Properties and mechanism for selective adsorption of Au(iii) on an ionic liquid adsorbent by grafting N-methyl imidazole onto chloromethylated polystyrene beads

To recover Au(iii) from an acidic chloride-containing solution efficiently, an ionic liquid absorbent (CMPS-IL) was synthesized by grafting N-methyl imidazole onto chloromethylated polystyrene beads (CMPS). The adsorption capacity, selectivity, and reusability were systematically evaluated by a series of adsorption experiments. The maximum adsorption capacity reached up to 516.5 mg g⁻¹ at 318 K. The adsorbent can selectively recover Au(iii) from binary system solutions with a higher separation factor β_Au/M (10⁴–10⁶). Moreover, the adsorption–desorption cycles (7 cycles) showed that the CMPS-IL maintained a stable adsorption performance and high adsorption efficiency. Finally, the adsorption mechanism of CMPS-IL for Au(iii) was investigated by SEM, TEM, XPS, and FT-IR, then proposed with a combination of electrostatic interactions and d–π interaction between imidazolium and AuCl₄⁻. This study provides an easily-prepared and economical adsorbent for Au(iii) with high selectivity and large adsorption capacity to boost its practical applications.

The synthesis and adsorption properties for Au(iii) of CMPS-IL synthesized by grafting N-methyl imidazole onto chloromethylated polystyrene beads (CMPS).     

Creating magnetic ionic liquid-molecularly imprinted polymers for selective extraction of lysozyme

A novel magnetic (Fe₃O₄) surface molecularly imprinted polymer (MIP) based on ionic liquid (IL) (Fe₃O₄@VTEO@IL-MIPs) was prepared for the selective extraction of lysozyme (Lys). As the functional monomer of the MIPs, an imidazolium-based IL with vinyl groups was prepared. It can provide multiple interactions with template molecules. The amount of IL was optimized (200 mg). Fourier transform infrared spectrometry (FT-IR), transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA) and a vibrating sample magnetometer (VSM) were used to characterize the MIP. The results indicate the successful formation of an imprinting polymer layer. The concentration of Lys in the supernatant was determined by UV-vis spectrophotometry at a wavelength of 280 nm. The maximum adsorption capability of the MIP is 213.7 mg g⁻¹ and the imprinting factor (IF) is 2.02. It took 2.5 h for the MIP to attain adsorption equilibrium. The structure of the protein was evaluated using circular dichroism (CD) spectra and UV-visible spectra. The adsorption performance was further investigated in detail by selective adsorption experiments, competitive rebinding tests, and reusability and stability experiments. Furthermore, it was utilized to separate the template protein from a mixture of proteins and real samples successfully because of the high adsorption capacity for Lys.

A novel magnetic (Fe₃O₄) surface molecularly imprinted polymer (MIP) based on ionic liquid (IL) (Fe₃O₄@VTEO@IL-MIPs) was prepared for the selective extraction of lysozyme (Lys).     

Amide-functionalised phosphonium-based ionic liquids as ligands for rhodium(iii) extraction

Seven new amide-functionalised phosphonium-based ionic liquids (APILs) with chloride anions are synthesised and applied to extraction of rhodium(iii) from HCl solution. The effects of structural modification of the APILs on the extraction performance are examined by liquid–liquid extraction using toluene as a diluent and the results compared with those for trihexyltetradecylphosphonium chloride ([P₆₆₆₁₄][Cl]), a typical commercial extractant. The performance of the APILs as rhodium(iii) extractants is influenced by three main factors: (1) the length of the alkyl chains attached to the P atom; (2) the length of the linker between the amide and phosphonium moiety; and (3) the type of amide group. A novel ligand, [3°C₂P₄₄₄][Cl], had outstanding performance in the effective recovery of rhodium(iii). Extraction of rhodium(iii) from a 1.0 mol dm⁻³ HCl solution with 0.5 mol dm⁻³ [3°C₂P₄₄₄][Cl] proceeded quantitatively (>98%) and the extraction efficiency was higher than that of the commercial extractant [P₆₆₆₁₄][Cl]. The mechanism of rhodium(iii) extraction by [3°C₂P₄₄₄][Cl] was investigated by slope analysis, UV-vis, and FT-IR spectroscopy. These results indicate that [RhCl₄(H₂O)₂]⁻ in aqueous solution is extracted by [3°C₂P₄₄₄][Cl] through an anion-exchange mechanism and slowly converted into a dimer, [Rh₂Cl₉]³⁻, in the organic phase.

