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Waste oil, like waste cooking and acidic oil, are two promising carboxylic acids feedstocks that can be converted into hydrocarbons by the pyrolytic method, usually through DCO2 and DCO processes. DFT is employed to investigate the deoxygenation mechanism using octanoic acid as a model compound in this work. Additionally, pyrolysis of the above samples was carried out at atmospheric pressure, temperature below 773.15K. GC-MS, GC and TG-FTIR-MS test measures were used to analyze pyrolytic products. The DFT results reveal that pyrolysis conversion of waste oil was a direct and effective deoxygenation method. And high alkene content endowing pyrolytic oil greatly potential to upgrade for high-quality biofuel production. Finally, pyrolytic oil was upgraded by SAPO-11-Pd/C can increase the components of iso-hydrocarbons, further can faction cut to obtain three biofuel fractions. Fraction blending with fuels could decrease the cold filter plugging point of final fuels, dramatically improving the commercial value of pyrolytic oil and effectively solving the waste oil disposal problem.

An efficient and highly selective decarboxylation catalyst has been developed for the production of diesel-range alkanes from the conversion of higher aliphatic esters under mild reaction conditions. Using methyl stearate as a model substrate, the NiCu/Al2O3 bifunctional catalysts derived from layer double hydroxide (LDHs) precursors showed excellent catalytic performance with 100% conversion and 97.5% selectivity to heptadecane at 260 °C and 3.0 MPa H2. On the other hand, the catalytic performance of NiCu/Al2O3 catalyst was also tested in the conversion of soybean and waste cooking oils under the mild conditions. The results showed that a high yields of diesel-range alkanes (>80 wt%) were obtained from the conversion of soybean oil and waste cooking oil, respectively. Detailed characterization (XRD, H2-TPR, HRTEM, XPS, and NH3-TPD) indicates, after reduction at 500 °C in H2 atmosphere, the NiCu alloy phase is the predominant phase and the Ni, Cu, Al species exhibited homogeneous distribution in the NiCu/Al2O3 catalyst. The remarkable decarboxylation performance mainly results from the synergistic effect between the metal active sites of NiCu alloy and Lewis acid sites of support Al2O3. The Lewis acid sites (Al3+) of support serve as active sites for the activation of carbonyl group of higher aliphatic esters, while H2 dissociation and decarbonylation of intermediate fatty aldehyde are achieved on the NiCu alloy sites. Compared with the monometallic Ni/Al2O3 catalyst (183.8 kJ/mol), the introduction of Cu species in the bimetallic NiCu/Al2O3 catalyst greatly reduced the activation energy (138.1 kJ/mol) of fatty acid ester conversion via promoting the dispersion of Ni species, reducing the dissociation energy of hydrogen on Ni, and increasing the electron density of Ni, which results in high decarboxylation performance of NiCu/Al2O3 under mild reaction conditions.

WDFY4 (WD repeat and FYVE domain-containing 4) is a susceptibility gene involved in several autoimmune diseases and plays an important role in the immune system. However, it is not clear how WDFY4 affects T cells. We have generated a Wdfy4-knockout mouse and found that selective deficiency of Wdfy4 in T cells led to a reduction in the number of CD8+ T cells in the periphery, thus promoting tumor growth when mice were challenged with a transplantable tumor. Moreover, conditional ablation of Wdfy4 in T cells enhanced the apoptosis of CD8+ T cells and increased the intracellular levels of reactive oxygen species accompanied by the upregulation of Nox2. Mechanistically, the decrease in the CD8+ T-cell numbers in Wdfy4-knockout mice was associated with activation of the p53 pathway and inhibition of the extracellular signal-regulated kinase pathway. In addition, WDFY4 participated in cell proliferation. In conclusion, our results elucidate the biological role of WDFY4 in apoptosis and establish a link between WDFY4 and T cells.

The hydrate-based method provides a potential method to remove heavy metal ions. In this work, the phase equilibrium conditions of methane hydrate in chromium hydroxide sulfate solutions and nickel...

Background: Adipogenesis and fibrogenesis can be considered as a competitive process in muscle, which may affect the intramuscular fat deposition. The CCAAT/enhancer-binding protein beta (C/EBPβ) plays an important role in adipogenesis, which is well-characterized in mice, but little known in bovine so far. Results: In this study, real-time qPCR revealed that the level of C/EBPβ was increased during the developmental stages of bovine and adipogenesis process of preadipocytes. Overexpression of C/EBPβ promoted bovine fibroblast proliferation through mitotic clonal expansion (MCE), a necessary process for initiating adipogenesis, by significantly downregulating levels of p21 and p27 (p

Although metal silicates are considered as the promising electrode materials for lithium-ion batteries, metal silicate-based materials suffer from inadequate cycling performance and dimensional unreliability evoked by the large volume changes during cycling, which hinders their practical applications. In principle, the poor electrochemical kinetics during the redox reactions of metal silicates is originated from the instinct structure. Hence, the precise and delicate ability to construct hetero-layers to tailor intercalation reaction remains elusive. Herein, a facile strategy of designing and constructing heterostructure in a cobalt-copper silicates nano-architecture (CNT@CoCuSiOx) with synergistic interaction between cobalt silicate (Co2SiO4) with copper silicate (CuSiO3) on the surface of carbon nanotubes (CNTs). Moreover, Co2SiO4/CuSiO3 heterojunction with unbalanced charge distributions that rooted from in-situ generation on CNTs by a facile one-step hydrothermal process, can efficiently tailor the electrochemical activities of Cu3+/Cu2+ and Co3+/Co2+ redox reactions by elevating transfer of electrons and delivering the heterointerface effect. The tough and conductive nanostructure of CNTs basement facilitate the ion diffusion and improve the rate capability. The heterostructure-incorporated CNT@CoCuSiOx-(2/1) exhibits not only outstanding electrochemical capacity (545 mAh g−1 at 0.1 A g−1), superior ion/electron transmission efficiency but also robust cycling performance (516 mAh g−1 after 900 cycles at 0.5 A g−1 and an excellent capacity retention rate of 95%). Beyond energy storage, our delicate methodology in manipulating the electrochemical behavior of metal silicates opens up a critical insight into rational fabrication of next-generation anodes for lithium-ion battery.

