Iodide-umpolung catalytic system for non-traditional amide coupling from nitroalkanes and amines.

An N-iodosuccinimide (NIS) catalyst was developed for use in the non-traditional synthesis of amide derivatives from nitroalkanes and amines. In contrast to traditional oxidative catalysis, this catalytic system involves reversing the polarities of two catalytic components (umpolung) by means of a hypervalent iodine reagent. A variety of functional groups were tolerated in the reaction, suggesting that they have the potential for use in other types of oxidative catalytic reactions.

Inhibition of continuous cropping obstacle of celery by chemically modified biochar: An efficient approach to decrease bioavailability of phenolic allelochemicals.

The accumulation of allelochemicals released by plants is commonly found in continuous monocropping systems. These chemicals, such as phenolic acids, were shown to be the major sources of autotoxin or pathogen accumulation in soils, leading to a direct or indirect continuous cropping obstacle. In this study, three types of agricultural residuals, i.e., rice husk, tea waste, and wood meal, were chosen as feedstocks. Biochar samples were prepared from these feedstocks to examine their abilities to remove gallic acid, a representative phenolic acid. Biochar, which was prepared from wood meal soaked with H3PO4 (1:1.5, w/w) and pyrolyzed at 400 °C (symbolized as WP400), exhibited the highest adsorption capacities of gallic acids and other phenolic acids. The mechanisms of phenolic acid removal by WP400 were evaluated via experimental and spectroscopic investigations to elucidate the notable adsorption capacity of WP400. The adsorption of gallic acids was pH-dependent and followed a pseudo-second-order kinetic model. The combination of high surface area, the existence of O-containing groups, and the enhancement of H bonds between CC groups and phenolic acids may contribute to the high adsorption capacity of WP400. In a pot experiment, we found that celery growth was promoted with the addition of 0.3% (w/w) WP400 to soils that were continuously monocropped with celery. A large decrease in the water-soluble phenolic compound by more than 40% may be responsible for the results. However, WP400 scavenged nitrate, and this study showed that the synergistic actions of WP400 and nutrients exhibited the greatest efficiencies in mitigating the continuous cropping obstacles of celery.

Synthesis and characterization of PCN-222 metal organic framework and its application for removing perfluorooctane sulfonate from water.

Poly- and perfluoro alkyl substances (PFAS) are a group of man-made, notoriously persistent, and highly toxic contaminants in the environment reported worldwide. Many adsorbents including granular activated carbon, graphene, biochar, zeolites, and clay minerals have been tested for PFAS removal from water, but most of these materials suffer from high cost and/or poor removal performance. Here, we synthesized, characterized, and examined the efficiency of PCN-222(Fe), a new porous metal organic framework (MOF) with high water stability, for adsorptive removal of a frequently occurring PFAS, perfluorooctane sulfonate (PFOS), from water. The adsorption isotherm and kinetic studies revealed high PFOS adsorption capacity of PCN-222 (2257 mg/g), with rapid PFOS removal rate (within 30 min). The structure of PCN-222 was unaffected in water in the pH range of 2-10 but disintegrated and lost its PFOS removal ability at pH > 10. The PFOS adsorption on PCN-222 was an endothermic reaction. Electrostatic attraction was a dominant mechanism for PFOS adsorption at < 1694 mg/g PFOS concentration, while hydrophobic interaction accompanied with hydrogen-bonding was responsible at ≥ 1694 mg/g PFOS concentration. The interlayer morphology of PCN-222 did not change due to increasing PFOS loading. The findings of this study demonstrated superior features of PCN-222 over other conventional adsorbents for its potential application in removing PFOS from contaminated water to reduce PFOS transfer from water to living organisms.

A mechanistic insight into the shrinkage and swelling of Ca-montmorillonite upon adsorption of chain-like ranitidine in an aqueous system.

