Zn Species Research Articles

Algae and Hydrophytes as Potential Plants for Bioremediation of Heavy Metals from Industrial Wastewater

Aquatic bodies contaminated by heavy metals (HMs) are one of the leading issues due to rapidly growing industries. The remediation of using algae and hydrophytes acts as an environmentally friendly and cost effective. This study was performed to investigate the pollution load, especially HMs, in the wastewater of the Gadoon Industrial Estate and to utilize the hydrophytes (Typha latifolia (TL) and Eicchornia crassipes (EI)) and algae (Zygnema pectiantum (ZP) and Spyrogyra species (SS)) as bioremediators. The wastewater was obtained and assessed for physiochemical parameters before treating with the selected species. The pot experiment was performed for 40 days. Then the wastewater samples and selected species were obtained from each pot to analyze the metal removal efficiency and assess for metal concentrations using atomic absorption spectrophotometry. The dissolved oxygen (DO; 114 mg/L), total suspended solids (TSS; 89.30 mg/L), electrical conductivity (EC; 6.35 mS/cm), chemical oxygen demand (COD) (236 mg/L), biological oxygen demand (BOD; 143 mg/L), and total dissolved solids (TDS; 559.67 mg/L), pH (6.85) were analyzed. The HMs were noted as Zn (5.73 mg/L) and Cu (7.13 mg/L). The wastewater was then treated with the species, and significant reductions were detected in physicochemical characteristics of the wastewater such as DO (13.15–62.20%), TSS (9.18–67.99%), EC (74.01–91.18%), COD (25.84–73.30%), BOD (21.67–73.42%), and TDS (14.02–95.93%). The hydrophytes and algae removed up to 82.19% of the Zn and 85.13% of the Cu from the wastewater. The study revealed that the hydrophytes and algae significantly decreased the HM levels in the wastewater (p ≤ 0.05). The study found TL, EI, ZP, and SS as the best hyper accumulative species for Zn and Cu removal from wastewater. The HMs were removed in the order of Cu > Zn. The most efficient removal for Cu was found by Typha latifolia and Zn by Zygnema pectiantum. It was concluded that bioremediation is an environmentally friendly and cost-effective technique that can be used for the treatment of wastewater due to the efficiency of algae and hydrophytes species in terms of HM removal.

Simultaneously enhanced aromatics selectivity and catalyst lifetime in methanol aromatization over [Zn, Al]-ZSM-5 via isomorphous substitution with optimized acidic properties and pore structure

Zinc-modified HZSM-5 zeolites as efficient catalysts have been widely applied in methanol to aromatics (MTA) reactions, however, the relationship between aromatics selectivity and catalytic stability in traditionally loaded catalysts seems to be a stubborn trade-off. To improve both catalytic indicators simultaneously and reveal the relation of the states of introduced Zn species to the consequential influence in physiochemical properties, a series of [Zn, Al]-Z5 zeolites with different Zn contents were prepared via isomorphous substitution under a fixed Si/Me (Me = Al or Al and Zn) ratio. Results revealed that there were three possible states of the introduced Zn species, namely the highly-dispersed ZnO phase, the Zn(OH)+ occupying the ion-exchange sites, and the tetra-coordinated ZnO42- integrated into the zeolite framework. A portion of Zn was successfully integrated into the five-membered rings of zeolite in the form of Si-O(H)-Zn, which played the role of strong Brönsted acid sites and led to the formation of hierarchical structures aside from the intrinsic micropores. Besides, extra-framework Zn(OH)+ was formed by the interaction between dissociate Zn species and the Si-O(H)-Al structure, giving rise to larger proportions of Lewis acid sites. Benefitting from the optimized acidic properties and pore structure, 0.5[Zn, Al]-Z5 exhibited higher aromatics selectivity and longer catalyst lifetime (26.0% and 132 h) than [Al]-Z5 without Zn addition (19.6% and 52 h) in methanol aromatization. Overall, our findings opened a new way to improve the efficiency of MTA reaction and broadened the method to obtain metal-modified zeolite catalysts.