Novel amide-functionalised phosphonium-based ionic liquid can extract rhodium(iii) efficiently.     

Water-soluble carboxymethyl chitosan (WSCC)-modified single-walled carbon nanotubes (SWCNTs) provide efficient adsorption of Pb(ii) from water

Nanocomposites play a key role in the removal of toxic metal(loid)s from environmental water. In this study, we investigated the adsorption capability of water-soluble carboxymethyl chitosan (WSCC)-modified functionally oxidized single walled carbon nanotubes (oSWCNTs) for rapid and efficient removal of toxic Pb(ii) from water. The WSCC–oSWCNTs nanocomposite was prepared by an acid treatment of SWCNTs followed by an ultrasonic dispersion process using WSCC as dispersant. The morphology and chemical characteristics of the WSCC–oSWCNTs nanocomposite were further identified using various characterization techniques (i.e., transmission electron microscopy, TEM; scanning electron microscopy, SEM; Raman spectra; Fourier transform infrared spectroscopy, FTIR; X-ray photoelectron spectroscopy, XPS; nitrogen adsorption–desorption isotherm test). The efficiency of the adsorption process in batch experiments was investigated via determining various factor effects (i.e. WSCC–oSWCNTs nanocomposite concentration, solution pH, initial Pb(ii) concentration, contact time, and reaction temperature). Kinetic results showed that the adsorption process followed a pseudo-second-order, while an isotherm results study showed that the adsorption process followed the Langmuir and Freundlich isotherm models at the same time. In addition, the van''t Hoff equation was used to calculate thermodynamic parameters for assessing the endothermic properties and spontaneity of the adsorption process. The WSCC–oSWCNTs nanocomposite manifested a high adsorption capacity for Pb(ii) (113.63 mg g⁻¹) via electrostatic interactions and ion-exchange, as its adsorption rate could reach up to 98.72%. This study, therefore, provides a novel adsorbent for the removal and detection of harmful residues (i.e. toxic metal(loid)s) from environmental water, such as industry wastewater treatment and chemical waste management.

A water-dispersible WSCC–oSWCNTs nanocomposite prepared for efficient Pb(ii) uptake from water. The removal efficiency is still higher than 80% after 4 adsorption–desorption cycles, and the Pb(ii) can be adsorbed with high selectivity and stability.     

An efficient mercapto-functionalized organic–inorganic hybrid sorbent for selective separation and preconcentration of antimony(iii) in water samples

This work reported on the application of mercapto-functionalized silica-supported organic–inorganic hybrid sorbent as a solid phase extraction (SPE) extractant for effective separation and preconcentration of Sb(iii) species in real water samples. The influences of pH, sorbent amounts, flow rates and the concentration of eluent on the adsorption and desorption of Sb(iii) species had been evaluated. The recovery of Sb(iii) species at pH 5 with 100 mg mercapto-functionalized hybrid sorbent at the flow rate of 5.0 mL min⁻¹ was greater than 95% without interference from all of metal ions tested. The trapped Sb(iii) species by extractant was then eluted with 5% HCl solution at the flow rate of 5.0 mL min⁻¹. The proposed procedure permitted large enrichment factors of about 200 and higher for 10 μg L⁻¹ of Sb(iii) species. The merits of analytical figures for the determination of Sb(iii) species were as follows: detection limit (3σ, n = 11), 2 ng L⁻¹; precision, 1.6% (n = 11) for 10 μg L⁻¹ of Sb(iii) species; the linear calibration curve presented in the concentration range of 1.0–200.0 μg L⁻¹. The validity of the proposed procedure was checked by the analysis of standard reference materials. Excellent agreement between the analytical results and the certified values (t-test at 95% confidence level) was found. The mercapto-functionalized hybrid sorbent as a SPE extractant was applied to the determination of Sb(iii) species in various water samples with satisfactory results.

