Search

Microfluidics is characterized by the manipulation of fluids in submillimeter channels and has great application potential in encapsulation. To further extend the application of microfluidics in food industries, a 3D printed microfluidic device is used to encapsulate vitamin A and improve its stability. Two natural macromolecules, sodium alginate and gelatin, are added to water as the continuous phase to generate monodisperse emulsion. Under different flow rate ratios, the diameter of droplets decreases with the increase of continuous flow rate. However, at the same flow rate ratio, varying the dispersed and continuous flow rates does not significantly change the diameter and size distribution of emulsion collected. The prepared O/W (oil/water) single emulsion can form microgel particles and avoid degradation of vitamin A by simulated gastric acid; the encapsulated vitamin A will not be released until particles reach simulated intestinal tract. In the simulated digestion in vitro, no vitamin A is released for 2 h in the acidic environment; under an alkaline or neutral environment such as those in intestinal fluids, vitamin A can be released from the microgel particles within 2.5 h. Using the presented approach, emulsions encapsulating vitamin A have been prepared and can potentially be applied to encapsulate other oil-soluble substances in the food industry.

Human immunodeficiency virus type 1 (HIV-1) infection remains one of the worst crises in global health. The prevention of HIV-1 infection is a crucial task that needs to be addressed due to the absence of a licensed vaccine against HIV-1. DNA vaccines present a promising alternative approach to combat HIV-1 infection due to their excellent safety profile, lack of severe side effects, and relatively rapid fabrication. Traditional vaccines composed of a monomeric envelope or peptide fragments have been indicated to lack protective efficacy mediated by inducing HIV-1-specific neutralizing antibodies in clinical trials. The immunogenicity and protection against HIV-1 induced by DNA vaccines are limited due to the poor uptake of these vaccines by antigen-presenting cells and their ready degradation by DNases and lysosomes. To address these issues of naked DNA vaccines, we described the feasibility of CpG-functionalized silica-coated calcium phosphate nanoparticles (SCPs) for efficiently delivering DNA-based HIV-1 trimeric envelope vaccines against HIV-1. Vaccines comprising the soluble BG505 SOSIP.664 trimer fused to the GCN4-based isoleucine zipper or bacteriophage T4 fibritin foldon motif with excellent simulation of the native HIV-1 envelope were chosen as trimer-based vaccine platforms. Our results showed that SCP-based DNA immunization could significantly induce both broad humoral immune responses and potent cellular immune responses compared to naked DNA vaccination in vivo. To the best of our knowledge, this study is the first to assess the feasibility of CpG-functionalized SCPs for efficiently delivering DNA vaccines expressing a native-like HIV-1 trimer. These CpG-functionalized SCPs for delivering DNA-based HIV-1 trimeric envelope vaccines may lead to the development of promising vaccine candidates against HIV-1.

Crystalline covalent organic frameworks (COFs) are porous polymeric semiconductors with network topologies, which are built from the integration of selected organic blocks with covalent bond linkages. They have shown great promise for artificial photosynthesis, owing to broad light harvesting, high crystallinity, and high carrier mobility. This Minireview introduces state-of-the-art COF photocatalysts based on different linkages and discusses the origin of photocatalytic activities for hydrogen evolution. Three typical COF photocatalysts, with linkages including imine (-C=N-), β-ketoenamine (O=C-C=C-NH-), and vinylene (-C=C-), are discussed with a particular focus on the advancements in synthetic methodologies and structural design, as well as photoelectronic properties that are relevant to photocatalytic performance. The Minireview is expected to elucidate their structure-property relationships and the way to design photoactive COFs with enhanced performances.

This work describes a general strategy for metal-catalyzed cross-coupling of fluoroalkyl radicals with aryl halides under electrochemical conditions. The contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be well addressed by paired electrolysis, allowing for direct introduction of fluorinated functionalities into aromatic systems.

Background Despite multiple available fixed-dose combinations (FDCs) of inhaled long-acting β2-agonists (LABAs) plus long-acting muscarinic antagonists (LAMAs) and LABAs plus inhaled corticosteroids (ICS) for COPD, uncertainty remains regarding their comparative effects. Research Question Can comparative effectiveness and safety of LABA plus LAMA (LABA/LAMA) and LABA plus ICS (LABA/ICS) FDCs vary by different individual components of the dual combinations in COPD? Study Design and Methods We conducted a new user, propensity score-inverse probability of treatment weighting cohort study to compare the effectiveness and safety of two frequently used LABA/LAMA FDCs (indacaterol plus glycopyrronium [IND/GLY] and vilanterol plus umeclidinium [VI/UMEC]) vs three commonly prescribed LABA/ICS FDCs (salmeterol plus fluticasone propionate [SAL/FP], formoterol fumarate plus budesonide [FF/BUD], and formoterol fumarate plus beclomethasone dipropionate [FF/BDP]) using the Taiwanese nationwide health care claims from 2014 through 2017. The primary effectiveness outcome was the annual moderate to severe exacerbation rate, and safety outcomes included risks of severe pneumonia and cardiovascular disease requiring hospitalization. Weighted generalized linear mixed models and Cox proportional hazard models were used to assess the effectiveness and safety outcomes, respectively. Results Patients with COPD initiating IND/GLY and VI/UMEC showed an 11% (incidence rate ratio [IRR], 0.89; 95% CI, 0.80-0.98) and 20% (IRR, 0.80; 95% CI, 0.71-0.90) reduced annual rate of moderate to severe exacerbations, respectively, than those initiating SAL/FP, but showed a similar rate as those initiating FF/BUD or FF/BDP. Both LABA/LAMA FDCs, compared with SAL/FP and VI/UMEC vs FF/BDP, were associated with a 27% (hazard ratio [HR], 0.73; 95% CI, 0.59-0.90) to 42% (HR, 0.58; 95% CI, 0.48-0.70) reduced pneumonia risk. Cardiovascular risk was comparable in five groups. An intraclass difference existed in rates of moderate to severe COPD exacerbation and risks of pneumonia among LABA/ICS FDCs, but not between LABA/LAMA FDCs. Interpretation Both LABA/LAMAs vs SAL/FP are associated with a lower exacerbation rate and pneumonia risk, but exhibit similar effectiveness and safety outcomes compared with FF/BDP or FF/BUD, suggesting that comparative effects may differ by individual components of the dual therapies in COPD.