Remobilization characteristics and diffusion kinetic processes of sediment zinc (Zn) in a tidal reach of the Pearl River Estuary, South China

Exploration of the remobilization mechanism of trace metals in estuarine sediments remain challenging because of dynamic hydrochemical conditions. This study integrated a chemical sequential extraction procedure (BCR), the diffusive gradient in thin films (DGT) and high-resolution dialysis techniques, and Visual MINTEQ ver.3.1 to identify the seasonal mobilization characteristics of sediment Zn within a tidal reach, South China. The mobility of sediment Zn based on the BCR procedure contradicted the results of DGT analysis. In summer, reductive dissolution of Fe/Mn oxides was the key driver of sediment Zn remobilization; during winter, cation exchange reactions facilitated the mobilization of Zn in the brackish water zone. The time-dependence ratios of DGT-labile Zn and dissolved Zn concentrations (mean: 0.34–0.81) indicated the sediment solid phase had partially sustained capacity to resupply Zn to the porewater in both seasons. Sediments generally functioned as a source of Zn in the freshwater zone with organically complexed Zn being diffusively released into the water column at rates of 0.3–15.5 μg·m−2·d−1. In the brackish water zone, the dominant Zn species were transformed into free Zn ions and Zn–inorganic complexes and migrated into sediment, with respective influxes of 18.9–70.7 μg·m−2·d−1 and 18.9–68.3 μg·m−2·d−1, which shifted to a sink of Zn.

Biodegradable Imprinted Polymer Based on ZIF-8/DOX-HA for Synergistically Targeting Prostate Cancer Cells and Controlled Drug Release with Multiple Responses

Improving the drug loading and delivery efficiency of biodegradable nanomaterials used for targeting prostate cancer (PCa) remains a challenging task. To accomplish this task, herein, a new surface molecularly imprinted polymer (ZIF-8/DOX-HA@MIP) was designed and constructed with a hyaluronic acid (HA)-modified zeolitic imidazolate framework-8 (ZIF-8) metal-organic framework loaded with doxorubicin (DOX) as a substrate and a responsive molecularly imprinted polymer film as a shell. Owing to the large surface area of ZIF-8, DOX was successfully loaded into the ZIF-8/DOX-HA@MIP with a high drug loading efficiency (more than 88%). In vitro cell experiments have shown that the strengthened targeting ability of ZIF-8/DOX-HA@MIP to PCa cells was realized through the synergistic effect of HA and the molecularly imprinted membrane. Under the condition of simulated tumor microenvironment solution, Zn species were released and the particle size of ZIF-8/DOX-HA@MIP decreased gradually by the synergistic effect of hyaluronidase, pH, and glutathione, showing excellent biodegradability. In vivo antitumor research indicated the excellent antitumor activity and biocompatibility of ZIF-8/DOX-HA@MIP. The multifunctional ZIF-8/DOX-HA@MIP constructed herein provides a novel impetus for the development of targeted drug delivery in PCa treatment and a new strategy for treating other tumors.

In Situ Construction of Nitrogen-Doped and Zinc-Confined Microporous Carbon Enabling Efficient Na+-Storage Abilities.

Benefiting from the additional active sites for sodium-ion (Na+) adsorption and porous architecture for electrolyte accessibility, nitrogen-doped porous carbon has been considered the alternative anode material for Na+-storage applications. In this study, nitrogen-doped and zinc-confined microporous carbon (N,Z-MPC) powders are successfully prepared by thermally pyrolyzing the polyhedral ZIF-8 nanoparticles under an argon atmosphere. Following the electrochemical measurements, the N,Z-MPC not only delivers good reversible capacity (423 mAh/g at 0.02 A/g) and comparable rate capability (104 mAh/g at 1.0 A/g) but also achieves a remarkable cyclability (capacity retention: 96.6% after 3000 cycles at 1.0 A/g). Those can be attributed to its intrinsic characteristics: (a) 67% of the disordered structure, (b) 0.38 nm of interplanar distance, (c) a great proportion of sp2-type carbon, (d) abundant microporosity, (e) 16.1% of nitrogen doping, and (f) existence of sodiophilic Zn species, synergistically enhancing the electrochemical performances. Accordingly, the findings observed here support the N,Z-MPC to be a potential anode material enabling exceptional Na+-storage abilities.

