Amphiphilic HZSM-5 for Cyclopentene Hydration at the Liquid-Liquid Interface in Pickering Emulsion.

Zeolite is considered an ideal catalyst for olefin hydration due to its high specific surface area and abundant acid sites. However, the immiscibility of the water-oil two phases in olefin hydration limits mass transfer, and the side reaction of etherification occurs acutely, resulting in a low yield of alcohol. Thus, water-oil amphiphilic HZSM-5 was prepared by sulfonating silanized zeolite. The successful introduction of organic and sulfonic acid groups is demonstrated by FT-IR, TG, and water contact angles. Amphiphilic HZSM-5 can stabilize the Pickering emulsion and catalyze cyclopentene hydration at the phase interface. In addition, NH3-TPD and Py-IR show that the amount of strong BroÌ·nsted acid sites of zeolites increases significantly after sulfonation. This facilitates the rate-determining step of cyclopentene activation by H+ to form carbocation. Moreover, the nucleophilic side reactions are inhibited by a high concentration of H+. Finally, under the optimized reaction condition, the conversion of cyclopentene can achieve 5.066% with a selectivity of 85.37% to cyclopentanol, which almost reaches the reaction equilibrium.

Potential influence of fine aerosol chemistry on the optical properties in a semi-arid region.

The current understanding regarding the potential influence of aerosol chemistry on the optical properties does not satisfy accurate evaluation of aerosol radiative effects and precise determination of aerosol sources. We conducted a comprehensive study of the potential influence of aerosol chemistry on the optical properties in a semi-arid region based on various observations. Organic matter was the main contributor to the scattering coefficients followed by secondary inorganic aerosols in all seasons. We further related aerosol absorption to elemental carbon, organic matter, and mineral dust. Results showed that organic matter and mineral dust contributed to >40% of the aerosol absorption in the ultraviolet wavelengths. Therefore, it is necessary to consider the absorption of organic matter and mineral dust in addition to that of elemental carbon. We further investigated the potential influence of chemical composition, especially of organic matter and mineral dust on the optical parameters. Mineral dust contributed to higher absorption efficiency and lower scattering efficiency in winter. The absorption Ångström exponent (AAE) was mostly sensitive to organic matter and mineral dust in winter and spring, respectively; it was relatively high (i.e., 1.68) in winter and moderate (i.e., 1.42) in spring. Unlike in the other seasons, mineral dust contributed to higher mass absorption efficiency in winter. This work reveals the complexity of the relationship between aerosol chemistry and optical properties, and especially the influence of organic matter and mineral dust on aerosol absorption. The results are highly important regarding both regional air pollution and climate.

The differential inhibitive effects and fates of As(III) and As(V) mediated by Sulfobacillus thermosulfidooxidans grown on S0, Fe2+ and FeS2.

Arsenic often coexists with metal sulfide minerals and occurs in different speciation and different toxicity in responding to Fe/S biooxidation. The differential inhibitive effects and fates of As(III) and As(V) during biooxidations of elemental sulfur (S0), ferrous ions (Fe2+) and pyrite (FeS2) by Sulfobacillus thermosulfidooxidans were studied. The results revealed that the arsenic species hardly changed for the biooxidation of S0, but dramatically changed for the biooxidation of Fe2+ and FeS2. Different transformation degree between As(III) and As(V) occurred for biooxidation of FeS2 in the presence of arsenic, where about 72% of As(III) was transformed to As(V) for the group with As(III) added, and 16% of As(V) was transformed to As(III) for that with As(V) added. Both formation and dissolution of amorphous ferric arsenate occurred during biooxidation of FeS2 with the addition of As(III) or As(V) and for the group grown on Fe2+ with added As(V), which were controlled by the changes of Fe/As molar ratio and pH value in the solution. Jarosite was detected for the group grown on Fe2+ and could adsorb As(III) and As(V). The inhibitive effects of As(V) were higher than As(III) when the strain grew on FeS2, which was contrary to those when the strain grew on S0 and Fe2+. The above results signify that the fates and inhibitive effects of arsenic are much related to each other, and such a relationship is significantly affected by the utilization of Fe/S energy substrates by the sulfur- and ferrous-oxidizing microorganisms.

Eliminating the stabilizer antagonistic effects for efficiently stabilizing Pb and As co-contaminated soil by innovative stepwise steam flash heating.

