The electrocatalytic conversion of methane has attracted considerable attention owing to its ability to operate under mild conditions, thereby avoiding peroxidation. Recently, hydroxyapatite (HAP), an environmental-friendly and cost-effective electrocatalyst, was found to have high catalytic selectivity for the methane activation to produce alcohols. However, the overall activation mechanism still remains elusive and thus limits further improvement of the catalytic performance. In this study, we employed machine learning-assisted molecular dynamics simulations to analyze the structural modifications in the HAP with defects during sintering. Density functional theory calculations were performed to explore the catalytic mechanism of methane on various sintered surfaces of HAP. During the sintering of HAP, the presence of H2O or O vacancies causes the migration of H2O and OH species from the bulk phase toward the surface. On the basis of our simulations, the H2O or OH migration reduces the overpotential of oxygen evolution reactions and alters the stability of intermediates. It largely impacts the selectivity of methane activation and different products can be obtained depending on the defect modes. Our mechanistic proposal then fundamentally challenges the prevailing opinion that active sites are exclusively confined to the surface of HAP. Our work may pave the way for designing and synthesizing novel electrocatalysts with enhanced performance and efficiency.

Saturated C22-tailed ultra-long-chain imparts cationic surfactant stable chemical structure and strong hydrophobic interaction that favors the generation of wormlike micelles in brine. Such viscoelastic wormlike micellar fluid is expected to exhibit excellent salt-resistance and temperature-resistance. In this work, the self-assembled microstructures and microscopic flow properties of docosyl(trimethyl)aza-nium chloride (DCTAC) NaCl solutions were systematically investigated by means of cryogenic transmis-sion electron microscopy (cryo-TEM), rheo-small angle neutron scattering (rheo-SANS), steady-state and dynamic rheology. It is found that DCTAC forms long, linear or branched, flexible or stiff wormlike micelles depending on NaCl concentration. The increase in salt content simultaneously promotes the growth of worm length and the formation of branches. While the worm chain elongation plays a domi-nant role in mid-range of NaCl concentrations, the branching formation acts as a leading role in supper high NaCl concentrations, which results in rheological properties experiencing a significant increase fol-lowed by a certain decrease upon increasing NaCl content up to ti 20 wt%. Moreover, DCTAC shows much better thickening power than corresponding homologue surfactants bearing shorter hydrophobic tail in brine, and DCTAC solution also shows much better temperature-resistance than them. These findings are helpful to understand salt effect on cationic surfactant self-assemble behavior, and the relationship between microstructure and solution macroscopical properties.(c) 2023 Elsevier B.V. All rights reserved.

Herein, we disclose a chemoselective and diastereoselective synthesis of the medicinally significant 4-alkylidene-tetrahydroquinoline via a redox-neutral vinylogous cascade condensation/[1,7]-hydride transfer/6-endo-trig cyclization strategy, which features a novel product skeleton, high chemoselectivity and diastereoselectivity, facile introduction of 4-alkylidenyl motifs, employment of α,β,γ,δ-unsaturated dicyanoalkenes as novel hydride acceptors, and green and metal-free conditions with water as the only by-product. Additionally, the versatility of α,α-dicyanoalkenes has been fully exploited as hydride acceptors and γ-exclusive nucleophiles consecutively for accessing novel heterocyclic skeletons.

Two published genomes of Luffa cylindrica, 'SG2019' and 'SO3', were used to develop polymorphic SSR markers for L. cylindrica by searching and comparing the SSR motifs at the same site in the two genomes. Based on the SSR search conditions and primer design criteria, 2130 polymorphic SSR markers for L. cylindrica were developed. The main motif type was dinucleotide, accounting for 80.28% of the total; the main motif units were AT/AT and AAT/ATT, accounting for 87.80% of the total. Furthermore, 40 polymorphic SSR markers developed in this study were randomly selected and amplified in 24 Luffa samples. According to the results, the 40 polymorphic SSR markers showed an amplification rate of 100% and a polymorphism rate of 80%. Cluster analysis classified the 24 Luffa samples into two main groups, L. cylindrica and L. acutangula. Overall, the polymorphic SSR markers developed in this study display a high polymorphic rate and reliable utilization value.

