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Traditional chemotherapy exhibits a certain therapeutic effect toward malignant cancer, but easily induce tumor multidrug resistance (MDR), thereby resulting in the progress of tumor recurrence or metastasis. In this work, we deigned ternary hybrid nanodrugs (PEI/DOX@CXB-NPs) to simultaneously combat against tumor MDR and metastasis. In vitro results demonstrate this hybrid nanodrugs could efficiently increase cellular uptake at pH 6.8 by the charge reversal, break lysosomal sequestration by the proton sponge effect and trigger drugs release by intracellular GSH, eventually leading to higher drugs accumulation and cell-killing in drug-sensitive/resistant cells. In vivo evaluation revealed that this nanodrugs could significantly inhibit MDR tumor growth and simultaneously prevent A549 tumor liver/lung metastasis owing to the specifically drugs accumulation. Mechanism studies further verified that hybrid nanodrugs were capable of down-regulating the expression of MDR or metastasis-associated proteins, lead to the enhanced anti-MDR and anti-metastasis effect. As a result, the multiple combination strategy provided an option for effective cancer treatment, which could be potentially extended to other therapeutic agents or further use in clinical test., Graphical abstract Ternary hybrid nanodrugs were fabricated and exhibited the stepwise response to pH/GSH stimuli, thereby improving in vivo targeting delivery and high-effectively treating MDR and metastatic tumor.Image 1

Tumor microenvironment (TME) is known to play a critical role in cancer progression and contributes to treatment failure or success. Herein, a versatile nanoplatform [HAFOE-Ce6/Pt-NPs(O2)] with cis...

Nanoscale hydroxyapatite (nHA) is considered as a promising drug carrier or therapeutic agent against malignant tumors. But the strong agglomeration tendency and lack of active groups seriously hamper their usage in vivo. To address these issues, we fabricated an organic-inorganic hybrid nanosystem composed of poly(acrylic acid) (PAA), nHA, and indocyanine green (ICG), and further modified with glucose to give a targeting nanosystem (GA@HAP/ICG-NPs). These hybrid nanoparticles (∼90 nm) showed excellent storage and physiological stability assisted by PAA and had a sustained drug release in an acidic tumor environment. In vitro cell experiments confirmed that glucose-attached particles significantly promoted cellular uptake and increased intracellular ICG and Ca2+ concentrations by glucose transporter 1 (GLUT1)-mediated endocytosis. Subsequently, the excessive Ca2+ induced cell or organelle damage and ICG triggered photothermal and photodynamic effects (PTT/PDT) under laser irradiation, resulting in enhanced cell toxicity and apoptosis. In vivo tests revealed that the hybrid nanosystem possessed good hemocompatibility and biosafety, facilitating in vivo circulation and usage. NIR imaging further showed that tumor tissues had more drug accumulation, resulting in the highest tumor growth inhibition (87.89%). Overall, the glucose-targeted hybrid nanosystem was an effective platform for collaborative therapy and expected to be further used in clinical trials.

International audience; The influences of the electrode/ionic liquids interfaces on the charge transfer kinetics are addressed with the example of the oxidation of chromocene at a single crystal Ag(111) electrode. We considered three different imidazolium-based room temperature ionic liquids (RTILs) with alkyl chains of different lengths but with a common anion. The standard charge transfer rate constants k° are extracted from cyclic voltammograms (CVs) by analyzing the peak potential variations with the scan rate and/or performing semi-integral electroanalysis with a careful treatment of the ohmic drop. Linear variations between the logarithms of k° and the longitudinal relaxation times τL or the dynamic viscosity η of the ionic liquids are obtained. However, the amplitude of the decrease is much larger than it could be expected from the sole bulk properties of the ionic liquid indicating a strong effect of the interface on the kinetics. These observations agree with a well-organized electrode/RTIL interface that behaves as a sort of self-assembled monolayer that controls the charge transfer kinetics with an exponential tunneling coefficient β of 5.51 nm−1.

Background Purple corn (Zea mays L.) is one of the main economic crops in China and has been used in the treatment of cystitis, urinary infections and obesity. However, purple corncobs, the by-product remaining after processing and having an intense purple-black color, are normally disposed of as waste or used as animal feed. Therefore, to further expand the medicinal value of purple corncob, its content was analyzed and, after purification, the effect and mechanism of purified purple corncob anthocyanins (PPCCA) on CCl4 -induced chronic liver injury in mice were investigated. Results It was observed that the total anthocyanin content (TAC) from PPCCA (317.51 ± 9.30 mg cyanidin 3-O-glucoside (C-3-G) g-1 dry weight) was significantly higher than that from the purified purple corn seed anthocyanin (266.73 ± 3.67 mg C-3-G g-1 dry weight), of which C-3-G accounted for 90.6% and 90.4% of the TAC, respectively. Furthermore, compared with the CCl4 group, PPCCA treatment significantly reduced liver index, serum total bilirubin, alanine transaminase, aspartate transaminase and liver malondialdehyde levels, but increased liver superoxide dismutase activity. The pathological changes were also improved, such as more regular arrangement of hepatocytes, less swelling, and fewer vacuoles and apoptotic cells. Additionally, mechanistic studies showed that PPCCA downregulated the expression of Caspase-3, Bax and cytochrome P450 2E1 proteins in the liver and upregulated the expression of Bcl-2. Conclusion These results demonstrated that PPCCA could ameliorate CCl4 -induced chronic liver injury by regulating oxidative stress and hepatocyte apoptosis pathways. © 2021 Society of Chemical Industry.