Chemical stabilization is frequently used to stabilize lead (Pb) or arsenate (As), but faces challenges in Pb-As co-contaminated soils because of the antagonistic reactions between chemical stabilizers and contaminants. In this work, we innovated an effective and cost-efficient stepwise steam flash heating (SSFH) strategy to simultaneously immobilize Pb and As, and unraveled the underlying mechanisms. The combination of 1.5% Ca(H2PO4)2 and 2% Fe2(SO4)3 only decreased 1.99% Pb by toxicity characteristic leaching procedure (TCLP-Pb) but increased 17.8% of TCLP-As due to the antagonistic effects. SSFH with Ca(H2PO4)2 in the first step and Fe2(SO4)3 in the second step achieved the minimal TCLP-Pb and TCLP-As of 0.778 and 0.327 mg/L, respectively. It also reduced 69.8% of leachable As in 100-year acid rain simulation, indicating a favorable long-term stabilization performance. Additionally, SSFH approach reduced 43.2% stabilizer dosage and 14.9% cost. X-ray absorption near edge structure (XANES) documented that the stepwise SFH promoted the transformation of Pb(NO3)2 and NaAsO2/NaAsO3/As2O3/As2O5 into stable Pb3(PO4)2 and FeAsO4, preventing the formation of AsO43- and FePO4. Our findings proved the state-of-the-art SSFH approach and unraveled its mechanisms to stabilize Pb and As co-contamination in soils, offering a green and sustainable remediation alternative for the management of heavy metal contaminated sites. ENVIRONMENTAL IMPLICATION: A novel stepwise SFH approach can be applied to overcome the stabilizer antagonist effects by separately immobilizing Pb and As in two sequential steps. It also decreased 43.2% of stabilizer dosage and 14.9% of cost comparing to conventional chemical stabilization. This approach can be used for other metal co-contaminated soils facing similar antagonistic challenges, and our work raises a state-of-the-art solution for cost-effective, green and sustainable remediation practices.

Mechanisms and influential factors of soil chromium long-term stability by an accelerated aging system after chemical stabilization.

Chemical stabilization is one of the most widely used remediation strategies for chromium (Cr)-contaminated soils by reducing Cr(VI) to Cr(III), and its performance is affected by human and natural processes in a prolonged period, challenging long-term Cr stability. In this work, we established a method for evaluating the long-term effectiveness of remediation of Cr-contaminated soils, and developed an accelerated aging system to simultaneously simulate acid rain leaching and freeze-thaw cycles. The mechanisms and influencing factors of long-term (50-year) change in soil Cr speciation were unravelled after stabilization with Metafix®. Chemical stabilization remarkably decreased the contents of Cr(VI)soil, Crtotal-leach and Cr(VI)leach, among which the removal rate of Cr(VI) in soil was up to 89.70 %, but it also aggravated soil Cr instability. During the accelerated aging process, Crtotal-leach change rates in chemically stabilized soil samples were 0.0462-0.0587 mg/(L·a), and soil Cr became instable after 20-year accelerated aging. The proportion of Cr bound to organic matter and residual Cr increased in soil, and exchangeable Cr decreased. Linear combination fitting results of XANES also showed that Cr(VI) and Cr3+ were transformed into OM-Cr(III), Fh-Cr(III) and CrFeO3 after restoration. During the accelerated aging process, acid rain leaching activated Cr(III) and dissolved Cr(VI), whereas freeze-thaw cycle mainly affected OM-Cr. Chemical stabilization, acid rain leaching and aging time were the major factors influencing the stability of soil Cr, and the freeze-thaw cycle promoted the influence of acid rain leaching. This study provided a new way to explore the long-term effectiveness and instability mechanisms at Cr-contaminated site after chemical stabilization.

Study of Dimorphism Transition Mechanism of Tremella fuciformis Based on Comparative Proteomics.

Tremella fuciformis is a dimorphic fungus that can undertake a reversible transition between yeast-like conidia and hyphal forms. The transformation mechanism and proteomic differences between these two forms have not been reported. Therefore, in this study, we attempted to explore the differential protein profiles of dikaryotic yeast-like conidia from fruiting bodies and mycelia (FBMds) and dikaryotic mycelia (DM) by synthetically applying high-resolution MS1-based quantitative data-independent acquisition (HRMS1-DIA) full proteomics and parallel reaction monitoring (PRM) targeted proteomics. The results showed that a total of 5687 proteins were quantified, and 2220 of them (39.01%) showed more than a two-fold change in expression. The functional analysis of the differentially expressed proteins (DEPs) confirmed that the DEPs were mainly located in the membrane and nucleus. The FBMds tended to express proteins involved in biosynthesis, metabolism, DNA replication and transcription, and DNA damage repair. At the same time, DM exhibited an increased expression of proteins involved in signal transduction mechanisms such as the mitogen-activated protein kinase (MAPK) signaling pathway and the Ras signaling pathway. Further, phosphorylation analysis confirmed the importance of the MAPK signaling pathway in T. fuciformis dimorphism, and comparative metabolism analysis demonstrated the metabolic difference between FBMds and DM. The information obtained in the present study will provide new insights into the difference between FBMds and DM and lay a foundation for further research on the dimorphism formation mechanism of T. fuciformis.

