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The conazole fungicide propiconazole is frequently found in vegetables although usage is not allowed. To overcome the high-cost and time-consuming labour requirements of instrumental methods, we developed a simple and visual lateral flow immunoassay for the sensitive determination of propiconazole. A hapten was carefully designed to raise a monoclonal antibody against propiconazole. Bal b/c mice were immunised with the hapten-carrier protein conjugate and a specific monoclonal antibody (mAb) was produced. Based on this mAb, a sensitive immunochromatographic strip assay (ICA) was established for rapid screening of propiconazole in vegetable samples. After optimisation of analytical parameters, the ICA strip showed a detection limit of 0.13 ng g���1 and a linear range from 0.5 to 80 ng g���1 using a strip reader. The assay also can be read by the naked eye with a visual limit of detection of 80 ng g���1. The recoveries for spiked vegetable samples by ICA ranged from 85.2% to 114.9%, with a coefficient of variation less than 11.7%. The assay time is within 45 min for a single sample including the sample pre-treatment. For spiked and blind samples, the detection capability of ICA was equivalent to liquid chromatography-mass spectrometry.

With the aim of developing novel annulations via ketene intermediates, allenyl imide and alkynoates bearing good leaving groups are used for their function in a tandem conjugate addition-elimination reaction (SN2' type) promoted by nucleophilic phosphine catalysts. By utilizing thioamides as 1S,3N-bis-nucleophiles, [3+3] and [3+2] annulations have been established to allow rapid access to 1,3-thiazin-4-ones and 5-alkenyl thiazolones in high yields, respectively. Furthermore, the possible reaction mechanisms are proposed on the basis of deuterium labeling experiments and density functional theory calculations.

1,3-Dipolar cycloaddition of azomethine ylides and electron deficient alkenes is widely studied for rapid installation of pyrrolidine frameworks. Despite significant advances, the major limitations of this process are creating chiral pyrrolidines bearing a quaternary stereogenic center and controlling the diastereoselectivity. Herein, we present an exo-selective asymmetric 1,3-dipolar cycloaddition to access chiral pyrrolidines with four contiguous stereogenic centers, including a fluorinated quaternary stereogenic center at C4, wherein a Cu(OAc)2/(S)-tol-BINAP catalyst and α-fluoro-α,β-unsaturated arylketone dipolarophiles are used. Epimerization promoted by 5.0 equiv of DBU at 90 °C results in the formation of chiral 4-fluoropyrrolidines (exo') while maintaining the optical purity.

By direct electrospinning poly(vinylidene fluoride) (PVDF)/Si3N4 blend solution on the Na2Ni[Fe(CN)6] electrode, a flexible separator@electrode combination is obtained. This combination is closely cross-linked by the -CH2 CF2- chain of β-PVDF in the separator and electrode, which delivers unique advantages in flexibility, thermal stability, tensile strength and interfacial resistance. Meanwhile, the PVDF/Si3N4 separator has a higher porosity (84.2%) and ionic conductivity (4.1 × 10−3 S cm−1), making the combination display an excellent electrochemical performance with a high initial coulombic efficiency of 96.8%, capacity retention rate of 92.2% after 503 cycles and rate capability of 78 mAh g − 1 at 5 C.

The Petasis reaction using (1S,2R)-1-amino-2-indanol as the substrate and an activator to construct α- and β-butadienyl amines in optically pure forms was realized, which are otherwise difficult to prepare. The reactions feature a metal-free nature, broad substrate scope, complete regioselectivities (γ-selectivity of pinacol homoallenyl- and isoprenylboronates), and high to excellent chirality induction (up to >20 : 1 dr). The favored nucleophilic addition across the Si-face of the imine intermediate was explained using DFT calculations of the six-membered chair-like transition state.

Traditional fermented soybean contains a variety of microflora. To obtain a comprehensive and accurate understanding of the microbial community structure and metabolic potential of fermented soybean, comparative metagenomics and metatranscriptomics were performed on a sample of fermented soybean in Yunnan Province. Metagenomic DNA and metatranscriptomic RNA were sequenced using Illumina HiseqTM2500, which yielded a total of 92,192,276 reads, with an average read length of 150 bp and 38,798,262 paired-end sequences, with an average length of 151 bp. The results show that Providencia stuartii was the most abundant species and the genes of carbohydrates (2296, 13.30%), protein metabolism (1530, 8.86%), and amino acids and amino acid derivatives (1423, 8.24%) were dominant. The expression levels of the genes belonging to amino acid transport and metabolism processes were the highest according to the reads per length of transcript in kilo-bases per million mapped reads (RPKM) values, followed by energy production and conversion and carbohydrate transport and metabolism. The metabolic pathways were primarily associated with carbohydrates, proteins and amino acids, which might be in accordance with the high levels of proteins and other nutrients in soybeans. Overall, these findings provide insights into the community structure and metabolic potential of the fermented soybean microbiome.