For a period of time, the O2 cathode has been the focus of research, while the study of lithium anodes and their interactions is quite rare in rechargeable lithium–oxygen (Li–O2) batteries. Actually, the unstable interface between a Li metal anode and the electrolyte in the presence of O2 will eventually lead to battery failure. It was proposed that lithium nitrate (LiNO3), a well-known stabilizing additive being able to form a passivation solid–electrolyte interphase (SEI) on the Li metal surface, could be introduced into the electrolyte of Li–O2 batteries to improve their performance. Nevertheless, the effective utilization of LiNO3 in this system has heretofore been limited due to the dissolution of NO2− species, one of the components of the SEI, as well as O2 corrosion issues on the Li metal side, thus resulting in unstable cycling of Li–O2 batteries. Herein, by combining the electrochemical polishing technology with the LiNO3 reduction chemistry, we construct on a Li metal surface a stable molecularly smooth SEI which possesses a unique multi-layered structure that encapsulates the soluble NO2− species inside the inner layer. Such an SEI film can not only avoid the negative effects caused by the dissolution of NO2−, but also effectively suppress the dendrite growth on and the O2 permeation to the Li surface. Consequently, the cycle lives of O2-saturated symmetric Li cells and Li–O2 batteries are both improved substantially. Our work offers an effective strategy to protect Li metal anodes in Li–O2 batteries, and meantime, provides a novel insight into the rational utilization of electrolyte additives.

An efficient eco-friendly procedure for the synthesis of spiro[indoline-3,11'-pyrazolo[3,4-a]acridine]-2,10'(1'H)-dione derivatives has been developed through a one-pot three-component condensation...

It has been decades since foams were adapted in further developing water-flooded oilfields. Foam stability is regarded as the governing factor that directly determines the enhanced oil recovery (EO...

Toehold-mediated strand displacement reaction, the fundamental basis in dynamic DNA nanotechnology, has proven its extraordinary power in programming dynamic molecular systems. Programmed activation of the toehold in a DNA substrate is crucial for building sophisticated DNA devices with digital and dynamic behaviors. Here we developed a detachable DNA circuit by embedding a pH-controlled intermolecular triplex between the toehold and branch migration domain of the traditional "linear substrate". The reaction rate and the "on/off" state of the detachable circuit can be regulated by varying the pHs. Similarly, a two-input circuit composed of three pH-responsive DNA modules was then constructed. Most importantly, a resettable self-assembly system of spherical nucleic acids was built by utilizing the high detachability of the intermolecular triplex structure-based DNA circuit. This work demonstrated a dynamic DNA device that can be repeatedly operated at constant temperature without generating additional waste DNA products. Moreover, this strategy showed an example of recycling waste spherical nucleic acids from a self-assembly system of spherical nucleic acids. Our strategy will provide a facile approach for dynamic regulation of complex molecular systems and reprogrammable nanoparticle assembly structures.

Li–S batteries have received unprecedented attention owing to their exceptionally high energy density and low cost. Nevertheless, the daunting challenges of insulating properties, soluble polysulfide shuttling, drastic volume change and sluggish polysulfide conversion kinetics, still hinder their application towards commercialization. Very recently, exciting progresses have been made on inorganic/organic polar hosts as either polysulfide immobilizers or polysulfide redox accelerators, targeting durable Li–S batteries. Herein, self-assembled NiCo2S4 granules comprising secondary open-hole tubular structures are first devised as highly-efficient host materials for high-sulfur-loading and durable Li–S batteries. NiCo2S4 hosts are featured with their large porosity, high electronic conductivity, rapid ion conduction, strong polysulfide immobilization capability and catalytic effect on polysulfide redox, thus greatly ameliorating the polysulfide-shuttle issue and accelerating the polysulfide conversion kinetics. Therefore, the NiCo2S4/S cathode shows a reversible capacity of 1387 ​mAh g−1 at 0.2C and retains a value of 543 ​mAh g−1 after 500 cycles at 2 ​C. Impressively, the NiCo2S4/S cathode with a sulfur loading of 8.9 ​mg ​cm−2 exhibits high areal capacity of 8.3 ​mAh cm−2, low polarization and high cycling stability. Moreover, the as-derived soft-package battery with a 4.5 ​mg ​cm−2 sulfur loading can power 169 light-emitting diodes, verifying its great potential for practical application.

A high-shear mixer was used in the process of chemical precipitation to prepare graphene oxide (GO) and Ni(OH)2 composites with different weight fractions of GO from 0 wt% to 2.6 wt%. The GO/Ni(OH)2 composite with 1.5 wt% GO prepared by high-shear mixing (1.5GO/Ni(OH)2–H) displayed a high specific capacitance (1836 F g−1 at 2 mV s−1), which was beyond that (1581 F g−1 at 2 mV s−1) of GO/Ni(OH)2 obtained by impeller agitator stirring (1.5GO/Ni(OH)2–M). 1.5GO/Ni(OH)2–H also showed excellent cycling stability, retaining 91.7% of its initial specific capacitance after 2000 cycles. Furthermore, the asymmetric device (the 1.5GO/Ni(OH)2–H as the positive electrode and active carbon as the negative electrode) exhibited a high energy density of 41.2 W h kg−1 at a power density of 1500 W kg−1 with a voltage of 1.5 V. In addition, the effects of high-shear mixing and impeller agitator stirring on the microstructures and electrochemical properties of the composites were discussed, which indicated that high-shear mixing could exfoliate graphene oxide and restrain the grain growth of Ni(OH)2, thus leading to excellent electrochemical performance.

Immunotherapy is a novel clinical approach that has shown clinical efficacy in multiple cancers. However, only a fraction of patients respond well to immunotherapy. Immuno-oncological studies have identified the type of tumors that are sensitive to immunotherapy, the so-called hot tumors, while unresponsive tumors, known as “cold tumors,” have the potential to turn into hot ones. Therefore, the mechanisms underlying cold tumor formation must be elucidated, and efforts should be made to turn cold tumors into hot tumors. N6-methyladenosine (m6A) RNA modification affects the maturation and function of immune cells by controlling mRNA immunogenicity and innate immune components in the tumor microenvironment (TME), suggesting its predominant role in the development of tumors and its potential use as a target to improve cancer immunotherapy. In this review, we first describe the TME, cold and hot tumors, and m6A RNA modification. Then, we focus on the role of m6A RNA modification in cold tumor formation and regulation. Finally, we discuss the potential clinical implications and immunotherapeutic approaches of m6A RNA modification in cancer patients. In conclusion, m6A RNA modification is involved in cold tumor formation by regulating immunity, tumor-cell-intrinsic pathways, soluble inhibitory mediators in the TME, increasing metabolic competition, and affecting the tumor mutational burden. Furthermore, m6A RNA modification regulators may potentially be used as diagnostic and prognostic biomarkers for different types of cancer. In addition, targeting m6A RNA modification may sensitize cancers to immunotherapy, making it a promising immunotherapeutic approach for turning cold tumors into hot ones.

