Recyclable and Efficient Recovery of Ca and S from Phosphogypsum by Using Multistep Precipitation.

The resource utilization of phosphogypsum (PG) is the key to promote the green development of the phosphorus chemical industry. The natural environment and public safety are significantly threatened by the enormous volume of PG storage. In this study, Ca and S were successfully recovered from the PG via a multistep precipitation in the NaOH-BaCO3 system. The alkali solution can be recycled five times, with a first recovery ratio of about 97.9%, and the decomposition ratio of PG remained above 70% after five cycles. In addition, the recovery ratios of Ca and S in PG are 99.9 and 82.5%, respectively. The product of BaSO4 can be used as a weighting agent for oil and natural gas drilling mud. The BaSO4 can also be used as wave-absorbing materials, and its reflection loss value reaches 97.8% of the analytical purity BaSO4. This work provides a new idea for the efficient recycling of Ca and S in PG with an outstanding application prospect.

Two-dimensional boron nanosheets for selective enrichment and detection of cis-diol compounds by surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

Surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) is an effective method for detecting of low-mass molecules. In this study, two-dimensional boron nanosheets (2DBs) were fabricated through thermal oxidation etching and coupling liquid exfoliation technologies, and applied as a matrix and selective sorbent for detecting cis-diol compounds by SALDI-TOF MS. The outstanding nanostructure and boric acid active sites of 2DBs endow them with sensitivity for cis-diol compound detection, excellent selectivity, and low background interference for complex samples. The specific in-situ enrichment faculty of the 2DBs as a matrix was investigated by SALDI-TOF MS using glucose, arabinose, and lactose as model analytes. In the presence of 100 -fold more interfering substances, the 2DBs showed high selectivity against cis-diol compounds, and exhibited a better sensitivity and a reduced limit of detection through enrichment treatment than graphene oxide matrices. The linearity, limit of detection (LOD), reproducibility, and accuracy of the method were evaluated under optimized conditions. The results showed that the linear relationships of six saccharides remained in the range of 0.05-0.6 mM with a correlation coefficient r ≥0.98. The LODs of six saccharides were 1 nM (glucose, lactose, mannose, fructose) and 10 nM (galactose, arabinose). Sample-to-sample (n = 6) with relative standard deviations (RSDs) of 3.2% to 8.1% were observed. Recoveries (n = 5) of 87.9-104.6% were obtained at three spiked levels in the milk samples. The proposed strategy promoted the development of a matrix for use with SALDI-TOF MS detection, in which the UV absorption properties and enrichment capabilities of 2DBs were combined.

A mesoporous graphene @ zirconium-based metal-organic frameworks as a matrix and an adsorbent for steroid detection using surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

Endocrine-disrupting chemicals (EDCs) in environmental water samples, a rapid, sensitive, and high-throughput method should be developed. In this study, an in situ-synthesized composite material of three-dimensional mesoporous graphene (3D-MG) and zirconium-based metal-organic frameworks (MOFs), denoted as MG@UiO-66, was used as both the adsorbent and matrix in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) for steroid detection. Both graphene-based materials and MOFs have proven to be ineffective in detecting steroids as a matrix; however, their composites can detect steroids with higher sensitivity and lower interference. After screening different types of MOFs, a composite of UiO-66 and 3D-MG was selected as the new matrix for steroid detection. The combination of 3D-MG and UiO-66 further enhanced the ability of the material to enrich steroids, and reduced the limit of detection (LOD) of steroids. The method was evaluated for linearity, LODs, limit of quantitation (LOQs), reproducibility, and precision under optimized conditions. The results showed that the linear relationships of three steroids are kept in the range of 0-300 nM/L with a correlation coefficient r ≥ 0.97. The LODs and LOQs of the steroids were in the range of 3-15 and 10-20 nM/L, respectively. Recoveries (n = 5) of 79.3-97.2% were obtained at three spiked levels in the blank water samples. This fast and efficient method of using SALDI-TOF MS can be extended to detect the steroids in EDCs in environmental water samples.

Leaching of phosphate ores with lower dissolution of metallic impurities: the dual role of sodium oleate.