Osteosarcoma (OS) is the most prevalent form of bone cancer. It has a high metastatic potential and progresses rapidly. The molecular mechanisms of OS remain unclear and this study aims to examine the functional role of circPVT1 and miR‐423‐5p in OS. Quantitative RT‐PCR (qRT‐PCR) and western blotting were used to examine levels of miR‐423‐5p, circPVT1, Wnt5a, Ror2, and glycolysis‐related proteins, including HK2, PKM2, GLUT1, and LDHA. Colony formation and transwell assays were used to test the roles of miR‐423‐5p, circPVT1, and Wnt5a/Ror2 in OS cell proliferation, migration, and invasion. Dual luciferase assay and Ago2‐RIP were used to validate the interactions of miR‐423‐5p/Wnt5a, miR‐423‐5p/Ror2, and circPVT1/miR‐423‐5p. Glucose uptake assay and measurement of lactate production were performed to assess the glycolysis process. A nude mouse xenograft model was used to evaluate the effects of sh‐circPVT1 and miR‐423‐5p mimics on tumor growth and metastasis in vivo. miR‐423‐5p was reduced in both OS tissues and OS cell lines, while Wnt5a/Ror2 and circPVT1 were elevated. miR‐423‐5p bound to 3′‐UTR of Wnt5a and Ror2 mRNA, and inhibited glycolysis and OS cell proliferation, migration, and invasion by targeting Wnt5a and Ror2. circPVT1 interacted with miR‐423‐5p and activated Wnt5a/Ror2 signaling by sponging miR‐423‐5p. Knockdown of circPVT1 or overexpression of miR‐423‐5p suppressed OS tumor growth and metastasis in vivo. miR‐423‐5p inhibited OS glycolysis, proliferation, migration, and metastasis by targeting and suppressing Wnt5a/Ror2 signaling pathway, while circPVT1 promoted those processes by acting as a sponge of miR‐423‐5p., miR‐423‐5p was diminished while circPVT1 and Wnt5a/Ror2 were increased in OS. miR‐423‐5p restrained glycolysis, OS cell proliferation, and migration by targeting Wnt5a/Ror2 signaling. circPVT1 bound to miR‐423‐5p and acted as a sponge. circPVT1 promoted glycolysis, OS cell proliferation, and metastasis by binding to miR‐423‐5p. Knockdown of circPVT1 or overexpression of miR‐423‐5p inhibited OS tumor growth and metastasis in vivo.

In the satisfactory design and synthesis of high-performance nonlinear optical (NLO) materials, for meeting the rapidly expanding demands of optoelectronic devices, a deeper understanding of the relationship between the structures and NLO properties has become a key issue. Herein, five novel mislinked expanded hexaphyrins with different connections of pyrrole units are selected to study the relationship between the structures and NLO properties. These five mislinked expanded hexaphyrins are neo-fused, neo-confused hexaphyrins, singly, doubly, and triply N-confused hexaphyrins. From theoretical results, the order of the static first hyperpolarizability (β0) values is found to be: neo-fused hexaphyrin (β0 = 4163 a.u.) < neo-confused hexaphyrin (β0 = 5494 a.u.) < singly N-confused hexaphyrin (β0 = 6510 a.u.) < doubly N-confused hexaphyrin (β0 = 15 130 a.u.) < triply N-confused hexaphyrin (β0 = 26 095 a.u.). Furthermore, β0 values of the doubly and triply N-confused hexaphyrins are improved 2.1 and 3.7 times over that of their usual parent hexaphyrin (β0 = 7120 a.u.), respectively. It is worth noting that increasing mislinked connection numbers and changing mislinked connection ways of the pyrrole units in these mislinked expanded hexaphyrins plays a crucial role in the tune of their second-order NLO responses.

The mechanism of the Cu(I)-catalyzed domino reaction furnishing 1-aryl-1,2,3-triazole assisted by CuI and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is explored with density functional theory (DFT) calculations. The overall mechanism for this domino reaction comprises four consecutive reactions: (i) deprotonation of terminal alkyne by DBU; (ii) cycloaddition of copper acetylide and N3−; (iii) C–N bond coupling of the cuprate–triazole anion and aryl bromide; and (iv) protodecupration. Our theoretical calculations indicate that the Cu-catalyzed azidation of the electron-rich aryl bromides with N3−, which would generate the aryl azide for subsequent Cu(I)-catalyzed alkyne–azide cycloaddition, is not the dominant reaction because of its high free energy barrier. In addition, the cycloaddition process can assist C(aryl)–N bond formation. Activation strain analyses suggest that oxidative addition of aryl bromide onto the cuprate–triazole anion is more facile mainly due to enhanced dCu– orbital interaction. A close attraction between copper and aryl bromide during oxidative addition is critical to the lower barrier.