The progressive and generalized loss of skeletal muscle mass and function, also known as sarcopenia, underlies disability, increasing adverse outcomes and poor quality of life in older people. Exercise interventions are commonly recommended as the primary treatment for sarcopenia. Nuclear factor erythroid 2-related factor 2 (Nrf2) plays a vital role in regulating metabolism, mitochondrial function, and the ROS-dependent adaptations of skeletal muscle, as the response to exercise. To investigate the contribution of Nrf2 to the benefits of exercise interventions in older age, aged (∼22 month old) Nrf2 knockout (Nrf2-KO) mice and age-matched wild-type (WT) C57Bl6/J mice were randomly divided into 2 groups (sedentary or exercise group). We found that exercise interventions improved skeletal muscle function and restored the sarcopenia-like phenotype in WT mice, accompanied with the increasing mRNA level of Nrf2. While these alternations were minimal in Nrf2-KO mice after exercise. Further studies indicated that Nrf2 could increase the stability of Drp1 through deubiquitinating and promote Drp1-dependent mitochondrial fission to attenuate mitochondrial disorder. We also observed the effects of sulforaphane (SFN), a Nrf2 activator, in restoring mitochondrial function in senescent C2C12 cells and improving sarcopenia in older WT mice, which were abolished by Nrf2 deficiency. These results indicated that some benefits of exercise intervention to skeletal muscle were Nrf2 mediated, and a future work should focus on Nrf2 signaling to identify a pharmacological treatment for sarcopenia.

Developing nonmetallic carbon-based electrocatalysts that are affordable and have high activity and stability for carbon dioxide (CO2) reduction to syngas is a new and challenging strategy for solving the energy crisis. Here, we prepared a highly active ultrathin nitrogen (N)-doped carbon nanosheet (UNCN) electrocatalyst. By tuning the applied potential of the UNCN-900 (900 represents the carbonization temperature) electrode, we could tune the H2/CO ratio in clean syngas within a wide range with extra-high Faradic efficiency (FE). The maximum FECO reached 91%, which represented the highest value among the reported nonmetallic carbon-based electrocatalysts for CO2 reduction to syngas. According to the results of experiments and density functional theory calculations, we proved that pyridinic-N in UNCNs-900 is the active site of the CO2 reduction reaction (CO2RR) and that graphitic-N may be the active site for the hydrogen evolution reaction. These results provide a useful case for electrochemical CO2 reduction to syngas with a tunable H2/CO ratio using nonmetallic carbon-based electrocatalysts.

Signal amplification is an important issue in DNA nanotechnology and molecular diagnostics. In this work, we report a strategy for the catalytic self-assembly of spherical nucleic acids (SNAs) programmed by two-layer cascaded DNA circuits through integrating an entropy-driven catalytic network, a catalytic hairpin assembly circuit, and a facile SNA assembly-based reporter system. This integrated system could implement ~100,000-fold signal amplification in the presence of 1 pM of input target. Possessing powerful amplification ability of nucleic acid signal, our strategy should be of great potential in fabricating more robust dynamic networks to be applied for signal transduction, DNA computing, and nucleic acid-based diagnostics.

Chronic heart failure affects myocardial energy metabolism and cardiac function. Puerarin has been reported to improve cardiac function through regulation of energy metabolism in mice with myocardial infarction. The aim of the current study was to determine whether puerarin can improve body weight and reduce inflammation and apoptosis in rats with chronic heart failure. Rats were divided into three groups: Puerarin, PBS and sham group. Transverse aortic constriction was performed to induce chronic heart failure in the puerarin an PBS groups. Cardiac function, apoptosis and inflammation were evaluated following a 4-week treatment in rats with chronic heart failure. The results demonstrated that puerarin significantly increased the survival rate of rats and improved cardiac function compared with the PBS group. In addition, puerarin decreased lactate dehydrogenase and succinate dehydrogenase activity compared with the PBS group. Puerarin treatment increased the expression levels of glucose transporter type 4 and decreased the expression levels of CD36. Additionally, puerarin decreased the levels inflammatory factors, including tumor necrosis factor α, interleukin (IL)-1β and IL-6 in serum and myocardial tissue compared with the PBS group. Puerarin upregulated peroxisome proliferator-activated receptor α (PPARα) and its downstream target genes nuclear respiratory factor 1, FOS proto-oncogene, YY1 transcription factor, acetyl-coenzyme A carboxylase a, Fas cell surface death receptor, L-type pyruvate kinase and acetyl-coenzyme A dehydrogenase medium chain in myocardial cells from rats with chronic heart failure. These results demonstrated that puerarin inhibited apoptosis and inflammation in myocardial cells via the PPARα pathway. In conclusion, the present study indicated that puerarin may exhibit antiapoptotic and anti-inflammatory activity through the PPARα pathway in rats with chronic heart failure.

In this study, the modification of TEMPO-mediated oxidized cellulose nanofibrils (TOCNFs) with cetyltrimethylammonium bromide (CTAB) was investigated to increase the hydrophobicity, improve the fibril separation from the hydrogel, and enhance the redispersibility of the separated nanofibrils. The results showed that when modifying the original TOCNFs at a CTAB loading of 2.16 mmol/g cellulose, the charge coupling was close to 100%. Moreover, with increasing the CTAB dosage, the turbidity of the modified CTAB–TOCNFs was significantly increased while the viscosity and water retention value were decreased. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated that the molecular chain of CTAB was successfully grafted onto the backbone of TOCNFs following modification. The thermogravimetric analysis results also indicated the modification of TOCNFs with CTAB improved its thermal stability. Water contact angle measurements of the original and CTAB modified TOCNFs showed that the modified CTAB–TOCNFs had better hydrophobicity. Moreover, the results from the evaluation of the redispersibility of the fibrils separated from both the original CNF and CTAB–TOCNF suspensions demonstrated that the modification of TOCNFs with CTAB improved the redespersibility in N,N-dimethylformamide (DMF). Additionally, the increase of CTAB loading also significantly decreased the particle size of the redispersed fibrils in DMF.

