whereas highly branched samples can as-crystallize into pure form III with uniform crystal size distribution. The corresponding thermomechanical properties can be modified by controlling fIII.

Tuning Li-Ion Diffusion in α-LiMn1-xFexPO4 Nanocrystals by Antisite Defects and Embedded ß-Phase for Advanced Li-Ion Batteries.

Olivine-structured LiMn1-xFexPO4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn1-xFexPO4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. Herein, olivine-structured α-LiMn0.5Fe0.5PO4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn1-xFexPO4 nanocrystals by inducing high concentrations of Fe2+-Li+ antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g-1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (ß-LiMn1-xFexPO4, which is first reported in this work) embedded in α-LiMn0.5Fe0.5PO4. Because of the coherent orientation relationship between ß- and α-phases, the ß-phase embedded would impede the Li+ diffusion along the [100] and/or [001] directions that was activated by the high density of Fe2+-Li+ antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe2+-Li+ antisite defects and suppressing ß-phase-embedded olivine structure, Li-ion diffusion properties in LiMn1-xFexPO4 nanocrystals can be tuned by generating new Li+ tunneling. These findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.

Excess Li-Ion Storage on Reconstructed Surfaces of Nanocrystals To Boost Battery Performance.

Because of their enhanced kinetic properties, nanocrystallites have received much attention as potential electrode materials for energy storage. However, because of the large specific surface areas of nanocrystallites, they usually suffer from decreased energy density, cycling stability, and effective electrode capacity. In this work, we report a size-dependent excess capacity beyond theoretical value (170 mA h g-1) by introducing extra lithium storage at the reconstructed surface in nanosized LiFePO4 (LFP) cathode materials (186 and 207 mA h g-1 in samples with mean particle sizes of 83 and 42 nm, respectively). Moreover, this LFP composite also shows excellent cycling stability and high rate performance. Our multimodal experimental characterizations and ab initio calculations reveal that the surface extra lithium storage is mainly attributed to the charge passivation of Fe by the surface C-O-Fe bonds, which can enhance binding energy for surface lithium by compensating surface Fe truncated symmetry to create two types of extra positions for Li-ion storage at the reconstructed surfaces. Such surface reconstruction nanotechnology for excess Li-ion storage makes full use of the large specific surface area of the nanocrystallites, which can maintain the fast Li-ion transport and greatly enhance the capacity. This discovery and nanotechnology can be used for the design of high-capacity and efficient lithium ion batteries.

Storage and Effective Migration of Li-Ion for Defected ß-LiFePO4 Phase Nanocrystals.

Lithium iron phosphate, a widely used cathode material, crystallizes typically in olivine-type phase, α-LiFePO4 (αLFP). However, the new phase ß-LiFePO4 (ßLFP), which can be transformed from αLFP under high temperature and pressure, is originally almost electrochemically inactive with no capacity for Li-ion battery, because the Li-ions are stored in the tetrahedral [LiO4] with very high activation barrier for migration and the one-dimensional (1D) migration channels for Li-ion diffusion in αLFP disappear, while the Fe ions in the ß-phase are oriented similar to the 1D arrangement instead. In this work, using experimental studies combined with density functional theory calculations, we demonstrate that ßLFP can be activated with creation of effective paths of Li-ion migration by optimized disordering. Thus, the new phase of ßLFP cathode achieved a capacity of 128 mAh g(-1) at a rate of 0.1 C (1C = 170 mA g(-1)) with extraordinary cycling performance that 94.5% of the initial capacity retains after 1000 cycles at 1 C. The activation mechanism can be attributed to that the induced disorder (such as FeLiLiFe antisite defects, crystal distortion, and amorphous domains) creates new lithium migration passages, which free the captive stored lithium atoms and facilitate their intercalation/deintercalation from the cathode. Such materials activated by disorder are promising candidate cathodes for lithium batteries, and the related mechanism of storage and effective migration of Li-ions also provides new clues for future design of disordered-electrode materials with high capacity and high energy density.

Research progress of stoichiogenomics.

Stoichiogenomics is a newly arisen research field, which concerns the element usage biases of biological macromolecules at genome, transcriptome, proteome, metabonome levels. Different biological macromolecules have different element compositions and contents. When the supply of some elements was constrained, natural selection might bias the usage of the monomers (amino acid or nucleotide) to reduce constrained element costs in the synthesis of biological macromolecules. This field is flourishing with the intensive applications of high throughput sequencing and assembly technologies, more and more available metagenomic and metatranscriptomic data, and the applications of new analysis strategies. As a newly emerged cross discipline field, stoichiogenomics integrates stoichiometry, ecology, evolutionary biology, genomics and bioinformatics to provide a whole new perspective for investigating the interactions of the macromolecular evolution and ecosystem, and data mining in the post genomic era. In this review, we summarize the latest research progress of stoichiogenomics from the aspect of the element usage biases in proteins and nucleic acids. Furthermore, new research directions are discussed to provide some valuable references for the research and application of stoichiogenomics.