This work reported on the application of mercapto-functionalized silica-supported organic–inorganic hybrid sorbent as a solid phase extraction (SPE) extractant for effective separation and preconcentration of Sb(iii) species in real water samples.     

Molecularly imprinted polymers for selective adsorption of quinoline: theoretical and experimental studies

The effects of solvent on the synthesis of molecularly imprinted polymers (MIPs) for the selective adsorption of quinoline were evaluated in this work. The MIPs were synthesized by the “bulk” method using the quinoline molecule (IQ) as a template in different solvents, such as toluene (MIPT) and chloroform (MIPC). The adsorbents were characterized by thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and N₂ adsorption/desorption measurements. The influences of time, adsorbate concentration, and temperature on the adsorption of quinoline by MIPT and MIPC were evaluated. Maximum adsorption capacities (q_e) of 35.23 and 24.10 mg g⁻¹ were obtained for MIPT and MIPC, respectively. Thermodynamic studies indicate that occur physisorption and a spontaneous process (Δ_adsG° < 0) entropically directed. Finally, the highest selectivity and reusability of MIPC for quinoline adsorption was ascribed to the better interaction between the chloroform and monomer, which favors the formation of porous adsorbents with higher numbers of adsorption sites.

Molecularly imprinted polymers synthesized by a one-pot synthesis absorb quinoline efficiently and selectively.     

Iodonium salts as efficient iodine(iii)-based noncovalent organocatalysts for Knorr-type reactions

Hypervalent iodine(iii)-derivatives display higher catalytic activity than other aliphatic and aromatic iodine(i)– or bromine(i)-containing substrates for a Knorr-type reaction of N-acetyl hydrazides with acetyl acetone to give N-acyl pyrazoles. The highest activity was observed for dibenziodolium triflate, for which 10 mol% resulted in the generation of N-acyl pyrazole from acyl hydrazide and acetyl acetone typically at 50 °C for 3.5–6 h with up to 99% isolated yields. ¹H NMR titration data and DFT calculations indicate that the catalytic activity of the iodine(iii) is caused by the binding with a ketone.

The dibenziodolium cation displays high catalytic activity for the Knorr-type reactions via binding with the carbonyl O atom.     

Density functional theory investigation on iridium(iii) complexes for efficient blue electrophosphorescence

The geometrical structures, electronic structures, optoelectronic properties and phosphorescence efficiencies of four blue-emitting phosphors [Ir(fpmi)₂(pyim)] (1), [Ir(pyim)₂(fpmi)] (2), [Ir(fpmi)₂(fptz)] (3), [Ir(tfmppz)₂(pyim)] (4), [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C,C²′; pyim = 2-(1H-imidazol-2-yl)pyridinato; fptz = 5-(trifluoromethyl-2H-1,2,4-triazol-3-yl)pyridine; tfmppz = 1-(4-trifluoromethylphenyl)pyrazolyl] were investigated by DFT and TDDFT methods. We first optimized geometrical structures in the ground and lowest triplet states, and computed the absorption and emission spectra of 1 and 5[Ir(fpmi)₂(pypz)] [pypz = 2-(1H-pyrazol-5-yl)pyridinato], which have been synthesized and characterized in a laboratory, using three functionals, B3LYP, CAM-B3LYP, and M062X. The calculation results were compared with relevant experimental data to assess the performance of the functionals. The suitable methods and functionals were then applied to study properties of the three other complexes. The HOMOs of 1–3 are composed of d(Ir) and π(cyclometalated ligands), however, the HOMO of 4 resides on the pyim ligand, while the LUMOs of all four complexes are dominantly localized on the chelating ligands. The calculated absorption results show that the corresponding absorption peaks for the four mainly studied complexes are almost at the same positions, however, the absorption intensities of the bands differ largely from each other. The lowest energy emissions of the four complexes are localized at 507, 512, 468, and 513 nm, respectively. In order to estimate their efficiencies, we carried out simplified radiative rate constant calculations. It turns out that complex 3, which possesses the shortest emission wavelength and the largest radiative rate constant (k_r) value, can be considered as a highly efficient blue-emitting iridium(iii) complex.