Foam stability is a crucial consideration in the view of its numerous applications. Herein, a series of nanocellulose fibrils containing lignin segment (L-NCF) was designed and then utilized for interfacial stabilization of liquid foams for eco-friendly oil recovery applications. The ability to form foams and their stability at bulk scale and bubble scale were thoroughly investigated using a foam scanner. Liquid drainage rate, bubble rupture, interfacial dilational viscoelasticity, and bubble transport in porous media were studied as a function of lignin content. We observed that in a vertical column the addition of L-NCF significantly mitigated the drainage of the liquid foams. The foam volume stability (FVS) index indicated that the stability of the foams in the presence of L-NCF was up to five times higher than that of surfactant-only foam. The hydrophobic interaction between the surfactant (mixture of alkyl polyglycoside (APG) and anion surfactant alpha olefin sulfonate (AOS)) and L-NCF (lignin segmen...

Foam has been applied in enhanced oil recovery (EOR) for more than sixty years. The surfactant-stabilized N2/CO2 foams are two of the most widely used foams in foam EOR processes, and numerous oil reservoirs could potentially benefit from them. This paper comprehensively reviews the development of these foams over the past decade. We focused on the promising surfactant formulas and their corresponding mechanisms under different reservoir conditions, especially harsh conditions. The most recent studies have shown that low interfacial tension foaming surfactants are efficient in fractured/tight reservoirs, while CO2-switchable surfactants are well suited to CO2 foam in carbonate reservoirs with high temperatures. Pure surfactants and mixed surfactants that combine anions and cations contain superior foam properties. The surfactant aggregates, such as vesicles and wormlike micelles, could distinctly enhance the foam stability. However, the adsorption of the mixed surfactants on reservoir rocks and the temperature sensitivity of the complex structures should be given particular consideration. The phase behaviors involved in foam EOR processes are vital and much more complicated than those in other EOR processes. Thus, a better knowledge of the phase behaviors could further improve foam EOR performance. The results of this paper provide clues to N2/CO2 foam EOR design and also promote the development of harsh reservoirs.

Due to the traditional therapies of cancer inducing huge pains to patients, the non-invasive photo-guided therapies are attracting massive attentions of researchers. Herein, the intelligent-designed carbon-dots/hemin nanoplatforms (HCDs NPs) were developed, owning high-authority photo-therapy for cancer. The fluorescence resonance energy transfer (FRET) effect enhanced the photo-thermal ability of HCDs NPs, endowing the synthesized nanoplatforms with photo-dynamic property simultaneously. Therefore, the obtained HCDs NPs could achieve synergetic photo-thermal and photo-dynamic therapies for cancer. Basing on the experimental results, the prepared HCDs NPs could induce the temperature enhancement high to ca 26 °C under laser irradiation, also with the outstanding photo-dynamic efficacy. More than 90% of cancer cells die after 10 min laser treatment. Thus, the dual-modal photo-therapeutic HCDs NPs are promising and excellent nanomaterials for potential application in synergistic cancer therapy.

In this study, a poplar high-yield pulp [preconditioning refiner alkaline peroxide mechanical pulp (P-RC APMP)] was used to produce lignin-containing cellulose nanofibril (LCCNF) dispersions throug...

Hit, Lead & Candidate Discovery This study investigated the effects of a natural phenolic compound quercetin on surgical-induced osteoarthritis (OA) in rabbits. Forty-eight New Zealand White rabbits were used to establish OA model by Hulth modified method, and subsequently randomized into untreated OA group (treatment was drinking water), celecoxib treated group (celecoxib 100 mg kg-1 by gavage), and quercetin treated group (25 mg kg-1 by gavage). Sixteen nonoperated rabbits served as the normal controls (drinking water was given). The treatment (length: 4 weeks) started on the 5th week postoperation when the OA pathological changes were manifested. Expressions of superoxide dismutase (SOD), matrix metalloproteinase-13 (MMP-13) and tissue inhibitor of metalloproteinases-1 (TIMP-1) in serum, synovial fluid, and synovial tissue were measured at 8 and 12 weeks postoperation. Pathological analysis was performed with synovial tissue section and Osteoarthritis Research Society International histopathology grading and staging scores were determined. The quercetin treated group showed higher SOD and TIMP-1 expressions but lower MMP-13 expression than untreated OA group in the serum, synovial fluid and synovial tissues (p < .05). There was no significant difference in the SOD, MMP-13 and TIMP-1 expressions between the quercetin-treated and celecoxib-treated groups. The MMP-13/TIMP-1 ratio of the quercetin treated group was significantly lower than that of the untreated OA group (p < .05). Quercetin can up-regulate SOD and TIMP-1, down-regulate MMP-13, and improve the degeneration of OA through weakening the oxidative stress responses and inhibiting the degradation of cartilage extracellular matrix.

This proof-of-concept study demonstrates a facile and scalable 'dry water' method for producing micrometer-sized microgel particles by use of 'water-in-air' droplets as micro-reactors. Solid microgel particles could be easily produced by this method with no further purification. The microgel particles comprise of porous hydrophobic shells and hydrophilic cores and could absorb both oil and water. The swelling of the particles could be triggered by a surfactant under a wide range of conditions.

