Reactions of Amine and Peroxynitrite: Evidence for Hydroxylation as Predominant Reaction and New Insight into the Modulation of CO₂

Peroxynitrite is related to numerous diseases including cardiovascular diseases, inflammation, and cancer. In order to expand the understanding for the toxicology of peroxynitrite in biological system, the reactions of amine (morpholine as a probe) with peroxynitrite and the modulation of CO₂ were investigated by using DFT methods. The results strongly indicate that the hydroxylation of amine by peroxynitrous acid ONOOH, which was previously overlooked by most studies, is predominant relative to the widely reported nitration and nitrosation in the absence of CO₂. The product <i>N</i>-hydroxylamine is proposed to be mainly generated via nonradical pathway (two-electron oxidation). The modulation of CO₂ exhibits two main functions: (1) inhibition of hydroxylation due to the promoted consumption of peroxynitrite via fast reaction of CO₂ with ONOO¯ to form ONOOCO₂¯; (2) dual effect (catalysis and inhibition) of CO₂ toward nitration and nitrosation. As a new insight, amine does react with CO₂ and produce inert amine carbamate R₂NCOO¯. This reaction has the potential to compete with the reaction of CO₂ and ONOO¯, which leads to inhibition of nitration and nitrosation. The concentration of CO₂ could be a critical factor determining the final effect, catalysis or inhibition. As a new finding, HCO₃¯ is probably an effective catalyst for the reaction of amine and CO₂. Moreover, further studies on how the different types of the amine might affect the outcome of the reactions would be an interesting topic

High-Performance Recovery of Vanadium(V) in Leaching/Aqueous Solution by a Reusable Reagent-Primary Amine N1519

Efficient extraction and stripping for recovering vanadium­(V) from the leaching/aqueous solution of chromium-bearing vanadium slag (V–Cr slag) are essential to the reuse of heavy metals. The performance characteristics of a new reagent, primary amine N1519, were first reported for extracting vanadium. With a phase ratio of organic to aqueous up to 1:1, 99.7% of vanadium­(V) can be effectively extracted from the leaching/aqueous solution, and powder of NH₄VO₃ was obtained through the stripping with ammonia. The new reagent can be recyclable in use for sustainable reuse after stripping. Different extraction conditions, e.g., the initial pH of the leaching/aqueous solution and the molar quantity of N1519 were investigated. The powder of vanadium-organic compounds (VOC) with N1519 formed in the process of extraction was obtained and purified through three-steps of solvent-out crystallizations. The hydrogen bond association mechanism of extraction was illustrated with the structure of VOC and the enthalpy change in extraction process. The fast extraction process and slow stripping procedure for recovering vanadium­(V) are suitable for use in annular centrifugal contactors with very short contact/resident times and mixed-settler extractors with very good mass transfer, respectively. The results offer significant advantages over conventional processes

Data_Sheet_1_Growth of Stipa breviflora does not respond to nitrogen addition because of its conservative nitrogen utilization.docx

Enhanced atmospheric nitrogen (N) deposition is threating species diversity in the desert steppe ecoregions. Needlegrass (Stipa breviflora) is the dominant specie in the desert steppe grasslands of China and southern Mongolia, and the response of S. brevifolia to N deposition is not well known. In this study, we conducted an experiment to determine the growth and N uptake of S. breviflora in response to several N addition rates. The results showed that N addition did not change plant growth, emergence rate, plant height, or biomass of S. breviflora, even at a N addition rate of 50 kg N ha−1 yr.−1 with sufficient soil moisture during a 120-day growth period. The absence of a N effect was due to the fact that N uptake in S. breviflora was not improved by N addition. These results indicated that S. breviflora is very conservative with respect to N utilization, which could possibly help it resist enhanced atmospheric N deposition. Moreover, conservative N utilization also enables S. breviflora to survive in N-limiting soils.</p

A Cleaner Process for Selective Recovery of Valuable Metals from Electronic Waste of Complex Mixtures of End-of-Life Electronic Products