The geometrical structures, electronic structures, optoelectronic properties and phosphorescence efficiencies of blue-emitting phosphors [Ir(fpmi)₂(pyim)], [Ir(pyim)₂(fpmi)], [Ir(fpmi)₂(fptz)], [Ir(fpmi)₂(pypz)] and [Ir(tfmppz)₂(pyim)]), were investigated by DFT and TDDFT methods.     

Synthesis of anionic ionic liquids@TpBd-(SO3)2 for the selective adsorption of cationic dyes with superior capacity

The discharge of industrial printing and dyeing wastewater is one of the main reasons for the increasing water shortage and deterioration. The treatment of dyestuff wastewater is an issue and needs to be urgently solved. In this work, anionic ionic liquid functional covalent organic materials (COMs) were firstly synthesized and used for the selective adsorption of cationic dyes. First, a series of sulfonic acid group (SO₃H)-functionalized anionic TpPa-SO₃, TpBd-(SO₃)₂, and TpCR-(SO₃)₂ were prepared, respectively, and then imidazole was grafted onto TpBd-(SO₃)₂ to obtain ImI@TpBd-(SO₃)₂. The full characterization using X-ray diffraction, FT-IR spectroscopy, ¹³C cross-polarization magic-angle spinning NMR spectroscopy, zeta-potentials, BET surface and pore analysis indicated that these COMs and ImI@TpBd-(SO₃)₂ exhibited different morphologies, porosities, and potentials. The effects of the type of dye, adsorption time, initial dye concentration, and pH on the adsorption of dyes on ImI@TpBd-(SO₃)₂ were systematically investigated, respectively. The results revealed that ImI@TpBd-(SO₃)₂ possessed good adsorption performance for nine different cationic dyes with adsorption capacities in the range from 2865.3 mg g⁻¹ for methylene blue (MB) to 597.9 mg g⁻¹ for basic orange 2 (BO), but little adsorption for anionic and neutral dyes, revealing charge selectivity. The adsorption ratio of ImI@TpBd-(SO₃)₂ for MB was as high as 74.0% at 10 min by using 1.0 mg material, owing to the post modification of TpBd-(SO₃)₂ with imidazole. The adsorption of MB on ImI@TpBd-(SO₃)₂ was pH dependent. The adsorption isotherm and kinetics fitted well with the Freundlich and pseudo second-order kinetic model, respectively. Finally, the very outstanding advantages of superior selective adsorption, desorption, convenient preparation, and low density of ImI@TpBd-(SO₃)₂ predicted its research and application potential in dye wastewater recovery.

Anionic ionic liquids@covalent organic materials for the selective adsorption of cationic dyes.     

Ion-imprinted modified molecular sieves show the efficient selective adsorption of chromium(vi) from aqueous solutions

Molecular sieve 5A was modified with (3-aminopropyl) triethoxysilane (APTES) as the support matrix, on which 4-VP was used as the ionic imprinting group. The as-prepared IIZMS-APTES was applied as the adsorbent for the recovery of chromium(vi) from aqueous solutions. The adsorbent was characterized via Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), and X-ray diffraction (XRD). The influences of adsorption time, concentration of the ions, initial pH, and temperature on the adsorption performance to Cr(vi) were investigated. The selectivity and reusability of IIZMS-APTES are also evaluated. The results showed that the maximum adsorption capacity reached 56.46 mg g⁻¹ when the initial concentration of metal ions was at 100 mg L⁻¹ at pH 2 and 30 °C. The adsorption process followed the pseudo-second-order kinetic model and Langmuir adsorption isotherm model. The IIZMS-APTES exhibits an efficient selective adsorption of Cr(vi) from aqueous solutions.

Molecular sieve 5A was modified with (3-aminopropyl) triethoxysilane (APTES) as the support matrix, on which 4-VP was used as the ionic imprinting group.     

