Zinc hydroxide nitrate nanosheets conversion into hierarchical zeolitic imidazolate frameworks nanocomposite and their application for CO2 sorption

Hierarchical porous zeolitic imidazolate frameworks (HZIFs) are promising materials for several applications, including adsorption, separation, and nanomedicine. Herein, the conversion of zinc hydroxide nitrate nanosheets into HZIF-8 nanocomposite with graphene oxide (GO) and magnetic nanoparticles (MNPs) is reported. The conversion takes place at room temperature in water. This approach has been successfully applied for the formation of leaf-like ZIF(ZIF-L), and their nanocomposites with nanoparticles, such as GO and MNPs. This method offers a simple approach for the synthesis of tunable pore structure using nanoparticles and fast room temperature conversion (30 min) without any visible residual impurities of zinc hydroxide nitrates. The applications of HZIF-8, ZIF-L, and their nanocomposites, for CO₂ sorption, exhibit excellent adsorption properties. The synthesized composites exhibit enhanced CO₂ adsorption capacity due to the synergistic effect between nanoparticles (GO, or MNPs), and ZIF-8. The materials have good potential for further applications.     

ZIF-8 based polysulfone hollow fiber membranes for natural gas purification

Mixed matrix membranes (MMMs) have received worldwide attention for natural gas purification due to their superior performance in terms of permeability and selectivity. The zeolitic imidazole framework-8 (ZIF-8) blended polysulfone (PSf) membranes have been fabricated for natural gas purification. ZIF-8 was selected due to its low cost, remarkable thermal and chemical stabilities, and tunable microporous structure. The neat PSf hollow fiber membrane and mixed matrix hollow fiber membranes incorporated with the various ZIF-8 loadings up to 1.25% were fabricated. The prepared membranes were evaluated using field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and gas separation performance. The low loading of ZIF-8 nanoparticles to the MMM improved thermal stability and glass transition temperature and yielded low surface roughness. MMMs were tested using pure gases with a significant improvement of 36% in CO₂ permeability and 28% in CO₂/CH₄ selectivity compared to the neat membrane. However, the high ZIF-8 loading reduced the separation performances. Moreover, CO₂/CH₄ selectivity decreased at elevated pressure (8 and 10 bar) due to CO₂-induced plasticization. Previously, the incorporation of ZIF-8 particles has primarily been subjected to the fabrication of flat sheet membranes, whereas this work focused on hollow fiber membranes which are rarely investigated. Hence, the promising results obtained at low feed pressure in this study demonstrated the potential of ZIF-8 based hollow fiber membrane for natural gas purification.     

Fabrication,rheological analysis,and in vitro characterization of in situ chemically cross‐linkable thermogels as controlled and prolonged drug depot for localized and systemic delivery

5‐Fluorouracil (5‐FU) is widely used against many types of solid cancer in clinics. However, because of its limitations such as short half‐life, poor oral absorption and rapid clearance by dihydropyrimidine dehydrogenase have limited its applications. In current study, new in situ chemically grafted thermogels for prolonged drug release are formed on the basis of poloxamer 407 (PF127) and carboxymethyl chitosan (CMCS) using glutaraldehyde as cross‐linking agent. The phase transition from sol to gel state at body temperature was confirmed by tube titling, rheological analysis, and optical transmittance determinations. Swelling and drug release experiments conducted at various pH and temperature demonstrated that developed formulations are thermoresponsive with maximum swelling and release below critical gelation temperature (CGT) (pH 7.4, 25°C). Cells growth inhibition study confirmed the biocompatibility of thermogels against L929 cell lines. Methyl thiazolyl tetrazolium (MTT) assay confirmed that 5‐FU–loaded thermogels have the potential to cause cells death against HeLa and MCF‐7 cancer lines. The IC₅₀ values calculated for pure 5‐FU solution (27 ± 0.81 μg/mL for HeLa and 24 ± 0.58 μg/mL for MCF‐7) were found higher in comparison with 5‐FU–loaded thermogels, against HeLa (17 ± 0.39 μg/mL) and MCF‐7 (14 ± 0.67 μg/mL). Fourier transform infrared (FTIR) confirmed the new structure formation and chemical grafting between PF127 and CMCS. Thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses proved the phase transition around physiologic temperature range, while scanning electron microscopy (SEM) analysis displayed the presence of connected pores in the cross section of thermogels facilitating the uptake of solvents and drug particles. Altogether, results concluded that developed chemically grafted thermogels can be used in vivo for prolonged drug release after subcutaneous administration.     