Highly sensitive and rapid detection of chloramphenicol antibiotics (CAPs) in aquatic products via lateral flow immunoassay (LFA) strips remains challenging. This study developed a surface-enhanced Raman scattering (SERS)–based LFA strip for ultrasensitive analysis of CAPs by using noble metal nanoparticles (NPs). A kind of core–shell Au@Ag NPs were employed to prepare SERS tags considering the stability and repeatability. In order to obtain higher stability and repeatability, we designed antibody-modified gold@silver core–shell nanoparticles (Au@Ag NPs) as SERS nanotags for quantitative Raman detection of the target in the LFA strip. Results showed that SERS-based LFA strip allowed quantified analysis of chloramphenicol (CAP), thiamphenicol (TAP), and florfenicol (FFC) with the limits of detection of 0.36 ng/mL, 0.20 ng/mL, and 0.78 ng/mL, respectively. Furthermore, SERS-based LFA strip exhibited favorable sensitivity (IC50 values of CAP, TAP, and FFC were 12.94 ng/mL, 8.76 ng/mL, and 12.22 ng/mL, respectively). This SERS-based LFA strip was finally applied in the detection of CAP in chub and the recovery was 91.5 to 106.4%. This SERS-based LFA strip could be used as an effective tool for detecting CAPs in aquatic products.

The current approaches remain insufficient for measuring chicken egg spoilage or present analytical limitations. This study aimed to complement the existing analyses and identify novel markers using liquid chromatography-high resolution mass spectrometry-based foodomics strategies. In the discovery set, comparative untargeted metabolomics was utilized to identify marker candidates in microbially inoculated chicken eggs. Markers were annotated by spectral matching with authentic standards, experimental libraries, or in silico fragmentation. In the validation set, targeted metabolomics was employed to verify the markers in stored chicken eggs from five farms. Statistical differences at a p-value < 0.001 revealed increases in lactic and 3-hydroxybutyric acids and decreases in phosphocholine, LPE(O-18:1), LPC(16:0), and LPC(18:0) in stored eggs. Receiver operating characteristic curve analysis of the six combined markers yielded an AUC of 0.956 and a sensitivity and specificity of ∼90%. Four phospholipids were highlighted as a novel class of spoilage markers. Our findings may contribute to further industrial implementation, benefiting the quality assurance and food safety of poultry egg production.

The difunctionalization of alkenes involving trifluoromethylthio group (SCF3) for the conversion of versatile and readily available olefins into more structurally complex molecules has been greatly studied. However, the disproportionate dithiolation of alkene is unknown. Herein, a transition-metal-free protocol is presented for vicinal trifluoromethylthio-thiolation of unactivated alkenes via a radical process under mild condition with broad substrate scope and excellent tolerance.

At present, cyclometalated iridium (Ir)(III) complexes are the most promising emitters for OLEDs. Contrary to well-developed Ir(III)-based red and green phosphorescent complexes, the efficient blue emitters are limited and the performances of blue OLEDs are still not satisfactory. Inspired by this, we designed two novel blue Ir(III) complexes employing 2-(2,4-difluoropyridyl)pyridine (dfpypy) and 2,6-difluoro-3-(pyridin-2-yl)benzonitrile (FCN) as the main ligands, respectively, and phenyl(pyridin-2-yl)phosphinate (ppp) as the ancillary ligand. The rational design of the molecular structure makes the two complexes achieve blue emission and possess good electron mobility simultaneously. The devices based on the Ir(III) phosphors exhibited good electroluminescence performances with low turn-on voltages, a peak current efficiency of 24.51 cd A−1, a maximum external quantum efficiency of 12.4%, a peak power efficiency of 21.99 lm W−1 and low efficiency roll-off. These results provide an effective strategy for the future molecular design of blue Ir(III) complexes with good electron transport property for OLEDs.

In this study, nitrilotriacetic acid (NTA) was used to enhance UV/Fe0/H2O2 process for highly salty wastewater at neutral pH. The addition of Fe0 could not accelerate the UV/H2O2 process for salty wastewater treatment at neutral pH due to the precipitation of Fe ions. While NTA added into UV/Fe0/H2O2 process which could form complex with Fe ion, the tartrazine removal could increase from 45.7% to 84.7% within 60 min. The k-value of the UV/Fe0-NTA/H2O2 system to remove tartrazine is also 2.2 times higher than that in UV/Fe0/H2O2 system. Meanwhile, the UV/Fe0-NTA/H2O2 process could obtain good performance for salt wastewater treatment under a wide salt concentration level of 0–0.2 M. It can also expand the application range of pH to neutral pH. SEM and XPS characterization showed that the corrosion rate of Fe0 in salty system was faster, and the presence of NTA could accelerate the recirculation of Fe3+/Fe2+ on the Fe0 surface. EPR spectroscopic analysis and scavenge experiments showed that •OH was the main reactive radical for the removal of tartrazine in the UV/Fe0-NTA/H2O2 system. In addition, the k-value for removing tartrazine in various types of salt systems in the UV/Fe0-NTA/H2O2 system was 3.2–4.2 times that of the UV/Fe0/H2O2 system. It demonstrated UV/Fe0-NTA/H2O2 processes fits to different types of salt system. Therefore, this study will provide a new method for the treatment of saline wastewater at neutral pH.