Rational design of a new cytarabine-based prodrug for highly efficient oral delivery of cytarabine

Because of the drawbacks of cytarabine (Ara-C) such as poor lipid solubility, deamination inactivation and low oral bioavailability limiting its application by oral administration, herein we propose a novel amphiphilic low molecular weight cytarabine prodrug (PA-Ara) by conjugating palmitic acid (PA) to Ara-C, making it possible to avoid the deamination inactivation by protecting the active 4-amino, as well as improving lipid solubility. Thanks to the rational design, the oil/water partition coefficient (P) of PA-Ara was improved tremendously compared with Ara-C, and the PA-Ara conjugation was stable enough in artificial digestive juice, ensuring that most molecules could be absorbed in the form of the prodrug. Results from an MTT assay conducted to measure the cytotoxicity of Ara-C and PA-Ara to HL60 (acute myeloblastic leukemia cell line) and K562 cells (chronic granulocytic leukemia cell line) showed that PA-Ara had significantly stronger antiproliferation activities than Ara-C. Significantly, we firstly compared the bioavailability of the oral fatty acid chain modified cytarabine prodrug preparation with injection and the relative bioavailability was up to 61.77% for our PA-Ara, which was much superior to that of oral Ara-C solution (3.23%). Overall, these findings make it clear that the PA-Ara suspension has the potential to be a promising new cytarabine oral preparation for leukemia therapy.

To overcome the drawbacks of cytarabine such as bad liposolubility and low bioavailability, we rationally designed a new cytarabine-based prodrug for oral cytarabine delivery, realizing significantly enhanced bioavailability for cancer therapy.     

Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries

Solvate ionic liquids (SILs), comprising long-lived, Li solvate cations and counter anions, serve as highly Li-ion-conductive and non-flammable electrolytes for use in lithium secondary batteries. In this work, we synthesized a series of novel redox-active glyme(oligoether)–Li salt-based SILs, consisting of a symmetric ([Li(G3)]⁺) or asymmetric ([Li(G3Bu)]⁺) triglyme–Li salt complex and redox-active tetrahalogenoferrate ([FeX]⁻ (X = Br₄, Cl₃Br, Cl₄)), for use as the catholyte in semi-liquid lithium secondary batteries. The successful formation of stable molten complexes of [Li(G3/G3Bu)][FeX] was confirmed by Raman spectroscopy and thermogravimetry. The melting point (T_m) depended on both the molecular weights of the complex anions and the structures of the complex cations. [Li(G3)][FeCl₄] comprised complex cations with a symmetric structure, and the smallest complex anions showed the lowest T_m of 28.2 °C. The redox properties of the [FeX]⁻/[FeX]²⁻ couple strongly suggested the suitability of [Li(G3/G3Bu)][FeX] as a catholyte. The discharge capacities of semi-liquid lithium secondary batteries utilizing the [Li(G3/G3Bu)][FeX] catholyte depended on the structure of the SILs, and the cell with [Li(G3)][FeCl₄] showed the highest capacity with relatively good capacity retention. This study confirmed the feasibility of the glyme-based redox-active SILs as catholytes for scalable redox-flow type batteries.

Solvate ionic liquids (SILs), comprising long-lived, Li solvate cations and counter anions, serve as highly Li-ion-conductive and non-flammable electrolytes for use in lithium secondary batteries.     

Design and controllable synthesis of ethylenediamine-grafted ion imprinted magnetic polymers for highly selective adsorption to perchlorate

