Furan Dearomatization: A Route to Diverse Fluoroalkyl/Aryl Triazoles.

The 5-fluoroalkyl-1,2,3-triazoles, serving as a pivotal element in medicinal chemistry, hold substantial research significance. In this work, we developed a furan dearomatization reaction for the synthesis of various 5-fluoroalkyl-1,2,3-triazoles, which contains -CF3, -CF2H, -CF2CF3, -CF2CF2CF3, -CF2CO2Et, and -C6F5. This methodology relies on the intermolecular [3 + 2] cycloaddition/furan ring-opening triggered by α-fluoroalkyl furfuryl cation with azides to stereoselectively synthesize a series of (E)-fluoroalkyl enone triazoles. The reaction proceeds without metal participation, exhibits excellent substrate tolerance, and has excellent synthetic utility.

Kinsenoside attenuates liver fibro-inflammation by suppressing dendritic cells via the PI3K-AKT-FoxO1 pathway.

Kinsenoside (KD) exhibits anti-inflammatory and immunosuppressive effects. Dendritic cells (DCs) are critical regulators of the pathologic inflammatory milieu in liver fibrosis (LF). Herein, we explored whether and how KD repressed development of LF via DC regulation and verified the pathway involved in the process. Given our analysis, both KD and adoptive transfer of KD-conditioned DCs conspicuously reduced hepatic histopathological damage, proinflammatory cytokine release and extracellular matrix deposition in CCl4-induced LF mice. Of note, KD restrained the LF-driven rise in CD86, MHC-II, and CCR7 levels and, simultaneously, upregulated PD-L1 expression on DCs specifically, which blocked CD8+T cell activation. Additionally, KD reduced DC glycolysis, maintained DCs immature, accompanied by IL-12 decrease in DCs. Inhibiting DC function by KD disturbed the communication of DCs and HSCs with the expression or secretion of α-SMA and Col-I declined in the liver. Mechanistically, KD suppressed the phosphorylation of PI3K-AKT driven by LF or PI3K agonist, followed by enhanced nuclear transport of FoxO1 and upregulated interaction of FoxO1 with the PD-L1 promoter in DCs. PI3K inhibitor or si-IL-12 acting on DC could relieve LF, HSC activation and diminish the effect of KD. In conclusion, KD suppressed DC maturation with promoted PD-L1 expression via PI3K-AKT-FoxO1 and decreased IL-12 secretion, which blocked activation of CD8+T cells and HSCs, thereby alleviating liver injury and fibro-inflammation in LF.

Dual Roles of Azide: Dearomative Dimerization of Furfuryl Azides.

A dearomative dimerization of furfuryl azides for the construction of furfuryl triazoles is developed. As a rare leaving group, azide is capable of initiating the generation of a furfuryl cation under the Lewis acid-catalyzed conditions, followed by reacting with the other azide to realize an intermolecular [3 + 2] cycloaddition/furan ring-opening cascade. By extending the reaction time, a fragmentation reaction of resulting furfuryl triazoles occurs to afford 1H-triazoles in high yield. Control studies demonstrated that key furfuryl cations also can be obtained from furfuryl triazoles. Furthermore, a chemoselective cross-cycloaddition can be achieved between furfuryl azides and a benzyl azide.

The construction of phosphonate triazolyl by copper(II)-catalyzed furan dearomatized [3 + 2] cycloaddition.

Triazole phosphonates are valuable structural motifs in chemical biology and the subject of growing recent interest. A novel methodology to synthesize triazolyl phosphonates starting from furfuryl phosphonate alcohols and organo-azides was developed. This method involved an intermolecular copper-catalyzed dearomatized [3 + 2] cycloaddition/furan ring-opening cascade reaction. A strategy involving a three-component reaction was realized for quick access to triazole phosphonates.

Manganese-Catalyzed Achmatowicz Rearrangement Using Green Oxidant H2O2.

Oxidation reactions have been extensively studied in the context of the transformations of biomass-derived furans. However, in contrast to the vast literature on utilizing the stoichiometric oxidants, such as m-CPBA and NBS, catalytic methods for the oxidative furan-recyclizations remain scarcely investigated. Given this, we report a means of manganese-catalyzed oxidations of furan with low loading, achieving the Achmatowicz rearrangement in the presence of hydrogen peroxide as an environmentally benign oxidant under mild conditions with wide functional group compatibility.

Taxonomic description of Pseudomonas rhizovicinus sp. nov., isolated from the rhizosphere of a desert shrub Haloxylon ammodendron.