The present communication aims to synthesise the plasmonic nanocomposite Au0(NPs)/TiO2 by a facile route and to utilize material in the efficient removal of Alizarin Yellow in aqueous solutions using the UV-A light. Au0-nanoparticles were in situ doped with titania network using template method. Polyethylene glycol was employed as filler media. The nanocomposites Au0(NPs)/TiO2 (non-template) and Au0(NPs)/TiO2(T) (template) were characterized by the XRD and DRS (Diffuse Reflection Spectroscopy) methods. Surface characteristics were discussed by the SEM and TEM pictures of these materials. The interplanar distance of Au(NPs) were found to be 0.14 nm and 0.20 nm for the materials Au0(NPs)/TiO2 and Au0(NPs)/TiO2(T), respectively. The Atomic Force Microscopy (AFM) analysis showed heterogeneous surface structure and TiO2 were pillared on the surface. Physico-chemical studies deduced the mechanistic pathways of removal. The pseudo-first order rate constant values were decreased with the increase in dye concentrations. Further, mineralization of Alizarin Yellow was obtained at wide range of pH (pH 4.0–8.0). The nanocomposite thin films showed fairly a good stability for repeated cycle of operations in removal of Alizarin Yellow. The photocatalyst shown greater applicability in the real matrix treatment using Tlwang river water.

The goal of this study was to explore the regulatory mechanisms of phenyllactic acid (PLA) overaccumulation in Lactobacillus plantarum. The dynamics of PLA production revealed that 24 h was a suitable fermentation time, at which one of the largest differences in PLA content between strains S1 and YM-4-3 was 22.42 mg/L. Additionally, an optimization experiment showed that PLA production under the optimal condition (sample YM-4-3y) was up to 400.74 mg/L, 7.61-13.26 times as those of YM-4-3 and S1. Subsequently, an integrated analysis of genomic, transcriptomic and metabolomic data revealed that, YM-4-3 and YM-4-3y, compared with S1, although lacking a complete de novo biosynthetic pathway, increased PLA production by strengthening the core pathway and central carbon metabolism, and weakening the biosynthesis pathway of amino acids and their derivatives. These changes can provide sufficient precursors and compensate for or balance the energy consumed by the reinforced core pathway.

Unprecedented phosphine-catalyzed [4+1] cycloadditions of allenyl imides have been discovered using various N-based substrates including methyl ketimines, enamines, and a primary amine. These transformations provide a one-pot access to cyclopentenoyl enamines and imines, or (chiral) γ-lactams via two geminal C-C bond or two C-N bond formations, respectively. Several P-based key intermediates including a 1,4-(bis)electrophilic α,β-unsaturated ketenyl phosphonium species have been detected by 31P NMR and HRMS analyses, which shed light on the postulated catalytic cycle. The synthetic utility of this new chemistry has been demonstrated through a gram-scaling up of the catalytic reaction as well as regioselective hydrogenation and double condensation to form cyclopentanoyl enamines and fused pyrazole building blocks, respectively.

The tetrapeptide Arg-Leu-Tyr-Glu (RLYE), a vascular endothelial growth factor (VEGF) receptor-2 antagonist, has been used previously either alone or in combination with chemotherapeutic drugs for treating colorectal cancer in a mouse model. We analyzed the half-life of the peptide and found that because of degradation by aminopeptidases B and N, it had a short half-life of 1.2 hours in the serum. Therefore, to increase the stability and potency of the peptide, we designed the modified peptide, N-terminally acetylated RLYE (Ac-RLYE), which had a strongly stabilized half-life of 8.8 hours in serum compared with the original parent peptide. The IC50 value of Ac-RLYE for VEGF-A-induced endothelial cell migration decreased to approximately 37.1 pM from 89.1 pM for the parent peptide. Using a mouse xenograft tumor model, we demonstrated that Ac-RLYE was more potent than RLYE in inhibiting tumor angiogenesis and growth, improving vascular integrity and normalization through enhanced endothelial cell junctions and pericyte coverage of the tumor vasculature, and impeding the infiltration of macrophages into tumor and their polarization to the M2 phenotype. Furthermore, combined treatment of Ac-RLYE and irinotecan exhibited synergistic effects on M1-like macrophage activation and apoptosis and growth inhibition of tumor cells. These findings provide evidence that the N-terminal acetylation augments the therapeutic effect of RLYE in solid tumors via inhibition of tumor angiogenesis, improvement of tumor vessel integrity and normalization, and enhancement of the livery and efficacy of the coadministered chemotherapeutic drugs. SIGNIFICANCE STATEMENT: The results of this study demonstrate that the N-terminal acetylation of the tetrapeptide RLYE (Ac-RLYE), a novel vascular endothelial growth factor receptor-2 (VEGFR-2) inhibitor, significantly improves its serum stability, antiangiogenic activity, and vascular normalizing potency, resulting in enhanced therapeutic effect on solid tumors. Furthermore, the combined treatment of Ac-RLYE with the chemotherapeutic drug, irinotecan, synergistically enhanced its antitumor efficacy by improving the perfusion and delivery of the drug into the tumors and stimulating the conversion of the tumor-associated macrophages to an immunostimulatory M1-like antitumor phenotype.

