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Iron (Fe) in aerosol particles is a major external source of micronutrients for marine ecosystems and poses a potential threat to human health. To understand the impacts of aerosol Fe, it is essential to quantify the sources of dissolved Fe and total Fe. In this study, we applied receptor modeling for the first time to apportion the sources of dissolved Fe and total Fe in fine particles collected under five different weather conditions in the Hangzhou megacity of Eastern China, which is upwind of the East Asian outflow. Results showed that Fe solubility (dissolved Fe to total Fe) was the largest on fog days (6.7 ± 3.0 %), followed by haze (4.8 ± 1.9 %), dust (2.1 ± 0.7 %), clear (1.9 ± 1.0 %), and rain (0.9 ± 0.5 %) days. Positive matrix factorization (PMF) analysis suggested that industrial emissions were the largest contributor to dissolved Fe (44.5 %–72.4 %) and total Fe (39.1 %–55.0 %, except for dust days) during haze, fog, dust, and clear days. Transmission electron microscopy analysis of individual particles showed that > 75 % of Fe-containing particles were internally mixed with acidic secondary aerosol species on haze, fog, dust, and clear days. Furthermore, Fe solubility showed significant positive correlations with aerosol acidity/total Fe and liquid water content. These results indicated that the wet surface of aerosol particles promotes heterogeneous reactions between acidic species and Fe aerosols, contributing to a high Fe solubility.

The non-uniform aggregation of fast-diffused Li on an anode surface would aggravate its tip-effect-induced nucleation/growth, leading to the notorious dendrite growth in Li metal batteries (LMBs). Tuning the Li diffusion on the anode surface has been regarded previously as a mainstream method to induce its uniform deposition, while the diffusion of Li in the anode bulk is usually ignored. Here, conceptually different from the classic surface modification, we propose a molecular tunnelling strategy to construct atomic channels in graphite bulk, which enables the fast diffusion of superdense Li. Density functional theory calculations and ab initio molecular dynamics simulations prove that the bulk diffusion through atomic channels could become a new and dominating path. Its reversible and efficient diffusion has been further visualized by in situ transmission electron microscopy. As a result, when coupled with high-loading LiFePO4 cathodes (20 mg cm−2), a high areal capacity and 100% capacity retention are achieved over 370 cycles. Through this work a new strategy is developed based on the bulk-diffusion of superdense Li for dendrite-free LMBs, which can be pervasive in other high-performance energy storage systems.

Using boron and SiC as additives, the pressureless densification of HfB2 powders synthesized by borothermal reduction with water-washing process was studied. The water-washing HfB2 powders showed good sinterability (relative density: 96.2%), due to the small grain size with the in-situ boron impurities, whereas the microstructure of the sintered sample was coarsened with average grain size of 10.19 ± 4.12 μm. After adding 5 wt% boron, the relative density was improved (98.7%) and the grain size was reduced (4.68 ± 1.17 μm). In order to further inhibit the grain growth, enhance densification and mechanical properties, 20 vol% SiC was added. Finally, fully dense HfB2-based ceramics (relative density: 99.9%) with small grain size of 3.45 ± 0.88 μm were fabricated by the combination of boron and SiC. The Vickers’ hardness and fracture toughness of HfB2 with additions of boron and SiC were 18.27 ± 1.95 GPa and 3.33 ± 0.16 MPa m1/2, respectively.

There is an urgent need for high-safety and high-energy lithium-ion batteries to satisfy the rapidly increasing need for energy storage. Nickel-rich layered cathodes have been at the forefront of the revolution for batteries due to their relatively high capacity and low cost. However, with the increase of nickel content, the batteries suffer from severe safety concerns, which caused by thermal runaway. Here we show that the ultraconformal cathode-electrolyte interphase (CEI) protective skin with high inorganic content dramatically enhances the safety of high-energy practical Li-ion pouch cells. We find that the robust CEI skin significantly improves the intrinsic thermal stability, mitigates the evolution of oxygen resulting from phase transition, and effectively suppresses the associated parasitic reactions between the delithiated cathodes and electrolyte. The in-situ CEI engineering strategy is simple and suitable for practical industrial manufacture, and it provides design ideas for aggressive nickel-rich cathodes towards safe and high-energy batteries.

Novel polyvinylidene fluoride/TiO2/UiO-66-NH2 (PVDF/TiUN) membranes were produced by the delay phase separation method via introducing the TiO2/UiO-66-NH2 (TiUN) nanocomposite into PVDF casting solution. Interconnection of TiO2 and UiO-66-NH2 improved photocatalysis capacity and endowed PVDF/TiUN membranes with self-cleaning capability. Quantitative measurements showed that, firstly, PVDF/TiUN membranes exhibited improved photodegradation kinetics and efficiency (up to 88.1%) to Rhodamine B (RhB). Secondly, the performances of bovine serum albumin (BSA) rejection and permeation of PVDF/TiUN membranes outperformed those of other check samples, indicating enhanced hydrophilicity. Thirdly, rejection rate of BSA reached a breathtaking 98.14% and flux recovery ratio (FRR) of BSA reached a breathtaking 95.37%. Thus, given their excellent anti-contamination property and separation performance, the PVDF/TiUN membrane is very likely to be a novel water treatment membrane. HIGHLIGHTS PVDF/TiUN membrane was prepared for the first time via phase separation process method.; The membrane exhibits excellent antifouling performance with flux recovery ratio of almost 100%.; PVDF/TiUN membrane showed better removal performance under light conditions.; Visible light cleaning of fouled membranes enabled high recovery of membrane performance.