Metal oxide modified nickel catalysts are highly desirable for the conversion of biomass-derived compounds to biofuels and valuable chemicals because of their low-cost and unique synergistic effects in catalytic reaction. Herein, a series of metal oxide modified nickel catalysts were scrutinized in the hydrodeoxygenation of steatic acid to diesel-range alkanes without any carbon loss as a model reaction. The results showed that MoOx modified Ni/SiO2 catalyst was the most active and selective for the hydrodeoxygenation of stearic acid under mild reaction conditions (260 °C and 3.0 MPa H2 partial pressure). The catalyst with an Ni/Mo molar ratio of 1, and that was reduced at an optimized temperature (500 °C), exhibited the best performance; this catalyst achieved a high selectivity (>95%) to diesel-range alkanes at 100% stearic acid conversion. A high selectivity (>60%) to C18 alkane and a less than 30% selectivity to C17 alkane were observed at 260 °C and 3.0 MPa H2 partial pressure. By selecting an appropriate support, the selectivity to C18 alkane can reach 95% at 100% stearic acid conversion over Ni–Mo/H-ZSM-5 catalysts. In contrast to Ni/SiO2, Ni–Mo/SiO2 was more efficient for C O hydrogenation and less active for C–C bond cleavage, which afforded a higher selectivity to long-chain hydrocarbons without any carbon loss. Detailed characterization, control experiments, and kinetic studies indicate that the high activity and selectivity to the C18 alkane arises from a synergy between Ni and MoOx. The Ni sites at the interface between the Ni metal and MoOx species play a role in the generation of hydride (Hδ−) species from H2 dissociation, and MoOx plays a role in promotion of fatty acids adsorption through adsorbing carboxylic groups at the oxygen vacancy of MoOx. The deep understanding of such synergic catalysis will provide significant clues for the rational design of bimetallic catalysts towards the production of diesel-range alkanes without any carbon loss from the hydrodeoxygenation of fatty acids/esters.

To improve the effective hydrogen-to-carbon ratio (H/Ceff) of a substrate, ex-situ catalytic co-pyrolysis of hydrogen donors and wood over ZSM-5 was conducted. The co-feeding of methanol and wood greatly increased the total aromatic content from 79.00% to 91.79% and the BTX content from 21.62% to 61.63%. To further improve the catalytic properties of ZSM-5, desilication with a Na2CO3 solution was applied. Treatment with the Na2CO3 solution gently removed the Si from ZSM-5, decreased the Bronsted site density, but created more mesopores, improving the accessibility of Bronsted sites in the pores and the diffusion properties of ZSM-5. Desilication of ZSM-5 with a 0.4 mol/L Na2CO3 solution increased the desirable BTX content from 61.63% to 66.35% and reduced the polycyclic aromatic content from 11.92% to 9.72%.

The interest in new emerging pollutants (NEPs) does not only focus on the main compounds but also the degradation or intermediate products. It is important to have an effective primary treatment for the removal/degradation of NEPs from hospital and clinical wastewater to protect the environment. In this study, nifedipine degradation was performed by an electro-oxidation method using titanium-based mixed metal oxide (MMO) electrode. The determination of nifedipine was carried out by differential pulse voltammetry at hanging mercury drop electrode using Britton–Robinson buffer (BRB). The nifedipine oxidation peak was observed at + 0.7 V at a scan rate of 20 mV s−1 in BRB pH 8. Titanium-based electrodes with different metal oxide compositions were assessed as an anode material for nifedipine degradation as follows: TiO2/Ti, IrO2–TiO2/Ti, RuO2–TiO2/Ti, and IrO2–RuO2–TiO2/Ti. The electro-oxidation of nifedipine was monitored using cyclic voltammetric techniques, and the degradation intermediates were confirmed using LC–MS. Approximately 65–83% of nifedipine degradation was achieved using RuO2–TiO2/Ti and IrO2–TiO2/Ti electrodes. Interestingly, RuO2–IrO2–TiO2 electrode showed complete (100%) electro-oxidation of nifedipine at 30 min. Two nifedipine degradation intermediates were identified, namely 5-methoxycarbonyl-2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3-carboxylic acid (compound I) and 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarbaldehyde (compound II) during the electro-oxidation process using RuO2–IrO2–TiO2 electrode. Finally, the degradation pathway of nifedipine by MMO electrode was proposed. This is the first report on the nifedipine degradation using MMO titanium electrode by the electro-oxidation process.

We report herein a catalytic deoxygenation strategy that allows the direct removal of oxygen atoms from triglycerides by lowering the activation energy through the use of metal-based catalysts. Activation energies were investigated by TG analysis, employing fatty acid salts as model compounds. Introducing different metal atoms into carboxyl groups has a substantial effect on the dynamic pyrolytic behavior, and decomposition activation energies varied in the range 80–260 kJ/mol. The catalytic cracking of soybean oil using SnO as a representative catalyst has been investigated in a 5 L reactor, whereby the catalyst lowered the decomposition temperature by approximately 40 °C and gave a conversion rate of approximately 66 wt%. A catalytic conversion mechanism has been proposed based on the results of TG-FTIR, GC, and GC-MS analyses. The pyrolysis products from the deoxygenation process had a high alkene content, endowing them with great potential for conversion into cyclic hydrocarbons used in real aviation fuels. Such conversion through aromatization and hydrogenation over ZSM-5 and Raney Ni catalyst has been investigated. Overall, a new refining process, including conversion of triglycerides to alkanes and terminal alkenes catalyzed by metal compounds, furnishing viable aviation and diesel fuels, is reported.

Synthesizing polymers with tailor-made molecular weight distribution (MWD) is an essential step toward better control and design of functional polymer materials. We propose a novel one-pot reaction...

The stereospecific design of the interface effects can optimize the electron/Li-ion migration kinetics for energy-storage materials. In this study, an electric field was introduced to silicon-based materials (C-SiOx@Si/rGO) through the rational construction of multi-heterostructures. This was achieved by manipulating the physicochemical properties at the atomic level of advanced Li-ion batteries (LIBs). The experimental and density functional theory calculations showed that the unbalanced charge distribution generated a large potential difference, which in turn induced a large-scale electric-field response with a boosted interfacial charge transfer in the composite. The as-prepared C-SiOx@Si/rGO anode showed advanced rate capability (i.e., 1579.0 and 906.5 mAh g-1 at 1000 and 8000 mA g-1, respectively) when the migration paths of the Li-ion/electrons hierarchically optimized the large electric field. Furthermore, the C-SiOx@Si/rGO composite with a high SiOx@Si mass ratio (73.5 wt %) demonstrated a significantly enhanced structural stability with a 40% volume expansion. Additionally, when coupled with the LiNi0.8Co0.1Mn0.1O2 (NCM) cathode, the NCM//C-SiOx@Si/rGO full cell delivers superior Li-ion storage properties with high reversible capacities of 157.6 and 101.4 mAh g-1 at 500 and 4000 mA g-1, respectively. Therefore, the electric-field introduction using optimized electrochemical reaction kinetics can assist in the construction of other high-performance LIB materials.