This work aims to uncover how glucose affected the production of phenyllactic acid (PLA) and p-hydroxyphenyllactic acid ( p-OH-PLA). The highest yields of PLA (68.53 mg/L) and p-OH-PLA (50.39 mg/L) were observed after Lactobacillus plantarum strain YM-4-3 fermentation in media containing 30 and 10 g/L glucose, respectively. Additionally, the antimicrobial activity of YM-4-3 against food-borne pathogens and the NADH/NAD+ ratio were positively correlated with the production of PLA and p-OH-PLA, respectively. In addition, a 2-oxoglutarate/malate translocator coding gene ( Omt1) was selected based on the qPCR results, and its knockout mutant, compared with the wild-type strain YM-4-3, showed that the PLA and p-OH-PLA production was decreased by 1.37-6.99 and 1.53-1.59 times, respectively. This result indicated that OMT1 was involved in the biosynthesis of PLA and p-OH-PLA. To conclude, this study suggests that glucose, NADH/NAD+ ratio and/or the Omt1 gene, PLA, and p-OH-PLA production, and antimicrobial activity contribute to a cause-and-effect relationship.

Vascular endothelial growth factor (VEGF) plays a pivotal role in pathologic ocular neovascularization and vascular leakage via activation of VEGF receptor 2 (VEGFR2). This study was undertaken to evaluate the therapeutic mechanisms and effects of the tetrapeptide Arg-Leu-Tyr-Glu (RLYE), a VEGFR2 inhibitor, in the development of vascular permeability and choroidal neovascularization (CNV). In cultured human retinal microvascular endothelial cells (HRMECs), treatment with RLYE blocked VEGF-A-induced phosphorylation of VEGFR2, Akt, ERK, and endothelial nitric oxide synthase (eNOS), leading to suppression of VEGF-A-mediated hyper-production of NO. Treatment with RLYE also inhibited VEGF-A-stimulated angiogenic processes (migration, proliferation, and tube formation) and the hyperpermeability of HRMECs, in addition to attenuating VEGF-A-induced angiogenesis and vascular permeability in mice. The anti-vascular permeability activity of RLYE was correlated with enhanced stability and positioning of the junction proteins VE-cadherin, β-catenin, claudin-5, and ZO-1, critical components of the cortical actin ring structure and retinal endothelial barrier, at the boundary between HRMECs stimulated with VEGF-A. Furthermore, intravitreally injected RLYE bound to retinal microvascular endothelium and inhibited laser-induced CNV in mice. These findings suggest that RLYE has potential as a therapeutic drug for the treatment of CNV by preventing VEGFR2-mediated vascular leakage and angiogenesis.

Microwave assisted extraction (MAE) technology was used to extract polysaccharides from Porphyra Haitanensis (PHP) with water. Polysaccharide yield was used as index to evaluate the extraction process. Effects of ratio of water to raw material (X1), microwave power (X2) and extraction time (X3) on polysaccharide yield were investigated. Based on single factor experiment, MAE process of PHP was optimized using response surface methodology. Chemical characterization of PHP was investigated based on analysis of chemical compositions, monosaccharide and thermal gravimetric. The antitumor activities of PHP in vivo and in vitro were evaluated. The results indicated that the optimal conditions for MAE of PHP were ratio of water to raw material 28.98(mL/g), microwave power 77.84 W and extraction time 14.14 min. MAE was a suitable and efficient technique for PHP extraction compared with traditional hot water extraction. Analysis of chemical characterization showed that PHP contained 75.36 ± 1.48% of total carbohydrates, 24.63 ± 1.69% of uronic acid residue and no proteins with monosaccharides such as rhamnose, arabinose, xylose, mannose, glucose, and galactose in a molar ratio of 10.25:9.38:1:12.45:9.9:11.55. Thermal gravimetric analysis suggested that PHP was relatively stable below 170℃. PHP had obvious effect on inhibiting proliferation, inducing apoptosis of SGC-7901 tumor cells in vitro and antitumor effect on SGC-7901 tumor-bearing mice in vivo. The results suggested that PHP had the potential for clinical use in cancer prevention and treatment.

Prussian blue analogues are considered as the promising cathodes for sodium-ion batteries. Since the electrochemical properties are closely related to the morphology, the monodisperse copper hexacyanoferrate nanoflakes with highly crystalline are synthesized by a glycol-assisted coprecipitation method and a tentative synthetic mechanism is proposed to explain the formation of nanostructures. The structure and electrochemical properties are characterized by X-ray photoelectron spectroscopy, FTIR spectra and galvanostatic cycle tests, respectively. Due to the novel architecture of copper hexacyanoferrate, a high electrochemical activity is obtained, resulting a high initial coulombic efficiency of 93%, a capacity retention of 73% at 1 C after 300 cycles and 51 mAh g −1 is maintained at high rate of 15 C at 25 °C.

It has been shown previously that a novel tetrapeptide, Arg-Leu-Tyr-Glu (RLYE), derived from human plasminogen inhibits vascular endothelial growth factor (VEGF)-induced angiogenesis, suppresses choroidal neovascularization in mice by an inhibition of VEGF receptor-2 (VEGFR-2) specific signaling pathway. In this study, we report that a modified tetrapeptide (Ac-RLYE) showed improved anti-choroidal neovascularization (CNV) efficacy in a number of animal models of neovascular age-related macular degeneration (AMD) which include rat, rabbit, and minipig. The preventive and therapeutic in vivo efficacy of Ac-RLYE via following intravitreal administration was determined to be either similar or superior to that of ranibizumab and aflibercept. Assessment of the intraocular pharmacokinetic and toxicokinetic properties of Ac-RLYE in rabbits demonstrated that it rapidly reached the retina with minimal systemic exposure after a single intravitreal dose, and it did not accumulate in plasma during repetitive dosing (bi-weekly for 14 weeks). Our results suggested that Ac-RLYE has a great potential for an alternative therapeutics for neovascular (wet) AMD. Since the amino acids in human VEGFR-2 targeted by Ac-RLYE are conserved among the animals employed in this study, the therapeutic efficacies of Ac-RLYE evaluated in those animals are predicted to be observed in human patients suffering from retinal degenerative diseases.