Sodium 9,10-anthraquinone-2,6-disulfonate (Na2AQ26DS, 130 mAh g−1) with polyanionic character and two O–Na ionic bonds is used as an organic cathode for Li-ion batteries. Na2AQ26DS exhibits highly impressive cycle stability in ether electrolytes due to its polyanionic character and the effective suppression of solvent-molecule co-intercalation. In half cells (1–3.9 V vs. Li+/Li) using 1 M bis(trifluoromethanesulphonyl)imide lithium salt (LiTFSI) in 1,3-dioxolane/dimethoxyethane (DOL/DME), Na2AQ26DS delivers a highly stable specific capacity of 123 mAh g−1 at 50 mA g−1 for 900 cycles (6-month test) and realizes ∼69 mAh g−1 for 2800 cycles at 500 mA g−1. In the full cells with the reduced state (Li4TP) of lithium terephthalate (Li2TP) as the organic anode, the resulting Li4TP II Na2AQ26DS organic lithium-ion batteries (OLIBs) can display a highly stable average discharge capacity of 120 mAh g−1cathode for 100 cycles at 50 mA g−1 and ∼63 mAh g−1cathode for 1200 cycles at 500 mA g−1 in 0.2–3.3 V.

SUMMARY OBJECTIVE: In this study, we aimed at investigating the role of isoleucyl-tRNA synthetase in the growth, migration, and angiogenesis of human umbilical vein endothelial cells and the underlying molecular mechanism. METHODS: To assess the role of isoleucyl-tRNA synthetase, we silenced isoleucyl-tRNA synthetase in human umbilical vein endothelial cells using lentiviral 2 specific short hairpin RNAs (short hairpin RNAs 1 and 2) and examined silencing efficiency using real time quantitative polymerase chain reaction and western blot analyses. Short hairpin RNAs 1-isoleucyl-tRNA synthetase had greater knockdown efficiency, it was used in the entire downstream analysis. Short hairpin RNAs 1- isoleucyl-tRNA synthetase silencing effects on cell proliferation, cell colony generation, cell migration, as well as angiogenesis were assessed using cell counting kit-8, colony development, cell migration, and angiogenesis tube formation assays, respectively. RESULTS: Compared to the control group, anti-isoleucyl-tRNA synthetase short hairpin RNAs significantly silenced isoleucyl-tRNA synthetase expression in human umbilical vein endothelial cells, and suppressed their proliferation, migration, and angiogenic capacity. To characterize the underlying mechanism, western blot analyses showed that isoleucyl-tRNA synthetase knockdown suppressed phosphorylation of extracellular-regulated kinase ½ and protein-serine- threonine kinase, as well as expression of vascular endothelial growth factor, GSK-3β, and β-catenin. CONCLUSIONS: We have shown, for the first time, the critical role of isoleucyl-tRNA synthetase in human umbilical vein endothelial cells. Our data show that isoleucyl-tRNA synthetase knockdown suppresses human umbilical vein endothelial cell proliferation, migration, and angiogenesis. We have also shown that isoleucyl-tRNA synthetase knockdown suppresses phosphorylation of extracellular-regulated kinase ½ and protein-serine- threonine kinase, as well as expression of vascular endothelial growth factor, GSK-3β, and β-catenin. Together, these data highlight isoleucyl-tRNA synthetase as a potential antitumor anti-angiogenic target.

Potassium naphthalene-1,4,5,8-tetracarboxylate (K4NTC, 117 mAh g-1) is a new organic anode for K-ion batteries, which possesses four strong K-O ionic bonds within a -4-valent naphthalene-1,4,5,8-tetracarboxylate skeleton (NTC4-). And thus, K4NTC is a polyanionic organic salt. Simultaneously, new insights are provided by comparing two typical electrolyte systems (carbonate and ether electrolytes) with KPF6 as the same solute. Finally, the pure organic K-ion batteries (OKIBs) are fabricated by using perylene-3,4,9,10-tetracarboxydianhydride (PTCDA) as the organic cathode and the reduced state (K6NTC) of K4NTC as the anode. And this OKIB can deliver a peak discharge capacity of 121 mAh g-1anode and run over 1500 cycles in 0.5-3 V using ether electrolytes.

Layered Ni-rich LiNixMnyCo1-x-yO2 (NMC) materials are the most promising cathode materials for Li-ion batteries due to their favorable energy densities. However, the low thermal stability typically caused by detrimental oxygen release leads to significant safety concerns. Determining the pathways of oxygen evolution reaction is essential, as the ideal safety countermeasure is to break the reaction chain of thermal runaway. In this study, we demonstrate that two endogenous pathways of oxygen involved in strong exothermic reactions lead the NMC811|graphite pouch cell to an uncontrollable state, and we quantify the individual contribution of the pathways to thermal runaway. Approximately 41% of thermal-induced oxygen reacts aggressively with ethylene carbonate (EC) at the cathode/electrolyte interface with 16% heat generation, accelerating the self-heating rate and thereby further triggering thermal runaway. The residual oxygen that survives the reaction with carbonate spreads to the lithiated anode with major heat generation (65%), bringing the battery to the maximum destructive temperature during thermal runaway. By confirming the significant roles of EC and anode, a deeper understanding on battery fire was achieved. The revealed mechanism can help guide studies on stopping the two reaction pathways, allowing for the safer use of high-energy lithium-ion batteries in the future.