Formation and characterization of magnetic barium ferrite hollow fibers with high specific surface area via sol–gel process

The magnetic barium ferrite (BaFe₁₂O₁₉) hollow fibers with a high specific surface area about 22–38 m² g^?1, diameters around 1 μm and a ratio of the hollow diameter to the fiber diameter estimated about 1/2–2/3 have been prepared by the gel-precursor transformation process. The precursor and resulting ferrite hollow fibers were analyzed by thermo-gravimetric and differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy and X-ray diffraction. The specific surface area was measured by the Brunauer–Emmett–Teller method. The gel formed at pH 5.5 has a good spinnability. A pure barium ferrite phase is formed after calcined at 750 °C for 2 h and fabricated of nanograins about 38 nm with a hexagonal plate-like morphology, which are increased to about 72 nm with the calcination temperature increased up to 1050 °C. The barium ferrite hollow fibers obtained at 750 °C for 2 h have a specific surface area 38.1 m² g^?1 and average pore size 6.5 nm and then the specific surface area and average pore size show a reduction tendency with the calcination temperature increasing from 750 to 1050 °C owing to the particle growth and fiber densification. These barium ferrite hollow fibers exhibit typical hard-magnetic materials characteristics and the formation mechanism for hollow structures is discussed.     

Fabrication of hollow mesoporous silica-based nanoreactors for enzyme immobilization: high loading capacity,effective protection,and recyclability

The poor stability and low reusability of enzymes have always been the hindrances to their large-scale applications. Herein, hollow mesoporous silica (HMS) nanoparticles have been constructed as nanoreactors for in situ enzyme immobilization, hemoglobin (Hb) was selected as a model enzyme. By utilizing zeolitic imidazolate framework-8 (ZIF-8) as the sacrificial template, the synthesis mechanism of Hb@ZIF-8 has been explored by adjusting the molar ratios of Zn²⁺ and 2-methylimidazole. When the amount of Hb was constant, the shape of Hb@ZIF-8 gradually changed from flake to granular (from 50:200 mM to 50:800 mM). Furthermore, when the molar ratio of Zn²⁺ and 2-methylimidazole was fixed, with the amount of Hb increasing, the size of Hb@ZIF-8 decreased gradually, with maximum loading capacity of 460 μg/mg. Subsequently, Hb@ZIF-8 was coated with silica shells and followed by the removal of ZIF-8 in phosphate-buffered saline (pH 5), resulting in Hb@HMS. Compared to free Hb, Hb in HMS nanoreactors maintained over 74% of original catalytic activity under extreme conditions, showing significant improvements on the stability. Further, Hb@HMS still retains 80% of enzymatic activity after 5 cycles, exhibiting its excellent reusability. This work provides an efficient strategy for enzyme immobilization, giving new horizons for biosensing, biocatalysis and biomedicine.     