Long-term variation of nitrate in the East Sea was monitored in order to investigate impact of Three Gorges Dam (TGD) in the Changjiang River’s upstream, China and Nakdong River’s estuary dam, Korea. Tracing source of nitrate was another objective in this study. For this study, nutrient data were collected for 20 years from 1999 to 2018 in the East Sea, and divided into 4 sections, and evaluated whether a significant difference exists among the averages of nitrate concentrations. The concentrations of nitrate were affected by the major rivers (the Nakdong and the Taehwa Rivers) and Tsushima Warm Current (TWC) which diverged from the Kuroshio Current passing through East China Sea (ECS). Our results also indicated that long-term nitrate concentrations decreased and its reasons. First, the construction of TGD in the upstream of the Changjiang River may have resulted in the decrease of the nitrate supply in the river and ECS which is carried by TWC, toward the East Sea. Second, decrease in the nitrate flux of the Nakdong River’s estuary due to the construction of the estuary dam and sewer treatment plant could also be a factor for the nitrate decrease in the East Sea. Therefore, anthropogenic activities from the Nakdong River and Changjiang River had a long-term effect on the East Sea’s nitrate concentrations. The amount of nitrate runoff reduced by the anthropogenic activities influenced the nitrate levels over a long period by the flow of currents in the East Sea.

Staphylococcus aureus and Pseudomonas aeruginosa are bacteria that cause biofilm-associated infections. The aim of this study was to determine the activity of combined betacyanin fractions from Amaranthus dubius (red spinach) and Hylocereus polyrhizus (red pitahaya) against biofilms formed by co-culture of S. aureus and P. aeruginosa on different polymer surfaces. Various formulations containing different concentrations of the betacyanin fractions were investigated for biofilm-inhibiting activity on polystyrene surfaces using crystal violet assay and scanning electron microscopy. A combination of each betacyanin fraction (0.625 mg mL−1) reduced biofilm formation of five S. aureus strains and four P. aeruginosa strains from optical density values of 1.24–3.84 and 1.25–3.52 to 0.81–2.63 and 0.80–1.71, respectively. These combined fractions also significantly inhibited dual-species biofilms by 2.30 and reduced 1.0–1.3 log CFU cm−2 bacterial attachment on polymer surfaces such as polyvinyl chloride, polyethylene, polypropylene and silicone rubber. This study demonstrated an increase in biofilm-inhibiting activity against biofilms formed by two species using combined fractions than that by using single fractions. Betacyanins found in different plants could collectively be used to potentially decrease the risk of biofilm-associated infections caused by these bacteria on hydrophobic polymers.

Chiral phosphoric acid-catalyzed asymmetric aldehyde prenylation has been established using an α,α-dimethyl allyl boronic ester. The transformation provides an expedient access to a wide array of aryl, heteroaryl, aryl-substituted alkenyl as well as primary and secondary aliphatic homoprenyl alcohols with excellent asymmetric induction. The utility of this asymmetric catalysis strategy has been demonstrated through a short and efficient total synthesis of the two natural products (‒)-rosiridol and (‒)-bifurcadiol.

Chinese jujube (Zizyphus jujuba Miller) is a well-known oriental medicinal plant that has various biological activities. In this study, a novel water-soluble proteoglycan (ZSG4b) was isolated from Zizyphus jujuba cv. Jinsixiaozao and its effect on the complement system was investigated. ZSG4b was extracted with hot water and purified by DEAE-Sepharose CL-6B and Sepharose CL-6B column chromatography. It was eluted as a single symmetrical narrow peak on high-performance gel-permeation chromatography (HPGPC) and the average molecular weight was estimated to be 1.4 × 10^5 Da. ZSG4b contained 83.5% glycan and 9.7% protein. Gas chromatography analysis result indicated that the glycan portion of ZSG4b was composed mainly of rhamnose, arabinose, mannose and galactose in a molar ratio of 13.8:4:3:8. It also contains 29% uronic acid as determined by m-hydroxybiphenyl method. The presence of galacturonic acid was estimated by the increase of galactose content in the carboxyl-reduced ZSG4b. The amino acid composition showed that it was rich in aspartic acid, glutamic acid, serine, threonine and leucine; the molar content of these five amino acids constituted 62.8% of the total amino acids. The β-elimination reaction demonstrated that the protein and glycan were linked by O-linkage. ZSG4b exhibited high anti-complement activity which was increased in accordance with the concentration below 120 μg/mL in vitro.