The design of artificial receptors with a specific recognition function and enhanced selectivity is highly desirable in the electrochemical sensing field, which can be used for detection of environmental pollutants. In this facet, metal-organic frameworks (MOFs) featured adjustable porosities and specific host-guest recognition properties. Especially, the large hydrophobic cavity formed in the porous MOFs may become a potential artificial receptor. We herein designed a new porous MOF [Zn2(L)(IPA)(H2O)]·2DMF·2MeOH·3H2O (Zn-L-IPA) by using a functionalized sulfonylcalix[4]arene (L1) and isophthalic acid (H2IPA) (DMF = N,N'-dimethylformamide). The specific pore size and pore shape of Zn-L-IPA made it efficiently selective for absorption of bisphenol A (BPA), bisphenol F (BPF), and bisphenol S (BPS). Therefore, a rapid, highly selective, and ultrasensitive electrochemical sensing platform Zn-L-IPA@GP/GCE was fabricated by using Zn-L-IPA as a host to recognize and absorb bisphenol guests (GP = graphite powder, GCE = glassy carbon electrode). Most strikingly, the extremely low detection limits were up to 3.46 and 0.17 nM for BPA and BPF, respectively, using the Zn-L-IPA@GP/GCE electrode. Furthermore, the "recognition and adsorption" mechanism was uncovered by density functional theory with the B3LYP function. This work offered a prospective strategy for selective absorption and detection of harmful bisphenols with the MOF-based porous material.

Graphite, a robust host for reversible lithium storage, enabled the first commercially viable lithium-ion batteries. However, the thermal degradation pathway and the safety hazards of lithiated graphite remain elusive. Here, solid-electrolyte interphase (SEI) decomposition, lithium leaching, and gas release of the lithiated graphite anode during heating were examined by in situ synchrotron X-ray techniques and in situ mass spectroscopy. The source of flammable gas such as H2 was identified and quantitively analyzed. Also, the existence of highly reactive residual lithium on the graphite surface was identified at high temperatures. Our results emphasized the critical role of the SEI in anode thermal stability and uncovered the potential safety hazards of the flammable gases and leached lithium. The anode thermal degradation mechanism revealed in the present work will stimulate more efforts in the rational design of anodes to enable safe energy storage., The role of the lithiated graphite anode in battery thermal runaway failure remains under intense investigation. In this work, with multiple in situ synchrotron X-ray characterizations, the phase evolution, gas release, and lithium leaching of lithiated graphite anode are illustrated in detail.

The development of unnatural base pairs (UBPs) has greatly increased the information storage capacity of DNA, allowing for transcription of unnatural RNA by the heterologously expressed T7 RNA polymerase (RNAP) in Escherichia coli. However, little is known about how UBPs are transcribed by cellular RNA polymerases. Here, we investigated how synthetic unnatural nucleotides, NaM and TPT3, are recognized by eukaryotic RNA polymerase II (Pol II) and found that Pol II is able to selectively recognize UBPs with high fidelity when dTPT3 is in the template strand and rNaMTP acts as the nucleotide substrate. Our structural analysis and molecular dynamics simulation provide structural insights into transcriptional processing of UBPs in a stepwise manner. Intriguingly, we identified a novel 3'-RNA binding site after rNaM addition, termed the swing state. These results may pave the way for future studies in the design of transcription and translation strategies in higher organisms with expanded genetic codes.

An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 °C was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum electrode. The reduction of In(III) was found to be a two-step process involving In(III)/In(I) and In(I)/In couples at the potentials of about −0.4 and −0.8 V versus Ag/AgCl, respectively. The redox mechanism was further confirmed by the theoretical evaluation of the number of transferred electrons based on cyclic voltammetry and characterizations of the precipitates generated by the potentiostatic electrolysis. The diffusion coefficients of indium ions in the eutectic LiCl-KCl melt at 450 °C were estimated by cyclic voltammetry and chronopotentiometry. The results obtained through the two methods are in fair agreement, delivering an average diffusion coefficient of approximately 1.8×10−5 cm2/s for In(III), and 1.4×10−4 cm2/s for In(I).

Accompanied by the adoption of aggressive cathodes to continuously improve batteries energy density, enhancing their safety is becoming increasingly urgent for the electric vehicle development. In-situ controllable formation of robust cathode-electrolyte interphase (CEI) with high inorganic content seems to be the most promising strategy to address the thermal runaway concerns. Moreover, the in-situ formation strategy via suitable electrolyte replacement or electrolyte additives is extremely simple yet effective, especially for industrial manufacture of batteries. Here, this paper briefly reviews recent advanced CEIs formed by conventional carbonate-based electrolytes, fluorinated electrolytes, concentrated electrolytes, and solid state electrolytes. The focus on the thermal stability of the cathodes after CEI modification, and at the same time conduct safety tests at the material, cell, and module levels for comprehensive evaluation are encouraged. The review will provide inspiration for future developments in battery safety and push forward the practical applications of newly developed high-energy density batteries.

Zinc (Zn) possesses desirable degradability and favorable biocompatibility, thus being recognized as a promising bone implant material. Nevertheless, the insufficient mechanical performance limits its further clinical application. In this study, reduced graphene oxide (RGO) was used as reinforcement in Zn scaffold fabricated via laser additive manufacturing. Results showed that the homogeneously dispersed RGO simultaneously enhanced the strength and ductility of Zn scaffold. On one hand, the enhanced strength was ascribed to (i) the grain refinement caused by the pinning effect of RGO, (ii) the efficient load shift due to the huge specific surface area of RGO and the favorable interface bonding between RGO and Zn matrix, and (iii) the Orowan strengthening by the homogeneously distributed RGO. On the other hand, the improved ductility was owing to the RGO-induced random orientation of grain with texture index reducing from 20.5 to 7.3, which activated more slip systems and provided more space to accommodate dislocation. Furthermore, the cell test confirmed that RGO promoted cell growth and differentiation. This study demonstrated the great potential of RGO in tailoring the mechanical performance and cell behavior of Zn scaffold for bone repair., Graphical abstract Image 1, Highlights • Zn/RGO composite scaffold was successfully fabricated by laser additive manufacturing. • RGO refined the grains and significantly weakened the texture with random grain orientation. • The uniformly distributed RGO simultaneously enhanced the strength and ductility of scaffold. • The incorporated RGO exerted a positive effect on cell growth and differentiation.