Delta-like 1 homolog in Capra hircus: molecular characteristics, expression pattern and phylogeny.

To research the molecular characteristics, expression pattern and phylogeny of the Delta-like 1 homolog gene (Dlk1) in goats. Dlk1 transcripts were identified in the Jianyang Da'er goats by reverse-transcription polymerase chain reaction (RT-PCR). Phylogenetic trees were constructed by Bayesian inference and neighbor-joining methods. Quantitative real-time PCR (qPCR), western blotting and in situ hybridization were performed to analyze the expression pattern of Dlk1. Five alternatively transcripts were identified in different tissues and designated as Dlk1-AS1, 2, 3, 4 and 5. Compared with the normal transcript Dlk1-AS1, Dlk1-AS4 and Dlk1-AS5 retained the identical open reading frame (ORF) and encoded proteins with truncated epidermal-growth-factor like repeats of 121 and 83 amino acids, respectively. Using the Bayesian inference method, the consensus phylogenetic tree indicated that caprine Dlk1 had a closer relationship with bovine Dlk1 than with Dlk1 from pigs, humans and mice. qPCR revealed high expression levels of Dlk1 in the kidney (P < 0.01). However, mRNA and protein levels presented an inconsistent correlation, possibly because of post-transcriptional regulation. RNA in situ hybridization indicated that Dlk1 mRNA was localized in the interlobular bile duct and alongside the hepatocyte nuclei, in the epithelial cells of proximal and distal convoluted tubules and in the connective region between the mesothelium and myocardium in the heart. The Dlk1 gene in goats produces alternatively spliced transcripts, with specific expression and cellular localization patterns. These findings would lay the foundation for further study.

Janus Solid-Liquid Interface Enabling Ultrahigh Charging and Discharging Rate for Advanced Lithium-Ion Batteries.

LiFePO4 has long been held as one of the most promising battery cathode for its high energy storage capacity. Meanwhile, although extensive studies have been conducted on the interfacial chemistries in Li-ion batteries,1-3 little is known on the atomic level about the solid-liquid interface of LiFePO4/electrolyte. Here, we report battery cathode consisted with nanosized LiFePO4 particles in aqueous electrolyte with an high charging and discharging rate of 600 C (3600/600 = 6 s charge time, 1 C = 170 mAh g(-1)) reaching 72 mAh g(-1) energy storage (42% of the theoretical capacity). By contrast, the accessible capacity sharply decreases to 20 mAh g(-1) at 200 C in organic electrolyte. After a comprehensive electrochemistry tests and ab initio calculations of the LiFePO4-H2O and LiFePO4-EC (ethylene carbonate) systems, we identified the transient formation of a Janus hydrated interface in the LiFePO4-H2O system, where the truncated symmetry of solid LiFePO4 surface is compensated by the chemisorbed H2O molecules, forming a half-solid (LiFePO4) and half-liquid (H2O) amphiphilic coordination environment that eases the Li desolvation process near the surface, which makes a fast Li-ion transport across the solid/liquid interfaces possible.

Sequestering uranium from UO2(CO3)3(4-) in seawater with amine ligands: density functional theory calculations.

The polystyrene-supported primary amine -CH2NH2 has shown an at least 3-fold increase in uranyl capacity compared to a diamidoxime ligand on a polystyrene support. This study aims to understand the coordination of substitution complexes from UO2(CO3)3(4-) and amines using density functional theory calculations. Four kinds of amines (diethylamine (DEA), ethylenediamine (EDA), diethylenetriamine (DETA) and triethylenetetramine (TETA)) were selected because they belong to different classes and have different chain lengths. The geometrical structures, electronic structures and the thermodynamic stabilities of various substitution complexes, as well as the trends in their calculated properties were investigated at equilibrium. In these optimized complexes, DEA groups bind to uranyl as monodentate ligands; EDA groups serve as monodentate and bidentate ligands; DETA groups act as monodentate and tridentate ligands; while TETA groups serve as monodentate, bidentate and tridentate ligands. The thermodynamic analysis confirmed that the primary amines coordinate to uranyl more strongly than does the secondary amine. The stabilities of substitution complexes with primary amines were calculated to decrease with increasing chain length of the amine, except for UO2(L2)(2+). Of the complexes analyzed, only UO2L(CO3)2(2-) (L = EDA and DETA) and UO2L2CO3 (L = EDA) were predicted to form from the substitution reactions with UO2(CO3)3(4-) and protonated amines as reactants in aqueous solution. Amines were calculated to be comparable to, or sometimes weaker than, amidoximate in replacing CO3(2-) in UO2(CO3)3(4-) to coordinate to uranium. Therefore, the coordination mechanism, in which amines replace carbonates to bind to uranyl, is not primarily responsible for the experimentally observed 3-fold or greater increase in uranyl capacity of primary amines compared to a diamidoxime ligand. Based on the results of our calculations, we believe that the cation exchange mechanism, in which the protonated amines bind to uranyl tricarbonate directly, plays a leading role in the uranium recovery from seawater by amines.