The objective of this study was to evaluate the effects of a three-strain yogurt formulation in slow-transit constipation (STC) patients. Each individual in both treatment groups consumed 250 mL of the formulated yogurt daily for a week (7 days), and fecal samples were collected for gut microbiota and short-chain fatty acid (SCFA) analyses. A significant increase in the defection frequency (p<0.001) and bacterial diversity (p=0.027) at the 100% sequence homology level and a decrease in the concentrations of acetic acid (p=0.014), propionic acid (p=0.019), and butanoic acid (p=0.005) were observed after the STC patients consumed three-strain yogurt formulation. In addition, the consumption of the three-strain yogurt formulation significantly altered the composition of the intestinal bacteria in the STC patients. The relative abundances of 23 genera in the top dominating genera were altered significantly after the STC patients consumed the yogurt. In summary, the consumption of 250 mL day− the three-strain yogurt formulation described in this study can play a role in improving the symptoms of STC.

The intermolecular [2 + 2] cycloaddition/isomerization between allenyl imides and N-(2-methoxyphenyl) aldimine counterparts catalyzed by a Ni(ClO4)2·6H2O Lewis acid at room temperature was discovered, providing a facile access to 1-azadiene derivatives with high atom economy. The incorporation of an 2-oxazolidinone group into allene amides resulted in unusual reactivity for the imine-metathesis and synthetic application to a chiral γ,δ-unsaturated β-ketoimide. A mechanistic experiment using density functional theory (DFT) computation in CH2Cl2 with the B3LYP functional rationalized the proposed catalytic pathway involving initial stepwise [2 + 2] cycloaddition to provide an azetidine species, two-time proton transfer to form a 2-azetine intermediate, and final conrotatory ring opening for trans-1-azadiene-based substances.

Red pitahaya fruit is rich in purplish-red color water-soluble betacyanins. The effect of refrigerated storage at 4 °C on the betacyanin composition of red pitahaya was monitored each day, for one week, using HPLC. The betacyanin content of red pitahaya had increased by 57.2% after storage for six days at 4 °C. From day 2 to day 7, the phyllocactin content decreased from 45.4 ± 1.5% to 38.3 ± 3.1%, whereas the betanin content increased from 37.9 ± 1.6% to 42.7 ± 1.5%. Antimicrobial activity was determined using the broth microdilution assay and expressed as minimum inhibitory concentration (MIC). As compared to the freshly harvested fruits (MIC values: 50,000–>50,000 μg mL−1), fruits that were stored for six days at 4 °C demonstrated better antimicrobial activity (MIC values: 3130–6250 μg mL−1) against 10 pathogenic Gram-positive and 6 Gram-negative bacteria. Betacyanin rich extract was also examined against normal human cell lines (HEK-293 and THP-1) and found to be not cytotoxic at the levels of 0.39–3.13 mg mL−1. In summary, refrigerated storage for 6 days increased the betacyanin content, changed the betacyanin composition in red pitahaya and contributed to higher antimicrobial activity.

We herein report an unprecedented addition reaction of pinacol gem-difluoroallylborates and imines enabled by a neighboring phenolic group in an N-protecting group under catalyst-free conditions, thus facilitating the construction of a wide range of racemic gem-difluorohomoallylamine derivatives. Based on the control experiments, a plausible transition state via the Zimmerman-Traxler model was proposed to elucidate the significance of the neighboring phenolic group, as well as the γ-selectivity of the boronate reagents.

The first chiral Brønsted acid-catalyzed asymmetric cascade allylboration/oxo-Michael reaction between o-formyl chalcones and allylboronate has been successfully discovered, which afforded chiral 1,3-disubstituted 1,3-dihydroisobenzofurans with a yield, diastereoselective ratio (dr) and enantioselective excess (ee) up to 94%, 2.5:1, and 98%, respectively. In addition, 2,3-dienylboronic pinacol ester was also applied into this cascade reaction with good catalytic results.

Ferrate(VI) was utilized to treat micro-pollutants—4-tert-octylphenol (TOP) and 17α-ethynylestradiol (EE2)—from aqueous solutions. Batch studies were conducted at various pHs (7.0 to 12.0) and concentrations of TOP/or EE2 (0.03 to 0.3mmol/L) using 0.1mmol/L ferrate(VI). Time-dependent degradation of TOP and EE2 was assessed as a function of pH and micro-pollutant concentrations and we found that significant mineralization of micro-pollutants was achieved by ferrate(VI) treatment. Second-order kinetics showed 1: 1 stoichiometry was obtained between the ferrate(VI) and TOP/or EE2. Further, the effect of several background electrolytes on degradation of TOP and EE2 by ferrate(VI) was evaluated, showing insignificant effect of degradation.

The aza-addition of aziridines to obtain vicinal-diamines was achieved under catalyst- and solvent-free conditions for the first time. Various aryl, alkyl and meso-bicyclic aziridines with a Ts-protecting group were tolerated, and aromatic amine-nucleophiles containing electron withdrawing and donating groups in the phenyl ring were applied. The plausible reaction mechanism involving hydrogen bonding and proton transfer was proposed. The synthetic utility of one addition adduct to the 4-amino-1,2,3,4-tetrahydroisoquinoline derivative through the Pictet–Spengler reaction was realized.