Proteomic Investigation of the Antibacterial Mechanism of Cefiderocol against Escherichia coli.

This study aimed to investigate the antibacterial mechanism of cefiderocol (CFDC) using data-independent acquisition quantitative proteomics combined with cellular and molecular biological assays. Numerous differentially expressed proteins related to the production of NADH, reduced cofactor flavin adenine dinucleotide (FADH2), NADPH and reactive oxygen species (ROS), iron-sulfur cluster binding, and iron ion homeostasis were found to be upregulated by CFDC. Furthermore, parallel reaction monitoring analysis validated these results. Meanwhile, we confirmed that the levels of NADH, ROS, H2O2, and iron ions were induced by CFDC, and the sensitivity of Escherichia coli to CFDC was inhibited by the antioxidant vitamin C, N-acetyl-l-cysteine, and deferoxamine. Moreover, deferoxamine also suppressed the H2O2 stress induced by CFDC. In addition, knockout of the NADH-quinone oxidoreductase genes (nuoA, nuoC, nuoE, nuoF, nuoG, nuoJ, nuoL, nuoM) in the respiratory chain attenuated the sensitivity of E. coli to CFDC far beyond the effects of cefepime and ceftazidime; in particular, the E. coli BW25113 ΔnuoJ strain produced 60-fold increases in MIC to CFDC compared to that of the wild-type E. coli BW25113 strain. The present study revealed that CFDC exerts its antibacterial effects by inducing ROS stress by elevating the levels of NADH and iron ions in E. coli. IMPORTANCE CFDC was the first FDA-approved siderophore cephalosporin antibiotic in 2019 and is known for its Trojan horse tactics and broad antimicrobial activity against Gram-negative bacteria. However, its antibacterial mechanism is not fully understood, and whether it has an impact on in vivo iron ion homeostasis remains unknown. To comprehensively reveal the antibacterial mechanisms of CFDC, data-independent acquisition quantitative proteomics combined with cellular and molecular biological assays were performed in this study. The findings will further facilitate our understanding of the antibacterial mechanism of CFDC and may provide a theoretical foundation for controlling CFDC resistance in the future.

Highly-efficient and sequential recovery of rare earth elements, alumina and silica from coal fly ash via a novel recyclable ZnO sinter method.

A novel sinter method using ZnO as the activator instead of the conventional Na2CO3/CaCO3, (NH4)2SO4, and K2S2O7 was developed to achieve efficient sequential extraction of rare earth elements (REEs), alumina (Al), and silica (Si) from coal fly ash (CFA). Up to 93.3% Si, 87.1% REEs (70.7% Ce, 82.5% La, 83.2% Gd, 87.1% Nd, 62.3% Dy, and 81.7% Y), and 92.9% Al were extracted from CFA, respectively. Moreover, 93.1% of the ZnO activator was efficiently recycled, and the yield of red mud was only 14.9%. X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) results showed that the speciation transformation of Al/Si during CFA/ZnO roasting was as follows: mullite, quartz, amorphous Al2O3, and SiO2 → Zn0.75Al1.5Si1.5O6, kyanite and willemite → gahnite and quartz/cristobalite solid solutions. The change in the REEs occurrence mode hinted at the migration of most REEs in aluminosilicates forms with Si during roasting, and disassociation with Si into the acid-soluble form after alkali leaching. These results indicate that the coupling of Al-Si-REE in CF was broken by this ZnO sinter method, promoting the sequential and efficient extraction of REEs, Al, and Si from CFA. This study provides a green and efficient strategy for element recovery from CFA, substantially reducing residues and favoring REEs concentration.

Molecular characteristics and abundance of insulin-like androgenic gland hormone and effects of RNA interference in Eriocheir sinensis.

Insulin-like androgenic gland hormone (IAG) has an important function in sexual differentiation and somatic growth in crustaceans. In this study, there was cloning of the full-length sequence of IAG from Eriocheir sinensis (Es-IAG). The full-length Es-IAG gene was 1392 base pairs long and encoded a protein of 151 amino acid residues. The precursor peptide included a signal peptide, and the protein was a protein that is secreted from the cell in which it is produced with no transmembrane domain. Amino acid sequence alignment indicated there was the greatest homology between E. sinensis and Chaceon quinquedens (47 %), followed by Callinectes sapidus (44 %). Results from analysis of the relative abundances of Es-IAG mRNA transcript at different developmental stages indicated that Es-IAG may have an important endocrine function in early embryonic development, and that Stages I through Ⅲ may be an important period for sexual differentiation in juvenile E. sinensis. In vivo treatment with siRNA-391 resulted in a 66.7 % lesser relative abundance of the Es-IAG mRNA transcript. Three treatments with siRNA-391 to inhibit Es-IAG production during Stages Ⅲ to Ⅴ period resulted in about 10 % of male crabs being transformed into "neo-females." These results provide the basis for further research into the sexual differentiation mechanism and monosex breeding of E. sinensis.