It is crucial to develop high-performance and cost-effective bifunctional electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) toward overall water splitting. Herein, a unique heterostructure of reduced graphene oxide (rGO) and CoNiO2 nanosheets directly grown on nickel foam (NF) were successfully fabricated and applied as a kind of highly efficient bifunctional electrocatalyst. The optimum CoNiO2@rGO/NF electrode exhibits excellent electrocatalytic OER performance with an overpotential of only 272 mV to drive a current density of 100 mA·cm−2, and HER performance with an overpotential of 126 mV to achieve a current density of 10 mA·cm−2. Meanwhile, the electrodes also display outstanding long-term stability for OER and HER with negligible activity and morphology degradation after at least 40 h testing. Furthermore, when employed as both cathode and anode for overall water splitting, CoNiO2@rGO/NF electrode only requires 1.56 V at 10 mA·cm−2 and operates stably for over 40 h, which is among the best performing Co-based and Ni-based non-precious metal electrocatalysts. Detailed characterizations reveal that the extraordinary electrocatalytic performance should be attributed to the synergistic effect of the unique heterostructure of CoNiO2 nanosheets and rGO for increasing the electrode conductivity and integrity, ultrasmall primary particle size for providing larger electrode/electrolyte contact area and abundant active sites, and three-dimensional (3D) conductive networks for facilitating the electrochemical reaction.

Vinylboronates and alkylboronates are key components in variegated transformations in all facets of chemical science. The synthesis of vinylboronates and alkylboronates suffers from step-tedious and poor stereoselective procedures. We have developed a regulated radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with an integrated redox-active reagent IMDN-SO2RF. This bench-stable imidazolium sulfonate cationic salt offers a scalable and operational protocol for the fluoroalkylation-borylation of unsaturated hydrocarbons in a high regio- and stereoselective manner. The products can be further transformed into valuable fluorinated building blocks., The synthesis of vinylboronates and alkylboronates often suffers from step-tedious and poorly stereoselective procedures. Here, the authors report a bench-stable redox-active reagent for the radical difunctionalization of alkenes and alkynes affording fluorine-containing vinylboronates and alkylboronates.

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the CuI -catalyzed azide-alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide-alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide-alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide-alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.

Motivation: The interactions of proteins with DNA, RNA, peptide, and carbohydrate play key roles in various biological processes. The studies of uncharacterized proteinmolecules interactions could be aided by accurate predictions of residues that bind with partner molecules. However, the existing methods for predicting binding residues on proteins remain of relatively low accuracies due to the limited number of complex structures in databases. As different types of molecules partially share chemical mechanisms, the predictions for each molecular type should benefit from the binding information with other molecules types. Results: In this study, we employed a multiple task deep learning strategy to develop a new sequence-based method for simultaneously predicting binding residues/sites with multiple important molecule types named MTDsite. By combining four training sets for DNA, RNA, peptide, and carbohydrate-binding proteins, our method yielded accurate and robust predictions with AUC values of 0.852, 0836, 0.758, and 0.776 on their respective independent test sets, which are 0.52 to 6.6% better than other state-of-the-art methods. To my best knowledge, this is the first method using multi-task framework to predict multiple molecular binding sites simultaneously. Availability: http://biomed.nscc-gz.cn/server/MTDsite/ Contact: yangyd25@mail.sysu.edu.cn

Reactive oxygen species (ROS)-induced vascular endothelial cell apoptosis is strongly associated with atherosclerosis progression. Herein, we aimed to examine whether Kansuinine A (KA), extracted from Euphorbia kansui L., prevents atherosclerosis development in a mouse model and inhibits cell apoptosis through oxidative stress reduction. Atherosclerosis development was analyzed in apolipoprotein E-deficient (ApoE−/−) mice fed a high-fat diet (HFD) using Oil Red O staining and H&amp, E staining. Human aortic endothelial cells (HAECs) were treated with KA, followed by hydrogen peroxide (H2O2), to investigate the KA-mediated inhibition of ROS-induced oxidative stress and cell apoptosis. Oil Red O staining and H&amp, E staining showed that atherosclerotic lesion size was significantly smaller in the aortic arch of ApoE−/− mice in the HFD+KA group than that in the aortic arch of those in the HFD group. Further, KA (0.1–1.0 μM) blocked the H2O2-induced death of HAECs and ROS generation. The H2O2-mediated upregulation of phosphorylated IKKβ, phosphorylated IκBα, and phosphorylated NF-κB was suppressed by KA. KA also reduced the Bax/Bcl-2 ratio and cleaved caspase-3 expression, preventing H2O2-induced vascular endothelial cell apoptosis. Our results indicate that KA may protect against ROS-induced endothelial cell apoptosis and has considerable clinical potential in the prevention of atherosclerosis and cardiovascular diseases.

Objective: Puerarin has been proven to treat diverse cancers, but its function on ovarian cancer (OC) is still blurry and needs further research.Methods: After OC cells were treated with 10, 20, 40, 80, or 160 μg/mL pue, cell vitality, colony number, apoptosis, the positive expression of P53, migration, and invasion were examined by cell function experiments, TUNEL staining, and immunofluorescence. P53, P21, PTEN, FGF1, GLI2, and ERK1/2-NF-κB pathway-related marker expressions were examined by western blot. Results: Pue weakened the OC cell vitality, colony number, and the positive expression of P53 but enhanced apoptosis in a dose-dependent manner. Next, we discovered that pue enhanced the P53, P21, PTEN, and GLI2 levels but restrained the FGF1 level. Pue also alleviated the OC cell migration and invasion activity. We also confirmed that pue weakened the ERK1/2-NF-κB pathway-related marker expressions.Conclusion: Puerarin restrained the OC progression via modulating P53 and PTEN expressions.

Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne., Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation.