Osteosarcoma (OS) is one of the most common malignant tumors in young adults and has a high distant metastasis rate. The p53 protein, a potent prognostic biomarker for patients with OS, is altered in ~50% of OS cases. p53 was reported to exert its effects through regulating the transcription of microRNAs (miRNAs/miRs) and other genes. In the present study, the expression of miR‑181b, a critical OS oncomiR, was shown to be significantly upregulated whereas p53 expression was downregulated within OS tissues and cells; in tissue samples, miR‑181b and p53 were negatively correlated. p53 inhibited the transcription of miR‑181b via targeting its promoter region, whereas miR‑181b bound the TP53 3'‑untranslated region (UTR) to inhibit p53 expression. miR‑181b silencing considerably increased p53, p21, and epithelial‑Cadherin protein levels but decreased Cyclin D1 protein levels in OS cells. In addition, miR‑181b inhibition reduced OS cell proliferation and invasion. In contrast, p53 knockdown had the opposite effects on these proteins and OS cell proliferation and invasion. Above all, p53 knockdown significantly attenuated the effects of miR‑181b inhibition. Moreover, OS cell xenograft assays further confirmed the roles of the miR‑181b/p53 axis in OS growth. In conclusion, miR‑181b and p53 are negatively regulated by one another and therefore form a negative feedback axis that regulates the proliferation and invasion abilities of OS cells. Targeting miR‑181b to inhibit its abnormal upregulation might be a potent strategy for OS treatment.

Surface-enhanced Raman scattering (SERS) has become a mature spectroscopic technique with the fast development in the past four decades, and its detection applications in the fields of chemistry, materials science, biochemistry and life sciences are rapidly expanding. In particular, advances in the design and construction of SERS-based biosensors have delivered tremendous development in the biological and biomedical sensing applications. Electromagnetic enhancement contributes dominantly to SERS enhancement, and the hotspot structures are crucial to sensitive and reproducible detection performance. SERS-based biosensors can be produced by direct and indirect techniques according to the sensing needs. In this mini-review, the enhancing mechanism and SERS structures are briefly described and the various common fabrication techniques are discussed. Recent state-of-the-art applications of SERS-based biosensors such as detection of ex vivo biofluids and biomolecules such as proteins, DNAs and microRNAs, as well as monitoring of cellular properties including pH, temperature and ion concentrations, are reviewed.

Accurate and effective sensing of H2S is one of the most complex and challenging tasks. Recent studies have demonstrated that the development of an Sb-doped SnO2 nanoribbon sensor can enhance the detection limit of H2S. To clarify the enhancement mechanism, various factors that regulate the sensing processes, such as the Sb-doped sites, surface oxygen defects and possible pre-adsorbed oxygen species, are considered in this study. Theoretical calculations reveal a thorough and extensive understanding of the gas-sensing mechanisms. Once the H2S gas interacted with the Sb-doped SnO2(110) surface, the molecule released electrons back to the surface, together with a decreased resistance level and strengthened detection signal. In addition, the dissociative adsorption of the O2 molecule also plays a significant role in the sensing processes. It is expected that the present work can provide effective guidance for improving the sensitivity of metal oxide surfaces and shed new light on the development of next generation gas-sensing materials.

MicroRNAs (miRs) are a class of small non-coding RNAs, and negatively regulate gene expression through directly binding to the 3'-untranslational region (UTR) of their target mRNA, which further leads to translational repression or mRNA degradation. Recently, various miRs have been implicated in the development and progression of osteosarcoma (OS). However, the underlying mechanism has not been fully uncovered. Our study aimed to reveal the exact role of miR-205 in OS, as well as the regulatory mechanism. In this study, we found that the expression of miR-205 was significantly reduced in a total of 34 OS tissue specimens compared to their matched adjacent normal tissues. Besides, it was also remarkably downregulated in OS cell lines (Saos-2, U2OS, SW1353, and MG63) compared to human osteoblast hFOB1.19 cells. Overexpression of miR-205 caused a significant decrease in the proliferation, migration and invasion of MG63 and U2OS cells. Runt-related transcription factor 2 (RUNX2) was further identified as a target gene of miR-205. Moreover, the mRNA and protein expression of RUNX2 was reduced after miR-205 overexpression, but increased after knockdown of miR-205 in MG63 and U2OS cells. Furthermore, overexpression of RUNX2 effectively reversed the suppressive effect of miR-205 on the proliferation, migration, and invasion of MG63 and U2OS cells. The RUNX2 level was significantly increased in OS tissues compared to their matched adjacent normal tissues, as well as in OS cell lines compared to hFOB1.19 cells. In addition, the RUNX2 level was reversely correlated with the miR-205 level in OS tissues. Taken together, our data demonstrate that miR-205 acts as a tumor suppressor in OS via directly targeting RUNX2. Therefore, we suggest that the miR-205/RUNX2 axis may serve as a potential target for the treatment of OS.

The nucleotide binding protein 35 (Nbp35)/cytosolic Fe-S cluster deficient 1 (Cfd1)/alternative pyrimidine biosynthetic protein C (ApbC) protein homologs have been identified in all three domains of life. In eukaryotes, the Nbp35/Cfd1 heterocomplex is an essential Fe-S cluster assembly scaffold required for the maturation of Fe-S proteins in the cytosol and nucleus, whereas the bacterial ApbC is an Fe-S cluster transfer protein only involved in the maturation of a specific target protein. Here, we show that the Nbp35/ApbC homolog MMP0704 purified from its native archaeal host Methanococcus maripaludis contains a [4Fe-4S] cluster that can be transferred to a [4Fe-4S] apoprotein. Deletion of mmp0704 from M. maripaludis does not cause growth deficiency under our tested conditions. Our data indicate that Nbp35/ApbC is a nonessential [4Fe-4S] cluster transfer protein in methanogenic archaea.