Betacyanins are reddish to violet pigments that can be found in red pitahaya (Hylocereus polyrhizus) and red spinach (Amaranthus dubius). This study investigated the impact of sub-fractionation (solvent partitioning) on betacyanin content in both plants. Characterization of betacyanins and evaluation of their antimicrobial activities were also carried out. Betanin was found in both plants. In addition, isobetanin, phyllocactin and hylocerenin were found in red pitahaya whereas amaranthine and decarboxy-amaranthine were found in red spinach. Sub-fractionated red pitahaya and red spinach had 23.5 and 121.5 % more betacyanin content, respectively, than those without sub-fractionation. Sub-fractionation increased the betanin and decarboxy-amaranthine content in red pitahaya and red spinach, respectively. The betacyanin fraction from red spinach (minimum inhibitory concentration [MIC] values: 0.78-3.13 mg/mL) demonstrated a better antimicrobial activity profile than that of red pitahaya (MIC values: 3.13-6.25 mg/mL) against nine Gram-positive bacterial strains. Similarly, the red spinach fraction (MIC values: 1.56-3.13 mg/mL) was more active than the red pitahaya fraction (MIC values: 3.13-6.25 mg/mL) against five Gram-negative bacterial strains. This could be because of a higher amount of betacyanin, particularly amaranthine in the red spinach.

Ethnopharmacological relevance Larix laricina , a native tree of North America, is a highly respected medicinal plant used for generations by Indigenous Peoples across its range, including the Cree of northern Quebec who use the bark to treat symptoms of diabetes. This study investigates the antioxidant capacity and bioavailability of active constituents identified in L. laricina bark extracts. Materials and methods (1) Oxygen radical absorbance capacity (ORAC) assay was employed to test antioxidant capacity of organic extracts (80% ethanol) from bark of L. laricina as well as fractions, isolated compounds, and media samples collected during permeability assays. (2) Caco-2 cell monolayer cultures were used to determine the permeability of identified antioxidants, which were quantified in basolateral media samples using liquid chromatography – tandem mass spectrometry (HPLC-ESI-MS/MS). Results Crude ethanolic extract possessed strong antioxidant potential in vitro (7.1±0.3 Trolox equivalents (TE) μM/mg). Among the 16 L. laricina fractions obtained by chromatographic separation, fraction 10 (F10) showed the highest antioxidant capacity (21.8±1.7 µm TE/mg). Among other identified antioxidants, the stilbene rhaponticin (isolated from F10) was the most potent (24.6±1.1 µm TE/mg). Caco-2 transport studies revealed that none of the identified compounds were detectable in basolateral samples after 2-h treatment with crude extract. In monolayers treated with F10 (60% rhaponticin), small quantities of rhaponticin were increasingly detected over time in basolateral samples with an apparent permeability coefficient (P app ) of 1.86×10 −8 cm/s (0–60 min). To model potential effects on blood redox status, we evaluated the antioxidant capacity of collected basolateral samples and observed enhanced activity over time after exposure to both extract and F10 (75 μg/mL) relative to control. Conclusions By profiling the antioxidant constituents of L. laricina bark, we identified rhaponticin as the most potent oxygen radical scavenger and observed low permeability in Caco-2 cell monolayers but an increase in basolateral antioxidant capacity.

Benzidine was found to be a novel transient directing group to enable Pd-catalyzed direct selenylation of inert C(sp2)–H bonds of benzaldehydes. Diverse diarylselenides were readily constructed in ...

A CuII -catalyzed asymmetric 1,3-dipolar cycloaddition using β-fluoroalkyl alkenyl arylsulfones as dipolarophiles and glycine/alanine iminoesters as azomethine ylide precursors has been developed. Remarkably, a catalyst loading as low as 0.5 mol % is highly efficient. Accordingly, a wide range of enantioenriched 3-fluoroalkyl pyrrolidines, as well as Δ2 -pyrroline and pyrrole derivatives, are generated in good to excellent yields with high asymmetric induction. This synthetic approach is diastereodivergent in that exo-adducts could be converted into the corresponding exo'-adducts by 1,8-diazabicyclo[5.4.0]undec-7-ene mediated epimerization at C2 of the pyrrolidine core. The free-energy profiles from DFT calculations suggest the Michael addition of the 1,3-dipole to be the rate- and enantiodetermining step, and the origin of stereoselectivity is studied by means of the noncovalent interaction (NCI) analysis.

Folate is an important intermediate in cellular metabolism. However, because of a lack of key enzymes in the folate biosynthetic pathway, humans require supplementation with dietary folate. Some Lactobacillus plantarum strains have the ability to produce folate. To gain a better understanding of the folate biosynthetic pathway in the L. plantarum strain 4_3, which generates high folate yields, L. plantarum strain 4_3 was grown in folic acid casei medium (FACM) and fermented soybean, after obtaining a draft genome sequence. The pH values and folate yields were monitored during culturing, as were the transcriptomic profiles of cultured bacteria. The folate content increased for 12 h and then decreased before increasing again. All the genes involved in the de novo biosynthesis of folate were detected in both the genomic and transcriptomic data. The upregulation of the para-aminobenzoate biosynthesis pathway could explain the folate production in fermented soybean. Soybeans are a good substrate for the production of functional foods because of their well-suited cultivation and nutritional quality. The results of this study provide a good explanation for the high folate production observed during the fermentation of soybeans.