Partitioning of heavy metals in sediments and microplastics from stormwater runoff

Microplastics could act as vehicles for transporting heavy metals from urban environments to water resources via stormwater runoff. Although the transport of heavy metals by sediments has been widely studied, there is a lack of mechanistic understanding of their competition with microplastics (MPs) for heavy metal uptake. Therefore, this study was conducted to examine the partitioning of heavy metals in microplastics and sediments from stormwater runoff. For this purpose, new low density polyethylene (LDPE) pellets were selected as representative MPs, and accelerated UV-B irradiation experiments were conducted for eight weeks to generate photodegraded MPs. The competition of Cu, Zn, and Pb species for the occupation of available surface sites on sediments and new and photodegraded LDPE MPs was examined through 48 h kinetics experiments. Additionally, leaching experiments were conducted to identify the extent of organics released into the contact water by new and photodegraded MPs. Moreover, 24 h metal exposure experiments were conducted to identify the role of initial metal concentrations on their accumulation onto the MPs and sediments. The photodegradation process altered the LDPE MPs’ surface chemistry by creating the oxidized carbon functional groups [>CO, >C–O–C<], and it also enhanced their dissolved organic carbon (DOC) leaching into the contact water. The results showed significantly greater levels of Cu, Zn, and Pb accumulations on photodegraded MPs compared to the new MPs in either absence or presence of sediments. Heavy metal uptake by sediments when photodegraded MPs were present was significantly reduced. This might be due to the organic matter leached by photodegraded MPs into the contact water.

Novel Reaction-Adsorption Method for Preparation of Ru–Zn–La/ZrO2 Catalysts with High Catalytic Performance for Selective Hydrogenation of Benzene

A novel wet-chemistry reaction-adsorption strategy via the facile acid–base interaction under mild conditions is demonstrated to fabricate the state-of-the-art Ru–Zn–La/ZrO2 catalysts for selective hydrogenation of benzene to cyclohexene. The catalyst preparation process is systematically investigated and verified with the combination of various characterization techniques. Preloading of lanthanide salts and alkali treatment after calcination not only favor the introduction of ruthenium and zinc species in the later stages but also help enhance the dispersion of the catalysts. The reaction rate constants (k1 and k2) decrease with the increment of the Zn/Ru molar ratio, and the selectivity at 40% conversion (S40) is positively correlated with the k1/k2 ratio, demonstrating the role of Zn species in retarding the hydrogenation activity of Ru and improvement of the selectivity to cyclohexene. In general, the catalytic behavior is dependent on the particle size of Ru, the La-to-Ru electron transfer effect, the content of Zn species, and the surface hydrophilicity of catalyst. These factors are generated by using different precursors and various predesigned La/Ru molar ratios in the preparation recipe. Moreover, a passivation treatment before the hydrogenation reaction can promote the cyclohexene selectivity of the catalyst Ru–Zn–La/ZrO2 (1.6 La/Ru) to 80.6% at a benzene conversion of 43.7%, which meets the industrial requirement. Notably, the specific activity of the catalyst is as high as 1224 gBZ·gRu–1·h–1, over 10 times higher than the industrial criterion. This work provides new insights into the design of Ru-based catalysts for benzene hydrogenation and other hydrogenation reactions as well.

The inclusion of engineered ZnO nanoparticles and bulk ZnSO4 in the growth medium distinctively modulate the root and leaf metabolome in bean plants.

Together with toxicity, beneficial effects on plant growth have been ascribed to nanoparticles (NPs). This study aimed to survey the growth performance and metabolome adjustment of beans grown in a growth medium containing ZnONPs at different concentrations and compared to bulk ZnSO4 as a positive control. Growth parameters showed a reduction in shoot height starting from the lowest (25 mg l-1 ) concentration of ZnONPs. In comparison, growth was inhibited from 50 mg l-1 ZnSO4 , suggesting more toxic effects of nano forms of Zn. Untargeted metabolomics allowed us to unravel the biochemical processes involved in both promising and detrimental aspects. Multivariate statistics indicated that the tested Zn species substantially and distinctively altered the metabolic profile of both roots and leaves, with more metabolites altered in the former (435) compared to leaves (381). Despite having Zn forms in the growth medium, also leaf metabolome underwent a significant and extensive modulation. In general, the elicitation of secondary metabolism (N-containing compounds, phenylpropanoids, and phytoalexins) and the down-accumulation of fatty acid biosynthesis compounds were common responses to different Zn forms. However, an opposite trend could be observed for amino acids, fatty acids, carbohydrates, and cofactors being down-accumulated in ZnONPs treatment. Osmolytes, especially in ZnSO4 treatment, contributed to mitigating the effect of Zn toxicity and maintaining plant growth. Overall, the results indicated a complexity of tissue-specific and Zn-dependent response differences, resulting in distinctive metabolic perturbations. This article is protected by copyright. All rights reserved.