A new approach in which a low symmetry cluster meets a low symmetry ligand to sharply boost the thermal stability of a MOF via additional inter-linker interactions is presented for the first time, leading to the successful synthesis of a novel binuclear Co-based MOF, {[Co2(L1)2DMF]·1.5DMF·0.75MeOH·1.5H2O}∞ (H2L1 = 5-(pyridin-3-yl) isophthalic acid, NJU-Bai62: NJU-Bai for Nanjing University Bai group), with exceptional thermal stability of up to 450 °C. This work may open up a new avenue for constructing robust MOFs from abundant, unstable, and low symmetry binuclear clusters, which have usually been ignored by most MOF chemists.

In our study, octenyl succinic anhydride (OSA)-modified dextrin was prepared and characterized as a novel emulsifier to improve the stability of emulsion and curcumin encapsulation. Fourier-transform infrared spectroscopy demonstrated the occurrence of esterification between OSA and dextrin (Mw = 1.041 × 104 g/mol). The absolute value of ζ-potential of OSA-dextrin increased (from 25.37 mV to 34.57 mV) with increasing OSA addition (from 0% to 8%), and then kept constant. Confocal laser scanning microscope results showed that the debranching and esterification of starch improved the oil droplets distribution and reduced the droplet size of emulsions. The emulsifying stability of emulsions coated by dextrin was greatly improved with OSA modification. The particle size of emulsion decreased significantly when the addition of OSA increased during storage. OSA-modified dextrin was in a position to increase encapsulation efficiency of curcumin. This research may increase the utilization of emulsions stabilized by OSA dextrin in food industry.

Flora forest is a major component that contribute to the natural resource in which natural pigment can be derived from. Tree leaves produce various pigments during leaf senescence. This study investigates natural pigment changes of Cinnamomum Camphora leaves at different life stages (young, mature, and old) and their applications in the dyeing and UV protection of silk and wool textile. It is shown that FTIR spectra can be used to assist the leaf pigment examination, and that the pigment of chlorophyll (from young leaves), anthocyanin (from mature leaves) and dark brown pigment (from old leaves) can be extracted effectively using ethanol, acid and alkaline. Both silk and wool showed excellent dyeing ability when dyed with the extracted pigments. Fabrics dyed with leaf pigments (except for the chlorophyll) showed an unchanged or increased colour fastness to light, wash and storage. This is because the rich content of phenolic hydroxyl within leaf chemical structure is sensitive to light and alkaline condition, and can result in a hyperchromic effect. All the fabrics dyed in this work showed an excellent UV protection performance compared with that of undyed.

Asymmetric Friedel–Crafts conjugate addition reactions that generate an α-chiral center are challenging because the configuration-determining step is a proton-transfer reaction of a highly active e...

We analyzed the number of circulating tumor cells (CTCs) and Epstein-Barr virus DNA (EBV DNA) for diagnosis, monitoring and prognosis of patients with metastatic nasopharyngeal carcinoma (mNPC). The levels of CTCs and EBV DNA were measured at baseline and after first-line chemotherapy in 148 mNPC patients prospectively enrolled between December 2014 and August 2016. We also collected 122 non-mNPC cases within the same time frame for examining CTCs and EBV DNA at baseline. In 270 NPC patients, we observed improved specificity (86.0% vs. 41.0%) and inferior sensitivity (42.3% vs. 81.3%) of CTCs as compared to EBV DNA for diagnosis of distant metastasis. mNPC patients were stratified into unfavorable and favorable prognostic groups, respectively, based on CTC of 12 at baseline and 1 after first-line chemotherapy and EBV DNA of 10,000 at baseline and 4,000 after first-line chemotherapy. Conversion of baseline unfavorable CTCs and EBV DNA to favorable after first-line chemotherapy was associated with significantly longer progression-free survival (PFS) and overall survival (OS) compared to patients with unfavorable CTCs and EBV DNA at both time points. Among patients with a complete/partial response as per imaging evaluation, favorable CTCs and EBV DNA levels after first-line chemotherapy were associated with significantly longer PFS and OS. In conclusion, our data demonstrated the number of CTCs and EBV DNA before, after and during first-line chemotherapy were strong predictive markers for mNPC patients. When utilized in conjunction with imaging studies, CTCs and EBV DNA could provide additional prognostic information.

The oil-in-water (O/W) Pickering emulsions stabilized by octenyl succinic anhydride (OSA) modified gliadin nanoparticles (OGNPs), which were prepared through a facile anti-solvent precipitation procedure and ultrasound treatment using gliadin powders, then modified by OSA, have been successfully fabricated. FT-IR result confirmed that the gliadin nanoparticles were modified by OSA. The mean size and three-phase contact angle of OGNPs were larger than those of gliadin nanoparticles, and the zeta potential reversed from positive to negative while the surface and shape of gliadin nanoparticles were destroyed. The effects of OGNPs concentration, OSA content and environment factors viz, pH and ionic strength on the properties of emulsions were investigated. The images, optical microscopy, confocal laser scanning microscopy (CLSM), and droplet size measurement of Pickering emulsions were evaluated. An increase in OGNPs concentration led to a formation of smaller droplets, which increased emulsification efficiency. Similar results were obtained with the addition of OSA from 2% to 10%. Stable emulsions could be developed at the low pH value due to high electrostatic repulsion. Increasing the NaCl concentration destabilized the Pickering emulsions. CLSM showed that OGNPs could be absorbed at the oil-water interface and form a densely packed layer on the surface of spherical oil droplets, which exhibited good stability for 14 days storage. These results suggested that OGNPs may be a promising stabilizer of Pickering emulsions, which may be used as delivery carriers of bioactives.

The paired electrolysis triggers multiple oxidative and reductive processes to occur simultaneously, which ensures the steady transformation of the intermediates to the desired coupling products. However, fluoroalkyl radicals have not been harnessed for metal-catalyzed cross-coupling with aryl halides under electrochemical conditions. This work describes a general strategy for rapid access to various fluoromethyl and difluoromethyl aromatics by paired electrolysis. The contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be well addressed under mild cell conditions, allowing for direct introduction of fluorinated functionalities into aromatic systems.