Adsorption behavior of ranitidine hydrochloride (RT) on a Ca-montmorillonite (SAz-1) was studied in aqueous system through batch experiments. The adsorption kinetics revealed that the equilibrium reached within 0.25 h and the data fitted well to the pseudo-second order kinetic equation (R2 = 0.98). The maximum RT adsorption capacity of SAz-1 was 369.2 mg/g and the adsorption isotherm data followed the Langmuir model (R2 = 0.99). The adsorption of RT and desorption of exchangeable cations from the clay mineral were linearly correlated, suggesting that cation exchange was the dominant mechanism of RT adsorption. The XRD examination of RT-adsorbed SAz-1 samples (unsaturated/saturated) after heating enabled the calculation of RT occupied area in the interlayer of the clay mineral. The results suggested that adsorbed-RT at low loading rate could lay on the internal surfaces in a free style to reduce the basal spacing (d001 value) of SAz-1. When the RT loading rate was increased, a limited surface space enforced more RT molecules to lay in a tilted style and caused interlayer swelling of SAz-1 increasing the d001 value. The trend of rising decomposition temperature of RT with increasing RT loading rates confirmed intercalation of RT molecules in SAz-1. Infrared spectral analysis revealed the participation of amide and furan groups of RT in binding between RT and SAz-1. Thus, this study indicated that SAz-1 is an efficient adsorbent to remove RT from contaminated water, and the chain-like molecular structure of RT could cause an irregular change in the basal spacing of swelling type clay minerals.

Adsorption Mechanism of Novel Porous Materials in Wastewater Treatment: A New Open Special Issue in Materials Science.

The special titled Adsorption Mechanism of Novel Porous Materials in Wastewater Treatment: A New Open Special Issue in Materials aims to publish high-quality research and review articles on the basic and applied science of porous materials and make great contributions to the understanding of metal-organic frameworks (MOFs) in removing pollutants from aqueous and soil environments [...].

Nano Minerals Applications in Pollutants Removal: A New Open Special Issue in Materials.

'Nano Minerals Applications in Pollutants Removal: A New Open Special Issue in Materials', aims to publish high-quality research and review articles on the basic and applied science of clay mineralogy and make great contributions to the understanding of applied mineralogy in removing pollutants from aqueous and soil environments [...].

The Aerodynamic Effect of an Alula-like Vortex Generator on a Revolving Wing.

An alula is a small structure of feathers that prevents birds from stalling. In this study, the aerodynamic effect of an alula-like vortex generator (alula-VG) on a revolving wing was investigated using the PIV technique in a water tank. The alula-VG was mounted on a rectangular wing model at two spanwise positions. The wing model with a revolving motion was installed at different angles of attack, which included pre-stall and post-stall conditions. The velocity fields around the wing model with/without an alula-VG were measured and analyzed, including the vorticity contour, the circulation of vortex structures, and the corresponding sectional lift coefficient, which are used to explain the aerodynamic effect induced by an alula-VG. The lift-off and bursting of the leading-edge vortex (LEV) affect the magnitude of the chordwise circulation and the section lift coefficient. The results show that compared to an alula-VG mounted fixed wing model, the flow interactions among the alula-VG induced spanwise flow, the inertial force caused by the revolving motion, and the wing-tip vortex play important roles in the vortex bursting and the resultant aerodynamic performance. The effect of an alula-VG on a revolving wing depends on its spanwise position and the angle of attack of a wing model, which need to be properly matched.

Novel MOF-808 metal-organic framework as highly efficient adsorbent of perfluorooctane sulfonate in water.

Perfluorooctane sulfonate (PFOS) is a highly persistent contaminant of emerging concern causing harmful effects to human and ecosystem health. In this study, a novel MOF-808 metal-organic framework (MOF) was prepared and evaluated for adsorptive removal of PFOS from aqueous solution. The MOF-808 had high specific surface area (SSA; 1610 m2/g) and was structurally stable in aqueous medium for 7 days under different pH conditions. The MOF-808 reached PFOS adsorption equilibrium within 30 min (at 500 mg/L initial PFOS) and attained the maximum adsorption capacity of 939 mg/g at pH 4.1 - 5.4 (with 50 - 500 mg/L initial PFOS). The PFOS adsorption capacity of MOF-808 was unaffected at pH 2 to 7, but gradually decreased at pH > 7. High SSA, favorable pore size and abundant active adsorption sites on MOF-808 triggered high PFOS adsorption onto the adsorbent. The PFOS adsorption process was endothermic and spontaneous in nature. Electrostatic interaction between the cationic central cluster ([Zr6O4(OH)4]12+) of MOF-808 and PFOS anion was identified as the key mechanism of PFOS adsorption onto MOF-808, as evident from the infrared spectroscopic investigation of the adsorbent. This study suggests that MOF-808 can be considered as a highly efficient adsorbent for PFOS removal from water and warrants future research to evaluate the application and performance of the material under wastewater conditions.