Controlling the growth of ZnNiMoSx on biomass-derived porous carbon materials for deep hydrodesulfurization

Controlling the growth of small-sized catalysts with more accessible active sites and low cost is of great significance to promote their hydrodesulfurization (HDS) performance. Herein, we have synthesized an efficient ZnNiMoSx/C composite catalyst by using biomass-derived porous carbon as the support. With ZnCl2 to regulate porous structure, the obtained carbon support presents an enhanced specific surface area (1581.1 m2/g), which promotes the dispersion of ZnNiMoSx catalysts. The ZnNiMoSx on ZnNiMoSx/C-3 shows fewer layers (2–4 layers) and shorter length (about 4–5 nm), indicating more corner and edge active sites. Besides, the addition of Zn species improves the sulfurization degree of ZnNiMoSx and provides more sulfur vacancies for the enhanced HDS performance. The synthesized ZnNiMoSx/C-3 catalyst shows the kHDS value of dibenzothiophene to be 39.42 × 10−7 mol/(g s) and the direct desulfurization selectivity up to 94.5 %. This study provides a new thought for the development of HDS catalysts with cheap biomass-derived materials.

Ruthenium nanoclusters modified by zinc species towards enhanced electrochemical hydrogen evolution reaction.

Ruthenium (Ru) has been considered a promising electrocatalyst for electrochemical hydrogen evolution reaction (HER) while its performance is limited due to the problems of particle aggregation and competitive adsorption of the reaction intermediates. Herein, we reported the synthesis of a zinc (Zn) modified Ru nanocluster electrocatalyst anchored on multiwalled carbon nanotubes (Ru-Zn/MWCNTs). The Ru-Zn catalysts were found to be highly dispersed on the MWCNTs substrate. Moreover, the Ru-Zn/MWCNTs exhibited low overpotentials of 26 and 119mV for achieving current intensities of 10 and 100mA cm-2 under alkaline conditions, respectively, surpassing Ru/MWCNTs with the same Ru loading and the commercial 5wt% Pt/C (47 and 270mV). Moreover, the Ru-Zn/MWCNTs showed greatly enhanced stability compared to Ru/MWCNTs with no significant decay after 10,000 cycles of CV sweeps and long-term operation for 90h. The incorporation of Zn species was found to modify the electronic structure of the Ru active species and thus modulate the adsorption energy of the Had and OHad intermediates, which could be the main reason for the enhanced HER performance. This study provides a strategy to develop efficient and stable electrocatalysts towards the clean energy conversion field.

In situ/operando XAFS investigation of the sorption/precipitation of Zn(II) on palygorskite surface at the molecular scale: Implications for Zn stable isotope fractionation

In aqueous geological environments, the fate and transport of Zn are controlled by geochemical reactions (e.g., sorption) occurring at the mineral/water interface. However, many of the underlying Zn fixation mechanisms, especially the kinetics of surface-induced precipitation, are still unclear. Additionally, Zn stable isotope fractionation during sorption has recently been shown to be an important process, but the relationship between Zn isotope fractionation and sorption mechanisms (e.g., surface complexation, precipitation) is also not well understood. To address these issues, we employed X-ray absorption fine structure (XAFS) spectroscopy, high-resolution transmission electron microscopy (HRTEM), and in situ/operando quick-scanning XAS (QXAS) spectroscopy to elucidate the sorption/precipitation mechanisms of Zn at palygorskite/solution interfaces. We also measured Zn isotope ratios during some sorption experiments to illustrate how Zn isotope fractionation behavior is affected by the evolution of coordination environments at different pH values, initial concentrations, and reaction times. Our results demonstrate that Zn sorption mechanisms vary as a function of pH, ionic strength, initial concentration, and reaction time. At low pH (pH < 7.0) and low ionic strength (I ≤ 0.01 M), Zn(II) predominantly forms an outer-sphere surface complex in octahedral coordination. At low pH (pH < 7.0) and high ionic strength (I = 0.1 M), Zn(II) is predominantly sorbed as an inner-sphere octahedral surface complex with insignificant isotopic fractionation (Δ66Znsorbed-aqueous = −0.02 ± 0.05‰). At high pH and high initial Zn concentration (pH 7.5, C0 ≥ 0.2 mM), the formation of octahedral Zn phyllosilicate precipitates is observed, yielding a small fractionation with an average Δ66Znsorbed-aqueous of 0.10 ± 0.07‰. In addition, in situ/operando QXAS of Zn sorption at pH 7.5 in a flow cell revealed that the predominant sorbed Zn species shifted from inner-sphere tetrahedral complexes during the initial stage (e.g., within minutes) to inner-sphere octahedral complexes during later stages (e.g., within hours), followed by the formation of Zn-phyllosilicate precipitates (e.g., within days). This molecular evidence coincides with the evolution of Zn isotope fractionation from a large Δ66Znsorbed-aqueous value (0.53 ± 0.05‰) to a small value of 0.05 ± 0.04‰ during the sorption process. The combination of QXAS and isotope fractionation results reveals a change in the Zn local environment from tetrahedral coordination to octahedral coordination. The findings in this study not only provide new insight into surface adsorption/precipitation mechanisms but also demonstrate that stable isotope fractionation is linked with the local molecular/bonding environments at mineral–water interfaces.