Noncovalent interaction between small molecules can generate a charge-transfer (CT) state, achieving the effect of a conjugated large molecule as well as a transition-metal complex. Herein, we demonstrate a room-temperature stable dianion biradical conveniently produced by noncovalent intermolecular CT interaction between anthraquinone (AQ) and potassium tert-butoxide (KOtBu). Essentially, CT from KOtBu to AQ boosts absorption bands from the UV to visible and near-infrared (NIR) range, enabling AQ-KOtBu to have new absorption bands around 400, 550, and 900 nm. The absorption bands of AQ-KOtBu are dramatically enhanced after blue-to-green or NIR light excitation. Interestingly, both ground state AQ-KOtBu (C(1)) and photoexcited AQ-KOtBu (C(2)) are quenched by oxygen to produce singlet oxygen. Furthermore, C(1) can be photoactivated by purged nitrogen in solution, and C(2) can be regenerated after the photoexcitation and purged nitrogen in solution, which may serve as a photosensitizer under visible and NIR light excitation.

Among the solution-based purification methods of as-produced single-walled carbon nanotubes (SWCNTs), conjugated polymer sorting is one of the most promising approaches to obtain semiconducting SWCNTs (s-SWCNTs) with high purity. In order to meet the demand for pure polymer-free s-SWCNTs after polymer wrapping, we synthesized several degradable fluorene- and carbazole-based copolymers for selective extraction of s-SWCNTs. The copolymers are interlinked by imine bonds, and thus, the cleavage can be easily accomplished by acid treatment. The polymer/SWCNT complex dispersions were prepared with as-produced HiPco SWCNTs in toluene and characterized with absorption, photoluminescence excitation and emission mapping, and Raman spectroscopy. Among the synthesized polyimines, fluorene-carbazole copolymers show extremely high separation yield toward s-SWCNTs and high separation purity, while the fluorene–fluorene and fluorene-p-phenylene copolymers show lower yield but higher selectivity to s-SWCNT with specific pairs of (n,m) indices. Quantitative removal of the polymer after acid-triggered degradation was confirmed by X-ray photoelectron spectroscopy. Moreover, the released dispersant-free s-SWCNTs can be further rewrapped by different polymers. Our results pave the way toward the use of dispersant-free semiconducting carbon nanotubes (CNTs) to develop the next generation of CNT devices.

Melanoma is a serious malignant form of skin cancer. Euphorbiaceae compound B (ECB, 2,4-dihydroxy-6-methoxy-3-methylacetophenone) is an acetophenone compound that is isolated from Euphorbia ebracteolata Hayata (EEH), an herbaceous perennial, and has antitumor activity. Here, we transplanted human melanoma cells into zebrafish embryos to establish a zebrafish/melanoma model. We showed that this model can be used to evaluate the therapeutic effect of EEH and ECB and discussed its potential mechanism of action. The results showed that ECB was an active ingredient of EEH in inhibiting melanoma-induced hyperplasia of blood vessels in zebrafish embryos, similar to the angiogenic inhibitor vatalanib. ECB inhibited the number and length of subintestinal veins ( p < 0.05 ), as well as the distribution of melanoma in zebrafish embryos ( p < 0.05 ). More importantly, unlike vatalanib, ECB only inhibited melanoma-induced abnormal and excessive growth of blood vessels in xenografts. In addition, ECB inhibited the mRNA expression of vegfr2 and vegfr3 in zebrafish. Both vegfr2 and vegfr3 are essential genes that regulate blood vessel formation and upregulate the expression of p53 and casp3a genes in zebrafish. Together, the above-mentioned results indicate that ECB has a potential antimelanoma effect in vivo, which may be mediated by inhibiting vascular endothelial growth factor receptors.

Fe-N-C with atomically dispersed Fe single atoms is the most promising candidate to replace platinum for the oxygen reduction reaction (ORR) in fuel cells. However, the conventional synthesis procedures require quantities solvents and metal precursors, sluggish adsorption process, and tedious washing, resulting in limited metal doping and uneconomical for large-scale production. For the first time, Fe2O3 is adopted as the Fe precursor to derive abundant single Fe atoms dispersed on carbon surfaces. The Fe-N-C catalyst synthesized by this simple method shows an excellent ORR activity with half-wave potentials of 0.82 and 0.90 V in acidic and alkaline solutions, respectively. A single fuel cell with an optimized Fe-N-C cathode shows a high peak power density of 0.84 W cm-2. The solid-state transformation synthesis method developed in this study may shed light on mass production of single-atom-based catalysts.

