Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Characterization of ovarian progenitor cells for their potential to generate steroidogenic theca cells in vitro.

In brief: Progenitor cells with ovulation-related tissue repair activity were identified with defined markers (LGR5, EPCR, LY6A, and PDGFRA), but their potentials to form steroidogenic cells were not known. This study shows that the cells can generate progenies with different steroidogenic activities. Abstract: Adult mammalian ovaries contain stem/progenitor cells necessary for folliculogenesis and ovulation-related tissue rupture repair. Theca cells are recruited and developed from progenitors during the folliculogenesis. Theca cell progenitors were not well defined. The aim of current study is to compare the potentials of four ovarian progenitors with defined markers (LY6A, EPCR, LGR5, and PDGFRA) to form steroidogenic theca cells in vitro. The location of the progenitors with defined makers was determined by immunohistochemistry and immunofluorescence staining of ovarian sections of adult mice. Different progenitor populations were purified by magnetic-activated cell sorting (MACS) and/or fluorescence-activated cell sorting (FACS) techniques from ovarian cell preparation and were tested for their abilities to generate steroidogenic theca cells in vitro. The cells were differentiated with a medium containing LH, ITS, and DHH agonist for 12 days. The results showed that EPCR+ and LGR5+ cells primarily distributed along the ovarian surface epithelium (OSE), while LY6A+ cells distributed in both the OSE and parenchyma. However, PDGFRA+ cells were exclusively located in interstitial compartment. When the progenitors were purified by these markers and differentiated in vitro, LY6A+ and PDGFRA+ cells formed steroidogenic cells expressing both CYP11A1 and CYP17A1 and primarily producing androgens, showing characteristics of theca-like cells, while LGR5+ cells generated steroidogenic cells devoid of CYP17A1 expression and androgen production, showing a characteristic of progesterone-producing cells (granulosa- or lutea-like cells). In conclusion, progenitors from both OSE and parenchyma of adult mice are capable of generating steroidogenic cells with different steroidogenic capacities, showing a possible lineage preference.

MOF-derived porous carbon microspheres Ni@C-acid as solid-phase microextraction coating for extraction of polycyclic aromatic hydrocarbons from tea infusions.

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL-1), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL-1), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants.

Confinement effect of ionic liquid: Improve of the extraction performance of parent metal organic framework for phthalates.

In order to better identify the hazards of pollutants, developing the analytical methods that can sensitively detect and precisely monitor the content of trace pollutants has been the constant pursuit. In this paper, a new solid phase microextraction coating-ionic liquid/metal organic framework (IL/MOF) was obtained through the IL-induced strategy and used for the solid phase microextraction (SPME) process. IL was introduced into metal-organic framework (MOF) cage based on the anion of ionic liquid could interact strongly with the zirconium nodes of UiO-66-NH2. The introduction of IL not only increased the stability of composite, the hydrophobicity of IL also changed the environment of MOF channel, providing the hydrophobic effect to the targets. The confinement effect of IL effectively improved the extraction performance of parent MOF and the extraction performance of synthesized IL/UiO-66-NH2 for phthalates (PAEs) were 1.3-3.0 times that of parent UiO-66-NH2. Thanks to the strong interaction force (hydrogen bonding interaction, π-π stacking, hydrophobic interaction force), the IL/UiO-66-NH2-coated fiber coupled with gas chromatography-mass spectrometer showed a wide linear ranges (1-5000 ng L-1) with good correlation (R2, 0.9855-0.9987), lower detection limit (0.2-0.4 ng L-1) and satisfactory recoveries (95.3-119.3%) for PAEs. This article is dedicated to provide another way to improve the extraction performance of material.

Pubertal lead exposure affects ovary development, folliculogenesis and steroidogenesis by activation of IRE1α-JNK signaling pathway in rat.

Epidemic studies showed that lead exposures are associated with various female reproductive dysfunctions, including infertility, miscarriage, preterm delivery, and early menopause. However, the mechanism involved is still unclear. In the current study, SD rats were exposed to lead at doses of 0, 5, 25, 50 or 250 mg/L through drinking water from postnatal day 21-56. Lead exposures did not affect the body weight or ovary weight. However, the puberty initiation (ages by which vagina opens and estrous cycle occurs) was significantly delayed by as many as 5.8 and 6.8 days respectively (P < 0.05). Also, lead exposures disrupted the estrous cycles, reduced the numbers of primordial and primary follicles and increased the number of atretic follicles by adult. Furthermore, for the highest does group, serum levels of progesterone and testosterone decreased by 80.2% (P < 0.01) and 49.9% (P < 0.05) respectively, while estradiol level increased by 69.8% (P < 0.01). Western blot analyses indicated that lead exposures specifically down-regulated the expressions of steroidogenic protein STAR, CYP17A1, and HSD3B1, while up-regulated FSHR and CYP19A1. Also, the exposure stimulated the endoplasmic reticulum stress (ERS)-related IRE1α-JNK signaling pathway members. Such activation may also result in apoptosis since the death-signaling molecules CHOP and cleaved-CASP3 were up-regulated while BCL2 was down-regulated. In conclusion, lead exposure during juvenile and puberty significantly affected ovary development and functions. The effects may relate to ERS response since the 6 members related to the pathway were all consistently activated.

Enhancement of Thermoelectric Performance of Sr0.9La0.1TiO3-Based Ceramics Regulated by Nanostructures.