A fast and sensitive ultra–high performance liquid chromatography–electrospray ionization–tandem mass spectrometry (UHPLC–ESI–MS/MS) method was developed for simultaneously analyzing 10 phthalates in perfume, which are forbidden by the hygienic standards for cosmetics in China (2007 edition). Matrix effect is significant on a phthalate when it is co–eluted with other phthalates. Improving the resolution between adjacent phthalate peaks is found effective in reducing the matrix effects. Thus, simultaneous analysis of the 10 phthalates requires successful resolutions of each phthalate. Nonetheless, a trade–off between the resolution and analysis time results either incomplete separation or prolonged analysis time. Here, the UHPLC elution gradient is optimized considering the predicted retention time of each phthalate. The resolutions and matrix effects of targeted compounds are evaluated to determine the optimal elution gradient for UHPLC-MS analysis method. Under the optimized gradient, the resolution between closest phthalate peaks is beyond 1.7, while the analysis time is merely 7 min. Except for dimethyl phthalate (DMP) and dicyclohexyl phthalate (DCHP), insignificant matrix effects have been found on all the phthalates. Direct quantifications through external calibration curve are appropriate for such analytes. Nonetheless, DMP and DCHP suffering obvious matrix effects require extra analyses of spiked samples for the quantifications through the standard addition method. Instrumental limits of quantitation (iLOQs) are 0.12–89 μg L−1 for the targeted phthalates. Meanwhile, the accuracy and precision of the analytical method are good. Finally, the forbidden phthalates in 26 sampled perfumes are successfully analyzed by the developed method.

Organosulfurs are promising cathode materials for rechargeable metal batteries due to their high capacities, diverse structures, and electrochemical properties. Herein, the electrochemical behavior of three organosulfur compounds, i.e., 4,4'-thiobisbenzenethiol (TBBT), 1,4-benzenedithiol (1,4-BDT), and diphenyl disulfide (DPDS), is revealed in room-temperature rechargeable sodium (Na) batteries, which show significantly improved performances when sodiated Nafion membranes are used. Large oligomers of organosulfur can be formed during charging, and they are readily blocked by the nanosized ion-conducting clusters in the Nafion membrane. In addition, large organosulfur monomers can also be blocked. Only 5.4% of TBBT diffuses through the Nafion membrane after 800 h. The Na|TBBT cell sustains 77% of the theoretical capacity after 300 cycles (2420 h). Moreover, the Na|TBBT redox flow cell shows promising rechargeability. Due to the medium molecular size, the organosulfur oligomers are expected to provide a new avenue to develop high-capacity chalcogen cathodes, besides inorganic S and S-containing polymers.

With the rapid development of the phosphorus chemical industry, the accumulation of by-product phosphogypsum has increased year by year. The comprehensive utilization of phosphogypsum has received extensive attention. In this paper, physical simulation is used to investigate the effects of the shape of agitator, stirring speed, inlet gas flow, eccentric stirring (the ratio of the distance from the center of the agitator to the radius of the cylinder), and height of agitator (the distance between the agitator and the bottom of the reactor) on the bubble size distribution. The optimized conditions are: the agitator is SSB-D, and the stirring speed is 600 r/min, inlet gas flow is 0.12 m3/h, eccentric stirring is 0.4, and the height of agitator is 3 cm, the size of the bubbles is distributed between 0.5 and 3 mm. Under this condition, the conversion rate of phosphogypsum can reach 91.95%. The experiment has certain guiding significance for the resource utilization of phosphogypsum.

Research question What is the association between homocysteine (Hcy) and IVF/intracytoplasmic sperm injection (ICSI) outcomes, stratified by methylenetetrahydrofolate reductase (MTHFR) C677T polymorphisms? Design This prospective cohort study recruited 1011 infertile women undergoing IVF/ICSI treatment for the first time at the International Peace Maternity and Child Health Hospital between June 2015 and March 2018. Results The concentration of total serum Hcy was significantly negatively associated with clinical pregnancy and implantation rate. When adjusted for maternal and paternal age and educational level, maternal body mass index, and FSH and oestradiol concentrations, logistic regression analysis showed that women with higher Hcy had a higher risk of unsuccessful pregnancy. After stratification by MTHFR C677T polymorphisms and adjustment for confounding factors, a higher risk of unsuccessful pregnancy and a significantly lower implantation rate only existed in women with higher Hcy concentration in the MTHFR C677T TT genotype. There was no significant association between Hcy concentrations and other ovarian stimulation outcomes (oocytes retrieved, metaphase II stage oocytes, fertilization rate, cleavage rate, high-quality embryo rate) or neonatal outcomes (preterm birth, gestational age at delivery, Caesarean section, birthweight, small for gestational age, large for gestational age or birth defects). Conclusions Hcy is highly negatively associated with clinical pregnancy and implantation rate during the first IVF/ICSI cycle, especially in women carrying the MTHFR C677T TT genotype. Other factors with impacts on reproductive outcomes, such as stage of embryo transferred, other factors involved in folate metabolism, preimplantation genetic testing, etc., should be taken into account in further research.

A new avenue for fabricating ultra-high specific surface area (SSA) carbons with hierarchical porous and excellent energy storage ability is achieved from the biomass-waste of pitaya peel with the pre-treating process by ethanol and KOH to optimize the microstructure and porosity, displaying excellent supercapacitance in different electrolytes.

Glovebox-AFM-based force curve measurements have been employed to investigate the effect of controlled small amounts of water on the interfacial structure of mica/a pyrrolidinium-based ionic liquid. A close examination reveals that with the increase of water content, the long-range monotonic force, which is beyond the region of the short-range oscillatory structure, switches from van der Waals attraction-dominated force to double layer repulsion-dominated force.

The success of an in situ combustion process is dependent on the stability and movement of the combustion front. During an in situ combustion process, coke is an important product for maintaining the stability of the combustion front. However, before being consumed by the combustion reaction, coke is deposited in the porous media; thus, it may cause the blockage of the pore throat and affect the subsequent air injection. In this study, the low-field nuclear magnetic resonance technique was applied to examine the influence of oxidized coke and pyrolyzed coke on the porous media. The results revealed that the coke deposition phenomenon was considerable in porous media and affected porosity. The formation damage was considerably severe in oxidized coke because of the drastic low-temperature oxidation. In case of the pyrolyzed core, the influence of coke on porosity is limited because of the low amount of coke generation. The average reduction in porosity was 21.90%, while that of the pyrolyzed coke is only 9.09%. Montmorillonite had the greatest catalytic effect on coke deposition for both oxidation and pyrolysis processes. Illite, kaolinite, and chlorite have an impact on coke deposition; however, because the change in porosity is attribute to a combination of multiple factors, the result is a lack of regularity. Heat causes the pore to reform and the fracture to form. The change in porous media can reduce the impact of coke deposition phenomenon on total porosity. Because of the high-temperature environment, this influence is more pronounced in the pyrolyzed core.