We systematically attempt to evaluate the influencing factors of drug treatment compliance in childhood asthma and to provide evidence for improving patient’s treatment compliance and improving treatment success rate. The Chinese literatures that met the inclusion and exclusion criteria, such as Wanfang Medical Database, China National Knowledge Infrastructure, VIP Chinese Science and Technology Periodical Database and Chinese Biomedical Database were systematically searched. Two researchers screened the literature, conducted strict quality evaluation, extracted data from literatures that met the quality standards and used RevMan5.3 statistical software to make forest charts for outcome indicators and analyze effects. A total of 13 literatures were included. Meta-analysis results showed that lack of asthma knowledge, bad psychology and parent’s trust in medical staff had no statistically significant effects on children’s treatment compliance, while the degree of illness had a statistically significant impact on compliance (p<0.1), the pooled odds ratio and 95 % confidence interval was 0.31 (0.22-0.43). The severity of illness is the main factor for drug treatment compliance in childhood asthma.

Antioxidant and hepatoprotective activities in vitro of saffron petals were examined in this study for better utilizing saffron (Crocus sativus L.) biowaste. Using the DPPH and ABTS radical scavenging method, we compared the antioxidant activity and the content of total flavonoid extracts from petals (TFESP), stamens (TFESS), and both saffron petals and stamens (TFEMS). The results showed that the antioxidant capacity and the flavonoid content of TFESP were higher than those of TFESS and TFEMS. Then, the hepatoprotective activity of TFESP was determined, and the silymarin was used as a positive control. The main components of TFESP were analysed by ultrahigh performance liquid chromatography (UPLC) photodiode array (PDA)/mass spectrometry (MS) and nuclear magnetic resonance (NMR). The result showed that (1) TFESP could release oxidative liver injury induced by tert-butyl hydroperoxide (t-BHP). (2) TFESP could reduce the accumulation of reactive oxygen species (ROS); enhance the activity of superoxide dismutase (SOD), catalase (CAT), and glutathione (GSH); and then improve the total antioxidant capacity (T-AOC) in BRL-3A cells. (3) TFESP could enhance the expression of B-cell lymphoma-2 (BCL-2) and decrease the expression of caspase-3 and caspase-9; increase the expression of Kelch-like ECH-associated protein-1 (Keap-1), nuclear factor, erythroid 2-related factor 2 (Nrf2), superoxide dismutase, and heme oxygenase 1 (HO-1); and downregulate inducible nitric oxide synthase (INOS), interleukin-6 (IL-6), and nuclear factor kappa B-9 (NF-κB-9). (4) The main hepatoprotective component of TFESP was identified as kaempferol-3-o-sophoroside. The mechanism may be that kaempferol-3-o-sophoroside can protect t-BHP-induced cell injury by regulating the expression of antioxidant, antiapoptotic, and anti-inflammatory genes. Thus, saffron petals are a potential hepatoprotective resource worthy of development.

Greengage wine is gaining increasing attention in Asia for its rich nutritional elements and medicinal value. However, the treatment of the fermentation waste after brewing is a problem that remains unsolved. This work proposed to valorize the fermentation waste extract by a simple centrifugation. The bioactive compounds of the fermentation waste were investigated, including total flavonoids, total phenols, specific phenols and volatile compounds. The antioxidant and antibacterial capacities of the waste extract were also evaluated. The results revealed that the total phenol (1.34 mg GAE/g EPW) and total flavonoid (1.17 mg RE/g EPW) of the fermentation waste extract were still considerable. The fermentation waste also showed high DPPH radical scavenging capacity (5.39 μmol TE/g EPW) and high ABTS radical scavenging capacity (9.80 μmol TE/g EPW). Both GC-MS and LC-MS analysis identified key bioactive compounds, such as linalool, terpineol, β-ionone, neochlorogenic acid and chlorogenic acid, which have high antioxidant capacity and strong, thermal-stable antibacterial capacity. All these characteristics show a promising future for valorized fermentation waste, for example, in food additives or mouthwash.