Hybrid histidine kinase (HHKs) are widespread in fungi, but their roles in the regulation of fungal adaptation to environmental stresses remain largely unclear. To elucidate this, we cloned HisK2301 from Rhodosporidium kratochvilovae strain YM25235, characterized HisK2301 as a novel HHK, and further investigated the role of HisK2301 by overexpressing it in YM25235. Our results revealed that HisK2301 can promote adaptation of YM25235 to cold, osmotic, and salt stresses. During cold stress, HisK2301 significantly enhanced the biosynthesis of polyunsaturated fatty acids (PUFA) and intracellular glycerol. HisK2301 also augmented the expression levels of Δ12/Δ15 fatty acid desaturase ( RKD12) and glycerol-3-phosphate dehydrogenase1 ( GPD1), which are responsible for PUFA and glycerol biosynthesis, respectively. To conclude, our findings give the first insight into the defense and mechanisms of HisK2301 in fungi against cold stress and suggest the potential use of the novel cold-adapted HHK HisK2301 in industrial processes, such as large-scale production of PUFA.

Due to small size, strong fluorescence and low cytotoxicity, fluorescent carbon dots (CDs) attract people's attention. The CDs-Ws derived from Weissella sp. Kl-3 with bright blue photoluminescent were obtained via hydrothermal method. The CDs-Ws could selectively label dead bacterial and yeast cells, and show the potential for the differentiation of live/dead microbe. It showed that the prepared CDs-Ws had multicolor fluorescence emission properties, excellent biocompatibility and low biotoxicity with cell and in vivo imaging. In addition, CDs-Ws sensitized by ampicillin sodium was employed as fluorescence nanosensor (CDs-Ws-Amp Na) to detect Cr(VI) and VB12 based on inner filter effet mechanism. The linear correction was obtained for VB12 detection in 0–25 μM with 51.50 nM detection limit, and the linear range was 0–50 μM with 106.57 nM detection limits for Cr(VI) by CDs-Ws-Amp Na. The fluorescent nanosensor was used for detection of Cr(VI) in water and VB12 in serum and milk. It shows excellent potential in bioimaging, Cr(VI) and VB12 detection.

N,O-aminals, molecules bearing a geminally N,O-substituted (stereogenic) carbon center, have been recently recognized as an important class of building blocks in organic synthesis. As direct precursors of imines and iminium ions, N,O-aminals were converted through asymmetric organocatalysis or metal catalysis to diverse enantiomerically enriched compounds including N-heterocycles. Furthermore, cyclic N,O-hemiaminals acted as acyclic amino aldehyde surrogates, which were transformed to enantioenriched products otherwise challenging to access. Finally, cyclic N,O-aminals were formed in situ as key intermediates in asymmetric catalysis. In this review, we introduce a wide array of catalytic asymmetric protocols involving the use of four distinct types of N,O-aminals as starting materials or key intermediates.

The research was conducted to evaluate the sludge quality as fertilizer after heavy metal removal by using free nitrous acid (FNA, HNO2) solution. To meet up the Korean criteria of fertilizer, FNA treatment with the ultrasonic process was studied here. The sample was taken from a local wastewater and sewage treatment plants and FNA with FNA plus ultrasonic used to treat them. As and Cd concentrations were met the Korean criteria after FNA treatment. In contrast, Al of sludge from sewage treatment plant did not decrease down to the criteria, possibly suggesting that it may be related to the coagulants of the sludge during thickening and dewatering. FNA treatment showed satisfactory results in comparison with the other acidic treatment of citric acid, oxalic acid, HNO3 or HCl. Removal efficiency of the Fenton-like reaction was more effective than the FNA method. Despite this result, the FNA treatment may be better for sludge recycling as fertilizer because the Fenton-like process removed the necessary organic matter, nitrogen as well as metals. Moreover, the addition of ultrasound process has in conserving time and expenditure in metal removal and FNA with ultrasound became more effective in shorter reaction time. Therefore, FNA treated sludge could be a better option for sludge recycling as fertilizer. In conclusion, a proper plan of sludge management should be required for future work to use sludge as fertilizer.

Air- and light-stable electrophilic difluoromethylating reagents, S-(difluoromethyl)- S-phenyl- S-(2,4,6-trialkoxyphenyl) sulfonium salts were successfully developed, and the introduction of intramolecular hydrogen bonds plays a crucial role for the stabilities and reactivities of these reagents. C-selective difluoromethylation of a broad range of β-ketoesters and malonates proceeded smoothly under mild reaction conditions to give good to excellent yields with excellent C/O regioselectivities.

The photolytic and photocatalytic degradation rates of Rhodamine B (RhB) in wastewater were investigated and compared through irradiation with UV light of three wavelengths (207 nm, 222 nm, and 254 nm). UV light of all three wavelengths exhibited good RhB degradation capability under both acidic and alkaline conditions. When UV light energy is about 690 J, the RhB degradation rate is the highest (78.93%) under UV 222 nm, followed by that under UV 207 nm (70.44%) and UV 254 nm (25.17%). At each wavelength, the reaction kinetics of RhB was investigated with and without the addition of H2O2. The degradation rate of RhB was found to increase at the presence of H2O2. Photolysis mechanisms under the three UV light wavelengths were proposed based on the electrospray ionization mass spectra results, which indicated that RhB underwent different degradation pathways at different UV wavelengths. This study could help enhance understanding of the capability of the UV light of 207, 222, and 254 nm to degrade water pollutants.