In this work, we report the use of surfactants to improve the performance of phosphate ore leaching while reducing the concentration of metallic impurities in the leaching solution. Based on the zeta potential analysis, sodium oleate (SOL) is determined as a suitable surfactant because it can change interfacial properties and improve ionic diffusion. This is experimentally demonstrated by the high leaching performance. After that, the reaction conditions on the leaching performance are systematically investigated. Under the optimal experimental conditions (SOL concentration of 10 mg L-1, sulfuric acid concentration of 1.72 mol L-1, leaching temperature of 75 °C, and leaching time of 180 min), a high phosphorus leaching efficiency of 99.51% is achieved. Meanwhile, the leaching solution presents a lower content of metallic impurities. Further measurements performed on the leaching residues indicate that the additive SOL can promote the growth of platy crystals and facilitate PO leaching. Overall, this work demonstrates that the SOL-assisted leaching method allows for highly-efficient utilization of PO and high-purity phosphoric acid production.

Mixed-Solvent-Mediated Strategy for Enhancing Light Absorption of Polydopamine and Adhesion Persistence of Dopamine Solutions.

Mussel-inspired polydopamine (PDA) and its derivative materials have exhibited a huge potential as a facile and versatile route to fabricate multifunctional coatings on virtually any substrate surface. However, their performance and applicability are frequently obstructed by limited optical absorption in visible regions of PDA and poor surface adhesion persistence of dopamine solutions. Herein, we report a facile strategy to improve these problems by rationally regulating the dopamine polymerization pathway through mixed-solvent-mediated periodate oxidation of dopamine. The spectral analysis, ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry, and density functional theory simulations systematically demonstrate that the mixed-solvent reaction systems can effectively accelerate the periodate-induced formation of cyclized moieties in the PDA microstructure and inhibit their further oxidative cleavage, thus contributing to narrowing the inherent energy band gap of PDA and improving the long-lasting surface deposition performance of aged dopamine solutions. Moreover, the newly constructed cyclized species-rich PDA coatings have excellent surface uniformity and significantly enhanced chemical stability. Benefiting from these fascinating properties, they have been further used for permanent dyeing of natural gray hair with remarkably improved blackening effect and excellent practicability, which exhibited their promising prospect in real-world applications.

Preparation of Fe3O4@SW-MIL-101-NH2 for selective pre-concentration of chlorogenic acid metabolites in rat plasma, urine, and feces samples.

An innovative sandwich-structural Fe-based metal-organic framework magnetic material (Fe3O4@SW-MIL-101-NH2) was fabricated using a facile solvothermal method. The characteristic properties of the material were investigated by field emission scanning electron microscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction, vibrating sample magnetometry, and Brunauer-Emmett-Teller measurements. Fe3O4@SW-MIL-101-NH2 is associated with advantages, such as robust magnetic properties, high specific surface area, and satisfactory storage stability, as well as good selective recognition ability for chlorogenic acid (CA) and its metabolites via chelation, hydrogen bonding, and π-interaction. The results of the static adsorption experiment indicated that Fe3O4@SW-MIL-101-NH2 possessed a high adsorption capacity toward CA and its isomers, cryptochlorogenic acid (CCA) and neochlorogenic acid (NCA), and the adsorption behaviors were fitted using the Langmuir adsorption isotherm model. Then, a strategy using magnetic solid-phase extraction (MSPE) and ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF MS/MS) was developed and successfully employed for the selective pre-concentration and rapid identification of CA metabolites in rat plasma, urine, and feces samples. This work presents a prospective strategy for the synthesis of magnetic adsorbents and the high-efficiency pretreatment of CA metabolites.

A metal-organic framework@hydrogen-bond framework as a matrix for MALDI-TOF-MS analysis of small molecules.

A novel MOF@HOF composite that can serve as a matrix for analysis of small molecules by MALDI-TOF-MS was fabricated through a simple solvothermal method. Taking falvonoids as an example, this composite/matrix presents high desorption/ionization efficiency, low background interference, high salt tolerance, and satisfactory signal reproducibility for MALDI-TOF-MS analysis.

Versatile scaffold applications based on MoS2 quantum dots for imaging mitochondrial pH in living cells.

Sensitive and accurate detection and imaging of mitochondrial pH have become significant methods in biological and biomedical research to elucidate the biological functions of mitochondria. Herein, a mitochondria-targeted ratiometric fluorescent nanoprobe was developed to image mitochondrial pH in living cells. This nanoprobe was prepared by covalently linking a mitochondria-targeted ligand (triphenylphosphonium, TPP) and a pH recognition fluorescent indicator (rhodamine, RhB) onto the surface of MoS2 quantum dots (QDs). In this multifunctional fluorescent nanoprobe, MoS2 QDs serve not only as nanocarrier for the targeting ligand and pH fluorescent indicator, but also as a fluorescent reference for the ratiometric signal. Indeed, the fluorescence intensity of the MoS2 QDs is highly resistant to increasing proton concentrations, while that of RhB is sensitive to pH. Ratiometric detection of pH was carried out by comparing the pH-sensitive fluorescence of the RhB-based group with the pH-resistant fluorescence of MoS2 QDs. After uptake in living cells, the nanoprobe could stain mitochondria specifically, and allowed to image and monitor pH in mitochondria in a satisfactory manner.