To study the functions of bHLH TFs in Brassica napus, five fulllength cDNA sequences of BnbHLH92 genes are cloned from Brassica napus by the homologous cloning method and named as BnbHLH92-1, BnbHLH92-2, BnbHLH92-3, BnbHLH92-4, BnbHLH92-5, respectively. And the length of the coding region for each gene is 738, 657, 684, 741, 717 bp, respectively. The qRTPCR result shows that BnbHLH92-1 gene is expressed in the root of the bolting stage and flowering stage as well as the two leaves stage, but the other BnbHLH92 genes mainly expressed in the roots of the bolting stage and the flowering stage. The expression of BnbHLH92 genes is significantly affected by abiotic stress, which increases the amount of genes expression. The expression level of five BnbHLH92 genes reach its highest under a low temperature stress for 4, 6, 6, 6 and 6 h, under a high temperature stress for 2, 6, 6, 8 and 4 h, under a salt stress for 6, 6, 24, 24 and 24 h, respectively. The expression of each BnbHLH92 gene is also increased in different degrees under ABA induction. It is found that there is an ABA response element (ABRE) on the promoter sequence of each BnbHLH92 gene.

Davidia involucrata Baill. is a rare plant endemic to China. Its exclusive evolutionary position and specific floral organs endow it with a high research value. However, a lack of genomic resources has constrained the study of D. involucrata functional genomics. Here, we report D. involucrata transcriptome reads from different floral tissues pooled from six individuals at two developmental stages using Illumina HiSeq technology and the construction of a high-quality reference gene set containing a total of 104,463 unigenes with an N50 of 1,693 bp and 48,529 high-quality coding sequences. The transcriptome data exhibited 89.24% full-length completeness with respect to the benchmarking universal single-copy (BUSCO) dataset and a PLAZA CoreGF weighted score of 98.85%. In total, 65,534 (62.73%) unigenes were functionally annotated, including 58 transcription factor families and 44,327 simple sequence repeats (SSRs). In addition, 96 known and 112 novel miRNAs were identified in the parallel small RNA sequencing of each sample. All these high-quality data could provide a valuable annotated gene set for subsequent studies of D. involucrata.

A visible-light induced radical silylation to dibenzosiloles from biarylhydrosilanes is described. The products were obtained in satisfactory yields under mild and water/air compatible conditions, providing an efficient and practical method for the synthesis of difunctionalized siloles by using a cheap organic dye photocatalyst. The method is tolerated by a wide range of functional groups and has a broad substrate scope. Light/dark experiments and quantum yield measurements provided support for a photocatalytic pathway rather than a chain process.

Cadmium (Cd) is a widespread toxic heavy metal trace pollutant worldwide. The ability of Cd absorption and accumulation highly varies among different species and varieties. In order to screen oilseed rape cultivars which are appropriate for cultivation and application in Cd-contaminated soils, we conducted the field trial of 32 oilseed rape varieties in Shifang County of Chengdu Plain. The various biomass, Cd accumulation, and distribution patterns were investigated via determining the Cd concentration in different plant tissues. Moreover, the food safety risks of rapeseeds were finally assessed. The results indicated diverse responses to Cd stress appeared in various tested varieties, including plant biomass, seed yield, Cd concentration, and proportion in different tissues. And most Cd were concentrated in non-edible parts. Through cluster analysis, we found that Nanchongjie, Pengzhoubai, and J-25 belong to high-biomass and high-Cd-accumulated groups in experimental cultivars, which indicated that they could possess more biomass and gather higher Cd content in overground part, so they could be great materials for phytoremediation in Cd-polluted area. Besides, combined with the risk assessment of food safety in rapeseeds, cultivars 72A and 47 with the traits of high yield, low-Cd concentration, and low food safety risk can be considered as suitable materials to widely plant as cash crop. These results provide valuable reference for practical planting and application of oilseed rape in Cd-polluted areas.