Unravelling the mechanism of amitriptyline removal from water by natural montmorillonite through batch adsorption, molecular simulation and adsorbent characterization studies.

Amitriptyline (AMI) is one of the most common tricyclic antidepressant personal care medications. Due to its environmental persistence and bioaccumulation, release of AMI into the environment via wastewater streams in elevated levels could lead to significant ecological and human health impacts. In this study, the adsorption of AMI by montmorillonite (SWy-2), a naturally abundant smectite clay with sodium ions as the main interlayer cations, was investigated. Maximum AMI adsorption (276 mg/g) occurred at pH 7-8. After adsorption, examination of the adsorbent's X-ray diffraction pattern indicated that interlayer expansion had occurred, where chemical stoichiometry confirmed cation exchange as the principal adsorption mechanism. AMI adsorption reached equilibrium within 4 h, with kinetic data best fitting the pseudo-second order kinetic model (R2 = 0.98). AMI adsorption was unaffected by solution pH in the range 2-11, where adsorption was endothermic, and molecular simulations substantiated by Fourier transform infrared spectroscopy and thermogravimetric investigations indicated that the orientation of AMI molecules in the interlayer was via an amine group and a benzene ring. Overall this research shows that SWy-2 has significant potential as a low cost, effective, and geologically derived natural material for AMI removal in wastewater systems.

Chitosan 3D cell culture system promotes naïve-like features of human induced pluripotent stem cells: A novel tool to sustain pluripotency and facilitate differentiation.

A simplified and cost-effective culture system for maintaining the pluripotency of human induced pluripotent stem cells (hiPSCs) is crucial for stem cell applications. Although recombinant protein-based feeder-free hiPSC culture systems have been developed, their manufacturing processes are expensive and complicated, which hinders hiPSC technology progress. Chitosan, a versatile biocompatible polysaccharide, has been reported as a biomaterial for three-dimensional (3D) cell culture system that promotes the physiological activities of mesenchymal stem cells and cancer cells. In the current study, we demonstrated that chitosan membranes sustained proliferation and pluripotency of hiPSCs in long-term culture (up to 365 days). Moreover, using vitronectin as the comparison group, the pluripotency of hiPSCs grown on the membranes was altered into a naïve-like state, which, for pluripotent stem cells, is an earlier developmental stage with higher stemness. On the chitosan membranes, hiPSCs self-assembled into 3D spheroids with an average diameter of ~100 µm. These hiPSC spheroids could be directly differentiated into lineage-specific cells from the three germ layers with 3D structures. Collectively, chitosan membranes not only promoted the naïve pluripotent features of hiPSCs but also provided a novel 3D differentiation platform. This convenient biomaterial-based culture system may enable the effective expansion and accessibility of hiPSCs for regenerative medicine, disease modeling, and drug screening.

Mechanistic insights into ethidium bromide removal by palygorskite from contaminated water.

Ethidium bromide (EtBr)-containing wastewater can be hazardous to biodiversity when released into the soil and water bodies without treatment. EtBr can mutate living microbial cells and pose toxicity to even higher organisms. This work investigated the removal of EtBr from aqueous solutions by a naturally occurring palygorskite (PFl-1) clay mineral via systematic batch adsorption experiments under different physicochemical conditions. EtBr existed in an undissociated form at pH ~7, and was adsorbed on PFl-1 obeying the Freundlich isotherm model. The maximum EtBr adsorption capacity was 285 mmol/kg. The best fitted kinetic model for EtBr adsorption was the pseudo-second order model. The amounts of exchangeable cations desorbed from PFl-1 during EtBr adsorption was linearly correlated to the amounts of EtBr adsorbed, with a slope of 0.97, implying that a cation exchange-based adsorption mechanism was dominating. Additionally, dimerization of EtBr molecules via bromide release assisted an increased EtBr removal by PFl-1 at high adsorbate concentrations. Detailed x-ray diffraction, Fourier transform infrared, scanning electron imaging and energy dispersive x-ray analyses confirmed that EtBr adsorption occurred dominantly on the surface of palygorskite which mineralogically constituted 80% of the bulk PFl-1 adsorbent. A small portion of EtBr was also adsorbed by PFl-1 through intercalation onto the smectite impurity (10%) in PFl-1. This study suggested that PFl-1 could be an excellent natural material for removing EtBr from pharmaceutical and laboratory wastewater.