Multiphoton microscopy (MPM) excited at the 1700-nm window has enabled deep-tissue penetration in biological tissue, especially brain. MPM of skin may also benefit from this deep-penetration capability. Skin is a layered structure with varying refractive index (from 1.34 to 1.5). Consequently, proper immersion medium should be selected when imaging with high numerical aperture objective lens. To provide guidelines for immersion medium selection for skin MPM, here we demonstrate comparative experimental investigation of deep-skin MPM excited at 1600 nm in vivo, using both silicone oil and deuterium dioxide (D2 O) immersion. We specifically characterize imaging depths, signal levels and spatial resolution. Our results show that both immersion media give similar performance in imaging depth and spatial resolution, while signal levels are slightly better with silicone oil immersion. We also demonstrate that local injection of fluorescent beads into the skin is a viable technique for spatial resolution characterization in vivo.

Uranyl cation (UO22+) has been identified as highly oxidizing agent to abstract hydrogen atoms from C-H bonds for the formation of carbon-centered radicals. This work described a photocatalytic strategy to utilize uranyl peroxo complexes for direct alkynylation and olefination of C(sp3) aliphatics. Crystallographic analysis revealed that the in situ generated uranyl peroxide accelerated the reaction.

In this study, modified whey protein hydrolysates (WPH) were obtained after succinic anhydride succinylation and linear dextrin glycation, and emulsion gels were prepared on the basis of unmodified/modified WPH stabilized emulsions with sugar beet pectin (SBP) addition and laccase-catalyzed cross-linking. The influences of emulsifier types and SBP contents on the texture of emulsion gels were estimated. The texture and rheological properties of emulsion gels were characterized. An ideal gel emulsion was formed when the SBP content was 3% (w/w). A uniform network was observed in emulsion gels stabilized by W-L, W-L-S, and W-S-L. In addition, the effect of the emulsifier type on the bioaccessibility of curcumin encapsulated in emulsion gels was investigated and the W-S-L stabilized emulsion gel exhibited the highest curcumin bioaccessibility (65.57%). This study provides a theoretical basis for the development of emulsion gels with different textures by SBP addition and laccase cross-linking as encapsulation delivery systems.

Background and Aim. Although a strong antitumor effect of lenvatinib has been noted for patients with unresectable hepatocellular carcinoma (HCC), its efficacy requires improvement. It is imperative to seek therapeutic strategies that combine Lenvatinib with other anticancer agents. In this study, we investigated the anticancer effect of combining lenvatinib with alisertib, aurora A kinase (AURKA) target drug, against HCC in vitro and in vivo. Methods. Immunohistochemical staining, sequencing, and genetic analysis of liver cancer tissues were performed. The antitumor efficacy of single-agent or combination treatment was measured by cell counting kit-8 assay and colony formation assays. Their antiproliferative and apoptosis activity is evaluated by cell cycle analyses and wound healing assays. The DNA-related proteins were also measured by Western blotting and immunohistochemical staining. The HepG2 xenograft model was used to detect the effects of lenvatinib-alisertib on the antitumor activity. Results. AURKA was found to be upregulated in HCC tissues (77.3%, 17/22). Combined alisertib and lenvatinib treatment significantly enhanced the inhibition of proliferation and migration in HepG2 and Hep3B cell lines compared to single-agent treatments (all P s < 0.01 ). Alisertib alone or in combination with lenvatinib demonstrated a significant increase in the percentage of super-G2 cells (lenvatinib 1 μM vs. lenvatinib 1 μM + alisertib 0.1 μM 8.84 ± 0.84 vs. 34.0 ± 1.54 , P < 0.001 ). Discontinuous spindles and missegregated chromosomes in HCC cells treated with alisertib in combination with lenvatinib were observed. We further revealed that combined treatment inhibited the expression of DNA damage pathway proteins compared to those of single-agent treatments. In nude mice, combined administration of alisertib combined with lenvatinib significantly enhanced the suppression of tumor growth and induced apoptosis (all P s < 0.01 ). Conclusions. Our findings provide evidence for the possible use of alisertib in combination with lenvatinib in the treatment of HCC for better therapeutic outcomes.

The temperature dependence of the refractive indices of potassium titanyl phosphate (KTP) are shown to enable quasi-phasematched type II spontaneous parametric downconversion (SPDC) with low temperature sensitivity. Calculations show the effect to be maximised for emission of photons at around 1165nm, as well as producing potentially useful regions for wavelengths throughout the telecommunications bands. We demonstrate the effect experimentally, observing temperature-insensitive degenerate emission at 1326nm, within the telecommunications O band. This result has practical applications in the development of entangled photon sources for resource-constrained environments, and we demonstrate a simple polarization entangled source as a proof of concept., 5 pages, 7 figures

The spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) virus poses serious threats to the global public health and leads to worldwide crisis. No effective drug or vaccine is readily available. The viral RNA-dependent RNA polymerase (RdRp) is a promising therapeutic target. A hybrid drug screening procedure was proposed and applied to identify potential drug candidates targeting RdRp from 1906 approved drugs. Among the four selected market available drug candidates, Pralatrexate and Azithromycin were confirmed to effectively inhibit SARS-CoV-2 replication in vitro with EC50 values of 0.008μM and 9.453 μM, respectively. For the first time, our study discovered that Pralatrexate is able to potently inhibit SARS-CoV-2 replication with a stronger inhibitory activity than Remdesivir within the same experimental conditions. The paper demonstrates the feasibility of fast and accurate anti-viral drug screening for inhibitors of SARS-CoV-2 and provides potential therapeutic agents against COVID-19., Author summary Currently, a novel coronavirus called SARS-COV-2 is spreading across many parts of the world. Unfortunately, there is still a lack of effective drugs against the virus. Additionally, it usually takes much longer time to develop a new drug using traditional methods. Thus, it is now better to rely on some alternative methods to develop drugs that can treat such a disease effectively. In this paper, we have proposed a deep learning and molecular dynamics simulation based hybrid drug screening procedure for identifying potential drug candidates targeting RdRp from 1906 market available drugs. Our screening have successfully identified a FDA-approved drug called Pralatrexate that strongly inhibits the replication of 2019-nCoV in vitro with EC50 values of 0.008μM. This work demonstrated the feasibility of accurate virtual drug screening for inhibitors of SARS-CoV-2 and provides potential therapeutic agents against COVID-19.