A Gram-negative aerobic bacterium, strain M30-35 T, was isolated from the rhizosphere of Haloxylon ammodendron in Tengger desert, Gansu province, northwest China. Our previous research indicated that strain M30-35 T can promote the growth of ryegrass (Lolium perenne L.). In this study, strain M30-35 T was subjected to a polyphasic taxonomic study. Phylogenetic analysis of the 16S rRNA gene and two other housekeeping genes (gyrB, rpoD) showed that strain M30-35 T is a member of Pseudomonas anguilliseptica group. The average nucleotide identity (ANI) scores for strains KMM 3042 T and FR1439T were 76.5% and 83.7%, respectively, and DNA-DNA hybridization (DDH) were 21.6% and 26.6%, respectively, and the rates were less than the threshold range for species determination. The dominant cellular fatty acids of strain M30-35 T were C16:0 (22.7%), summed feature 3 (C16:1ω7c and/or C16:1ω6c; 18.5%), summed feature 8 (C18:1ω7c and/or C18:1ω6c; 23.1%). The major polar lipids were diphosphatidylglycerol, phosphatidylethanolamine, phosphatidylglycerol, phospholipid and aminophospholipid and the predominant respiratory quinone was ubiquinone (Q9). On the basis of above data, it can be concluded that strain M30-35 T represents a novel species in the genus Pseudomonas, for which the name Pseudomonas rhizovicinus sp. nov. is proposed. The type strain is M30-35 T (= MCCC 1K03247T = KCTC 52664 T).

Altererythrobacter rhizovicinus sp. nov., isolated from rhizosphere soil of Haloxylon ammodendron.

A salt-tolerant, Gram-negative, rod-shaped and yellow-pigmented bacterium, designated strain AY-3RT, was isolated from rhizosphere soil of a desert xerophyte, Haloxylon ammodendron, sampled at Badain Jaran Desert, Alxa region, Inner Mongolia, PR China. Growth of this strain was observed at 20-42 °C (optimum, 28-30 °C), at pH 6.0-9.0 (optimum, pH 6.0-7.0) and at 0-8 % (w/v) NaCl (optimum, 3 %). Results of phylogenetic analysis based on 16S rRNA gene sequences showed that strain AY-3RT was a member of the genus Altererythrobacter, with the highest similarity to Altererythrobacter aerophilus Ery1T (97.6 %), followed by Altererythrobacter xinjiangensis S3-63T (96.9 %). The predominant fatty acids (>10.0 %) were C18 : 1ω7c, C17 : 1ω6c and summed feature 3 (C16 : 1ω7c and/or C16 : 1ω6c). The major polar lipids were diphosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, sphingoglycolipid and one unknown polar lipid. The predominant respiratory quinone was ubiquinone-10. The G+C content of the genomic DNA of strain AY-3RT was 66.3 mol%. On the basis of the data from this polyphasic taxonomic study, strain AY-3RT represents a novel species of the genus Altererythrobacter, named Altererythrobacter rhizovicinus sp. nov. (=MCCC 1K03572T=KCTC 72280T).

Biofertilizers with beneficial rhizobacteria improved plant growth and yield in chili (Capsicum annuum L.).

Chemical fertilizers can supply essential nutrients to crops increasing their yield, however, they can also cause serious environmental problems. Biofertilizer has received more and more attention because of its environmentally friendly and pollution-free characteristics. Haloxylon ammodendron, a desert succulent shrub, has become an important plant species for vegetation restoration in several deserts in China because of its strong drought tolerance. Its extensive root systems and unique rhizosphere bacterial community aid H. ammodendron adapt to this extreme environment. In this study, Bacillus sp. WM13-24 and Pseudomonas sp. M30-35 isolated from the rhizosphere of H. ammodendron in our previous study and Bacillus amyloliquefaciens GB03 and Sinorhizobium meliloti ACCC17578 as well-studied beneficial strains were used to prepare two types of biofertilizer, WM13-24 biofertilizer containing Bacillus sp. WM13-24 and integrated biofertilizer containing all the four strains. Results presented here showed that WM13-24 biofertilizer and the integrated biofertilizer improved chili plant growth, fruit yield and quality and the rhizosphere soil nitrogen content, enzyme activities, and the quantity and biodiversity of viable bacteria. Compared to the control, WM13-24 biofertilizer and a commercial biofertilizer, the integrated biofertilizer performed best in significantly increasing plant height, stem diameter, leaf length and width, chlorophyll content, fruit yield, soluble sugar content, ascorbic acid content, organic acid content, soil urease activity, catalase activity and the quantity and biodiversity of viable bacteria. This study provided a theoretical and practical basis for large scale development of integrated biofertilizers using beneficial rhizobacterial strains from the desert plant rhizosphere.