Reversible polyelectrolyte capsules as carriers for protein delivery

A reversible drug delivery system based on spontaneous deposition of a model protein into preformed microcapsules has been demonstrated for protein delivery applications. Layer-by-Layer assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) onto polystyrene sulfonate (PSS) doped CaCO₃ particles, followed by core removal yielded intact hollow microcapsules having a unique property to induce spontaneous deposition of bovine serum albumin (BSA) at pH below its isoelectric point of 4.8, where it was positively charged. These capsules showed reversible pH dependent open and closed states to fluorescence labeled dextran (FITC-Dextran) and BSA (FITC-BSA). The loading capacity of BSA increased from 9.1 × 10⁷ to 2.03 × 10⁸ molecules per capsule with decrease in pH from 4.5 to 3. The loading of BSA-FITC was observed by confocal laser scanning microscopy (CLSM), which showed homogeneous distribution of protein inside the capsule. Efficient loading of BSA was further confirmed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The interior capsule concentration was as high as 209 times the feeding concentration when the feeding concentration was increased from 1 to 10 mg/ml. The deposition was initially controlled by spontaneous loading mechanism at lower BSA concentration followed by diffusion controlled loading at higher concentration; which decreased the loading efficiency from 35% to 7%. Circular dichroism (CD) measurements and Fourier transform infrared spectroscopy (FTIR) confirmed that there was no significant change in conformation of released BSA in comparison with native BSA. The release was initially burst in the first 0.5 h and sustained up to 5 h. The hollow capsules were found to be biocompatible with mouse embryonic fibroblast (MEF) cells during in vitro cell culture studies. Thus these pH sensitive polyelectrolyte microcapsules may offer a promising delivery system for water soluble proteins and peptides.     

Synthesis of mesoporous hollow carbon hemispheres as highly efficient Pd electrocatalyst support for ethanol oxidation

The synthesis procedure of the highly mesoporous hollow carbon hemispheres (HCHs) using glucose as carbon source and solid core mesoporous shell silica (SCMSS) as template and the formation mechanism of the HCHs have been presented. The HCHs show an ultrahigh surface area of 1095.59 m² g^?1 and an average mesopore size of 9.38 nm. The hemispherical structure with large mesopores also results in the improvement in the mass transfer and therefore more concentrated ethanol solution can be used to increase the energy density. The additional advantage of the HCHs compared to the hollow carbon spheres is that they can provide the similar surface area at reduced volume. The current densities of ethanol oxidation on Pd nanoparticles supported on HCH (Pd/HCH) electrocatalyst are three times as many as on Pd/C at the same Pd loadings.     

Fabrication of ZnSe/C Hollow Polyhedrons for Lithium Storage

ZnSe has got extensive attention for high-performance LIBs anode due to its remarkable theoretical capacity and environmental friendliness. Nevertheless, the large volume variation for the ZnSe in the discharge/charge processes brings about rapid capacity fading and poor rate performance. Herein, ZnSe/C hollow polyhedrons are successfully synthesized by selenization of zeolitic imidazolate framework-8 (ZIF-8) with resorcinol-formaldehyde (RF) coating. The protection of C layer derived from RF coating layer and Ostwald ripening during the process of selenization play important roles in promoting formation of ZnSe/C hollow polyhedrons. The ZnSe/C hollow polyhedrons exhibit good rate performance and long-term cycle stability (345 mAh g⁻¹ up to 1000 cycles at 1 A g⁻¹) for lithium ion batteries (LIBs) anode. The improved electrochemical performance is benefit from the unique ZnSe/C hollow structure, in which the hollow structure can effectively avoid terrible volume expansion, and the thin ZnSe/C shell can not only provide adequate diffusion paths of lithium ions and but also enhance the electronic conductivity.     

Fast recovery of Au (III) and Ag(I) via amine-modified zeolitic imidazolate framework-8