The main purposes of this study were to screen the antioxidant activities of various fractions of Hemerocallis citrina Baroni and test their hepatoprotective effects in vitro. Antioxidant assays (2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3ethylbenzothiazoline-6-sulfonic acid) (ABTS), and reducing power experiments) and tert-butyl hydroperoxide- (t-BHP-) induced BRL-3A oxidative damage experiments were performed in vitro. The H. citrina ethyl acetate fraction (HCEA) was determined to have strong antioxidant activity because of its high flavonoid and polyphenol content. Ultraperformance liquid chromatography- (UPLC-) photodiode array (PDA)/mass spectrometry (MS) analysis showed that the main components of the HCEA were flavonoids and caffeic acid derivatives. A total of 17 compounds were identified. HCEA also effectively protected the liver against t-BHP-induced oxidative stress injury and significantly reduced reactive oxygen (ROS) accumulation. Moreover, HCEA significantly reduced levels of alanine aminotransferase (ALT), aspartate transaminase (AST), and lactate dehydrogenase (LDH). Further studies have shown that HCEA inhibits t-BHP-induced apoptosis by increasing B-cell lymphoma-2 (BCL-2) activity and decreasing caspase-3 and caspase-9 activity. Moreover, HCEA enhanced the activity of antioxidant enzymes superoxide dismutase (SOD) and catalase (CAT), as well as the total antioxidant capacity (T-AOC), and increased the antioxidant level of glutathione (GSH) in BRL-3A cells. HCEA increased the antioxidant capacity of cells by increasing the gene expression of AMP-activated protein kinase (AMPK), extracellular signal-regulated kinase (ERK), P38, nuclear factor, erythroid 2 like 2 (Nrf2), SOD, glutamate-cysteine ligase catalytic subunit (GCLC), glutamate-cysteine ligase modifier subunit (GCLM), and heme oxygenase 1 (HO-1), which are associated with antioxidant pathways to protect against oxidative stress. In conclusion, HCEA protected BRL-3A cells against t-BHP-induced oxidative stress damage via antioxidant and antiapoptosis pathways. Therefore, H. citrina Baroni may serve as a potential hepatoprotective drug.

Background Standard neoadjuvant concurrent chemoradiotherapy does not improve overall survival in stage II–III rectal cancer and total neoadjuvant treatment might be a better treatment option for patients with high risk factors. We aimed to evaluate the safety and efficacy of total neoadjuvant treatment (CAPOX [oxaliplatin and capecitabine] and intensity-modulated radiation therapy [IMRT] with volumetric-modulated arc therapy [VMAT]) in patients with rectal cancer with high risk factors. Methods We did this phase 2 trial in patients who were diagnosed with stage II–III rectal cancer. We recruited patients with at least one high risk factors: cT4b, cN2, extramural venous invasion positive, involved mesorectal fascia positive, or lateral lymph nodes positive. Three cycles of induction CAPOX were followed by pelvic IMRT with VMAT and two cycles of concurrent CAPOX. Three cycles of consolidation CAPOX were delivered after radiotherapy. Primary endpoints were pathological complete response and R0 resection. This study is registered with the Chinese Clinical Trial Registry, number ChiCTR-OIN-17012284. Findings From June, 2015, to April, 2017, 47 patients were evaluable. One patient (2%) who had acute intestinal obstruction after the first cycle of chemotherapy underwent emergency total mesorectal excision. A total of 29 patients (62%) completed eight cycles of chemotherapy and 46 patients (98%) completed the planned radiotherapy. 17 patients (36%) achieved a pathological complete response or clinical complete response, in which 12 patients (71%) completed eight cycles of chemotherapy. Five patients (11%) refused the operation and selected a watch and wait strategy. R0 resection for patients who underwent total mesorectal excision was 100%. The mean operation time was 207 min (median 195 min, range 120–370 min) and the mean estimated blood loss was 89 mL (median 50 mL, range 10–500 mL). The most common grade 3 or worse adverse events associated with the neoadjuvant administration were leucopenia (10%), diarrhoea (5%), radiation dermatitis (5%), and thrombocytopenia (2%). The most common grade 3 or worse surgery-related complications were pelvic abscesses, anastomotic leakage, and haemorrhage, which were observed in one patient, respectively. Interpretation Total neoadjuvant treatment is effective and safe for patients with local advanced rectal cancer with high risk factors. Long-term efficacies of total neoadjuvant treatment need to be evaluated. Funding Project of Health and Family Planning Commission of Sichuan Province.