A series of ethylenediamine-grafted ion imprinted magnetic polymers (Fe₃O₄@IIPs) were synthesized via ultrasonic assisted suspension polymerization with perchlorate (ClO₄⁻) as an ion imprinting template. They were characterized by XRD, EA, VSM, FTIR and XPS and applied as adsorbents for ClO₄⁻ removal from aqueous solutions. The effects of the usage amount of crosslinking agent divinylbenzene (DVB) used for preparation on the structure and the adsorptive performance of Fe₃O₄@IIPs were investigated. The results show that the Fe₃O₄@IIPs have an average size of 200–800 nm, which increases with the increase of the amount of DVB from 0 to 2 g during the preparation process. The saturation magnetization intensities are at 35.6–42.8 emu g⁻¹, which decrease with the increase of the usage amount of DVB. The addition of DVB is beneficial to the formation and stability of the ion imprinted cavity of Fe₃O₄@IIPs. The effects of the solution pH value, initial concentration of ClO₄⁻, and adsorption time on the adsorption properties of ClO₄⁻ in aqueous solutions were investigated. The results show that the adsorption capability is affected significantly by solution pH value and reaches the maximum adsorption capacity at pH 3.0. The best adsorption capacity and selectivity of Fe₃O₄@IIPs to ClO₄⁻ can be obtained when the usage amount of DVB is at 0.5 g for synthesis. The adsorption mechanisms might include both ion exchange and electrostatic interaction. The isothermal adsorption curves mainly obey the Langmuir model with the theoretical maximum adsorption capacities (q_m,c) at 76.92–111.1 mg g⁻¹ and the experimental maximum adsorption capacities (q_m,e) at 75.7–108.9 mg g⁻¹, respectively, which are much higher than those of the non-ion imprinted material (Fe₃O₄@NIP, q_m,NIP: q_m,c at 60.61 mg g⁻¹ and q_m,e at 59.0 mg g⁻¹). The adsorption kinetic studies show that the adsorption processes reach equilibrium within 10 min and the kinetic data are well fitted to the pseudo-second-order model. There is almost no interference by the coexisting anions for the selective adsorption of ClO₄⁻, with a imprinting factor (α) at 1.8, and selectivity factor (β) larger than 5.9 for several kinds of common co-existing anions, respectively. The Fe₃O₄@IIPs are ideal candidates for removal of ClO₄⁻ from aqueous solution.

A series of ethylenediamine-grafted ion imprinted magnetic polymers (Fe₃O₄@IIPs) were synthesized via ultrasonic assisted suspension polymerization with perchlorate (ClO₄⁻) as an ion imprinting template.     

Fluorescence determination of Fe(iii) in drinking water using a new fluorescence chemosensor

A new fluorescence chemosensor based on (Z)-2-(1-(3-oxo-3H-benzo[f]chromen-2-yl)ethylidene)hydrazine-1-carbothioamide (CEHC) has been developed for the determination of Fe(iii) in drinking water. The optimum conditions were acetate buffer solution with a pH 5.0. In this approach, the determination of Fe(iii) is based on static quenching of the luminescence of the probe upon increasing concentrations of Fe(iii). The CEHC sensor binds Fe(iii) in a 1 : 1 stoichiometry with a binding constant K_a = 1.30 × 10⁴ M⁻¹. CEHC responds to Fe(iii) in a way that is more sensitive, selective, and quick to turn off the fluorescence than to other heavy metal ions. Selectivity was proved against seven other metal ions (Mn(ii), Al(iii), Cu(ii), Ni(ii), Zn(ii), Pb(ii), and Cd(ii)). The calibration curve was constructed based on the Stern–Volmer equation. The linear range was 2.50–150 μM with the correlation coefficient of 0.9994, and the LOD was 0.76 μM. The method was successfully applied to determine Fe(iii) in drinking water samples, and the accuracy of the chemosensor was validated by atomic absorption spectrometry.

A new fluorescence chemosensor based on (Z)-2-(1-(3-oxo-3H-benzo[f]chromen-2-yl)ethylidene)hydrazine-1-carbothioamide (CEHC) has been developed for the determination of the fluorescence probe of Fe(iii) in drinking water.     