Electrochemical reduction of CO2 to chemicals and fuels is an interesting and attractive way to mitigate greenhouse gas emissions and energy shortages. In this work, we report the use of atomic In catalysts for CO2 electroreduction to CO. The atomic In catalysts were anchored on N-doped carbon (InA/NC) through pyrolysis of In-based metal-organic frameworks (MOFs) and dicyandiamide. It was discovered that InA/NC had outstanding performance for selective CO production in the mixed electrolyte of ionic liquid/MeCN. It is different from those common In-based materials, in which formate/formic acid is formed as the main product. The faradaic efficiency (FE) of CO and total current density were 97.2% and 39.4 mA cm-2, respectively, with a turnover frequency (TOF) of ∼40 000 h-1. It is one of the highest TOF for CO production to date for all of the catalysts reported. In addition, the catalyst had remarkable stability. Detailed study indicated that InA/NC had higher double-layer capacitance, larger CO2 adsorption capacity, and lower interfacial charge transfer resistance, leading to high activity for CO2 reduction. Control experiments and theoretical calculations showed that the In-N site of InA/NC is not only beneficial for dissociation of COOH* to form CO but also hinders formate formation, leading to high selectivity toward CO instead of formate.

Due to creating a passivated solid electrolyte interphase (SEI), high concentration (HC) electrolytes demonstrate peculiar physicochemical properties and outstanding electrochemical performance. However, the structures of such SEI remains far from clear. In this work, a hybrid abinitio and reactive molecular dynamics (HAIR) scheme is employed to investigate the concentration effect of SEI formation by simulating the reductive degradation reactions of lithium bis(fluorosulfonyl)imide (LiFSI) in 1,3 dioxalane (DOL) electrolytes at concentrations of 1 M, 4 M, and 10 M. The efficient HAIR scheme allows the simulations to reach 1 ns to predict electrolytes’ deep products at different concentrations. The simulation findings show that the most critical distinction between HC and its low concentration (LC) analogue is that anion decomposition in HC is much more incomplete when only S–F breaking is observed. These insights are important for the future development of advanced electrolytes by rational design of electrolytes.

Manganese-rich layered oxide materials hold great potential as low-cost and high-capacity cathodes for Na-ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn-rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn-rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g-1 . It delivers ca. 160 mAh g-1 specific capacity between 2-3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre-formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de-sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3-P3 phase transition.

Helical wrapping by conjugated polymer has been demonstrated as a powerful tool for the sorting of single-walled carbon nanotubes (SWCNTs) according to their electronic type, chiral index, and even handedness. However, a method of one-step extraction of left-handed (

CD45+CD71+ erythroid cells generated through splenic extramedullary erythropoiesis have recently been found to suppress anti-infection and tumor immunity in neonates and adults with malignances. However, their role in tumor microenvironment has not been investigated. In the present study, we found that the number of CD45+CD71+ erythroid cells was significantly elevated in hepatocellular carcinoma (HCC) tissues compared to that in paratumor region and circulation. Additionally, they were more abundant in HCC tissues compared to some immune suppressive cells as well as CD45-CD71+ erythroid cells. CD45+CD71+ erythroid cells suppressed T cells through generation of reactive oxygen species, IL-10, and TGF-β in a paracrine and cell-cell contact manner, and their suppressive effect was stronger than that of myeloid-derived suppressor cells. The abundance of CD45+CD71+ erythroid cells in tumor tissue, as illustrated via immunofluorescence, predicted disease-free survival and overall survival, and its prognostic value was better than that of Cancer of the Liver Italian Program score. This study demonstrated that accumulation of intratumoral CD45+CD71+ erythroid cells in HCC tissues could play a superior immunosuppressive role in tumor microenvironment and may serve as a valuable biomarker to predict recurrence of HCC.

A new synthesis of the bridged [6-6-6] ABE tricyclic ring analogues of methyllycaconitine with the C-1 oxygenated substituents has been developed using an efficient aza-annulation of β-enamino ketone followed by a facile decarboxylation to form BE rings. Subsequent elaboration to form the A ring was achieved by a transannular acyl radical cyclization with concomitant equipment of the key C-1 oxygen functionality.

Phase separation is an important microscopic phenomenon in aerosol particles and reflects the surface properties of particles and the aging degree of organic components. However, few data are available to directly reveal phase separation in ambient aerosol particles, although there are abundant data from laboratory experiments. In this study, different state-of-the-art microscopic technologies were used to study the phase separation of organic matter (OM) and inorganic salts in individual particles collected from different atmospheric environments, with one type of surrogate particles prepared in the laboratory. We found that most of the collected particles with an equivalent sphere diameter of >100 nm have a secondary inorganic aerosol core with OM coating in the continental atmosphere. In addition, secondary inorganic aerosol and OM phase separation are more frequent in rural particles than suburban particles, suggesting that particle aging enhances the phase separation. Our results show that the phase separation is a frequent phenomenon that forms organic coatings on inorganic particles of individual particles (>100 nm), and their number abundances depend on the particle size and OM aging degree. The resulting morphology shows that OM is an important particle surface in the atmosphere, which influences gas partitioning, optical and hygroscopic properties, and cloud condensation nuclei formation activities.

High-flux fine hollow fiber nanofiltration (HFNF) membranes were prepared by interfacial polymerization (IP) using polysulfone (PSF) ultrafiltration (UF) membranes with an outer diameter of 425 μm ...

Sodium-ion batteries are promising candidates for energy storage application, but the absence of high-capacity and low-cost anode materials significantly limits their practical specific energy and ...