Carbon dots could be extended in biological applications for drug delivery and photothermal therapeutics due to their ability to improving therapeutic effect and reducing side effects. Here, we use doxorubicin (DOX) as the model drug, the amino and carboxyl coated magnetofluorescent carbon quantum dots (GdN@CQDs) as a carrier, Genipin (GP) as cross-linking agent to design and prepare a multifunctional drug delivery system triggered by near-infrared (NIR) light and pH dual-stimuli. The cytotoxicity of the nanoparticles has been examined by MTT assay. The fluorescent GdN@CQDs/GP serves as both a controllable drug release gatekeeper and a fluorescent probe for the visualization of the drug delivery process. In vitro and in vivo experiments showed that this platform can deliver anti-cancer drugs to cells, releasing them intracellular upon NIR irradiation, and effectively eliminate tumors through chemo-photothermal synergistic therapeutic effect.

A new calcium(II) complex with anti-inflammatory drug naproxen as ligand was synthesized and characterized. The binding mechanisms of calcium(II)-naproxen complex to human serum albumin (HSA) were investigated under simulative physiological conditions. The acting forces for the binding mechanisms were hydrogen bonds and van der Waals forces. Calcium(II)-naproxen complex and naproxen sodium may competitively bind to HSA at the same active Site I. Albumin binding weakened under the coexistence of the two substances. Thus, combining naproxen sodium and calcium(II)-naproxen complex may enhance treatment efficacy because of the synergistic effect.

We report the observation of a screw-dislocation-driven spiral growth of DMDPC organic thin films using physical vapor deposition. The existence of screw dislocations was clearly confirmed by the observations of outcropped steps, single monolayer height helical periodicity and spiral fringes.

Binding interaction of human serum albumin (HSA) with allura red AC, a food colourant, was investigated at the molecular level through fluorescence, ultraviolet-visible, circular dichroism (CD) and Raman spectroscopies, as well as protein-ligand docking studies to better understand the chemical absorption, distribution and transportation of colourants. Results show that allura red AC has the ability to quench the intrinsic fluorescence of HSA through static quenching. The negative values of the thermodynamic parameters ΔG, ΔH, and ΔS indicated that hydrogen bond and van der Waals forces are dominant in the binding between the food colourant and HSA. The CD and Raman spectra showed that the binding of allura red AC to HSA induces the rearrangement of the carbonyl hydrogen-bonding network of polypeptides, which changes the HSA secondary structure. This colourant is bound to HSA in site I, and the binding mode was further analysed with the use of the CDOCKER algorithm in Discovery Studio.

AbstractA facile and efficient method for the synthesis of 1,8‐dioxapyrenes and 1,12‐dioxaperylenes through Rh‐catalyzed direct cyclization of 1,4‐naphthoquinones and 9,10‐phenanthraquinones with alkynes is developed.

A new potential drug aluminum(III)–baicalein complex (ALBC) was synthesized and characterized. The binding mechanisms of baicalein (BC) and ALBC to human serum albumin (HSA) under simulative physiological conditions were investigated, in order to understand the pharmacokinetics of BC and ALBC. Fluorescence spectroscopy results suggested that the binding level of BC is higher than that of ALBC. Results of UV–vis, synchronous fluorescence, 3D fluorescence, circular dichroism and Fourier transform infrared spectroscopic analyses consistently demonstrated that the conformation of HSA was altered when bound to BC or ALBC. The distance between HSA as a donor and BC (or ALBC) as an acceptor was determined via fluorescence resonance energy transfer. The results of competitive experiments and molecular docking studies indicated that BC was located in site I (subdomain IIA) on HSA and that ALBC was bound to HSA mainly within site II (subdomain IIIA). Copyright © 2015 John Wiley & Sons, Ltd.

This study employed near-infrared (NIR) spectroscopy to analyze content uniformity, moisture content, compression force, tablet hardness, average particle size, and particle-size distribution. The content uniformity, moisture content, compression force, tablet hardness, and average particle size models yielded high correlation coefficients (R2) of 0.99582, 0.99725, 0.99620, 0.96294, and 0.98421, respectively, whereas the particle size distribution models showed good predictive ability. Conventional criteria such as R2, root-mean-square error of calibration, and the root-mean-square error of prediction were used to evaluate the accuracy and precision of the model. To ensure the accuracy and predictability of the content model for low-dose tablets, additional validation and reliability evaluations were performed using 70%, 80%, 100%, 120%, and 130% drug concentrations as well as 90% and 110% active content formulations. Near-infrared spectroscopy with multivariate modeling is a rapid, nondestructive technique for the characterization of the manufacturing process.