Preparation of Fe3O4@SW-MIL-101-NH2 for selective pre-concentration of chlorogenic acid metabolites in rat plasma,urine,and feces samples / 药物分析学报

An innovative sandwich-structural Fe-based metal-organic framework magnetic material(Fe3O4@SW-MIL-101-NH2)was fabricated using a facile solvothermal method.The characteristic properties of the material were investigated by field emission scanning electron microscopy,transmission electron mi-croscopy(TEM),energy-dispersive X-ray spectroscopy,Fourier transform infrared spectroscopy,X-ray powder diffraction,vibrating sample magnetometry,and Brunauer-Emmett-Teller measurements.Fe3O4@SW-MIL-101-NH2 is associated with advantages,such as robust magnetic properties,high specific surface area,and satisfactory storage stability,as well as good selective recognition ability for chlorogenic acid(CA)and its metabolites via chelation,hydrogen bonding,and π-interaction.The results of the static adsorption experiment indicated that Fe3O4@SW-MIL-101-NH2 possessed a high adsorption capacity toward CA and its isomers,cryptochlorogenic acid(CCA)and neochlorogenic acid(NCA),and the adsorption behaviors were fitted using the Langmuir adsorption isotherm model.Then,a strategy using magnetic solid-phase extraction(MSPE)and ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry(UPLC-Q-TOF MS/MS)was developed and suc-cessfully employed for the selective pre-concentration and rapid identification of CA metabolites in rat plasma,urine,and feces samples.This work presents a prospective strategy for the synthesis of magnetic adsorbents and the high-efficiency pretreatment of CA metabolites.

Microwave-prepared mesoporous graphene as adsorbent and matrix of surface-assisted laser desorption/ionization mass spectrometry for the enrichment and rapid detection of polyphenols in biological samples.

In this work, a three-dimensional mesoporous graphene (3D-MG) prepared by microwave-assisted method was used as both the adsorbent and the matrix of SALDI-TOF MS for polyphenols analysis in biological samples. The outstanding microstructure of 3D-MG made it sensitive in small molecule analysis with low background interference and able to enrich trace polyphenols from complex samples. 3D-MG performed much better in the detection of small molecules than graphene prepared by ordinary method, and could further improve sensitivity and reduce detection limit by enrichment. Due to its unique hierarchical mesoporous structure, the interference of biological macromolecules in SALDI analysis could be eliminated after treatment by 3D-MG. Finally, 3D-MG was successfully applied to the screening of polyphenols in biological samples with simple process and high throughput. Moreover, this strategy had also promoted the development of new matrix in SALDI-TOF MS analysis, in which the matrix properties, adsorption capabilities and size effects of graphene-based materials were combined for the first time.

Debittering of lemon juice using surface molecularly imprinted polymers and the utilization of limonin.

In this work, surface molecularly imprinted polymers (SMIPs) were prepared as a specific sorbent to remove the limonin from the lemon juice for the first time, and then the MIPs containing limonin were directly made into a water-soluble gel to treat inflammation of mice. The resulting polymers were characterized by scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectrometer spectra. And the polymerization conditions and adsorption performances of the resultant nanomaterials were further investigated in detail. Results showed that the MIPs have higher adsorption capacity (27.72 mg/g) compared with surface molecularly non-imprinted polymers (NIPs) (8.12 mg/g). The selectivity experiment indicated that the polymers had excellent selective recognition for limonin and the selectivity factors were calculated as 2.75 and 1.83 for nomilin and obakunone, respectively. The MIPs were successfully used as adsorbent for selectively removing limonin from lemon juice and the MIPs extracted almost all the limonin from lemon juice according to the HPLC results. Furthermore, the MIPs with limonin were processed into water-soluble gel, which can be used to reduce the inflammation and enhance wound healing of model mice.

Curcumin-loaded galactosylated BSA nanoparticles as targeted drug delivery carriers inhibit hepatocellular carcinoma cell proliferation and migration.