Carbonate burial dissolution is generally associated with faults and fractures, accompanied by formation of the fracture–vug system that can provide important reservoir space for oil and gas accumulation. Taking the Lower Triassic Daye Formation in the Huandiqiao Section, Huangshi Area, Middle Yangtze Paraplatform, China, as an example, this study elaborates genetic mechanisms of faults and fractures, features of burial dissolution and cementation, and properties of karst water, accompanied by establishment of a genetic model that illustrates the whole process of burial dissolution and cementation. There are a total of nine reverse faults with dominant northwest dips in the study section. Fractures are selectively developed in hanging walls of the nine faults, with tensile features and dominant north–northeast and north–northwest strikes. Dendritic dissolution and subsequent cementation is prevalent in the hanging wall, while they are rare in the footwall. Most of the cements in the fractures of the hanging walls are calcites, with a fluid inclusion homogenization temperature range of 70∼120 °C, overgrowth bands at the pore edge with different luminous intensities, low contents of Na, Ba, K, and Sr, and high contents of Fe, Mn, and Mg. All these characteristics indicate the karst fluid to originate from calcium-rich formation water with hydrothermal genesis. The formation of the dendritic vug and fracture system is ascribed to the upward migration of hydrothermal fluids along the fault planes and fractures that result in selective dissolution. As the water circulation weakens, CaCO3 is gradually supersaturated in the distal zone with reference to the fault as well as the stagnant and weak-circulation zone, eventually forming a complex vug and fracture system.

The distribution, mineralization, and transformation of soil organic phosphorus (P) exhibits strong regional characteristics because of variations in climate and pear varieties in Yanbian apple–pear orchard. Soil samples were collected in 11, 25, 40, and 63-year-old apple-pear orchards, at the depths of 0–20 cm, 20–40 cm, and 40–60 cm. Soil aggregates were sieved using the dry sieving method, and the concentrations of organic P were determined using the improved Bowman-Cole method. Differences in organic P in soil aggregates were analyzed in respect to planting year, soil layer, and season. According to the results, with an increase in planting years, labile, moderately labile, moderately stable, highly stable, and total extracted organic P in soil aggregates increased and then decreased. The concentrations were the lowest in the 11-year-old orchard and the highest in the 25-year-old orchard. With an increase in soil layer depth, all the forms of organic P concentrations in soil aggregates decreased linearly, and there were significant differences among different levels. In addition, with shifting seasons from spring, summer, to autumn, the labile organic P concentrations in soil aggregates decreased gradually, and the moderately labile, highly stable, and total extracted organic P concentrations first increased and then decreased, while the moderately stable ones first decreased and then increased. All the forms of organic P concentrations in soil aggregates were the highest in the

This study reports the design and synthesis of NO-donating polymer to generate biodegradable polymeric micelle containing paclitaxel (NO/PTX) as a nanomedicine delivery system aimed to enhance the solubility and anti-cancer activity of paclitaxel (PTX). NO/PTX showed greater NO-releasing performance than nitroglycerin, displaying excellent tolerance in KM mice, and exhibited a two-fold stronger antiproliferative activity than PTX in vitro against HCT116, SW480, and SGC-7901 cell lines. In vivo tumor growth inhibition assay results indicated that NO/PTX displayed lightly stronger activities against tumor growth than PTX at a dose of 10 mg kg−1, while the anti-tumor effect of NO/PTX was significantly improved than that of PTX and Genexol®-PM groups at a dose of 15 mg kg−1 (the inhibition rate: 67% vs. 53% and 41%). In addition, NO/PTX showed an improved area under the plasma concentration-time curve and drug deposition in tumors in comparison to PTX. Wound healing assay and western blot analysis of EMT-related markers suggested that NO/PTX could inhibit the potential of HCT116 migration. Western blot analysis also demonstrated that NO/PTX dampened efflux activity of P-gp and up-regulated apoptosis-related proteins. Overall, these promising results suggested that the synergism between PTX and NO-donating micelles could contribute to the potent anti-cancer activity of NO/PTX.

Although liquid mercury (Hg) has been known since antiquity, the formation of stable solid nano forms of Hg at room temperature has not been reported so far. Here, for the first time, we report a simple sonochemical route to obtain solid mercury nanoparticles, stabilized by reduced graphene oxide at ambient conditions. The as-formed solid Hg nanoparticles were found to exhibit remarkable rhombohedral morphology and crystallinity at room temperature. Extensive characterization using various physicochemical techniques revealed the unique properties of the solid nanoparticles of Hg compared to its bulk liquid metal phase. Furthermore, the solid nature of the Hg nanoparticles was studied electrochemically, revealing distinctive properties. We believe that solid Hg nanoparticles have the potential for important applications in the fields of electroanalytical chemistry and electrocatalysis., Formation of the stable solid mercury nanoparticles by acoustic cavitation and their electrochemical activity compared to its bulk liquid metal.

Searching for economical low-dimensional materials to construct the highly efficient type-II heterojunction photocatalysts for splitting water into hydrogen is very strategic. In this study, using the first-principles calculations, we construct a novel SiH/CeO2(111) type-II heterojunction with a very small lattice mismatch of less than 1%. Based on AIMD simulation and phonon dispersion calculations, the SiH/CeO2(111) heterojunction reveals sufficient stability, and is easy to synthesize. Due to the vdW interaction between SiH and CeO2(111) components, electron and hole accumulation regions form at the heterojunction interface, which is very conducive to the separation of photoexcited electron-hole pairs. Besides, the SiH/CeO2(111) heterojunction has good visible light response, and even a strong absorption peak of up to 8.7 × 105 cm-1 in the high-energy visible region. More importantly, the SiH/CeO2(111) heterojunction exhibits good OER and HER performance because its oxidation and reduction potentials well meet the requirements of water splitting. Consequently, SiH/CeO2(111) is a potential photocatalyst for splitting water to hydrogen.