Taking insights into phenomics of microbe-mineral interaction in bioleaching and acid mine drainage: Concepts and methodology.

Phenomics is originally a biological concept. In the most recent years, the studies of plant and human phenomics have started, and show a strong momentum and trend of development. In this paper, based on the related research on bioleaching/acid mine drainage (AMD), we put forward the relevant concepts and methodology of phenomics of microbe-mineral interaction (MMI) in bioleaching/AMD environments. It refers to the systematic study on phenotypes of MMI on both levels of microbiome and mineralome under various environmental conditions, by which it gives the relationship between microbial/mineral genome and phenome of MMI responding to the varying environmental conditions. The pertinent methodology is of mainly (meta)-omics, synchrotron radiation-based techniques and supercomputing-based density function theory (DFT) calculation.

Humic acid promotes arsenopyrite bio-oxidation and arsenic immobilization.

The bio-oxidative dissolution of arsenopyrite, the most severe arsenic contamination source, can be mediated by organic substances, but pertinent studies on this subject are scarce. In this study, the bio-oxidative dissolution of arsenopyrite by Sulfobacillus thermosulfidooxidans and arsenic immobilization were evaluated in the presence of humic acid (HA). The mineral dissolution was monitored through analyses of the parameters in solution, phase and element speciation transformations on the mineral surface, and arsenic immobilization on the surfaces of cells and jarosites-HA. The results show that the presence of HA enhances the dissolution of arsenopyrite, e.g., 7.1% of arsenopyrite was in the residue after 12 d of bio-oxidation compared to 19.3% in the absence of HA. Meanwhile, the presence of HA led to changes of the fates of As and Fe and no accumulation of elemental sulfur (S0) or ferric arsenate on the mineral surface. Moreover, a flocculent porous structure was formed on the surfaces of both microbial cells and jarosites, on which a large amount of arsenic was adsorbed. These results clearly indicate that HA can simultaneously promote the dissolution of arsenopyrite and arsenic immobilization, which may be significant for bioleaching of arsenopyrite-bearing contaminated sites.

Reconstituting Arabidopsis CRY2 Signaling Pathway in Mammalian Cells Reveals Regulation of Transcription by Direct Binding of CRY2 to DNA.

In response to blue light, cryptochromes photoexcite and interact with signal partners to transduce signal almost synchronously in plants. The detailed mechanism of CRY-mediated light signaling remains unclear: the photobiochemical reactions of cryptochrome are transient and synchronous, thus making the monitoring and analysis of each step difficult in plant cells. In this study, we reconstituted the Arabidopsis CRY2 signaling pathway in mammalian cells and investigated the biological role of Arabidopsis CRY2 in this heterologous system, eliminating the interferences of other plant proteins. Our results demonstrated that, besides being the light receptor, Arabidopsis CRY2 binds to DNA directly and acts as a transcriptional activator in a blue-light-enhanced manner. Similar to classic transcription factors, we found that the transcriptional activity of CRY2 is regulated by its dimerization and phosphorylation. In addition, CRY2 cooperates with CIB1 to regulate transcription by enhancing the DNA affinity and transcriptional activity of CIB1 under blue light.

Epigenetic silencing of ITGA2 by MiR-373 promotes cell migration in breast cancer.

The loss of ITGA2 plays an important role in cancer metastasis in several solid cancers. However, the molecular mechanism of ITGA2 loss in primary cancers remains unclear. In this study, we found that a lower ITGA2 protein level was observed in breast cancers compared to adjacent non-cancerous breast tissues. Interestingly, the reduction degree of ITGA2 at the protein level was far more than that at the mRNA level. We further showed that the translation of ITGA2 mRNA was directly inhibited by miR-373 through binding to ITGA2-3'UTR. Silencing of ITGA2 detached cell-cell interactions, induced the deploymerization of stress fiber F-actin and stimulated cancer cell migration, similar to the effect of miR-373 over-expression. The co-expression of ITGA2, not ITGA2-3'UTR, could abrogate miR-373-induced cancer cell migration because that the expression of ITGA2-3'UTR was inhibited by co-transfected miR-373. ITGA2 protein level was inversely associated with miR-373 level in breast cancers (r = -0.663, P<0.001). 73.33% of breast cancer patients with high miR-373 and low ITGA2 expression exhibited the lymph node-positive metastases. Together, our results show that epigenetic silencing of ITGA2 by miR-373 stimulates breast cancer migration, and miR-373high/ITGA2low may be as a prognosis biomarker for breast cancer patients.