The effects of maleic anhydride (MA) acylation and pullulan glycation on casein hydrolysates (CH) and the physicochemical stability of modified or unmodified CH-stabilized emulsions were explored. Compared with casein, the solubility of CH was improved, and CH1 (hydrolysis degree 4%) exhibited the optimal emulsifying properties. After the acylation of MA, degrees of acylation (DA) increased with increasing addition of MA. Fourier-transform infrared spectroscopy revealed that a covalent bond was formed between MA and CH1. The results of pullulan glycation indicated that the degree of glycation decreased with increasing DA. Acylation combined with glycation effectively reduced the surface hydrophobicity of CH. Results of analysis of physicochemical stability and gastrointestinal fate of curcumin in emulsions revealed that CH modified by MA acylation and pullulan glycation played a positive role in enhancing the stability and bioaccessibility of curcumin loaded in emulsions.

Redox-active esters (RAEs) as active radical precursors have been extensively studied for C-B bond formations. However, the analogous transformations of stabilized radicals from the corresponding acid precursors remain challenging owing to the strong preference towards single-electron oxidation to the stable carbocations. This work describes a general strategy for rapid access to various aliphatic and aromatic boronic esters by mild photoinduced decarboxylative borylation. Both aryl and alkyl radicals could be generated from the leaving group-assisted N-hydroxybenzimidoyl chloride esters, even α-CF3 substituted substrates could be activated for further elaboration.

Difunctionalization of olefins represents a powerful synthetic tool and yet a challenging task. This work describes an electrochemically enabled fluoroalkylation-migration reaction of unactivated olefins in the absence of a strong oxidant or heavy metal catalyst, affording fluorinated (hetero)aryl ketones in good yields and excellent regioselectivities. The efficient and sustainable electrochemical strategy provides a rapid access to a dual functionalized fluorine-containing heterocyclic manifold.

Background:. Eucommia ulmoides Oliv. is a medicinal plant native to China, with its bark (Eucommiae Cortex) traditionally being used for medicinal purposes. Previous research has shown that Eucommia male flowers can exert anti-inflammatory, analgesic, antibacterial, and other pharmacological effects, including immune regulation. This study explored the anti-inflammatory effects of the 70% ethanol extract of male flowers (EF) of E. ulmoides in lipopolysaccharide (LPS)-stimulated RAW 264.7 cells and LPS-administered mice. Methods:. Cytotoxicity of EF for RAW 264.7 cells was investigated using Cell Counting Kit-8. The production of proinflammatory mediators, nitric oxide (NO), tumor necrosis factor (TNF)-α, interleukin (IL)-1β, and IL-6 was determined using enzyme-linked immunosorbent assays. IL-17, IL-23, and IL-10 mRNA levels were determined using quantitative real-time polymerase chain reaction. Activation of the nuclear factor (NF)-κB pathway in RAW 264.7 cells was investigated via Western blotting. In vivo anti-inflammatory effects of EF were studied in an LPS-induced acute inflammation mouse model by analyzing lung tissue histopathology, serum TNF-α and IL-6 levels, and myeloperoxidase (MPO) activity in lung tissue. Results:. EF showed no significant cytotoxicity at concentrations from 10 to 60 μg/mL (cell viability > 80%) in the CCK-8 cell viability assay. EF inhibited the RAW 264.7 cell proliferation (EF 60 μg/mL, 120 μg/mL, and 250 μg/mL vs. negative control: 87.31 ± 2.39% vs. 100.00 ± 2.50%, P = 0.001; 79.01 ± 2.56 vs. 100.00 ± 2.50%, P

Exploring and designing efficient non-noble catalysts formed by element doping and nanostructure modification for the hydrogen evolution reaction (HER) is of critical importance with respect to sustainable resources. Herein, we have prepared a three-dimensional binary NiCo phosphide with hierarchical architecture (HA) composed of NiCoP nanosheets and nanowires grown on carbon cloth (CC) via a facile hydrothermal method followed by oxidation and phosphorization. Due to its unique hierarchical nanostructure, the NiCoP HA/CC electrocatalyst exhibits excellent performance and good working stability for the HER in both acidic and alkaline conditions. The obtained NiCoP HA/CC shows excellent HER activity with a low potential of 74 and 89 mV at 10 mA cm−2, a small Tafel slope of 77.2 and 99.8 mV dec−1 and long-term stability up to 24 h in acidic and alkaline electrolyte, respectively. NiCoP HA/CC, a non-noble metal material, is a promising electrocatalyst to replace noble metal-based electrocatalysts for the HER.