A mild methanolysis pretreatment strategy was developed with a recyclable acid, p-TsOH, as the catalyst for the fractionation of lignocellulosic biomass toward its main components. Bamboo fiber was...

In this study, flavonoid myricetin-mediated gold nanoparticles (Myr-AuNPs) were synthesized and their molecular interactions were evaluated through a combined experimental and theoretical study. The physicochemical properties of the synthesized Myr-AuNPs were characterized using TEM, FT-IR, and XRD analysis. The average particle size of the Myr-AuNPs was found to be 6 nm with spherical in shape. FT-IR results indicated that the hydroxyl groups of myricetin interacts with Au 3+ ions during the nanoparticles formation. Consequently, density functional theory (DFT) was used to evaluate the possible molecular interactions of myricetin hydroxyl groups with Au 3+ ions. Interestingly, the DFT results confirmed that the 5′-hydroxyl group of ring B in myricetin was more suitable and highly stable to interact with Au 3+ ions during the nanoparticles formation in aqueous medium. Further, this study emphasized that the synthesized Myr-AuNPs exhibits excellent pH, temperature, and storage stability. In addition to this, biocompatibility study recommended that Myr-AuNPs is safe for therapeutic applications. This is the first detailed report on the molecular interaction between the hydroxyl groups of myricetin and Au 3+ ions during the nanoparticle formation.

Genome-wide association study of systemic lupus erythematosus (SLE) revealed tumor necrosis factor alpha-induced protein 3 (TNFAIP3, A20) as a susceptibility gene. Here, we report a de novo mutation in TNFAIP3 in a Chinese patient with neuropsychiatric SLE (NPSLE).Whole exome sequencing was performed for the patient and healthy members from the family. Suspected pathogenic variants were further analyzed and co-segregation was confirmed by Sanger sequencing. Real-time PCR and western blot were performed with peripheral blood mononuclear cells (PBMCs) and patient-derived T cells. Transfected HEK293T cells, human umbilical vein endothelial cells, normal human astrocytes, and microglia were used for in vitro studies.A de novo frameshift mutation in TNFAIP3 was found in the NPSLE patient. Western blot analysis showed activated NF-κB and mitogen-activated protein kinase pathways. Real-time PCR revealed elevated expression of pro-inflammatory cytokines. On immunoprecipitation assay, the mutant A20 altered the K63-linked ubiquitin level of TRAF6 via its ubiquitin-editing function.The mutant A20 may play a role in weakening the tight junction of the blood-brain barrier to cause neurologic symptoms. We report a rare variant of TNFAIP3 in a patient with NPSLE and reveal its autoimmune disease-causing mechanism in both peripheral tissues and the central nervous system.

Removal of oxygen atoms from triglycerides is the most important step in their conversion into hydrocarbons. Basic catalysts have proven to be highly efficient in deoxygenation, whereby the oxygen atoms are removed in the form of CO and CO2, yielding pyrolytic oil with acid number below 10 mg KOH⋅g−1. We have now investigated the deoxygenation abilities of composite basic catalysts during the thermochemical conversion process. The dynamics of the catalytic cracking reaction using metal oxides, such as calcium oxide, in the presence of sodium carbonate, has been tested. According to thermogravimetric analysis (TGA) data, the activation energy for catalytic cracking was influenced by cations. By using calcium oxide as a catalyst, the activation energy was reduced from 260 kJ/mol to 185 kJ/mol, leading to a reduction in the reaction temperature of approximately 20–40 °C. The yield of the cracked liquid fraction was of the order of 66–70%, more than 90% of which could be recovered as liquid hydrocarbons. The results presented herein indicate an alternative reaction pathway, allowing thermochemical conversion to be conducted at a lower operational temperature, which would be beneficial for industrial production with lower energy consumption.

The in situ polymerization of aniline as a nitrogen source was adopted to prepare nitrogen-doped mesoporous carbon (NMC), which further supported the molybdenum carbide catalyst for the hydrotreatment of fatty acids. The nitrogen doping drastically enhanced the catalytic performance of Mo2C/N1.0MC-700 with 92.7% conversion and 86.7% selectivity, which are much higher than the values of Mo2C/MC (84.8% and 70.1%, respectively). The kinetic study revealed that the apparent activation energy was reduced greatly after nitrogen doping. In addition, the nitrogen-doped catalyst showed decent stability, and the conversion and selectivity over Mo2C/N1.0MC-700 decreased by 4.4% and 6.9% respectively, after recycling three times. The deactivation mainly resulted from the coke deposition on the surface of catalyst. The high catalytic activity and stability were ascribed to the formation of pyridinic N and pyrrolic N in NMC, which resulted in the high dispersion of Mo, a decrease in the particle size as well as strong interactions between support and active sites. The hydrotreatment conditions of oleic acid were studied, and the optimal reaction conditions were as follows: reaction temperature, 350 °C; initial H2 pressure, 3.0 MPa; n-hexane as solvent. Moreover, the results indicated that a substrate with a saturated carbon double bond and ester group was more easily converted into hydrocarbons.

Exploring a new type of nonlinear optical switch molecule with excess electron character is extremely important for promoting the application of excess electron compounds in the nonlinear optical (NLO) field. Here, we report external electric field (EEF) induced second-order NLO switch molecules of inorganic alkaline–earth alkalides, M(NH3)6Na2 (M = Mg or Ca). The centrosymmetric structure of M(NH3)6Na2 is destroyed in the presence of an EEF, and then a long-range charge transfer process occurs. It has been found that excess electrons are gradually transferred from one Na atom to the other Na atom through the inorganic metal cluster M(NH3)6. Finally, the excess electrons are completely located on one of the two Na atoms. In particular, the electronic contribution of the static first hyperpolarizability (βe0) for M(NH3)6Na2 exhibits a large significant difference when the EEF is switched on. The βe0 value of M(NH3)6Na2 is 0 when EEF = 0, while the peak βe0 values are 5.95 × 106 (a.u.) for Mg(NH3)6Na2 (EEF = 58 × 10−4 (a.u.)) and 1.83 × 107 (a.u.) for Ca(NH3)6Na2 (EEF = 53 × 10−4 (a.u.)). This work demonstrates that the compounds M(NH3)6Na2 can serve as potential candidates for NLO switches.