In this paper, zeolitic imidazolate framework-8 modified by the ethanediamine (NH₂-ZIF-8) was employed for adsorbing Au (III) and Ag(I) from aqueous solutions. The adsorption capacities of NH₂-ZIF-8 towards Au (III) and Ag(I) were found to be significantly affected by the pH values of the solution. The adsorption kinetics studies show that NH₂-ZIF-8 presents a fast adsorption property towards metals, attaining 93% of adsorption equilibrium uptake for Au (III) within the first 30 min. This phenomenon can be ascribed to the coordination interaction between the amino group and Au (III). The thermodynamic data suggest that the adsorption of NH₂-ZIF-8 towards Au (III) is endothermic process, while that for Ag(I) is exothermic. The maximum adsorption capacities of NH₂-ZIF-8 toward Au (III) and Ag(I) can be achieved to 357 mg·g⁻¹ and 222.25 mg·g⁻¹, respectively. The metal ions interference results show that Cu (II) and Ni (II) hardly have no interference on Au (III) adsorption in e-waste containing 1500 mg·l⁻¹ Cu (II),100 mg·l⁻¹ Ni (II) and 10 mg·l⁻¹ Au (III); while for Ag(I), Cd (II) and Zn (II) have little interference on Ag(I) adsorption in the hybrid solutions containing Ag(I), Ni (II), Cd (II) and Zn (II) with equal concentration (50 mg·l⁻¹), but Ni (II) interference most. The XPS study shows that partial Au (III) was reduced to Au(I), and that Ag(I) was completely reduced to Ag(0) during the adsorption process. The abundant of active sites of NH₂-ZIF-8 containing C=N, N-H, and Zn-OH groups play a key role in the adsorption of Au (III) and Ag(I). In addition, electrostatic interaction can be responsible for the adsorption of Au (III) by NH₂-ZIF-8. The regeneration experiments results show that the adsorption capacities of NH₂-ZIF-8 towards Au (III) and Ag(I) can maintain after three cycles. This work provides a reliable method to improve the adsorption kinetics for metal ions.     

Boosting Supercapacitor Performance of Graphene by Coupling with Nitrogen-Doped Hollow Carbon Frameworks

Graphene as a suitable electrode has been extensively used for electrochemical double-layer capacitors based on its excellent properties, including high electrical conductivity and large specific surface area. However, one of the drawbacks is the unavoidable stacking tendency between the graphene nanosheets, resulting in limited electrochemically specific surface area. Herein, novel graphene nanosheets supported by hollow nitrogen-doped carbon frameworks derived from ZIF-8 (GPNC) were fabricated through a simple polyethyleneimine (PEI)-assisted pyrolysis strategy, to boost capacitance performance. Benefiting from the unique scaffold/support role of hollow nitrogen-doped carbon frameworks within the graphene interlayer, the GPNC with a large specific surface area, along with ample micropore/mesopore channels and high nitrogen content, is capable of facilitating electron and electrolyte ion migration kinetics and enhancing intrinsic electrochemical activity. Thus, the GPNC exhibits the highest charge storage of 218 F g⁻¹ and superior rate capability of 74 % when the current density increased from 0.5 to 20 Ag⁻¹ in comparison to pristine graphene and common ZIF-derived carbon/graphene electrodes. The assembled GPNC//GPNC two-electrode system further delivers a maximum power of 9080 Wkg⁻¹ with outstanding electrochemical retention of 84 % over 10 000 cycles.     

Metal–organic frameworks as efficient materials for drug delivery: Synthesis,characterization, antioxidant,anticancer, antibacterial and molecular docking investigation

Metal–organic framework (MOF) nano particles are a class of promising porous nano materials for biomedical applications. Owing to its high loading potential and pH-sensitive degradation, most promising of the MOFs is the zeolitic imidazolate crystal framework (ZIF-8), a progressive useful material for small molecule distribution. Doxorubicin (DOX), designated as a classical drug, was jobwise entrapped in ZIF-8 nano particles. ZIF-8 nano particles, as a novel carrier, were used to monitor the release of the anticancer drug DOX and prevent it from dissipating before reaching its goal. ZIF-8 nano particles with encapsulated DOX (DOX@ZIF-8) can be synthesized in a single pot by incorporation of DOX into the reaction mixture. MOFs and the designed drug delivery (DOX@ZIF-8) system were characterized by Fourier transfer infrared, scanning electron microscopy, N₂ sorption isotherm and X-ray diffraction. The impact of MOFs and the engineered drug delivery system on the viability of human breast and liver cancer cell lines was evaluated. The loaded drug was released at pH 5 faster than at pH 7.4. The nano particles of ZIF-8 showed low cytotoxicity, while DOX@ZIF-8 showed high cytotoxicity to HepG-2 and MCF-7 cells compared with free DOX at the equivalent concentration of DOX of >12.5 μg/ml. These findings indicate that DOX@ZIF-8 nano particles are a promising method for the delivery of cancer cells to drugs. Furthermore, ZIF-8, DOX and encapsulated DOX@ZIF-8 compounds were screened for their potential antibacterial activities against pathogenic bacteria compared with standard antibiotics by the agar well diffusion technique. The results demonstrate that the DOX@ZIF-8 exhibits a strong inhibition zone against Gram-negative strains (Escherichia coli) in comparison with the reference drug gentamycin. The docking active site interactions were evaluated to predict the binding between DOX with the receptor of breast cancer 3hb5-oxidoreductase and liver cancer 2h80-lipid binding protein for anticancer activity.     