Background This study aimed to evaluate whether the Homocysteine (Hcy) level was elevated in chronic obstructive pulmonary disease (COPD) patients and its correlation with the occurrence and acute progression of COPD. Methods From November 2014 to November 2015, COPD patients were enrolled from Beijing Chao-yang Hospital, and the the biological and clinical data were collected. These patients were tested in the non-acute exacerbation period and the acute exacerbation period, so they were defined as AECOPD group and Non-AECOPD group. Besides, 50 healthy subjects were recruited and defined as control group. Total plasma Hcy levels (antibodies-online, USA) were determined by enzyme-linked immunosorbent assay. Correlation analysis was used to analyze the correlation between serum Hcy level and ventilatory function. Using ROC curve, the diagnostic value of Hcy for the occurrence and acute progression of COPD was explored. Results In this study, we found that Hcy levels in the Non-AECOPD group or the AECOPD group were significantly higher than those in the control group (P P P r r P P Conclusion Hcy level is positively correlated with the severity of COPD patients, which has predictive value for the occurrence of COPD and acute progression.

Background Early progression after the first-line R-CHOP treatment leads to a very dismal outcome and necessitates alternative treatment for patients with diffuse large B-cell lymphoma (DLBCL). This study aimed to develop a genetic predictive model for early progression and evaluate its potential in advancing alternative treatment. Methods Thirty-two hotspot driver genes were examined in 145 DLBCL patients and 5 DLBCL cell lines using next-generation sequencing. The association of clinical features, cell-of-origin, double expression, positive p53 protein, and gene alterations with early progression was analyzed, and the genetic predictive model was developed based on the related independent variables and assessed by the area under receiver operating characteristic. The potential of novel treatment based on the modeling was investigated in in-vitro DLBCL cell lines and in vivo xenograft mouse models. Results The frequency of CD79B (42.86% vs 9.38%, p = 0.000) and PIM1 mutations (38.78% vs 17.71%, p = 0.005) showed a significant increase in patients with early progression. CD79B and PIM1 mutations were associated with complex genetic events, double expression, non-GCB subtype, advance stage and unfavorable prognosis. A powerful genetic predictive model (AUROC = 0.771, 95% CI: 0.689–0.853) incorporating lactate dehydrogenase levels (OR = 2.990, p = 0.018), CD79B mutations (OR = 5.970, p = 0.001), and PIM1 mutations (OR = 3.021, p = 0.026) was created and verified in the other cohort. This modeling for early progression outperformed the prediction accuracy of conventional International Prognostic Index, and new molecular subtypes of MCD and Cluster 5. CD79B and PIM1 mutations indicated a better response to inhibitors of BTK (ibrutinib) and pan-PIM kinase (AZD 1208) through repressing activated oncogenic signaling. Since the two inhibitors failed to decrease BCL2 level, BCL2 inhibitor (venetoclax) was added and demonstrated to enhance their apoptosis-inducing activity in mutant cells with double expression. Conclusions The genetic predictive model provides a robust tool to identify early progression and determine precision treatment. These findings warrant the development of optimal alternative treatment in clinical trials.

Homogeneous DNA-only keypad locks were built with multi-stranded scalable junction substrates and a series of double-stranded eliminators to differentially process correctly- and wrongly-added DNA inputs, respectively. Unlike conventional strategies that employed solid-phase platforms, one-pot assay of multiple DNA inputs was achieved, showing merits in fabricating complicated information security systems.

Knowledge of atomistic structures at solid/liquid interfaces is essential to elucidate interfacial processes in chemistry, physics, and materials sciences. The (√3 × √7) structure associated with a pair of sharp reversible current spikes in the cyclic voltammogram on a Au(111) electrode in sulfuric acid solution represents one of the most classical ordered structures at electrode/electrolyte interfaces. Although more than 10 adsorption configurations have been proposed in the past four decades, the atomistic structure remains ambiguous and is consequently an open problem in electrochemistry and surface science. Herein, by combining high-resolution electrochemical scanning tuning microscopy, electrochemical infrared and Raman spectroscopies, and, in particular, the newly developed quantitative computational method for electrochemical infrared and Raman spectra, we unambiguously reveal that the adstructure is Au(111)(√3 × √7)-(SO4···w2) with a sulfate anion (SO4*) and two structured water molecules (w2*) in a unit cell, and the crisscrossed [w···SO4···w]n and [w···w···]n hydrogen-bonding network comprises the symmetric adstructure. We further elucidate that the electrostatic potential energy dictates the proton affinity of sulfate anions, leading to the potential-tuned structural transformations. Our work enlightens the structural details of the inner Helmholtz plane and thus advances our fundamental understanding of the processes at electrochemical interfaces. The authors acknowledge funding by the National Natural Science Foundation of China (91950121, 21727807, 21403179, 21872115, and 21533006).

To improve the salt tolerance/sensitivity of cellulose nanofibrils (CNFs), zwitterionic cellulose nanofibrils (ZCNFs) were prepared from softwood bleached kraft pulp fibers via a sequential process of anionic modification with 2,2,6,6-tetramethylepiperidin-1-oxyl (TEMPO)-mediated oxidation, cationic modification with (2,3-epoxypropyl) trimethylammonium chloride (EPTMAC), and high-pressure homogenization. To produce ZCNFs with different contents of cation group, EPTMAC loadings of 0.15 to 1.15 g/g fiber were explored during cationization. The obtained ZCNFs were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and rheological measurements. The salt tolerance of the ZCNFs was investigated by adding mixed salts into the ZCNF dispersions. The results demonstrated that the ZCNFs with both anionic and cationic charges were produced. Compared with the TEMPO-mediated oxidized cellulose nanofibrils (TOCNFs), the ZCNFs exhibited an excellent "salt-thickening" behavior under the studied salt concentrations (2-24% w/w). Moreover, increasing the content of the cation group increased the salt tolerance/sensitivity of ZCNFs. This work demonstrated that introducing cationic charges to the anionic charged TOCNFs imparts the produced ZCNFs with excellent salt sensitivity and tolerance, which could expand the application of nanocellulose in oil recovery or wastewater treatment.