Biomimetic fabrication of superhydrophobic loofah sponge: robust for highly efficient oil–water separation in harsh environments

Oil/water separation has become an increasingly important field due to frequent industrial oily wastewater emission and crude oil spill accidents. Herein, we fabricate a robust superhydrophobic loofah sponge via a versatile, environmentally friendly, and low-cost dip coating strategy, which involves the modification of commercial loofah sponge with waterborne polyurea and fused SiO₂ nanoparticles without the modification of any toxic low-surface-energy compound. The as-prepared loofah sponge showed excellent superhydrophobic/superoleophilic properties and exhibited robustness for effective oil–water separation in extremely harsh environments (such as 1 M HCl, 1 M NaOH, saturated NaCl solution and hot water higher than 95 °C) due to the remarkably high chemical stability. In addition, the as-prepared loofah sponge was capable of excellent anti-fouling, has self-cleaning ability and could act as the absorber for effective separation of surfactant-free oil-in-water emulsions. More importantly, the as-prepared loofah sponge demonstrated remarkable robustness against strong sandpaper abrasion and finger wipes, while retaining its superhydrophobicity and efficient oil/water separation efficiency even after more than 50 abrasion cycles. This facile and green synthesis approach presented here has the advantage of large-scale fabrication of a multifunctional biomass-based adsorbent material as a promising candidate in anti-fouling, self-cleaning, and versatile water–oil separation.

Oil/water separation has become an increasingly important field due to frequent industrial oily wastewater emission and crude oil spill accidents.     

Practical,mild and efficient electrophilic bromination of phenols by a new I(iii)-based reagent: the PIDA–AlBr3 system

A practical electrophilic bromination procedure for phenols and phenol–ethers was developed under efficient and very mild reaction conditions. A broad scope of arenes was investigated, including the benzimidazole and carbazole core as well as analgesics such as naproxen and paracetamol. The new I(iii)-based brominating reagent PhIOAcBr is operationally easy to prepare by mixing PIDA and AlBr₃. Our DFT calculations suggest that this is likely the brominating active species, which is prepared in situ or isolated after centrifugation. Its stability at 4 °C after preparation was confirmed over a period of one month and no significant loss of its reactivity was observed. Additionally, the gram-scale bromination of 2-naphthol proceeds with excellent yields. Even for sterically hindered substrates, a moderately good reactivity is observed.

A practical electrophilic bromination procedure for the phenolic core was developed under efficient and very mild reaction conditions. The new I(iii)-based brominating reagent PhIOAcBr operationally easy to prepare by mixing PIDA and AlBr₃ was used.     

Novel electrospun fibers as carriers for delivering a biocompatible Sm(iii) nanodrug for cancer therapy: fabrication,characterization, cytotoxicity and toxicity

The current study represents the successful fabrication and characterization of a Sm(iii) nano complex based on 2-cyano-N′-((4-oxo-4H-chromen-3-yl)methylene)acetohydrazide (CCMA). The fibrous Sm(iii) nanocomplex has been fabricated by the electrospinning technique. SEM analysis of the electrospun fibers has revealed that the fibers have a uniform structure and smooth surface without observing Sm(iii) nanocomplex crystals, i.e. the Sm(iii) nanocomplex has been well incorporated into the fibers. In vitro antitumor activity against two carcinogenic cell lines (HepG-2 and E.A.C.) as well as in vivo toxicity of pure Sm(iii) nanocomplex and its electrospun fibers have been detected. The biological results have shown that there is a significant antitumor activity with low toxicity of the pure Sm(iii) nanocomplex and its electrospun fibers with respect to different standard antitumor drugs. Also, the electrospun fibers recorded higher cytotoxicity (IC₅₀ = 0.1 μM (Hep-G); 0.09 μM (E.A.C)) and lower toxicity (LD₅₀ = 350 mg kg⁻¹) than the pure ones. The in vitro release rate of the Sm(iii) nanocomplex from electrospun fibers has also been detected. The results have shown that the burst releasing of the Sm(iii) nanocomplex is about 22% after 1 h at the beginning, then a cumulative release increased gradually over the following hours. All results demonstrate the potential use of the Sm(iii) nanocomplex as a potent antitumor drug and its electrospun fibers as superior drug carriers for the treatment of tumors.

The current study represents the successful fabrication and characterization of a Sm(iii) nano complex based on 2-cyano-N′-((4-oxo-4H-chromen-3-yl)methylene)acetohydrazide (CCMA).     