A Co/CoO@NC hybrid material with high specific surface area and ultrafine particle size was prepared using a novel Co-MOF as a sacrificial template. The Co/CoO@NC shows excellent performance in the catalytic reduction of 4-nitrophenol (4-NP) and recyclability, the reaction rate constant k = 0.0139 s−1 (0.2 mg, 298 K) is better than some reported precious metal catalysts.

Radish (Raphanus sativus L.), an important root vegetable crop of the Brassicaceae family, has a high level of anthocyanin accumulation in its pigment root tissues. It was reported that MYB transcription factors (TFs) play vital roles in plant development and anthocyanin metabolism, and the PAP1/2 could promote expression of anthocyanin biosynthesis genes. In this study, a total of 187 radish MYB genes (RsMYBs) were identified in the radish genome and clustered into 32 subfamilies. Among them, 159 RsMYBs were localized on nine radish chromosomes. Interestingly, 14 RsMYBs exhibited differential expression profiles in different taproot developmental stages among four differently colored radish lines. A number of RsMYBs were highly expressed in the pigmented root tissues at the maturity stage, several genes including RsMYB41, RsMYB117, and RsMYB132 being homologous to PAP1/2, showed high expression levels in the red skin of NAU-YH (red skin-white flesh) taproot, while RsMYB65 and RsMYB159 were highly expressed in the purple root skin of NAU-YZH (purple skin-red flesh), indicating that these RsMYBs might positively regulate the process of anthocyanin accumulation in radish taproot. These results would provide valuable information for further functional characterization of RsMYBs, and facilitate clarifying the molecular mechanism underlying anthocyanin biosynthesis in radish.

An insoluble small-molecule organic compound [N,N′-bis(2-anthraquinone)]-perylene-3,4,9,10-tetracarboxydiimide (PTCDI-DAQ) can be a high-performance cathode in Li-ion batteries (LIBs). In half cells, PTCDI-DAQ delivers a peak specific capacity of 229 mA h g−1, along with the good retention of 82% over 3 months. Meanwhile, PTCDI-DAQ can still hold a capacity of 46 mA h g−1 at 25 A g−1. By using the reduced state (Li4TP) of lithium terephthalate (Li2TP) as an organic anode in the all-organic Li-ion batteries (OLIBs), our OLIBs can realize a high-energy density of 296 W h kg−1cathode in the voltage range of 0.2–3.2 V and fulfill a long lifespan over 20 000 cycles. To the best of our knowledge, the comprehensive performance of our PTCDI-DAQ II Li4TP OLIBs is currently one of the best pure-organic LIBs in the world.

The controlled syntheses of glycerol-based polymers, involving poly(glycidol) (PG)-backbones and thermoresponsive oligo(oxyethylene)-side chains, are described. The organocatalytic ring-opening polymerizations of benzyl glycidyl ether (BnGE) were performed to produce poly(benzyl glycidyl ether)s (PBnGEns) in which the degree of polymerization (n) was predetermined, followed by the removal of the inherent protection groups. For these polymerization/deprotection stages, the synthesis of two major types of polymers is emphasized, in which one is “pristine” PG without any specific end-groups (PGn) and the other is the α-end functionalized PG with hydrophobic aliphatic and aromatic groups (R-PGn). The post-modification reactions based on the addition reactions of isocyanate derivatives to the hydroxyl side groups were adopted for PGn and R-PGn, thus producing poly[glycidyl oligo(oxyethylene)carbamate]s with diverse structures. The structures can generally be expressed as PGn-EOmR′ and R-PGn-EOmR′, where (i) the degree of polymerization (n), (ii) the alkyl group at the periphery of the side groups (R′), (iii) the number of oxyethylene chains (m), and (iv) the α-end group (R) can be independently controlled and/or selected. The effects of the parameters/structures (i)–(iv) on the thermoresponsive properties and the supporting data for the phase transitions in aqueous media are described in detail.

Textured high-entropy boride ceramics, prototypically (Hf0.2Zr0.2Ta0.2Cr0.2Ti0.2)B2, with nearly single phase were fabricated for the first time by spark plasma sintering (SPS) of the corresponding powder, which was derived from boron/carbothermal reduction. Lotgering orientation factor calculation and the pole figures revealed that the c-axis of high-entropy boride grains aligned parallel to the SPS pressing direction after sintering and grains grew along the a,b-axis to form platelet-like morphology. The remarkably high Vickers’ hardness of ∼29 GPa was observed on both of the side surface and the top surface of textured ceramics. The surface perpendicular to the SPS pressing direction demonstrated an improved fracture toughness owing to the oriented elongated grains.

A synthetic method for a series of poly(glycidol) (PG)-based amphiphilic block copolymers is presented with an emphasis on the catalyst switch method from an organic superbase (t-Bu-P4) to another with reduced basicity (t-Bu-P2) during sequential ring-opening polymerization (ROP). This methodology allowed the first ROP of an epoxide monomer and the second ROP of cyclic ester monomers or a cyclic carbonate monomer to occur in a controlled manner, producing diblock copolymers with well-defined structures. Deprotection of the polyether segment resulted in amphiphilic block copolymers with PG as the effective hydrophilic segment and three different aliphatic polyesters or polycarbonate as the hydrophobic segments. The block copolymers’ physicochemical properties were systematically examined, demonstrating their excellent micelle-forming properties in aqueous media.