Induced Salt Tolerance of Perennial Ryegrass by a Novel Bacterium Strain from the Rhizosphere of a Desert Shrub Haloxylon ammodendron.

Drought and soil salinity reduce agricultural output worldwide. Plant-growth-promoting rhizobacteria (PGPR) can enhance plant growth and augment plant tolerance to biotic and abiotic stresses. Haloxylon ammodendron, a C4 perennial succulent xerohalophyte shrub with excellent drought and salt tolerance, is naturally distributed in the desert area of northwest China. In our previous work, a bacterium strain numbered as M30-35 was isolated from the rhizosphere of H. ammodendron in Tengger desert, Gansu province, northwest China. In current work, the effects of M30-35 inoculation on salt tolerance of perennial ryegrass were evaluated and its genome was sequenced to identify genes associated with plant growth promotion. Results showed that M30-35 significantly enhanced growth and salt tolerance of perennial ryegrass by increasing shoot fresh and dry weights, chlorophyll content, root volume, root activity, leaf catalase activity, soluble sugar and proline contents that contributed to reduced osmotic potential, tissue K⁺ content and K⁺/Na⁺ ratio, while decreasing malondialdehyde (MDA) content and relative electric conductivity (REC), especially under higher salinity. The genome of M30-35 contains 4421 protein encoding genes, 12 rRNA, 63 tRNA-encoding genes and four rRNA operons. M30-35 was initially classified as a new species in Pseudomonas and named as Pseudomonas sp. M30-35. Thirty-four genes showing homology to genes associated with PGPR traits and abiotic stress tolerance were identified in Pseudomonas sp. M30-35 genome, including 12 related to insoluble phosphorus solubilization, four to auxin biosynthesis, four to other process of growth promotion, seven to oxidative stress alleviation, four to salt and drought tolerance and three to cold and heat tolerance. Further study is needed to clarify the correlation between these genes from M30-35 and the salt stress alleviation of inoculated plants under salt stress. Overall, our research indicated that desert shrubs appear rich in PGPRs that can help important crops tolerate abiotic stress.

[A case of congenital bile acid synthesis disorder type 2 and literature review].

OBJECTIVE: To summarize the clinical features, biochemical change and genetic mutations of a neonate with congenital bile acid synthesis disorder type 2. METHODS: Clinical features, blood biochemical index, gene analysis and treatment of the patient were reviewed. RESULTS: The patient presented with the symptoms of jaundice 3 days after birth but without skin itching. Pale stool was noted. Subsequently, he presented with hepatomegaly, blood coagulation disorders, left cochlear nerve damage, liver cirrhosis and remarkable growth retardation. Serum biochemistries showed that bilirubin and transaminase were elevated, while γ -GT and total bile acid was normal. Abdominal ultrasonography indicated decline of gallbladder contraction. Cholangiography showed normal extra- and intrahepatic bile ducts and patent biliary tract. Liver biopsy showed intrahepatic cholestasis. Gene testing has identified a homozygous mutation in AKR1D1 gene. CONCLUSION: Congenital bile acid synthesis disorder should be suspected when a neonate has presented with jaundice, elevated bilirubin and transaminase, normal or reduced TBA and γ -GT. Genetic testing and urine mass spectrometry analysis can diagnose congenital bile acid synthesis disorder. Early therapy is crucial to patients with congenital bile acid synthesis disorder.

Bifunctional Furfuryl Cations Strategy: Three-Component Synthesis of Enamidyl Triazoles.

A new multicomponent synthesis of functionalized enamidyl triazoles starting from simple and readily available starting materials is described. A simple treatment of a dichloromethane solution of an azide, amine, and 5-bromo-2-furylcarbinol with a Lewis acid provides the enamidyl triazole in good to high yield. A triple domino sequence, formal [3+2] cycloaddition/ring-opening/amidation, is involved in this new skeleton-generating reaction.

Synthesis and Photoluminescence Characteristics of CaIn2O4:Dy3+ Phosphors Co-Doped with Gd3+, Zn2+ or AI3+ Ions.