Enhanced removal of ethidium bromide (EtBr) from aqueous solution using rectorite.

Ethidium bromide (EtBr) is an intercalating agent commonly used as nucleic acid fluorescent tag in various techniques of life science field. It is considered as a serious biohazard due to its mutagenicity and carcinogenicity. As such, developing high efficiency and low cost materials as cleanup kits is in urgent need although many methods have already been developed. In this study we take use of the affinity of organic cations for clay minerals of high cation exchange capacity (CEC) and large specific surface area (SSA) and tested the removal of EtBr using rectorite, a type of clay mineral made of 1:1 regularly mixed layers of illite and montmorillonite. Our results showed that the uptake of Et+ on rectorite could be as high as 400 mmol/kg and the removal of Et+ was extremely fast. Desorption of inorganic cation Ca2+ and sorption of counterion Br- revealed that cation exchange was the dominating mechanism of Et+ removal using rectorite. Thermal analyses revealed that the EtBr could be thermally destructed inside the interlayer of rectorite and the material could be thermally regenerated. Thus, clay minerals could have a great potential to be fabricated into cleanup kits for the removal of EtBr in case of spill.

The Triple Mechanisms of Atenolol Adsorption on Ca-Montmorillonite: Implication in Pharmaceutical Wastewater Treatment.

The adsorption of atenolol (AT) from aqueous solutions by Ca-montmorillonite (SAz-2) was investigated in batch studies under different physicochemical conditions. The AT existed in neutral un-dissociated form at pH 10, and was adsorbed on dioctahedral smectite (SAz-2) obeying the Langmuir isotherm with a maximum adsorption capacity of 330 mmol/kg. The kinetic adsorption suggested that both strong and weak adsorption sites existed on SAz-2 and participated in the adsorption mechanisms. The amount of exchangeable cations desorbed from SAz-2 during AT adsorption was linearly correlated with the amounts of adsorbed AT having slopes of 0.43, which implied that a cation exchange based adsorption mechanism was also in place. A comprehensive basal spacing change of SAz-2 was observed after AT adsorption on the clay mineral when tested with or without AT recrystallization. The intercalation of AT into the SAz-2 interlayers did not result in swelling due to the low adsorption capacity of the drug. Prominent interactions between the pharmaceutical molecule and SAz-2 were evidenced by apparent shifts of the infrared absorption bands after adsorption. The interlayer configurations and hydrogen bonding of AT on SAz-2 were also supported by infrared, X-ray diffraction and thermogravimetric analyses. This study suggested that SAz-2 is an excellent material to remove not only AT from pharmaceutical wastewater, but can potentially remove many other ß-receptor blocker drugs. The results helped us to understand the possible interlayer configurations and adsorption mechanisms of the drugs on natural clay mineral based adsorbents.

Mechanisms of Cu2+, triethylenetetramine (TETA), and Cu-TETA sorption on rectorite and its use for metal removal via metal-TETA complexation.

Uptake of metals, organics, and formation of metal-organic complexes on the surface or in the interlayer of clay minerals had been studied extensively over the last half century. In this study, we investigated the uptake mechanisms of Cu2+, triethylenetetramine (TETA), and Cu-TETA on rectorite and its use for metal removal via metal-TETA complexation. The uptake of Cu2+, TETA, and Cu-TETA by rectorite occurred on the external as well as in the interlayer space, resulting in a change of d001-spacing due to differences in sizes of interlayer cations or complexes. Although the uptake of Cu2+ and Cu-TETA by rectorite was via a cation exchange process as evidenced by the stoichiometric desorption of dominant interlayer cation Ca2+, the uptake of TETA alone on rectorite was via complexation with interlayer cation Ca2+. Due to strong affinity of TETA for Cu2+, significant amounts of Cu2+ uptake occurred on TETA-rectorite. Desorption of Ca2+ from TETA-rectorite confirmed the replacement of interlayer cation Ca2+ by Cu2+. However, the replacement of Ca2+ by Cu2+ in TETA-rectorite did not involved in removal of TETA. As such, TETA-modified clay minerals may serve as a type of sorbents for the removal of selected heavy metals via surface or interlayer via complexation.