Two positional isomers (regioisomers) through changing the substituted position of perylenetetracarboxylic diimide and benzanthrone moieties were designed and synthesized. These two regioisomers exhibit totally different aggregation behaviors. The meta (bay)-substituted product shows the aggregation-caused quenching feature as the fluorescence quantum yield in tetrahydrofuran–water mixtures is reduced by 80% with an increase in the water fraction of the medium from 0% to 60%. Interestingly, an aggregation-induced emission is observed for the ortho-substituted product as the fluorescence quantum yield is increased by nearly one order of magnitude with an increase in the water fraction. This fluorescence enhancement effect for the ortho-substituted product is because of the restriction of the intramolecular rotation between the perylene core and the benzanthrone substituent in the aggregated state. The ortho-substituted product also exhibits excellent two-photon absorption performance because the ortho-substitution retains the planarity of the perylene core and improves the intramolecular charge-transfer among the molecules. Moreover, the ortho-substituted product shows two-photon excited aggregation-induced emission, which has potential application in organic two-photon excited fluorescence imaging agents.

The sodium channel NaV1.5, which is encoded by the SCN5A gene, underlies the fast upstroke of cardiac action potential and thus plays a crucial role in cardiac electrophysiology, but the mechanism governing the regulation of NaV1.5 has not been fully elucidated. The newly developed clustered regularly interspaced short palindromic repeats (CRSPR)/Cas9 transcription factors offer a powerful and precise approach for modulating gene expression. We investigated the potential of this new tool for activating stringently silenced SCN5A in human cells. We first selected the most efficient single guide RNA (sgRNA) targeting upstream transcription start sites to induce effective expression of SCN5A mRNA. We observed significant transcriptional activation of endogenous SCN5A, with the highly effective activity of sgRNA targeting the human SCN5A promoter. The optimized dCas-VP64/sgRNA enhanced the endogenous SCN5A transcription up to 20-fold in human HEK293T cells and ultimately generated the NaV1.5 protein. Interestingly, multiple transcript variants of SCN5A were generated by endogenous transcriptional activation. Functionally, the NaV1.5 current produced by endogenous activation exhibited a similar electrophysiological property to that produced by ectopic overexpression of NaV1.5. The results of our study suggest that Cas9-mediated transcriptional activation is a useful tool for modulating gene expression and conducting electrophysiological studies in human cells.

Bone has a remarkable potential for self-healing and repair, yet several injury types are non-healing even after surgical or non-surgical treatment. Regenerative therapies that induce bone repair or improve the rate of recovery are being intensely investigated. Here, we probed the potential of bone marrow stem cells (BMSCs) engineered with chemically modified mRNAs (modRNA) encoding the hBMP-2 and VEGF-A gene to therapeutically heal bone. Induction of osteogenesis from modRNA-treated BMSCs was confirmed by expression profiles of osteogenic related markers and the presence of mineralization deposits. To test for therapeutic efficacy, a collagen scaffold inoculated with modRNA-treated BMSCs was explored in an in vivo skull defect model. We show that hBMP-2 and VEGF-A modRNAs synergistically drive osteogenic and angiogenic programs resulting in superior healing properties. This study exploits chemically modified mRNAs, together with biomaterials, as a potential approach for the clinical treatment of bone injury and defects., Geng et al. evaluate bone marrow stem cell (BMSC)-based system to deliver modified RNAs of BMP-2 and VEGF to enhance bone regeneration. They test its therapeutic efficacy in vivo on a rat skull defect model by inoculating these BMSCs in a collagen scaffold. This construct synergistically drives osteogenic and angiogenic pathways and can be a new approach for clinical treatment of bone injuries and defects.

Alkyloxalyl chlorides, generated from alcohols and oxalyl chlorides, are used as alkoxycarbonyl radicals in the reaction of N-acryloyl benzamides under photocatalysis at room temperature. In this report, we demonstrate that this approach can be compatible with a variety of alcohol-containing pharmaceutically active compounds under visible light irradiation. A variety of isoquinoline-1,3(2H,4H)-diones are prepared in moderate to good yields.

The surge of photocatalytic transformation not only provides unprecedented synthetic methods, but also triggers the enthusiasm for more sustainable photocatalysts. On the other hand, oxygen is an ideal oxidant in terms of atom economy and environmental friendliness. However, the poor reactivity of oxygen at the ground state makes its utilization challenging. Herein, a visible-light-induced oxidative dehydrogenative process is disclosed, which uses an organoboron compound as the photocatalyst and molecular oxygen as the sole oxidant. Via this approach, an array of N-heterocycles have been accessed under metal-free mild conditions, in good to excellent yields.

Very recently, an important two-dimensional material, MoSi2N4, was successfully synthesized. However, pure MoSi2N4 has some inherent shortcomings when used in photocatalytic water splitting to produce hydrogen, especially a low separation rate of photogenerated electron–hole pairs and a poor visible light response. Interestingly, we find that the MoSi2N4 can be used as a good modification material, and it can be coupled with C2N to form an efficient heterojunction photocatalyst. Here, using density functional theory, a type-II heterojunction, C2N/MoSi2N4, is designed and systematically studied. Based on AIMD simulations and phonon dispersion verification, C2N/MoSi2N4 shows sufficient thermodynamic stability. As well as its perfect interface electronic properties, its large interlayer charge transfer and good visible light response lay the foundation for its excellent photocatalytic performance. In addition, the oxidation and reduction potentials of the C2N/MoSi2N4 heterojunction not only can meet the requirements of water splitting well but can also maintain a delicate balance between oxidation and reduction reactions. More importantly, the |ΔGH*| value of the C2N/MoSi2N4 heterojunction is very close to zero, indicating great application potential in the field of photocatalytic water splitting. In brief, our research paves the way for the design of future MoSi2N4-based efficient heterojunction photocatalysts.