The effects of quercetin liposomes (Q-PEGL) on streptozotocin (STZ)-induced diabetic nephropathy (DN) was investigated in rats. Male Sprague Dawley rats were used to establish a STZ induced DN model. DN rats randomly received one of the following treatments for 8 weeks: blank treatment (DN), free quercetin (Que), pegylated liposomes (PEGL) and pegylated quercetin liposomes (Q-PEGL). A group of healthy rats served as the normal control. The fasting blood glucose (FBG), body weights (BWs), renal hypertrophy index (rHI), serum and urine biochemistry, renal histopathology, oxidative stress and immunohistochemical measurements of AGEs were analyzed to compare the effect of different treatments. Que and Q-PEGL significantly improved DN biochemistry and pathological changes, although the treated rats still had some symptoms of DN. The therapeutic effect of Q-PEGL surpassed that of Que. Pegylated quercetin liposomes allow maintaining higher quercetin concentrations in plasma than non-encapsulated quercetin. In conclusion the use of quercetin liposomes allows to reduce disease symptoms in a rat model of DN.

Despite numerous investigations into AgNP-induced toxicity, little has been taken into consideration the potential health impacts of aged AgNPs in comparison to fresh AgNPs. In the current study, we scrutinized the potential effects of aged AgNPs in animals. We first found that AgNPs underwent morphological transformations after natural ageing in aqueous solution upon exposure to air and sunlight for 9 days, as characterized by significant aggregation with increase of particle size approximately by 2 fold. Meanwhile, dissolved Ag ions from aged AgNPs increased by 33% compared to fresh AgNPs. Strikingly, the acute exposure results showed that aged AgNPs induced lower toxicity in mice relative to fresh AgNPs. Aged AgNPs caused milder local inflammation in the peritoneal cavity of mice, as evidenced by 63% reduction of tumor necrosis factor α (TNF-α) than that induced by fresh AgNPs. The deposition mass of aged AgNPs in the liver, spleen, lung and kidney was diminished by 69%, 39%, 83% and 40%, respectively, compared to the distribution profiles in response to fresh AgNPs. Whereby, milder splenic hyperemia was observed, and no significant hepatoxicity was found. Additionally, aged AgNPs provoked milder increase of periphery leukocytes and malondialdehyde (MDA) in mice in comparison to fresh AgNPs. Taken together, this study unraveled that the ageing process elicited remarkable alterations to physicochemical properties and toxic effects as well. This study would provide new insights into the potential health impacts of AgNPs under transformation-determined exposure scenarios.

Humid hydrophobic ionic liquids—widely used as electrolytes—have narrowed electrochemical windows due to the involvement of water, absorbed on the electrode surface, in electrolysis. In this work, we performed molecular dynamics simulations to explore effects of adding Li salt in humid ionic liquids on the water adsorbed on the electrode surface. Results reveal that most of the water molecules are pushed away from both cathode and anode, by adding salt. The water remaining on the electrode is almost bound with Li+, having significantly lowered activity. The Li+-bonding and re-arrangement of the surface-adsorbed water both facilitate the inhibition of water electrolysis, and thus prevent the reduction of electrochemical windows of humid hydrophobic ionic liquids. This finding is testified by cyclic voltammetry measurements where salt-in-humid ionic liquids exhibit enlarged electrochemical windows. Our work provides the underlying mechanism and a simple but practical approach for protection of humid ionic liquids from electrochemical performance degradation., Water adsorbed on the electrode surface of electrochemical energy storage devices narrows the electrochemical windows. Combining atomistic simulations and cyclic voltammetry experiments the authors demonstrate an approach to expand the voltage window of humid ionic liquids based on the addition of lithium salt.

Nano-material enhanced viscoelastic surfactant (VES) systems have attracted considerable attention as clean fracturing fluids due to their improved rheological properties compared to conventional VES systems. In this study, a pseudo-interpenetrating network VES (PINVES) fracturing fluid, which was composed of sodium oleate (NaOA), potassium chloride (KCl) and surface-modified cellulose nanofibril (SMCNF), was proposed. The rheological behavior of the PINVES fracturing fluid and the interaction mechanism between SMCNF and wormlike micelles (WLMs) were comprehensively studied. The zero-shear viscosity of PINVES increased with appropriate SMCNF addition but decreased with excess SMCNF addition. Meanwhile, the typical viscosity-flat of WLMs gradually disappeared when the concentration of SMCNF exceeded the optimum value. The optimum value was closely related to the functional groups on the surface of SMCNF. The SMCNF physically crosslinked the WLMs through hydrogen bonding but the sulfonic groups and hydrophobic groups on the surface of SMCNF destroyed the network of WLMs at relatively high SMCNF concentration. The network formed by SMCNF dominated the rheological behavior of the PINVES fracturing fluid simultaneously. In addition, due to the competition between the network of WLMs and the network of SMCNF, the PINVES fracturing fluid exhibited higher concentration dependence of surfactant in rheological behavior than conventional VES fracturing fluid. The SMCNF network also endowed the PINVES with better temperature-resistance. Furthermore, the relaxation time and elasticity of PINVES fracturing fluid increased with the increase in SMCNF concentration. The static proppant settling tests demonstrated that the addition of SMCNF improved the sand-carrying capability of PINVES fracturing fluid. The results of the study could provide some enlightenments on the application of SMCNFs in reservoir stimulation.