In recent years, recovery of metals from electronic waste within the European Union has become increasingly important due to potential supply risk of strategic raw material and environmental concerns. Electronic waste, especially a mixture of end-of-life electronic products from a variety of sources, is of inherently high complexity in composition, phase, and physiochemical properties. In this research, a closed-loop hydrometallurgical process was developed to recover valuable metals, i.e., copper and precious metals, from an industrially processed information and communication technology waste. A two-stage leaching design of this process was adopted in order to selectively extract copper and enrich precious metals. It was found that the recovery efficiency and extraction selectivity of copper both reached more than 95% by using ammonia-based leaching solutions. A new electrodeposition process has been proven feasible with 90% current efficiency during copper recovery, and the copper purity can reach 99.8 wt %. The residue from the first-stage leaching was screened into coarse and fine fractions. The coarse fraction was returned to be releached for further copper recovery. The fine fraction was treated in the second-stage leaching using sulfuric acid to further concentrate precious metals, which could achieve a 100% increase in their concentrations in the residue with negligible loss into the leaching solution. By a combination of different leaching steps and proper physical separation of light materials, this process can achieve closed-loop recycling of the waste with significant efficiency

The Hydrogen Abstraction Reaction H₂S + OH → H₂O + SH: Convergent Quantum Mechanical Predictions

The hydrogen abstraction reaction H₂S + OH → H₂O + SH has been studied using the “gold standard” CCSD­(T) method along with the Dunning’s aug-cc-pVXZ (up to 5Z) basis sets. For the reactant (entrance) complex, the CCSD­(T) method predicts a HSH···OH hydrogen-bonded structure to be lowest-lying, and the other lower-lying isomers, including the two-center three-electron hemibonded structure H₂S···OH, have energies within 2 kcal/mol. The similar situation is for the product (exit) complex. With the aug-cc-pV5Z single point energies at the aug-cc-pVQZ geometry, the dissociation energy for the reactant complex to the reactants (H₂S + OH) is predicted to be 3.37 kcal/mol, and that for the product complex to the products (H₂O + SH) is 2.92 kcal/mol. At the same level of theory, the classical barrier height is predicted to be only 0.11 kcal/mol. Thus, the OH radical will react promptly with H₂S in the atmosphere. We have also tested the performance of 29 density functional theory (DFT) methods for this reaction. Most of them can reasonably predict the reaction energy, but the different functional give quite different energy barriers, ranged from −10.3 to +2.8 kcal/mol, suggesting some caution in choosing density functionals to explore the PES of chemical reactions

The PeptideAtlas of the Domestic Laying Hen

Proteomics-based biological research is greatly expanded by high-quality mass spectrometry studies, which are themselves enabled by access to quality mass spectrometry resources, such as high-quality curated proteome data repositories. We present a PeptideAtlas for the domestic chicken, containing an extensive and robust collection of chicken tissue and plasma samples with substantial value for the chicken proteomics community for protein validation and design of downstream targeted proteome quantitation. The chicken PeptideAtlas contains 6646 canonical proteins at a protein FDR of 1.3%, derived from ∼100 000 peptides at a peptide level FDR of 0.1%. The rich collection of readily accessible data is easily mined for the purposes of data validation and experimental planning, particularly in the realm of developing proteome quantitation workflows. Herein we demonstrate the use of the atlas to mine information on common chicken acute-phase proteins and biomarkers for cancer detection research, as well as their localization and polymorphisms. This wealth of information will support future proteome-based research using this highly important agricultural organism in pursuit of both chicken and human health outcomes

Sustainable Preparation of LiNi_1/3Co_1/3Mn_1/3O₂–V₂O₅ Cathode Materials by Recycling Waste Materials of Spent Lithium-Ion Battery and Vanadium-Bearing Slag

Waste streams containing heavy metals are always of concern from both environmental and resource-depleting points of view. The challenges are in most cases related to the effectiveness for high-value-added materials recovery from such waste, with which the environmental impacts during recycling shall be low. In this research, two typical heavy-metal-containing waste streams, i.e., spent lithium-ion batteries and vanadium-bearing slag, were simultaneously treated, and this enables regeneration of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials which was considered difficult because of the dislocation of nickel and lithium ions during electrochemical performance. By using the intermediate product during vanadium-bearing slag treatment, the vanadium-embedded cathode material can be prepared which delivers excellent electrochemical performances with a specific capacity of 156.3 mA h g^–1 after 100 cycles at 0.1C with the capacity retention of 90.6%; even the additive amount is only 5%. A thin layer of vanadium oxide is found to be effective to promote electrochemical performance of the cathode material. Using the principles of green chemistry, this process enables high-performance cathode material regeneration without introducing extraction chemicals and with much lower environmental impacts as compared to traditional metallurgical technologies

Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-Loop Process

A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H₂O₂ amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li₂CO₃ with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB

Experimental and Theoretical Investigation of Effects of Ethanol and Acetic Acid on Carcinogenic NDMA Formation in Simulated Gastric Fluid

<i>N</i>-nitrosodimethylamine (NDMA), as a representative of endogenously formed N-nitroso compounds (NOCs), has become the focus of considerable research interest due to its unusually high carcinogenicity. In this study, effects of ethanol and acetic acid on the formation of NDMA from dimethylamine (DMA) and nitrite in simulated gastric fluid (SGF) were investigated. Experimental results showed that ethanol in the concentrations of 1–8% (v/v) and acetic acid in the concentrations of 0.01–8% (v/v) exhibit inhibitory and promotion effects on the formation of NDMA, respectively. Moreover, they are both in a dose-dependent manner with the largest inhibition/promotion rate reaching ∼70%. Further experimental investigations indicate that ethanol and acetic acid are both able to scavenge nitrite in SGF. It implies that there are interactions of ethanol and acetic acid with nitrite or nitrite-related nitrosating agents rather than DMA. Theoretical calculations confirm the above experimental results and demonstrate that ethanol and acetic acid can both react with nitrite-related nitrosating agents to produce ethyl nitrite (EtONO) and acetyl nitrite (AcONO), respectively. Furthermore, the reactivities of ethyl nitrite, acetyl nitrite, and dinitrogen trioxide reacting with DMA were found in the order of AcONO > N₂O₃ ≫ EtONO. This is probably the main reason why there are completely different effects of ethanol and acetic acid on NDMA formation. On the basis of the above results, two requirements for a potential inhibitor of NOCs formation in SGF were provided. The results obtained in this study will be helpful in better understanding the inhibition/promotion mechanisms of compounds on NDMA formation in SGF and searching for protective substances to prevent carcinogenic NOCs formation

Level table of orthogonal test factors.

ObjectiveTo explore the potential mechanism of Shenkang injection (SKI) in the treatment of chronic renal failure based on network pharmacology and molecular docking technology, and to verify the core targets and key pathways by using the renal failure model.MethodsThe active components and targets of Shenkang injection were retrieved by TCMSP database, and the disease related targets were obtained by OMIM, GeneCards and other databases. Then, the intersection was obtained, and were imported into String database for PPI analysis. After further screening of core targets, GO and KEGG analysis were performed. Autodock software was used to predict the molecular docking and binding ability of the selected active ingredients and core targets. Chronic renal failure (CRF) model was established by adenine induction in rats, and the pathological observation of renal tissues was conducted. Meanwhile, the effects of Shenkang injection and its active components on core targets and pathways of renal tissues were verified.ResultsThe results of network pharmacology showed that the main components of Shenkang injection might be hydroxysafflor yellow A (HSYA)、tanshinol、rheum emodin、Astragaloside IV. Through enrichment analysis of core targets, it was found that Shenkang injection may play an anti-chronic renal failure effect through PI3K-Akt signaling pathway. Molecular docking results showed that the above pharmacodynamic components had strong binding ability with the target proteins PI3K and Akt. The results of animal experiments showed that renal function indexes of Shenkang injection group and pharmacodynamic component group were significantly improved compared with model group. HE staining results showed that the pathological status of the kidney was significantly improved in SKI and pharmacodynamic component treatment groups. Immunohistochemical results showed that the renal fibrosis status was significantly reduced in SKI and pharmacodynamic component treatment groups. q-RTPCR and WB results showed that the expression levels of PI3K and Akt were significantly decreased in the treatment groups (PConclusionsShenkang injection may inhibit PI3K-Akt signaling pathway to play an anti-chronic renal failure role through the pharmacodynamic component hydroxysafflor yellow A (HSYA), tanshinol, rheum emodin, Astragaloside IV.</div