Catalytic asymmetric reactions in which water is a substrate are rare. Enantioselective transition-metal-catalyzed insertion of carbenes into the O-H bond of water can be used to incorporate water into the stereogenic center, but the reported chiral catalysts give good results only when α-aryl-α-diazoesters are used as the carbene precursors. Herein we report the first highly enantioselective O-H bond insertion reactions between water and α-alkyl- and α-alkenyl-α-diazoesters as carbene precursors, with catalysis by a combination of achiral dirhodium complexes and chiral phosphoric acids or chiral phosphoramides. Participation of the phosphoric acids or phosphoramides in the carbene transfer reaction markedly suppressed competing side reactions, such as β-H migration, carbene dimerization, and olefin isomerization, and thus ensured good yields of the desired products. Fine-tuning of the ester moiety facilitated enantiocontrol of the proton transfer reactions of the enol intermediates and resulted in excellent enantioselectivity. This protocol represents an efficient new method for preparation of multifunctionalized chiral α-alkyl and α-alkenyl hydroxyl esters, which readily undergo various transformations and can thus be used for the synthesis of bioactive compounds. Mechanistic studies revealed that the phosphoric acids and phosphoramides promoted highly enantioselective [1,2]- and [1,3]-proton transfer reactions of the enol intermediates. Maximization of molecular orbital overlap in the transition states of the proton transfer reactions was the original driving force to involve the proton shuttle catalysts in this process.

This work describes a nickel-catalyzed Ullmann-type thiolation of aryl iodidesunder mild electrochemical conditions. The simple undivided cell with graphene/nickel foam electrode setups offers excellent substrate tolerance, affording aryl and alkyl sulfides in good chemical yields. Furthermore, the mechanism for this electrochemical cross-coupling reaction has been investigated by cyclic voltammetry.

Circularly polarized organic light-emitting diodes (CP-OLEDs) are of great value for facilitating the development of next generation display technologies, especially for implementing real 3D displays. However, most CP-OLEDs have insufficient efficiency and serious efficiency roll-off. In this study, a pair of octahydro-binaphthyl (OBN)-based chiral emitting enantiomers, (R/S)-OBN-DPA, were synthesized by ingeniously merging the chiral source and the luminophore skeleton of cyan and diphenylamine groups. The chirality–acceptor–donor (C–A–D) type enantiomers concurrently demonstrate a high photoluminescence quantum yield of 84.67%, and intense circularly polarized photoluminescence with dissymmetry factors (|gPL|) around 2.0 × 10−3 in the films. The non-doped and doped CP-OLEDs achieve markedly circularly polarized electroluminescence signals with |gEL| up to 2.9 × 10−3, high brightness over 25 000 cd cm−2, high efficiency with a maximum external quantum efficiency (EQEmax) of 12.4%, and negligible efficiency roll-off with an EQE of 11.5% at a practical luminance of 1000 cd m−2, which are the best results among the reported CP-devices to date.

To boost intrinsic circularly polarized luminescence (CPL) properties of chiral emitters, an axially chiral biphenyl unit is inlaid in thermally activated delayed fluorescent (TADF) skeleton, urging the participation of chiral source in frontier molecular orbital distributions. A pair of enantiomers, (R)‐BPPOACZ and (S)‐BPPOACZ, containing the cyano as electron‐withdrawing moieties and carbazole and phenoxazine as electron‐donating units are synthesized and separated. The circularly polarized TADF enantiomers exhibit both high photoluminescence quantum yield of 86.10% and excellent CPL activities with maximum dissymmetry factor |g PL| values of almost 10−2 in solution and 1.8 × 10−2 in doped film, which are among the best values of previously reported small chiral organic materials. Moreover, the circularly polarized organic light‐emitting diodes based on the TADF enantiomers achieve the maximum external quantum efficiency of 16.6% with extremely low efficiency roll‐off. Obvious circularly polarized electroluminescence signals with |g EL| values of 4 × 10−3 are also recorded., Taking a new design strategy, a pair of axially chiral thermally activated delayed fluorescent enantiomers are developed with high photoluminescence quantum yield and excellent circularly polarized luminescence signals. Moreover, the resulting circularly polarized organic light‐emitting diodes achieve both high external quantum efficiency with low efficiency roll‐off and obvious circularly polarized electroluminescence signals.

To better understand and implement the CO2 sequestration project, it is of significance to investigate the interaction of shales with CO2 and its potential effects on the pore morphology. In this study, two marine shale samples and two terrestrial shale samples were prepared and treated with subcritical CO2 (30 ℃ and 5 MPa) and supercritical CO2 (80 ℃ and 20 MPa) in a geochemical reactor. Various methods, including low-pressure carbon dioxide adsorption (LP-CO2A), low-pressure nitrogen adsorption (LP-N2A), high-pressure mercury intrusion porosimetry (HP-MIP) and fractal theory, were used to gain insights into the changes in the shale pore structure after 14 days of CO2 saturation. According to the results, the phase states of CO2 obviously affected the variations of pore structure parameters during the physical and chemical reactions in shales. Interactions of supercritical CO2 with shales created a more obvious effect on the pore structure compared to those of subcritical CO2, which was attributed to the greater dissolution and expansion effect as well as the extraction mechanism associated with supercritical CO2. After exposing the shale samples to subcritical CO2, the pore size distributions (PSDs) of the treated shale samples were lower than those of the raw samples at all diameter scales, indicating that the number of pores decreased due to the reactions. Furthermore, it was found that after supercritical CO2 treatment, the micropore and mesopore structure parameters of the marine shale samples obviously decreased with an increase in macropore structure parameters, leading to the reduction in fractal dimensions in smaller pores, while the terrestrial shale samples appeared to represent a contrary trend. These findings will provide experimental evidence for further assessment of the mechanisms for CO2 geological sequestration with enhanced shale gas recovery.

This review is an update on recent developments in emissive iridium(III) phosphorescent complexes and their applications in organic light-emitting diodes (OLEDs). The emphasis is focused on complexes with emission colors spanning the whole visible spectral region, which is extremely important for applications of OLEDs in display and white-light luminance. In each color section, materials are classified according to their coordination configuration, including homoleptic, heteroleptic and tridentate, trying to clarify the relationship between the molecular structure and the photophysical properties. Since the emission color, photoluminescence efficiency and carrier mobility of the phosphors are critical for device performances, we endeavor to dig out these values along with the measuring methods from the publications, and rational chemical modifications aiming for high efficiency and carrier mobility with different colors are also discussed.