BACKGROUND: The main objective of this study was to develop novel BSA nanoparticles (BSA NPs) for improving the bioavailability of curcumin as an anticancer drug, and those BSA NPs were galactosylated for forming the curcumin-loaded galactosylated BSA nanoparticles (Gal-BSA-Cur NPs), thus enhancing their ability to target asialoglycoprotein receptor (ASGPR) overexpressed on hepatocellular carcinoma (HCC) cells. MATERIALS AND METHODS: Gal-BSA-Cur NPs were prepared by the desolvation method and showed a spherical shape and well distribution with the average particle size of 116.24 nm. RESULTS: In vitro drug release assay exhibited that Gal-BSA-Cur NPs had higher release rates and improved the curcumin solubility. Cell uptake studies confirmed that Gal-BSA-Cur NPs could selectively recognize receptors on the surface of HCC (HepG2) cells and improve internalization ability of drug compared with BSA NPs-loaded curcumin (BSA-Cur NPs), which might be due to high affinity to galactose. Further, the effects of Gal-BSA-Cur NPs were evaluated by cytotoxicity assay, crystal violet assay, cell apoptosis assay, and wound healing assay, respectively, which revealed that Gal-BSA-Cur NPs could inhibit HepG2 cells proliferation, induce cell apoptosis, and inhibit cell migration. CONCLUSION: Immunofluorescence staining has proved that the effects of Gal-BSA-Cur NPs related to the suppression of the nuclear factor κB-p65 (NF-κB-p65) expression in HepG2 cell nucleus. Therefore, these results indicate that novel Gal-BSA-Cur NPs are potential candidates for targeted curcumin delivery to HCC cells.

Quality assessment of Penthorum chinense Pursh through multicomponent qualification and fingerprint, chemometric, and antihepatocarcinoma analyses.

An efficient method combined with fingerprint and chemometric analyses was developed to evaluate the quality of the traditional Chinese medicine plant Penthorum chinense Pursh. Nine samples were collected from different regions during different harvest periods, and 17 components in the form of extracts were simultaneously examined to assess quality by using high-performance liquid chromatography. The hepatoprotective effects of components were investigated by assessing the inhibition of SMMC-7721 cell growth. The results indicated that the quality control method was accurate, stable, and reliable, and the hierarchical heat-map cluster and the principle component analyses confirmed that the classification of all nine samples was consistent. Quercetin and ellagitannins including pinocembrin-7-O-[3''-O-galloyl-4'',6''-hexahydroxydiphenoyl]-ß-glucose (PGHG), thonningianin A, thonningianin B, and other flavonoids were abundant in the extracts, and significantly contributed to the hepatoprotective effects.

Adsorption and desorption characteristics of endosulfan in two typical agricultural soils in Southwest China.

Endosulfan is an organochlorine pesticide widely used in Southwest China. In this paper, the adsorption and desorption characteristics of endosulfan in two typical agricultural soils (latosol and lateritic red soil) in this area were studied. The results showed that Langmuir isothermal equation could well describe the adsorption thermodynamic characteristics of endosulfan in latosol and lateritic red soil, and the maximum adsorption capacities of α-endosulfan were 0.186 and 0.209 mg/g, while those of ß-endosulfan were 0.140 and 0.148 mg/g, respectively. Endosulfan adsorption in the two soils was an exothermic physicochemical process, but dominated by physical process. The adsorption kinetic characteristics of endosulfan in the two soils could be well described by second-order kinetic equation, and the initial rate constants were 0.228 and 0.325 mg/(g min) for α-endosulfan, while those were 0.119 and 0.125 mg/(g min) for ß-endosulfan, respectively. The adsorbed endosulfan in the two soils was difficult to be desorbed into the liquid phase, and showed weak desorption hysteresis. These results implied that endosulfan could be firmly adsorbed by the two soils, and their adsorption and desorption abilities may be related to the contents of soil clay and organic matter.

Microbial degradation of endosulfan in contaminated soil with the elution of surfactants.

In this work, an endosulfan-degrading strain was isolated from the aged soil contaminated by endosulfan, and identified as Ochrobactrum sp. EB-4 by 16S rDNA sequence analysis. The microbial degradation characteristics of endosulfan in three eluents (Tween 80 + SDS, Tween 80 + Na2SiO3, Tween 80 + SDS + Na2SiO3) were investigated. The results showed that the degradation percents of α-, ß-endosulfan in the three eluents were 86.83 %∼92.91 % and 88.90 %∼93.94 % in 15 days, respectively. The degradation process can be well described by the first-order kinetic model, and the half-times of α-endosulfan in eluent 1∼eluent 3 were 3.83, 5.29, and 4.53 days, while those of ß-endosulfan were 3.35, 4.50 and 3.79 days, respectively. The endosulfan diol and endosulfan sulfate as main metabolites were detected, and the former can be further degraded by this strain, which revealed that the simultaneously happened hydrolysis and oxidation reactions were the main degradation processes, and dominated by hydrolysis reaction. After 5 days of washing with the eluents, 56.00∼84.33 % of α-endosulfan, and 46.49∼68.56 % of ß-endosulfan in soil were eluted, respectively, and can be entirely biodegraded in 12 days, which indicated that the microbial degradation was the rate-determining step.