Preparation of non-spherical hollow carbon nanocapsules from nickel nanoprecursors

Hollow carbon nanocapsules (NCs) are prepared from nickel nanoplate precursors through carburizing, decomposition, and leaching steps. The carburizing step was carried out by heating the nickel nanoplates in oleylamine at 250 °C for 4 h. Decomposition was then performed in a nitrogen atmosphere at 530 °C for 3 min. Characterization of the resulting product of the first two steps shows the intermediates to be Ni₃C/Ni–C alloy and Ni/C core–shell nanostructures. Hollow carbon NCs are recovered from the products by leaching the Ni/C core–shell nanostructures in concentrated nitric acid. The NCs are found to have a high specific surface area (1081 m² g⁻¹) and a mesoporous structure (i.e., a pore volume of 2.81 cm³/g and a narrow pore size distribution of 2.9–3.4 nm). In addition, it is found that the hollow carbon NCs retained the same morphology as the original nickel precursors; demonstrating the robustness of the nickel templates and the ability of the carbon shells to maintain a non-spherical shape.     

ZnO hollow nanospheres via Laux-like oxidation of Zn0 nanoparticles

Zinc oxide hollow nanospheres were obtained via a Laux-like oxidation of zinc nanoparticles using nitrobenzene as oxidizing agent. The ZnO hollow nanospheres exhibit an outer diameter of 10.4 ± 1.3 nm and a well crystallized sphere wall with a thickness of 2.9 ± 0.4 nm. Laux-like oxidation and formation of the ZnO hollow nanospheres were performed instantaneously after sodium naphthalenide ([NaNaph]) driven reduction of ZnCl₂ to Zn⁰ nanoparticles in the liquid phase without any separation of the intermediate Zn⁰ nanoparticles. The diameter of the resulting ZnO hollow nanospheres (10.4 ± 1.3 nm) reflects the diameter of the intermediate Zn⁰ nanoparticles (10.1 ± 2.3 nm). In accordance with the small diameter of the ZnO sphere wall, quantum-size effects occur with a band gap that is blue-shifted by 0.2 eV in comparison to bulk-ZnO.     

Facile and Controllable Synthesis of Monodisperse CaF2 and CaF2:Ce3+/Tb3+ Hollow Spheres as Efficient Luminescent Materials and Smart Drug Carriers

Highly uniform and well‐dispersed CaF₂ hollow spheres with tunable particle size (300–930 nm) have been synthesized by a facile hydrothermal process. Their shells are composed of numerous nanocrystals (about 40 nm in diameter). The morphology and size of the CaF₂ products are strongly dependent on experimental parameters such as reaction time, pH value, and organic additives. The size of the CaF₂ hollow spheres can be controlled from 300 to 930 nm by adjusting the pH value. Nitrogen adsorption–desorption measurements suggest that mesopores (av 24.6 nm) exist in these hollow spheres. In addition, Ce³⁺/Tb³⁺‐codoped CaF₂ hollow spheres can be prepared similarly, and show efficient energy transfer from Ce³⁺ to Tb³⁺ and strong green photoluminescence of Tb³⁺ (541 nm, ⁵D₄→⁷F₅ transition of Tb³⁺, the highest quantum efficiency reaches 77 %). The monodisperse CaF₂:Ce³⁺/Tb³⁺ hollow spheres also have desirable properties as drug carriers. Ibuprofen‐loaded CaF₂:Ce³⁺/Tb³⁺ samples still show green luminescence of Tb³⁺ under UV irradiation, and the emission intensity of Tb³⁺ in the drug‐carrier system varies with the released amount of ibuprofen, so that drug release can be easily tracked and monitored by means of the change in luminescence intensity. The formation mechanism and luminescent and drug‐release properties were studied in detail.     