A pair of chiral aggregation-induced emission (AIE) enantiomers and their racemate exhibit not only distinctively different circularly polarized luminescence behaviors, but also completely opposite mechanoluminescence (ML) activities. The data from single crystal analysis identifies that the bright ML of the AIE enantiomers is probably activated by their molecular chirality, which enables unique chiral crystal structures with a polar space group and compact molecular packing. These experimental findings provide a direction for harvesting prominent ML from AIE luminogens. Concurrently, high contrast mechanochromism with larger ΔλPL,max and ΔΦF,s values by up to 140 nm and 0.61 respectively have been achieved from this AIE system, which represents the state-of-the-art mechanochromic performance for ML emitters. Moreover, force-induced white-light emission and thermally activated delayed fluorescence have also been observed. The results of theoretical calculations suggest that the destruction of intermolecular interactions and conversion of molecular conformation account for the significant multiple-variations in emission properties triggered by a single mechanical stimulus.

Non-small cell lung cancer (NSCLC) patients with epidermal growth factor receptor (EGFR)-sensitive mutations benefit from epidermal growth factor receptor tyrosine kinase inhibitors (EGFR- TKIs). However, drug resistance is a major cause of therapeutic failure. This study examined whether saikosaponin-d (SSD) enhances the anti-tumor effect of gefitinib in NSCLC cells. Cell Counting Kit-8 (CCK-8) was used to determine cell viability. Cell apoptosis was examined by flow cytometry. Signal transducer and activator of transcription (STAT3), phosphor-STAT3 (P-STAT3), and B-cell lymphoma 2 (Bcl-2) were detected by Western blot. An HCC827/GR tumor model was established to observe the effect of combination therapy in vivo. The combination of SSD with gefitinib had an enhanced inhibitory effect by reducing cell viability and inducing cells apoptosis in NSCLC cells. Furthermore, SSD decreased and increased the expression of P-STAT3 and Bcl-2, respectively. Down-regulated STAT3 promoted the sensitivity of lung cancer cells to gefitinib. The results of animal experiments also showed that SSD enhanced the anti-tumor effect of gefitinib. These results indicated that the combination of SSD with gefitinib had an increased antitumor effect in NSCLC cells and that the molecular mechanisms were associated with the inhibition of STAT3/Bcl-2 signaling pathway. Our findings suggest a promising approach for the treatment of NSCLC patients with EGFR-TKI resistance.

Understanding the atmospheric fate of hydrofluoroolefins (HFOs) is of great significance to assess their potential risk to the environment. As an important type of HFO, the comprehensive transformation mechanism and kinetics of Z(E)-CF3CH[double bond, length as m-dash]CHF initiated by OH radicals were investigated by performing quantum chemical calculations at the CCSD(T)/aug-cc-pVTZ//MP2/cc-pVDZ level. The results show that the OH-addition pathways are the most favorable for the title reaction. The rate constants are obtained by transition state theory with Wigner tunneling correction (TST/W). The calculated total rate constants are in good agreement with the experimental data. At 298 K, the computed rate constant and lifetime of Z(E)-CF3CH[double bond, length as m-dash]CHF are 9.66 × 10-13 (4.02 × 10-13) cm3 molecule-1 s-1 and 12.3 (29.7) days, respectively, which demonstrates that Z(E)-CF3CH[double bond, length as m-dash]CHF is atmospherically persistent.

This study presents an efficient methodology to remove hemicellulose and lignin from lignocellulosic biomass by a three-step process to obtain C5 sugars, phenolics and high purity cellulose. The first step, a CO2-assisted hydrolysis pretreatment was conducted for the selective extraction of the hemicellulose fraction. The process effectively extracted hemicellulose at 180 °C with CO2 at 20 bar initial pressure for 10 min, during which a variety of monosaccharides and other intermediates were obtained. The second step, the catalytic hydrogenolysis of the pretreated feedstock, was performed in a cosolvent isopropyl alcohol–water system with Raney Ni as the catalyst, which can catalyze the depolymerization of lignin components for phenolic products. A variety of phenolic components with lower molecular weights were detected via GC–MS and HSQC. Further treatment with alkaline hydrogen peroxide was used to extract the remaining small amount of lignin and hemicellulose fractions in biomass and to obtain high pu...

An integrated multichannel all-fiber optofluidic biosensing platform (M-AOB) has been developed for a sensitive, rapid, and simultaneous detection of up to three trace analytes. The M-AOB platform employs a 1 × 3 fiber optical switch and three single-multimode fiber optic couplers for the transmission of excitation light and fluorescence and one photodiode detector for the simultaneous detection of fluorescence signals of multiple channels based on the time-resolve effect of the fiber optical switch. This design greatly simplified the entire system structure and improved light transmission efficiency. Through an indirect competitive immunoassay mechanism, we detected two highly regulated small molecules, namely, atrazine and 2,4-D, to demonstrate the value of M-AOB to the simultaneous measurement of trace analytes in water samples. The limits of detection of 0.03 μg/L and 0.04 μg/L were obtained for atrazine and 2,4-D, respectively, and were highly comparable with those of other analytical techniques. The high sensitivity of M-AOB benefited from the high light collective efficiency and low light loss of the excellent all-fiber optical structures and from the advantages of the evanescent wave technique. The regeneration of the biosensor surface, 200 assay cycles, were performed without any significant activity loss. Each assay cycle was less than 15 min. The immunoassay performance of the M-AOB, evaluated in several spiked water samples, showed good recovery, accuracy, and precision, indicating that the M-AOB was less susceptible to matrix effects of water samples. All these results illustrated that M-AOB can be readily extended toward the simultaneous and rapid detection of other trace small molecules using different biosensors modified by other analyte conjugates and their respective fluorescence-labeled antibodies.