A three-component Petasis-type gem-difluoroallylation reaction of using pinacol gem-difluoroallylboronates, aldehydes or isatin, and β-amino alcohols enabled by the neighboring hydroxyl group in amine is reported, affording various racemic and chiral gem-difluorohomoallylamine derivatives with good to excellent results. Based on the control experiment and stereochemistry of the product, a proposed reaction pathway is illustrated to clarify the origin of regio- and stereoselectivity under protic solvent conditions.

In this report, we presented a new approach to access a (1,3-butadiene-2-yl)carbinol, (1R,2R)- and (1S,2S)-1-(hydroxymethyl)-1-vinyl-1,2,3,4-tetrahydronaphthalene-2-ols. Starting from commercially available 1,4-diol-2-butyne, a six-step synthesis involving dibromination, Zn-mediated addition reaction of phenylpropyl aldehyde, epoxidation, epoxy–arene cyclization, and resolution with D(+)-Camphor afforded the title compounds. We herein presented a new approach to access a (1,3-butandien-2-yl)carbinol, (1R,2R)- and (1S,2S)-1-(hydroxymethyl)-1-vinyl-1,2,3,4-tetrahydronaphthalen-2-ols.

Kringle 5, derived from plasminogen, is highly capable of inhibiting angiogenesis. Here, we have designed and synthesized 10 tetrapeptides, based on the amino acid properties of the core tetrapeptide Lys-Leu-Tyr-Asp (KLYD) originating from anti-angiogenic kringle 5 of human plasminogen. Of these, Arg-Leu-Tyr-Glu (RLYE) effectively inhibited vascular endothelial growth factor (VEGF)-induced endothelial cell proliferation, migration and tube formation, with an IC{sub 50} of 0.06–0.08 nM, which was about ten-fold lower than that of the control peptide KLYD (0.79 nM), as well as suppressed developmental angiogenesis in a zebrafish model. Furthermore, this peptide effectively inhibited the cellular events that precede angiogenesis, such as ERK and eNOS phosphorylation and nitric oxide production, in endothelial cells stimulated with VEGF. Collectively, these data demonstrate that RLYE is a potent anti-angiogenic peptide that targets the VEGF signaling pathway. - Highlights: • The tetrapeptide RLYE inhibited VEGF-induced angiogenesis in vitro. • RLYE also suppressed neovascularization in a zebrafish model. • Its effect was correlated with inhibition of VEGF-induced ERK and eNOS activation. • RLYE may be used as a therapeutic drug for angiogenesis-related diseases.

Asymmetric C(sp)-C(sp(2)) bond formation to give enantiomerically enriched 1,3-butadienyl-2-carbinols occurred through a homoallenylboration reaction between a 2,3-dienylboronic ester and aldehydes under the catalysis of a chiral phosphoric acid (CPA). A diverse range of enantiomerically enriched butadiene-substituted secondary alcohols with aryl, heterocyclic, and aliphatic substituents were synthesized in very high yield with high enantioselectivity. Preliminary density functional theory (DFT) calculations suggest that the reaction proceeds via a cyclic six-membered chairlike transition state with essential hydrogen-bond activation in the allene reagent. The catalytic reaction was amenable to the gram-scale synthesis of a chiral alkyl butadienyl adduct, which was converted into an interesting optically pure compound bearing a benzo-fused spirocyclic cyclopentenone framework.

A new kind of chiral conjugated copolymer P-2 with (S)-BINAP [BINAP = 2,2′-bis(diarylphosphino)-1,1′-binaphthyl] and fluorene as the building blocks was synthesized involving Pd[P(p-tolyl)3]3-catalyzed Suzuki-coupling reaction together with reduction of phosphine oxide with HSiCl3/NEt3. The chiral polymer was used to construct chiral Ru/Ir bimetallic dendronized polymer catalysts P-5-m with different generations of Frechet-type dendritic DPEN [DPEN = 1,2-diphenylethylenediamine] ligands through a programmed metal–ligand coordination strategy. These dendronized polymer catalysts were applied to the Ir-catalyzed asymmetric hydrogenation of quinaldine and exhibited excellent activity with moderate enantioselectivity. The reaction rate was increased with increasing generation of the dendronized polymer catalysts, which are better than that obtained from the monomeric catalyst. This interesting positive dendrimer effect might be due to effective shielding of the catalytically active iridium center by the bulky dendritic pendants, which reduced the formation of the inactive iridium dimer.

The excessive ammonia nitrogen ions and nitrate in the domestic water and industrial water have seriously detriment of health of human being. The application of optimization solution for water purification is a main method to analyze the function of water purification device. In this paper, an automatic mixing system is designed to analyze the performance of ion-exchange column using LabVIEW. This system can solve the problem such as discontinuous proportion, complicated operation and low proportion precision which exists in the current proportion device. The accuracy of over 97% is shown by the experimental results in this study and it is also found that the quality of water can satisfy the requirement of drinking water.

The-NH2 groups, as grafting initiators, are introduced to the surface of meta-aramid fibers by treating the fiber surface with dilute sodium hydroxide solution. A kind of new aramid fibers liquid crystalline polymer were synthesized by interfacial polymerization of mesogenic monomer DDBA, main-chain LCI containing sulfonate ionic monomer BY, sebacoyl dichloride and aramid fibers hydrolysed. The structure and properties of aramid fibers before and after modification were characterized by SEM, FTIR, and POM.