Removal of perfluorooctanoic acid from water using calcined hydrotalcite - A mechanistic study.

Calcined hydrotalcite (CHT) was evaluated for its potential removal of perfluorooctanoic acid (PFOA) from water in this study. The uptake of PFOA by CHT could be as high as 1587 mg/g (ca. 3.8 mmol/g), slightly larger than the anion exchange capacity (AEC) of the hydrotalcite (HT). Such a high removal was fast and pH independent, suggesting the versatile use of CHT. Due to the structural memory effect of HT, the removal involved adsorption of PFOA during HT recovery and intercalation of PFOA into the interlayer of restructured HT at low and high initial concentrations, respectively. Limited by the specific surface area and AEC, the intercalated PFOA would form a vertical bilayer or admicelle conformation. As such, the HT intercalated with PFOA became one-layer stacking with a basal spacing of 2.04 nm in contrast to the 3R polytype of recovered HT having a layer thickness of 0.78 nm, as confirmed by X-ray diffraction, thermogravimetric, and infra-red analyses. Due to its high PFOA removal capacity and large partitioning coefficient, the amount of CHT used, thus, the disposal of PFOA-laden solid could be minimized.

Mechanism of tyramine adsorption on Ca-montmorillonite.

Tyramine (TY) adsorption on a Ca-montmorillonite (SAz-2) was investigated with batch experiments and complementary analyses utilizing ultra-high performance liquid chromatography, ion chromatography, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetry (TG). The adsorption reached equilibrium in 8 h, complying with the pseudo-second-order rate equation, and came to an adsorption capacity of 682 mmol kg-1 at pH 6-8.1, utilizing the Langmuir isotherm model. The adsorption of TY and desorption of exchangeable cations exhibited a linear relationship with a slope of 0.9, implying that the adsorption was largely influenced by a cation exchange mechanism. The effective adsorption was further verified by the characteristic TY bands in the FTIR spectra and the signals of mass loss due to TY decomposition in the TG measurements of the clay after adsorption experiments. Intercalation of hydrated TY into the clay interlayer was confirmed by XRD and TG analyses of the heated samples loaded with TY. The adsorption reached only 0.57 cation exchange capacity of the clay which was probably limited by the low charge density of TY as compared to the negative charge density of the clay surface and by the steric effects arising from the hydration of TY that increased its molecular size. Adsorption of TY on montmorillonite can make TY more resistant to thermal decomposition and possibly better preserved in aquatic and soil environments.

Chitosan promotes cancer progression and stem cell properties in association with Wnt signaling in colon and hepatocellular carcinoma cells.

Cancer stem cells (CSCs), a small population of cancer cells, have been considered to be the origin of cancer initiation, recurrence, and metastasis. Tumor microenvironment provides crucial signals for CSCs to maintain stem cell properties and promotes tumorigenesis. Therefore, establishment of an appropriate cell culture system to mimic the microenvironment for CSC studies is an important issue. In this study, we grew colon and hepatocellular carcinoma (HCC) cells on chitosan membranes and evaluated the tumor progression and the CSC properties. Experimental results showed that culturing cancer cells on chitosan increased cell motility, drug resistance, quiescent population, self-renewal capacity, and the expression levels of stemness and CSC marker genes, such as OCT4, NANOG, CD133, CD44, and EpCAM. Furthermore, we demonstrated that chitosan might activate canonical Wnt/ß-catenin-CD44 axis signaling in CD44positive colon cancer cells and noncanonical Wnt-STAT3 signaling in CD44negative HCC cells. In conclusion, chitosan as culture substrates activated the essential signaling of CSCs and promoted CSC properties. The chitosan culture system provides a convenient platform for the research of CSC biology and screening of anticancer drugs.

Y-box binding protein-1 promotes hepatocellular carcinoma-initiating cell progression and tumorigenesis via Wnt/ß-catenin pathway.