A microwave synthesized mesoporous carbon sponge as an efficient adsorbent for Cr(vi) removal

Mesoporous carbon materials have recently attracted immense research interest because of their potential application in water purification fields. Herein, we report the synthesis of a mesoporous carbon sponge (MCS) from a supramolecular microcrystalline cellulose–polymer system triggered by microwave-assisted treatment. Benefiting from the three-dimensional (3D) interconnected mesopores and an evenly distributed ball-like protuberance on the inner surfaces of the macropores, the MCS exhibited a high adsorption capacity (93.96 mg g⁻¹) for fast Cr(vi) removal within 5 min. Additionally, the MCS can be regenerated and reused after the adsorption–desorption process, and maintained an adsorption capacity of ∼86% after 10 cycles. The high adsorption capacity, significantly reduced treatment time, and reusability make the MCS promising for the purification of wastewater on a large scale.

Mesoporous carbon sponge (MCS) is successfully prepared from a supramolecular microcrystalline cellulose–polymer system triggered by microwave-assisted treatment. The MCS exhibits high adsorption capacity for fast Cr(vi) removal within 5 min.     

Magnetic surface molecularly imprinted poly(3-aminophenylboronic acid) for selective capture and determination of diethylstilbestrol

Diethylstilbestrol (DES) is considered a representative example of an exogenous endocrine disrupting compound (EDC). It can retard development in infants, lead to serious metabolic regulation disorders, and even result in distortion and cancer in the reproductive system. Therefore, achieving rapid and accurate analysis of trace amounts of DES in complex environments is of great importance to human health and for environmental protection. Novel magnetic molecularly imprinted polymers (MIPs) with excellent molecular recognition ability and super water-compatibility were developed for the selective capture of DES in water samples. Fe₃O₄@SiO₂ magnetic nanoparticles (NPs) were synthesized and used as support cores. Molecularly imprinted poly(3-aminophenylboronic acid) (poly(APBA)), synthesized on magnetic cores based on a surface-imprinting strategy, can preferentially bind DES molecules in water samples. The magnetic core–shell MIPs (denoted as Fe₃O₄@SiO₂@APBA/MIPs) exhibited high binding capacity and favorable recognition specificity for DES in water. The adsorption kinetics and experimental isotherm data of DES on magnetic MIPs can be well described by the pseudo-second-order kinetic model and the Langmuir isotherm, respectively. The imprinted nanoparticles were subjected to magnetic solid-phase extraction (MSPE) of DES from water samples. The DES content in the samples was determined by high-performance liquid chromatography (HPLC). The peak area increased linearly with increasing DES concentration over the range 0.08–150 μg L⁻¹, with a detection limit of 0.03 μg L⁻¹. The recoveries for spiked lake water samples were in the range 97.1–103.2%, with relative standard deviation (RSD) of 2.8–4.3% (n = 6).

Imprinted poly(APBA) nanoshell on Fe₃O₄@SiO₂ surface was first synthesized and used for MSPE of diethylstilbestrol followed by HPLC determination.     

Enhancing mechanism of arsenic(iii) adsorption by MnO2-loaded calcined MgFe layered double hydroxide

The use of MnO₂/MgFe-layered double hydroxide (MnO₂/MgFe-LDH) and MnO₂/MgFe-layered double oxide (MnO₂/MgFe-LDO_{400 °C}) for arsenic immobilization from the aqueous medium is the subject of this research. Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy were used to characterise MnO₂/MgFe-LDH and MnO₂/MgFe-LDO_{400 °C}. Based on our developed method, MnO₂ was spread on the clay composites'' surfaces in the form of a chemical bond. The clay composite exhibited a good adsorption effect on arsenic. The experimental findings fit the pseudo-second-order model well, indicating that the chemisorption mechanism played a significant role in the adsorption process. Furthermore, the Freundlich model suited the adsorption isotherm data of all adsorbents well. The recycling experiment showed that MnO₂/MgFe-LDH and MnO₂/MgFe-LDO_{400 °C} exhibited good stability and reusability. In summary, MnO₂/MgFe-LDH and MnO₂/MgFe-LDO_{400 °C} are promising for developing processes for efficient control of the pollutant arsenic.

Fabrication of materials and the adsorption of arsenic.