Carrier-mediated hollow fiber liquid-phase microextraction for preconcentration followed by spectrophotometric determination of amoxicillin

Preconcentration followed by ultraviolet spectrophotometric determination of amoxicillin (Amox) in pharmaceuticals and water samples by using a three-phase hollow fiber microextraction technique based on carrier-mediated transport has been presented. Amox was extracted from an aqueous solution (source phase) at pH 9.0 into 1-octanol containing 5% (w/v) Aliquat-336 impregnated in the pores of a hollow fiber. It was then back-extracted into NaCl solution (pH = 4.0) which was already positioned as the receiving phase inside the lumen of the hollow fiber. The extraction took place due to the concentration gradient of the counterion between the source and the receiving phases. Under the optimized conditions, an enrichment factor of 240 and a limit of detection of 0.2 μmol L⁻¹ were obtained. The calibration curve was linear (R² = 0.9967) in the concentration range of 0.5–10.0 µmol L⁻¹ Amox. The interday relative standard deviation (n = 9) and the intraday relative standard deviation (n = 3) for 1.0 × 10⁻⁶ mol L⁻¹ Amox solution were 7.3 and 6.4%, respectively.

     

Shellfish waste-derived mesoporous chitosan for impressive removal of arsenic(V) from aqueous solutions: A combined experimental and computational approach

Novel shellfish waste-derived chitosan (CS) has been developed to adsorb As(V) from simulated wastewater under evaluating adsorption process parameters. The coexistence of some competing ions, like SiO₃^2-, Cl^-, NO₃^– and PO₄^3- as well as the regeneration capacity of the spent adsorbent, was explored. The experimental data were modeled using several kinetics and isotherm models to understand the mechanism related to the uptake process. As(V) uptake was relatively rapid and highly dependent on pH. The Avrami-fractional-order expression supported data best, while the Liu equation described well isotherm data at pH 5.0. The maximum uptake capability (Liu) was 12.32 mg/g, and the highest removal performance (99 %) was obtained at optimum pH 5.0. Molecular dynamics simulations were performed to more clearly illuminate the atomic-level interactions between arsenic species and CS surface in both acidic and basic mediums. After four adsorption–desorption cycles, CS exhibited more than 90 % As(V) removal efficiency. The results of this study indicates that low cost shellfish derived chitosan is promising for efficient removal of As(V) from water body and can be used to remove other pollutants from watewater.     

Shell-in-Shell TiO2 hollow microspheres and optimized application in light-trapping perovskite solar cells

The shell-in-shell structured TiO₂ hollow microspheres with enhanced light scattering ability were synthesized via a facile one step hydrothermal process. The diameter of the microsphere is about 1.5 μm, the core of the unique shell-in-shell structure is composed of TiO₂ nanoparticles with a diameter of about 15 nm, while the shell is constructed with ∼50 nm TiO₂ nanocubes. The hollow space between the outer shell and the inner shell is about 230 nm. The formation mechanism of the unique shell-in-shell structure is interpreted. The design and the optimized application of shell-in-shell structured TiO₂ hollow microspheres in the light-trapping perovskite solar cells are also investigated. Owing to the light scattering properties of the shell-in-shell structure of the hollow microsphere, the optimized photoelectrode exhibits an enhanced photoelectric conversion efficiency of 4.29% using perovskite CH₃NH₃PbI₃ as the sensitizer. The shell-in-shell hollow TiO₂ microsphere shows a 21.2% increase in conversion efficiency when compared with P₂₅ nanoparticels photoanode. The conversion efficiency enhancement is mainly attributed to the increase of short-current density induced by the light scattering effect.     