The depression of the current global oil market makes the majority of chemical EOR projects worldwide nearly unprofitable, especially in China. Therefore, economic alternative methods and technologies must be quickly developed. This proof of concept research evaluates a chemical flooding method using pre-formed mild O/W emulsions, which were produced by saponification between a low-cost alkali (NaOH) and a petroleum acid-rich oil. Our focus was first given to the dynamics of the saponification with an aim to quantify alkali consumption. Afterward, the composition of the crude oil before and after the reaction was characterized using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) to determine the preferred compounds in saponification. The physiochemical properties of the generated emulsions were further investigated through direct measurements of rheology, morphology, particle size distribution, and stability. Particular attention was placed on the oil displacement mechanisms of ...

Tumor extracellular matrix (ECM) still remains a major barrier that hinders the diffusion of drug in tumor parenchyma. We design a lactobionic acid (LA) and bromelain dual-functional nanoparticles as doxorubicin carriers. LA can increase the nanoparticles' tumor-targeting ability, while bromelain can enhance the permeation of nanoparticles in tumor parenchyma due to the hydrolytic activity to ECM. The chemical structures of these modified macromolecules were characterized by 1H NMR, FT-IR and UV spectrum. Drug-loaded nanoparticles as final drug formulations were observed in terms of size, zeta potential and micromorphology. Monolayer cells and three-dimensional cell spheroids were used to investigate the influence of LA and bromelain on the nanoparticles' cellular uptake, cytotoxicity, accumulation and penetration. In vivo drug distribution and antitumor activity results demonstrated that bromelain increased nanoparticles penetration and diffusion ability in tumor area upon the digestion of ECM, leading to higher drug concentration in tumor area and superior antitumor effect.

Versatile building blocks are essential for building complex and scaled-up DNA circuits. In this study, we propose a conceptually new scalable architecture called a "junction substrate" (J-substrate) that is linked by prepurified double-stranded DNA molecules. As a proof-of-concept, this novel type of substrate has been utilized to build multi-input DNA circuits, offering several advantages over the conventional substrate (referred to as a "linear substrate", L-substrate). First, the J-substrate does not require long DNA strands, thus avoiding significant synthetic errors and costs. Second, the traditional PAGE purification method is technically facilitated to obtain high-purity substrates, whereby the initial leakage is effectively eliminated. Third, the asymptotic leakage is eliminated by introducing the "junction". Finally, circuits with the optimized J-substrate architecture exhibit fast kinetics. We believe that the proposed architecture constitutes a sophisticated chassis for constructing complex circuits.

Low immunogenicity is one of the major problems limiting the clinical use for DNA vaccines, which makes it impossible to obtain a strong protective immune response after vaccination. In order to explore whether Ag85A DNA vaccine could mount more efficiently protective immune response through new RNA sensor and its signal transduction pathway of antigen presentation we designed and synthesized Ag85A gene fragment containing multiple points mutations and transfected the gene fragment into the dendritic cell line (DC2.4) by CRISPR/Cas9. Subsequently, we focused on the changes of RNA sensors RIG-I, Mda-5, and the downstream adaptors MAVS, IRF3, IRF7 and IFN-β. The results indicated the significant increases in the mRNA and protein expression of RNA sensors RIG-I, Mda-5 and related adaptors MAVS, IRF3, IRF7, and IFN-β in the mutant DC 2.4 cells. The flow cytometry results demonstrated that the expression of MHC II on the surface of DC 2.4 significantly increased when compared with that in control. Therefore, it is suggested that Ag85A mutant DNA could release immunogenic message through RNA sensors and related adaptors via non protein pathway. There is at least one RNA signal transduction pathway of Ag85A DNA in DC2.4 cell. The work provides a new mode of action for nucleic acid vaccine to improve immunogenicity and meaningful data for the better understanding of the mechanisms of DNA vaccine.

Ionic liquids (ILs) are novel type of electrolytes and have found various applications in electrochemistry. Understanding their electrochemical stability has been one of fundamental and important subject of researches, which would promote further application of ionic liquids in electrochemistry. Electrochemical surface enhanced Raman spectroscopy (EC-SERS) can provide abundant finger print information of surface-bound species for elucidating reaction mechanism, while normal Raman (NR) spectroscopy of thin layer region near electrode surface can provide more information about products without interference of signals from surface adsorption. Here we report combined EC-SERS and NR studies with DFT calculations on the cathodic process of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMITFSI) on Ag electrodes, aiming to identify reaction products and to reveal reaction mechanisms. It has been found that during the reduction of EMI cation, N-heterocyclic carbenes (NHCs) as an intermediate product were formed first and then underwent dimerization to form double-bond dimer. Single-bond dimer were also generated through single-electron radicals whose lifetime was too short to be detected directly though. In addition, dealkylation may happen, leading to formation of methylimidazole and ethylimidazole. This work not only deepens our insight into the cathodic process of EMI + , but also provides a guideline for electrochemical Raman study to be employed for tracing and understanding the process of electrode reaction.

To assist in understanding the progress of polysaccharide biopolymers in EOR, this review collects and summarizes the available data for the first time and thoroughly discusses the structure–property–EOR performance relationship from flask to field scale application. Attentions were given to xanthan, scleroglucan, hydroxyethylcellulose (HEC), carboxymethycellulose (CMC), welan gum, guar gum, schizophyllan, and other newly developed family members. This review provides a synopsis of EOR polysaccharides, which are rapidly emerging as eco-friendly and tough injectants compared to synthetic polymers.

A novel series of 1,2,3-substituted ferrocene-based wires a1-a2 and b4-b5 have been synthesized by using an iterative Pd-mediated Sonogashira cross-coupling methodology. The molecular structures of a2 and b3 were determined by single-crystal X-ray analysis. Electrochemical data showed that there was a strong electronic communication among the ferrocenyl moieties in b1-b5. The UV absorption spectra indicated that replacing the 1,1'-substituted ferrocene unit with a 1,2,3-substituted ferrocene moiety causes delocalization of electrons in the extended π orbitals. The self-assembled monolayers of wire a1 and a2 on Au surfaces have been comprehensively characterized by electrochemistry and scanning tunneling microscopy break junction. The data demonstrated that 1,2,3-substituted ferrocene-based wires reduced the intermolecular π-π stacking, and furthermore solved the rotation problem in the 1,1'-substituted ferrocene-based wires.