Background The retinal homeobox (rx/rax) gene is a transcription factor expressed in the developing eye field that is necessary for normal eye development. rax is necessary for retinal specification and stem cell development. The genetic program of early retinal development, including rax expression, can be induced in naive ectoderm by activation of insulin-like growth factor (IGF) signaling. We have undertaken a microarray-based approach to identify rax-dependent IGF-induced genes. Results We identified 21 IGF-induced genes that exhibit at least a two-fold decrease in expression when rax expression is knocked down. Ten of these genes were expressed in the developing eye, eight were expressed in the ciliary marginal zone of the mature tadpole retina, and four could significantly rescue the rax knockdown phenotype. One of these, the nei endonuclease VIII-like 3 (neil3) gene, rescued the rax knockdown phenotype to a remarkable degree. We found that neil3 is necessary for normal retinal lamination and retinal neuron differentiation. Conclusions We have identified neil3 as a component of the rax genetic pathway necessary for normal retinal progenitor cell development. neil3 is involved in the base excision DNA repair pathway, suggesting that this pathway is essential for normal rax-dependent progenitor cell development in the mature retina. Developmental Dynamics 247:1199-1210, 2018. © 2018 Wiley Periodicals, Inc.

Effects of pectin with different molecular weight (Mw) on gelatinization behavior, textural properties, retrogradation, and in vitro digestibility of corn starch (CS) were investigated. The pectin addition led to the decrease of peak, setback, and final viscosities of CS, and a further decrease was provided with the pectin of high Mw, whereas the pasting temperature was increased. The syneresis of starch gel during freeze-thaw process was reduced by the addition of pectin. High Mw pectin significantly lowered the hardness of the starch gel from 238.9 and 350.2 N to 222.7 and 318.5 N after 7 and 14 days storage (P < 0.05), respectively. Compared with the retrograded CS alone, the relative crystallinity of starch-pectin mixtures significantly decreased (P < 0.05), but the crystal type of starch remained unchanged. A significant increase was observed in both the proportion of slowly digestible starch and resistant starch for retrograded starch-pectin mixtures.

Motivation Scaffolding is an essential step during the de novo sequence assembly process to infer the direction and order relationships between the contigs and make the sequence assembly results more continuous and complete. However, scaffolding still faces the challenges of repetitive regions in genome, sequencing errors and uneven sequencing depth. Moreover, the accuracy of scaffolding greatly depends on the quality of contigs. Generally, the existing scaffolding methods construct a scaffold graph, and then optimize the graph by deleting spurious edges. Nevertheless, due to the wrong joints between contigs, some correct edges connecting contigs may be deleted. Results In this study, we present a novel scaffolding method SCOP, which is the first method to classify the contigs and utilize the vertices and edges to optimize the scaffold graph. Specially, SCOP employs alignment features and GC-content of paired reads to evaluate the quality of contigs (vertices), and divide the contigs into three types (True, Uncertain and Misassembled), and then optimizes the scaffold graph based on the classification of contigs together with the alignment of edges. The experiment results on the datasets of GAGE-A and GAGE-B demonstrate that SCOP performs better than 12 other competing scaffolders. Availability and implementation SCOP is publicly available for download at https://github.com/bioinfomaticsCSU/SCOP. Supplementary information Supplementary data are available at Bioinformatics online.

A photoredox and copper catalyzed asymmetric cyanoalkylation reaction of alkenes has been developed, which uses alkyl N-hydroxyphthalimide esters as alkylation reagents. In this radical cyanoalkylation reaction, the photoredox induced alkyl radical adds to styrene, and the generated benzylic radical couples with a chiral Box/CuII cyanide complex to achieve the enantioselective cyanation. This reaction features mild conditions, operational simplicity, broad substrate scope, high yields, and high enantioselectivities, which represents an efficient method for the asymmetric radical difunctionalization of alkenes.

Background Present study evaluates the neuroprotective effect of β-elemene alone and in combination with hyperbaric oxygen (HO) in traumatic brain injury (TBI). Methodology TBI was induced by dropping a weight from a specific height. All the animals were separated in to five groups (n=20) like control group; TBI group; β-elemene treated group which receives β-elemene (100 mg/kg, i.p.) half an hour after the injury; HO group which receives hyperbaric oxygen therapy and β-elemene + HO group which receives β-elemene (100 mg/kg, i.p.) half an hour after the injury and hyperbaric oxygen therapy. Neurological function was assessed to evaluate the effect of β-elemene in TBI rats. Thereafter level of inflammatory cytokines and expression of protein of inflammatory pathway was assessed in the brain tissues of TBI rats. In addition TUNEL assay was also done for the determination apoptosis in neuronal cells. Result Data of the report reveals that β-elemene alone and in combination with hyperbaric oxygen (HO) significantly decreases the neurological score Compared to TBI group. Moreover level of inflammatory cytokines and expression of LTR4 and casepase 3 significantly decrease and increase in the expression of IkB in β-elemene alone and in combination with hyperbaric oxygen (HO) treated group compared to TBI group. Data of TUNEL assay also reveals that β-elemene treated group shows significant decrease in the TUNEL positive cells and apoptosis index compared to TBI group. Conclusion Thus present study concludes the neuroprotective effect of β-elemene against TBI and it shows synergistic effect on TBI when treated with HO.

The transition-metal-catalyzed reaction of diazo compounds with arenes or heteroarenes is an efficient and straightforward approach to functionalize aromatic compounds. This digest summarizes recent progresses on transition-metal-catalyzed asymmetric reactions of diazo compounds with electron-rich (hetero-) arenes, including C–H functionalization, cascade reaction, cyclopropanation, cycloaddition, Buchner reaction and intramolecular dearomatization.