Y-box binding protein-1 (YB-1) is a pleiotropic molecule that binds DNA to regulate genes on a transcriptional level in the nucleus and binds RNA to modulate gene translation in the cytoplasm. In our previous studies, YB-1 was also characterized as a fetal hepatic protein that regulates the maturation of hepatocytes and is upregulated during liver regeneration. Moreover, YB-1 has been shown to be expressed in human hepatocellular carcinoma (HCC). However, the role of YB-1 in HCC remains unclear. Here, we aimed to characterize the role of YB-1 in HCC. Based on the results of loss-of-function in HCC and gain-of-function in mice liver using hydrodynamic gene delivery, YB-1 promoted hepatic cells proliferation in vitro and in vivo. YB-1 was also involved in HCC cell proliferation, migration, and drug-resistance. The results of extreme limiting dilution sphere forming analysis and cancer initiating cell marker analysis were also shown that YB-1 maintained HCC initiating cells population. YB-1 also induced the epithelial-mesenchymal transition and stemness-related gene expression. Knockdown of YB-1 suppressed the expression of Wnt ligands and ß-catenin, impaired Wnt/ß-catenin signaling pathway and reduced the numbers of HCC initiating cells. Moreover, YB-1 displayed nuclear localization particularly in the HCC initiating cells, the EpCAM+ cells or sphere cells. Our findings suggested that YB-1 was a key factor in HCC tumorigenesis and maintained the HCC initiating cell population.

Amitriptyline removal using palygorskite clay.

With the increased detections of commonly used pharmaceuticals in surface water and wastewater, extensive attentions were paid recently to the fate and transport of these pharmaceuticals in the environment. Amitriptyline (AMI) is a tricyclic antidepressant widely applied to treat patients with anxiety and depression. In this study, the removal of AMI with palygorskite clay (PFl-1) was investigated under different physico-chemical conditions and supplemented by instrumental analyses. The uptake of AMI on PFl-1 was well fitted by the Langmuir isotherm with an adsorption capacity of 0.168 mmol g(-1) at pH 6-7. The AMI uptake was fast and reached equilibrium in 15 min. The X-ray diffraction patterns showed no shift of the (110) peak position of palygorskite after AMI uptake. However, the (001) peak position of the minor component smectite (about 10%) shifted to lower angle as the amounts of AMI input increased. These results suggested surface uptake of AMI on palygorskite and interlayer uptake of AMI in smectite. As smectite is a common component of palygorskite clays, its role in assessing the properties and performances of palygorskite clays for the uptake and removal of contaminants should not be neglected. Overall, the high affinity of AMI for PFl-1 and strong retention of AMI on PFl-1 suggested that it could be a good adsorbent to remove AMI from wastewater. Palygorskite clays can also be a sink for many cationic pharmaceuticals in the environmental of the arid regions.

Interaction of ciprofloxacin and probe compounds with palygorskite PFl-1.

The adsorption of ciprofloxacin (CIP) as well as probe compounds, phenylpiperazine (PP) (NH) and fluorochloroquinolone carboxylic acid (FCQCA) (COOH), on palygorskite (PFl-1) obeyed the Langmuir isotherm at pH 2, 7, and 11 except the FCQCA adsorption at pH 2. The CIP and PP adsorption onto PFl-1 was 98-160 mmol/kg. In neutral solution the total amount of exchangeable cations desorbed correlated with the adsorbed amount of CIP and PP well with a slope of 0.9-1, indicating a cation-exchange mechanism. A low amount of FCQCA adsorption of 27-57 mmol/kg was observed and the amount of exchangeable cations desorbed negatively correlate with the amount of FCQCA adsorbed as influenced by surface complexation or cation bridging. FTIR band shifting due to the ring-stretch vibration of PP and the keto-carbonyl group stretching of FCQCA suggested strong interactions as PP and FCQCA absorbed on PFl-1 in neutral solution. In the interaction of CIP with PFl-1, the piperazine-amine group played an important role in cation-exchange interaction in acidic to neutral solution, while the deprotonated keto carbonyl group actively partook in cation bridging or surface complexation with metal cations adsorbed on PFl-1 when the CIP was in anionic form in alkaline solution.