The COVID-19 pandemic brings unprecedented crisis for public health and economics in the world. Detecting specific antibodies to SARS-CoV-2 is a powerful supplement for the diagnosis of COVID-19 and is important for epidemiological studies and vaccine validations. Herein, a rapid and quantitative detection method of anti-SARS-CoV-2 IgG antibody was built based on the optofluidic point-of-care testing fluorescence biosensor. Without complicated steps needed, the portable system is suitable for on-site sensitive determination of anti-SARS-CoV-2 IgG antibody in serum. Under the optimal conditions, the whole detection procedure is about 25 min with a detection limit of 12.5 ng/mL that can well meet the diagnostic requirements. The method was not obviously affected by IgM and serum matrix and demonstrated to have good stability and reliability in real sample analysis. Compared to ELISA test results, the proposed method exhibits several advantages including wider measurement range and easier operation. The method provides a universal platform for rapid and quantitative analysis of other related biomarkers, which is of significance for the prevention and control of COVID-19 pandemic., Graphical abstract Image 1

Artemisia lavandulaefolia, a traditional herbal medicine, has been utilized as anti-inflammatory and analgesia agent in clinic. Bioassay-guided fractionation resulted in a fraction (ALDF) with anti-inflammatory effect obtained from A. lavandulaefolia. Its main constituents were analyzed and identified by UPLC-ESI-Q-TOF-MS technology. ALDF showed the strong inhibitory activity on the nitrogen oxide (NO) production in LPS-induced RAW 264.7 macrophages with an IC50 value of 1.64±0.41 μg/mL. Further results displayed that ALDF also significantly suppressed the secretion of key pro-inflammatory mediators, including tumor necrosis factor-α (TNF-α), prostaglandin E2 (PGE2 ) and interleukin-1β (IL-1β), and the increase of the inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) protein expression induced by LPS stimulation. Mechanism study indicated that ALDF was able to block NF-κB signaling pathway through inhibiting IκB and p65 phosphorylation, as well as NF-κB p65 nuclear translocation. Furthermore, in vivo results in mice revealed that treatments with ALDF evoked significant inhibition on ear edema induced by xylene and on the writhing responses induced by acetic acid. These results suggest that ALDF holds great potential in the prevention and treatment of inflammatory disorders.

Alginate oligosaccharides produced by enzymatic degradation show versatile physiological functions and biological activities. In this study, a new alginate lyase encoding gene alyS02 from Flavobacterium sp. S02 was recombinantly expressed at a high level in Yarrowia lipolytica, with the highest extracellular activity in the supernatant reaching 36.8 &plusmn, 2.1 U/mL. AlyS02 was classified in the polysaccharide lyase (PL) family 7. The optimal reaction temperature and pH of this enzyme were 30 &deg, C and 7.6, respectively, indicating that AlyS02 is a cold-adapted enzyme. Interestingly, AlyS02 contained more than 90% enzyme activity at 25 &deg, C, higher than other cold-adapted enzymes. Moreover, AlyS02 is a bifunctional alginate lyase that degrades both polyG and polyM, producing di- and trisaccharides from alginate. These findings suggest that AlyS02 would be a potent tool for the industrial applications.

Six new eudesmane-type sesquiterpene derivatives, artemargyinins A-F were isolated from the leaves of Artemisia argyi. Their structures were elucidated based on the extensive analysis of spectroscopic data. Artemargyinins A-F feature a lactone ring-opening eudesmane-type sesquiterpene with an isoprenoid group at C(8). All compounds were tested for their inhibitory effects on lipopolysaccharide-induced nitric oxide (NO) production in RAW264.7 macrophages. Artemargyinins A-F showed more potent NO production inhibitory activity with IC50 values ranging from 7.66±0.53 to 61.19±2.54 μM than the positive control quercetin (IC50 =74.34±1.39 μM). Among them, artemargyinins C and D exhibited strong inhibitory activity with IC50 values of 8.08±0.21 and 7.66±0.53 μM, respectively.

Endochondral ossification is the major process of long bone formation, and chondrogenesis is the final step of this process. Several studies have indicated that bone morphogenetic proteins (BMPs) are required for chondrogenesis and regulate multiple growth plate features. Abnormal BMP pathways lead to growth plate defects, resulting in osteochondrodysplasia. The SPARC-related modular calcium binding 2 (SMOC2) gene encodes an extracellular protein that is considered to be an antagonist of BMP signaling. In this study, we generated a mouse model by knocking-in the SMOC2 mutation (c.1076 T > G), which showed short-limbed dwarfism, reduced, disorganized, and hypocellular proliferative zones and expanded hypertrophic zones in tibial growth plates. To determine the underlying pathophysiological mechanism of SMOC2 mutation, we used knock-in mice to investigate the interaction between SMOC2 and the BMP–SMAD1/5/9 signaling pathway in vivo and in vitro. Eventually, we found that mutant SMOC2 could not bind to COL9A1 and HSPG. Furthermore, mutant SMOC2 inhibited BMP signaling by competitively binding to BMPR1B, which lead to defects in growth plates and short-limbed dwarfism in knock-in mice.

Triglycerides are a promising biomass feedstock that can be used for production of organic hydrocarbons including long-chain olefins and paraffin. The challenge for this production process lies on the lack of a clear mechanism of the conversion process. In this work, the conversion mechanism from triglycerides to olefins and paraffin using alkali metal catalysts was investigated adopting both computational calculations using density functional theory and experimental studies. The bond dissociation energies of the main bonds were calculated, especially for the α carbon‑carbon bond, which leads to effective removal of carboxyl groups during the thermochemical conversion process. The dynamic behavior of triglycerides catalyzed by alkali metal catalysts was also investigated using thermogravimetric analysis, which found that Li ion has lowest activation energy below 200 kJ/mol when compared with the other alkali ions studied. The catalytic conversion mechanism was proposed in this work based on the results obtained from TG-IR, GC, GC–MS and XRD analyses. The O atoms are removed in the form of CO, CO2 and H2O, product M + O and M+, which generates M2CO3. A more detailed mechanism has been proposed in this paper, which has significance toward guiding the cleavage of triglycerides to produce long‑carbon-chain terminal olefins and normal paraffin.