Research on Component Variation and Factors Affecting Minimum Miscible Pressure in Low Viscosity Oil Miscibility Process.

Miscible gas flooding is an important approach for enhancing the recovery of unconventional oil reservoirs. The injected gas and crude oil components has a significant impact on the minimum miscible pressure. In order to clarify the miscibility characteristics and factors influencing the minimum miscibility pressure, combining PVT and slim tube experiments, the minimum miscibility pressure between Tuha low viscosity oil and different injected gas was measured. Additionally, chromatography experiments were conducted to study the composition changes of produced oil. The results indicate that when the injection pressure is higher than the minimum miscible pressure, the extraction effect of injected gas on heavy fraction (C16+) in crude oil is enhanced and the extraction effect on light alkanes (C1-C6) is reduced. The increase in the content of light alkanes (C1-C6) and middle distillates (C7-C15) in crude oil reduces the minimum miscibility pressure between crude oil and injected gas. Pipeline gas can effectively extract heavy fraction from crude oil, but its breakthrough time is early. Under the same pressure, earlier breakthrough time of injected gas makes it more difficult for the crude oil and injected gas to miscible. Through the analysis of experimental results, the following main conclusions are drawn: Immiscible flooding causes heavy fraction (C16+) in crude oil to remain, which might affect the physical properties of the reservoir, increasing the difficulty of subsequent development. Gas fingering phenomenon significantly influences the miscibility of injected gas and crude oil, and the viscosity ratio of injected gas and crude oil under high-pressure conditions can be used as an important criterion for screening injected gas.

In situ fast self-assembled preparation of dandelion-like Cu(OH)2@Cu3(HHTP)2 with core-shell heterostructure arrays for electrochemical sensing of formaldehyde in food samples.

Formaldehyde is known to harm the respiratory, nervous, and digestive systems of people. In this paper, a novel dandelion-like electrocatalyst with core-shell heterostructure arrays were fast self-assembled prepared in situ using copper foam (CF) as support substrate and 2,3,6,7,10,11 hexahydroxy-triphenyl (HHTP) as ligand (Cu(OH)2@Cu3(HHTP)2/CF) by a simple two-step hydrothermal reaction. The 1D Cu(OH)2 nanorods "core" and the 2D π-conjugated conducting metal-organic frameworks (Cu3(HHTP)2cMOF) "shell" with remote delocalized electrons give the dandelion-like heterogeneous catalysts excellent electrochemical activity such as a large specific surface area, high conductivity and a fast electron transfer rate. The Cu(OH)2@Cu3(HHTP)2/CF exhibited excellent electrocatalytic performance for formaldehyde under alkaline conditions with a linear range of 0.2 µmol/L - 125 µmol/L and 125 µmol/L - 8 mmol/L, a detection limit as low as 15.9 nmol/L (S/N = 3), as well as good accuracy, consistency, and durability, and it effectively identified FA in food.

Lithiation Depth Regulation of Silicon Anodes toward Excellent Stability.

Silicon (Si) is an appealing choice of anode for next-generation lithium ion batteries with high energy density, but its dramatic volume expansion makes it a tremendous challenge to achieve acceptable stability. Herein, we demonstrate that no capacity decay is observed during the testing period when the lithiation depth of Si nanoparticles is regulated at 2000 mAh g-1 or below, the fracture of Si anode films is well mitigated under suitable regulation of lithiation depth, and the cycled Si remains particulate without turning flocculent as under full lithiation. In addition, the solid electrolyte interphase (SEI) with a LiF-dominated outer region produced under lithiation regulation could better passivate the Si anodes and prevent further electrolyte decomposition than the mosaic-type SEI formed under full lithiation. Regulating lithiation depth proved to be a feasible solution to the pressing volume issues, and optimization of capacity utilization should be considered as much as materials-level optimization.