La-doped strontium titanite (Sr0.9La0.1TiO3) is a promising candidate for n-type oxide thermoelectric materials. However, the ZT values of this material are low, leading to low conversion efficiency. Improvements in this efficiency are required. In this work, a high ZT value of 0.50 was obtained for Sr0.9La0.1TiO3 ceramic samples by adding 10 wt % Bi2O3 sintering aids and 20 wt % nanosized Ti powders to the matrix material. Although Ti was oxidized to TiO2 during the sintering process, nanoscale phase interfaces were beneficial for phonon scattering and thermal conductivity reduction. Nanosized metallic Bi and Bi2O3 particles were observed. These two factors played an important role in reducing the thermal conductivity from 2.5 W/(m K) at room temperature to 1.31 W/(m K) at 1073 K. Nanostructure control using nanosized metal powders as additives combined with the Bi2O3 sintering aid paves a way for enhancement of thermoelectric properties of oxide thermoelectric materials.

Boosting the Thermoelectric Performance of Calcium Cobaltite Composites through Structural Defect Engineering.

Misfit-layered Ca3Co4O9 as a p-type semiconductor is difficult to commercialize because of its relatively poor performance. Here, Ca2.7-xLaxAg0.3Co4O9/Ag composites prepared by spark plasma sintering were systematically investigated in terms of La3+ dopant levels and nano-sized Ag compacts. Multiscale microstructures of stacking fault, dislocation, and oxygen vacancy-linked defects could be recognized as an effective strategy for tuning the transport of charge carriers and phonon scattering. An increasing concentration of charge carriers was caused by the introduction of nano-sized Ag particles at the grain boundary. The multiscale structural defects served as phonon scattering centers to reduce the thermal conductivity. Finally, the Ca2.61La0.09Ag0.3Co4O9/Ag sample exhibited a maximum ZT of 0.35 at 1073 K. The results suggest that the interplay of structural defects provides an impetus for a huge improvement in thermoelectric performance.

Annealing of Strontium Titanate Based Thermoelectric Materials by Graphite: Mechanistic Analysis by Spectroscopic and Chromatographic Techniques.

Strontium titanate (SrTiO3 ) based materials are promising for high-temperature thermoelectric applications. In order to enhance their performance, annealing is usually required and carried out under various atmospheres. Annealing with graphite is quite effective, but the mechanism is not yet clear. In this work, we use IR spectroscopy and gas chromatography (GC) to monitor the chemical environment under the annealing conditions (1350 °C for 8 h under 16.9 mL/min N2 with graphite) and quantify the various gases evolved in the process. It is shown that reducing agents, H2 and CO (concentrations peaked at ca. 0.4-0.5 %), are generated from graphite in the annealing process. H2 is produced in carbon gasification reaction, which also generates CO. Additional CO is produced from incomplete combustion of carbon. In the annealing of a La-doped SrTiO3 -based ceramic with graphite, higher levels of H2 O and CO2 are detected, which is resulted from the reduction of the ceramic by H2 and CO, respectively. About 67 % of the oxygen vacancies were created by CO reduction while about 33 % by H2 reduction. The conclusions are well supported by direct weight loss measurements with a difference of less than 6 %.

Co-expression network analysis of the transcriptomes of rice roots exposed to various cadmium stresses reveals universal cadmium-responsive genes.

BACKGROUND: The migration of cadmium (Cd) from contaminated soil to rice is a cause for concern. However, the molecular mechanism underlying the response of rice roots to various Cd stresses remains to be clarified from the viewpoint of the co-expression network at a system-wide scale. RESULTS: We employed a comparative RNAseq-based approach to identify early Cd-responsive differentially expressed genes (DEGs) in rice 'Nipponbare' seedling roots after 1 h of high-Cd treatment. A multiplicity of the identified 1772 DEGs were implicated in hormone signaling and transcriptional regulation, particularly NACs and WRKYs were all upregulated under Cd stress. All of the 6 Cd-upregulated ABC transporters were pleiotropic drug resistance proteins (PDRs), whereas all of the 6 ZRT/IRT-like proteins (ZIPs) were consistently downregulated by Cd treatment. To further confirm our results of this early transcriptomic response to Cd exposure, we then conducted weighted gene co-expression network analysis (WGCNA) to re-analyze our RNAseq data in combination with other 11 previously published RNAseq datasets for rice roots exposed to diverse concentrations of Cd for extended treatment periods. This integrative approach identified 271 transcripts as universal Cd-regulated DEGs that are key components of the Cd treatment coupled co-expression module. A global view of the 164 transcripts with annotated functions in pathway networks revealed several Cd-upregulated key functional genes, including transporter ABCG36/OsPDR9, 12-oxo-phytodienoic acid reductases (OPRs) for JA synthesis, and ZIM domain proteins JAZs in JA signaling, as well as OsWRKY10, NAC, and ZFP transcription factors. More importantly, 104 of these, including ABCG36/OsPDR9, OsNAC3, as well as several orthologs in group metalloendoproteinase, plastocyanin-like domain containing proteins and pectin methylesterase inhibitor, may respond specifically to various Cd pressures, after subtracting the 60 general stress-responsive genes reported to be commonly upregulated following multiple stresses. CONCLUSION: An integrative approach was implemented to identify DEGs and co-expression network modules in response to various Cd pressures, and 104 of the 164 annotatable universal Cd-responsive DEGs may specifically respond to various Cd pressures. These results provide insight into the universal molecular mechanisms beneath the Cd response in rice roots, and suggest many promising targets for improving the rice acclimation process against Cd toxicity.