Novel warm-white emitting phosphors CaIn2O4:Dy3+ co-doped with Gd3+, Zn2+, or Al3+ ions were prepared by solid state reaction. In this paper, a strategy of co-doping with different ions was used with the aim of affecting the luminescence properties of CaIn204:0.6%Dy3+ under NUV excitation. The luminescence intensities of CaIn2O4:0.6%Dy3+ were enhanced by 0.2% Gd3+ or 0.2% Zn2+ ions co-doping under 367 nm excitation, but lowered by co-doping with 0.2% Al3+ ions. Furthermore, the chromaticity coordinates of CaIn2O4:0.6%Dy3+ can be tuned from the cold-white region to warm-white region with Gd3+ or Zn2+ ions co-doping. These findings show that CaIn2O4:0.6%Dy3+,0.2% Gd3+, and CaIn2O4:0.6%Dy3+,0.2% Zn2+ have potential application value as new warm-white LED phosphors.

Absorption properties and effects of caffeic acid phenethyl ester and its p-nitro-derivative on P-glycoprotein in Caco-2 cells and rats.

CONTEXT: Caffeic acid phenethyl ester (CAPE), isolated from honeybee propolis, has pharmacological applications. A synthesized CAPE derivative, p-nitro-caffeic acid phenethyl ester (CAPE-NO2), showed similar activities with CAPE. The pharmacological activities of CAPE and CAPE-NO2 are related to their absorption properties. OBJECTIVE: To understand the pharmacokinetic profiles of CAPE and CAPE-NO2 in rats and investigate the absorption mechanisms and effects on P-glycoprotein in Caco-2 cells. MATERIALS AND METHODS: The pharmacokinetic profiles of CAPE and CAPE-NO2 were obtained after oral administration (10 mg/kg) to rats. Transport studies of CAPE and CAPE-NO2 (5, 10, 20 µM) were performed in Caco-2 cell model. P-gp activities were assayed by rhodamine 123 cellular retention. Expression of P-gp was determined after the cells were administrated with CAPE and CAPE-NO2 (5, 20 µM) for 48 and 72 h. RESULTS: The AUC(0-t) of CAPE-NO2 (3239.9 ± 352 ng × h/mL) was two-time greater than CAPE (1659.6 ± 152 ng × h/mL) in rats. The Papp values of CAPE and CAPE-NO2 were (4.86 ± 0.90) × 10-6 cm/s and (12.34 ± 1.6) × 10-6 cm/s, respectively. The accumulation of rhodamine 123 was increased by 1.3- to 1.9-fold and 1.4- to 2.3-fold in CAPE and CAPE-NO2 groups after 1 h administration, respectively. However, CAPE and CAPE-NO2 increased the P-gp levels by 2.1- and 1.7-fold, respectively. CONCLUSION: The absorption of CAPE-NO2 can be enhanced in rats and Caco-2 cells compared with CAPE. The two compounds are potential inhibitors of P-gp. The increased P-gp levels generated by CAPE and CAPE-NO2 played a role as a defense mechanism by limiting intracellular xenobiotic levels.

Self-activated long persistent luminescence from different trapping centers of calcium germanate.

Ca2Ge7O16 phosphor with a self-activated LPL was synthesized. The unique emission of Ca2Ge7O16 related to the creation of the oxygen vacancies was proved. With increasing concentration of Nd3+, the LPL peaks in these phosphors red-shift obviously, which results in the corresponding emitting color changing from purple to blue. The thermoluminescence spectra indicate that there are two different types of traps, which are attributed to oxygen and calcium vacancies, respectively. Both of them not only act as the trapping centers, but also as the exciton energy-level involved in the emission process. Accordingly, the mechanism of the LPL process was discussed briefly.

Phosphorous nitride dots induced efficient advanced oxidation with intrinsic chemiluminescence for organic pollutant degradation.

In this work, we introduced new metal-free catalysts, phosphorus nitride dots (PNDs), into an environmentally friendly H2O2-SO32- system to generate abundant reactive oxygen species (O2˙-, ˙OH and SO4˙-) with strong intrinsic chemiluminescence (CL). The excellent catalytic ability of PNDs not only improved the degradation efficiency of organic pollutants, but also provided a promising prospect for deeply probing the mechanism of advanced oxidation processes (AOPs) by combining with CL.

Europium-Functionalized Graphitic Carbon Nitride for Efficient Chemiluminescence Detection of Singlet Oxygen.