Previously study showed that SMOC, a matricellular protein, inhibits BMP signaling downstream of its receptor via activation of mitogen-activated protein kinase (MAPK) signaling. In our study, exome sequencing revealed a missense mutation (c.1076T>G, p.Leu359Arg) in EC domain of SMOC2 in a Chinese family with multiple epiphyseal disease (MED). The pathogenicity of this SMOC2 variant was verified by Smoc2L359R/L359R knock-in mice. Of note, decreasing phosphorylation of SMAD1/5/9 was detected in growth plates and primary chondrocytes from Smoc2L359R/L359R mice. Furthermore, binding affinity of mutant SMOC2 with collagen IX and HSPG in the extracellular matrix of cartilage were reduced while binding affinity with BMPRIB was intact. In addition, in contrast to previously results, that SMOC2 cannot antagonize BMP activity in the presence of a constitutively activated BMP receptor. These results support that SMOC2 with p.Leu359Arg variant act as an antagonist of canonical BMP pathway by competitively binding with BMP receptors.

Materials with outstanding nonlinear optical (NLO) response exhibit excellent prospects in electrooptic devices. Thus, it is essential to find a high-performance NLO material to meet the growing demand for high-speed data transmission. In this study, theoretical investigations on the second order NLO properties of the novel expanded mislinked thia-norhexaphyrin, sulfur-free pentaphyrin, and their substituted derivatives were performed using density functional theory. Theoretical calculations display that the approximate planar structures of sulfur-free pentaphyrin embedded with two five-membered rings exhibits a remarkable NLO response and holds large dipolar contribution (Φ

A compact evanescent wave detection platform (EWDP) is developed for the detection of fluorescence gold nanoclusters. The EWDP employs a simple optical system and a Si-based photodetector SOP-1000 assembly to improve the optical efficiency and detection sensitivity. A microfluidic sample cell is also used to decrease the amount of analyte to 200 μL (The volume of sample cell is really about 30 μL). On this basis, we design a strategy for detecting dopamine (DA) based on the photoinduced electron transfer (PET) quenching mechanism. By introduction of tyrosinase (TYR) during the detection, the testing time is shortened to 1 min. The fluorescence emission signal decreased dramatically and the quenching ratio (F0–F)/F0 is linearly related to the concentration of DA in the range of 0.03–60 μM with a detection limit of 0.03 μM. Additionally, this detection platform has potential applications for DA fast detection in the microsamples.

In this work, we investigated the nonlinear optical (NLO) properties of excess electron electride molecules of M[Cu(Ag)@(NH3 )n ](M = Be, Mg and Ca; n = 1-3) using density functional theory (DFT). This electride molecules consist of an alkaline-earth (Be, Mg and Ca) together with transition metal (Cu and Ag) doped in NH3 cluster. The natural population analysis of charge and their highest occupied molecular orbital suggests that the M[Cu(Ag)@(NH3 )n ] compound has excess electron like alkaline-earth metal form double cage electrides molecules, which exhibit a large static first hyperpolarizability ( β0e ) (electron contribution part) and one of which owns a peak value of β0e 216,938 (a.u.) for Be[Ag@(NH3 )2 ] and vibrational harmonic first hyperpolarizability ( βzzznr ) (nuclear contribution part) values and the ratio of βzzznr / βzzze , namely, η values from 0.02 for Be[Ag@(NH3 )] to 0.757 for Mg[Ag@(NH3 )3 ]. The electron density contribution in different regions on βzzze values mainly come from alkaline-earth and transition metal atoms by first hyperpolarizability density analysis, and also explains the reason why βzzze values are positive and negative. Moreover, the frequency-dependent values β(-2ω,ω,ω) are also estimated to make a comparison with experimental measures. © 2018 Wiley Periodicals, Inc.

In this work, seven complexes based on graphitic carbon nitride (g-C3N4) were systematically investigated. Density functional theory calculations demonstrated that the energy gap between the highes...

In this study, polyvinylidene fluoride (PVDF) nanocomposite membranes with different fillers were fabricated using electrospinning technique. The physico-chemical properties of electrospun membranes such as PVDF (NF1), PVDF-polyvinyl pyrrolidone (PVP) (NF2), PVDF-activated carbon (AC) (NF3), PVDF-MnO2 (NF4), PVDF-PVP-AC (NF5), and PVDF-PVP-MnO2 (NF6) were assessed using field emission scanning electron microscopy-energy dispersive X-ray spectroscopy (FESEM-EDX), tensile tester, contact angle measurement, zeta potential, and attenuated total reflection-fourier transform infrared spectroscopy (ATR-FTIR). The Bisphenol A (BPA) removal efficacy of the membranes was assessed using flat sheet membrane filtration unit. The single layer filtration for BPA removal at 30 min was found to be 27%, 100%, 24%, 54%, 100%, and 100% for NF1, NF2, NF3, NF4, NF5, and NF6, respectively. In particular, NF2 and NF6 membranes exhibited maximum removal of BPA with good retention potential for the entire sampling time. In recyclic application, the regenerated NF6 membrane showed better reusability for BPA removal. During the removal process, BPA attached with PVP and MnO2 present in NF6 membrane through hydrogen bonding interaction. The hydrogen bonding length and energies E H were calculated by density functional theory (DFT). Finally, this study suggests that PVP and MnO2 incorporated PVDF membrane might be an effective and reusable membrane for BPA removal from drinking water sources.