[Adsorption and Desorption Characteristics of Endosulfan in Purple Soil].

In order to reveal the residual process of endosulfan in purple soil and protect soil ecological environment, the adsorption and desorption characteristics of endosulfan in purple soil were investigated, and effects of temperature, adsorbent amount, and initial pH of adsorption solution on the adsorption capacity were also examined by static adsorption and desorption experiments. The results showed that the adsorption kinetic process could be well described by the second-order kinetic equation with the initial rate constants of α-, ß-endosulfan as 0. 157 and 0. 115 mg.(g.min)-1, respectively. The adsorption thermodynamic process could be well described by the Langmuir isotherm with the maximum adsorption capacities of α-, ß-endosulfan as 0. 257 mg . g -1 and 0. 155 mg . g -1, respectively. The adsorption process of endosulfan in purple soil may be an exothermic physicochemical process, and is dominated by physical adsorption. Under the experimental conditions examined in this study, the initial pH of adsorption solution had a relative great influence on the adsorption capacity, whereas the temperature and adsorbent amount had no significant influence. The desorption experiments found that the maximum desorption capacities of α-, ß-endosulfan adsorbed in purple soil were 0. 029 mg . g -1 and 0. 017 mg . g -1 at 6 and 4 h, and accounted for 10. 5% and 16. 1% in the maximum adsorption capacities, respectively.

Multiresidue analysis of 30 organochlorine pesticides in milk and milk powder by gel permeation chromatography-solid phase extraction-gas chromatography-tandem mass spectrometry.

A method for simultaneous determination of the 30 organochlorine pesticides (OCP) in milk and milk powder samples has been developed. Prior to the gas chromatography-tandem mass spectrometric analysis, the residual OCP in samples were extracted with n-hexane and acetone mixture (1/1, vol/vol) and cleaned up by gel permeation chromatography and solid phase extraction. Selected reaction monitoring mode was used for gas chromatography-tandem mass spectrometric data acquisition to identify and quantify the OCP. To avoid the matrix effects, matrix-matched calibration solutions ranging from 2 to 50 ng/mL were used to record the calibration curve. Limits of quantification of all OCP were 0.8 µg/kg. With the exception of endrin, limits of quantification are significantly lower than maximum residue limits set by the European Union and China. The average recoveries were in the range of 70.1 to 114.7% at 3 spiked concentration levels (0.8, 2.0, and 10.0 µg/kg) with residual standard deviation lower than 12.9%. The developed method was successfully applied to analyze the OCP in commercial milk products.

[Elution of endosulfan from contaminated soil by surfactants and their combination].

The elution efficiency and dynamic characteristic of endosulfan from the contaminated soil were studied using non-ionic surfactants and anionic/non-ionic surfactants in the presence or absence of Na2SiO3 with batch experiment and parallel desorption experiment. The results showed that the elution percents of alpha-, beta-endosulfan followed a decreasing order of Tween 80/SDS, Tween 80 and Triton X-100 in the absence of Na2SiO3, while that by Triton X-100/SDS at low concentration (100-500 mg x L(-1)) and high concentration (800-1000 mg x L(-1)) were lower and higher than those by the corresponding concentrations of Triton X-100, respectively. The elution efficiencies for four elution modes obviously increased in the presence of Na2SiO3, and the elution percents of alpha-, beta-endosulfan followed a decreasing order of Tween 80/SDS, Tween 80, Triton X-100/SDS and Triton X-100, and that of alpha-endosulfan were as 1.17-2.73, 1.87-4.02, 1.85-6.56 and 1.87-2.85 times as that in the absence of Na2SiO3. The elution process of endosulfan could be described by a 4-parameter biphasic first-order kinetic model, and obviously showed a rapid elution phase and a slow elution phase. Both of the elution percent and elution rate of beta-endosulfan were lower than those of alpha-endosulfan, which indicated that beta-endosulfan was difficult to be eluted from soil. The addition of Na2SiO3 could increase the rate constants of rapid elution and slow elution, and decrease the slow elution percent. Compared with other elution modes, Tween 80/SDS in the presence of Na2SiO3 could elute endosulfan from soil more effectively and rapidly, and shown as a fine mixed eluent for endosulfan.