Enhancing the sensitivity and selectivity of chemiluminescence (CL) sensors for detecting chemical species in complex samples poses a significant challenge in nanoparticle surface engineering. Graphitic carbon nitride (CN) shows promise but suffers from weak CL intensity and unknown luminescence mechanisms. In this study, we propose a nitrogen defect strategy to enhance the CL efficiency of europium-functionalized graphitic carbon nitride (Eu-CNNPs). By controlling the dosage of the europium modification, we can adjust the nitrogen defect content to reduce the energy gap and improve the CL performance. Remarkably, Eu-CNNPs with rich nitrogen defects exhibit strong chemiluminescence emission specifically for singlet oxygen (1O2) without responding to other reactive oxygen species (ROS). Building upon this finding, we developed a direct, selective, and sensitive CL sensing platform for 1O2 in PM2.5 and monitored 1O2 production in photosensitizers without interference from metal ions. Through extensive experiments, we attribute the 1O2-driven CL response to the presence of abundant nitrogen defects in the CN material, accelerating electron transfer and yielding a high generation of 1O2. Furthermore, chemiluminescence resonance energy transfer (CRET) between (1O2)2* (1O2 dimeric aggregate) and Eu-CNNPs contributes to strong CL emission. This work provides insights into enhancing the CL performance of CN and offers new possibilities for advancing the practical analysis of nanomaterials using the intriguing mechanism of nitrogen defects.

Modulated oxygen vacancies in europia clusters/black phosphorus induced signal amplification for efficient chemiluminescence sensing.

In this work, we proposed an oxygen vacancy engineering strategy to boost the chemiluminescence (CL) efficiency in europia clusters/black phosphorus quantum dots (Eu2O3/BPQDs), which could dramatically amplify the ClO- CL emission through electron transfer. Accordingly, a sensitive and direct CL sensing platform for hypochlorite and titanium ions was constructed. This work provides a neoteric methodology by modulating the surface state of nanoparticles to boost the CL sensitivity.

Prevalence and Subtype Distribution of Blastocystis in Tibetan Sheep in Qinghai Province, Northwestern China.

Blastocystis is one of the most common intestinal protists in humans and a great number of animals, including sheep and goats. High prevalence and multiple subtypes of Blastocystis have been reported in sheep in several regions of China and elsewhere. However, there is a dearth of knowledge about Blastocystis in Tibetan sheep. A total of 761 fecal samples were collected from Tibetan sheep in seven counties of Qinghai Province, northwestern China, and were examined for the prevalence and subtypes of Blastocystis using molecular technology based on the partial small subunit ribosomal RNA gene of Blastocystis. The overall prevalence of Blastocystis in the investigated Tibetan sheep was 7.5% (57/761) using PCR and DNA Sanger sequencing, and differences in prevalence were observed among the ruminants from the seven counties (P < 0.01), and across four seasons (P < 0.01). Sequence analysis revealed five subtypes (ST14 (57.9%), ST10 (26.3%), ST12 (5.3%), ST21 (5.3%), and ST30 (5.3%)) of Blastocystis sp. in these Tibetan sheep, with ST14 as the predominant subtype. To our knowledge, this is the first report of Blastocystis colonization in Tibetan sheep.

Intratumoral injection of norcantharidin liposome emulsion hybrid delivery system amplifies the cancer-fighting effects of oral sorafenib against hepatocellular carcinoma.

Interventional therapies are increasingly used in clinical trials for hepatocellular carcinoma (HCC). Sorafenib is the front-line remedy for HCC, however, chemoresistance occurs immutably and affects the effectiveness of treatment. In a previous study, a norcantharidin liposome emulsion hybrid (NLEH) delivery system for HCC was developed. This study aims to examine the therapeutic effects of the combination of intratumoral injection of NLEH and sorafenib in treating HCC. Sorafenib combined with NLEH activated the apoptosis pathway by synergistically upregulating caspase-9, promoting cytotoxicity, apoptosis (64.57%), and G2/M cell cycle arrest (48.96%). Norcantharidin could alleviate sorafenib resistance by counteracting sorafenib-induced phosphorylation of Akt. Additionally, intratumoral injection of NLEH exhibited a sustained accumulation in the tumor within 24 h and didn't distribute to other major organs. Intratumoral injection of NLEH in combination with oral sorafenib displayed the most potent tumor growth inhibitory effect (77.91%) in vivo. H&E staining results and the indicators of the renal and liver function tests demonstrated the safety of this combination therapy. Overall, these results showed that intratumoral injection of NLEH in combination with oral sorafenib treatment represented a rational potential therapeutic option for HCC.