Efficient synthesis of magnetic nanoparticle-Musa acuminata peel composite for the adsorption of anionic dye

The impregnation of magnetite (Mt) nanoparticle (NPs) onto Musa acuminata peel (MApe), to form a novel magnetic combo (MApe-Mt) for the adsorption of anionic bromophenol blue (BPB) was studied. The SEM, EDX, BET, XRD, FTIR and TGA were used to characterize the adsorbents. The FTIR showed that the OH and CO groups were the major sites for BPB uptake onto the adsorbent materials. The average Mt crystalline size on MApe-Mt was 21.13 nm. SEM analysis revealed that Mt NPs were agglomerated on the surface of the MApe biosorbent, with an average Mt diameter of 25.97 nm. After Mt impregnation, a decrease in BET surface area (14.89 to 3.80 m²/g) and an increase in pore diameter (2.25–3.11 nm), pore volume (0.0052–0.01418 cm³/g) and pH point of zero charge (6.4–7.2) was obtained. The presence of Pb(II) ions in solution significantly decreased the uptake of BPB onto both MApe (66.1–43.8%) and MApe-Mt (80.3–59.1%), compared to other competing ions (Zn(II), Cd(II), Ni(II)) in the solution. Isotherm modeling showed that the Freundlich model best fitted the adsorption data (R² > 0.994 and SSE < 0.0013). In addition, maximum monolayer uptake was enhanced from 6.04 to 8.12 mg/g after Mt impregnation. Kinetics were well described by the pseudo-first order and liquid film diffusion models. Thermodynamics revealed a physical, endothermic adsorption of BPB onto the adsorbents, with ΔH^o values of 15.87–16.49 kJ/mol, corroborated by high desorption (over 90%) of BPB from the loaded materials. The viability of the prepared adsorbents was also revealed in its reusability for BPB uptake.     

Fluorescent study of the keto-enol equilibrium of 5-fluorouracil tautomers in aqueous solutions

A spectral-luminescent study of the keto-enol tautomerism of 5-fluorouracil (FU) has been performed. A discrepancy between the absorption and fluorescence (FL) excitation spectra of aqueous FU solutions (pH 7) has been established. Photoexcitation at the long-wavelength band (340 nm) of the FU excitation spectrum made it possible to detect the fluorescence of its dienol tautomer (λ_max = 440 nm). The quenching of tryptophan fluorescence (K = 15 × 10³ l/mol) and blood fluorescence by 5-fluorouracil has been investigated.     

Water stability of cobalt doped ZIF-8: a quantitative study using optical analyses

Zeolitic imidazolate frameworks (ZIFs), in particular ZIF-8 (made of Zn²⁺ and 2-methyilimidazolate) and cobalt-doped-ZIF-8, are found important for many energy and environmental applications. It was reported that ZIFs show excellent structural stability in water and thus ideal for aqueous applications. However, recent studies also found some evidence that ZIF-8 undergoes hydrolysis in water. Despite the importance of ZIF's stability in many aqueous applications, the extent of ZIFs' degradation in water is still not yet fully understood. In this study, we report a quantitative study of the water stability of 0–100 at% cobalt-doped ZIF-8, using a new combination of analytical tools. The study demonstrated the importance of analyzing both filtered powders and the filtrate liquid systematically, in particular by using UV–Vis spectroscopy and thermogravimetric analysis. The combination of analytical tools allowed the study on the effects of ZIF concentrations in water, cobalt doping levels, and amounts of ligands in water on the water stability of ZIF samples. The effect of cobalt-doping was investigated by using ZIF particles with identical sizes (200–400 nm), in order to eliminate the effects of particle size on hydrolysis. Unlike other synthesis methods, a mechanochemical ball milling method allowed the production of nano-scale ZIF-8 particles with similar sizes, independent of cobalt-doping levels. The proposed combination of analytical tools including UV–Vis spectroscopy can be applied to the study of the water stability of other MOF materials.