Hydroisomerization of n-hexane over metal oxides-loaded fibrous silica catalyst for cleaner fuel production

Fibrous silica (KCC-1) was impregnated with cobalt (Co), iron (Fe), and zinc (Zn) oxides which are denoted as Co/KCC-1, Fe/KCC-1 and Zn/KCC-1 for hydroisomerization of n-hexane. The characterization analysis revealed that the introduction of Co, Fe, and Zn into KCC-1 significantly altered the physicochemical properties of KCC-1 including reduced surface area, pore volume as well as crystallinity. Pyridine adsorbed IR showed that higher amount of the Lewis acid sites (LAS) and Brønsted acid sites (BAS) when introduced the Co, Fe, and Zn into KCC-1. Interestingly, a new band at 1610 cm−1 of Zn/KCC-1, corresponds to the presence of LAS by the formation of binuclear species of Zn in the form of [ZnOZn]2+. The formation of [ZnOZn]2+ was further confirmed by the presence of a band at 350 nm and higher intensity of the binding energy at 1022.8 eV from UV-DRS and XPS analysis, respectively. From temperature-programmed reduction analysis, these binuclear species were formed at a higher temperature, which has a stronger interaction with the KCC-1. The proposed formation of [ZnOZn]2+ was also discussed in this work. Based on the n-hexane hydroisomerization, the Zn/KCC-1 possessed the most excellent catalytic performance amongst the catalysts owing to the existence of the binuclear species of [ZnOZn]2+, which acts as a new acidic center in the stabilization of generated protonic acid sites by trapping of electrons, resulting in increased isomers yield of n-hexane as well as no cracking products. Zn/KCC-1 showed the lowest activation energy compared to other catalysts within 423–673 K.

Combining ultrafiltration and diffusive gradients in thin films techniques for speciation/fractionation of Cu and Zn in cytosol of liver of Nile tilapia (Oreochromis niloticus).

This work aims to evaluate the size and lability of Cu and Zn bound to proteins in the cytosol of fish liver of Oreochromis niloticus by employing solid-phase extraction (SPE), diffusive gradients in thin films (DGT), and ultrafiltration (UF). SPE was carried out using Chelex-100. DGT containing Chelex-100 as binding agent was employed. Analyte concentrations were determined by ICP-MS. Total Cu and Zn concentrations in cytosol (1g of fish liver in 5ml of Tris-HCl) ranged from 39.6 to 44.3ng ml-1 and 1498 to 2106ng ml-1, respectively. Data from UF (10-30kDa) suggested that Cu and Zn in cytosol were associated with ∼70% and 95%, respectively, with high-molecular-weight proteins. Cu-metallothionein was not selectively detected (although 28% of Cu was associated with low-molecular-weight proteins). However, information about the specific proteins in the cytosol will require coupling UF with organic mass spectrometry. Data from SPE showed the presence of labile Cu species of ∼17%, while the fraction of labile Zn species was >55%. However, data from DGT suggested a fraction of labile Cu species only of 7% and a labile Zn fraction of 5%. This data, as compared with previous data from literature, suggests that the DGT technique gave a more plausible estimation of the labile pool of Zn and Cu in cytosol. The combination of results from UF and DGT is capable of contributing to the knowledge about the labile and low-molecular pool of Cu and Zn.

Influence of Zn and Fe promoters on Ni-Bi/γ-Al2O3 catalyst for oxidative dehydrogenation of n-butane to butadiene

This study investigated the effects of Zn and Fe metal oxide species as promoters on NiO-Bi2O3/γ-Al2O3 in the oxidative dehydrogenation (ODH) of n-butane to produce butadiene. Ni-Bi-O, Ni-Zn-Bi-O, Ni-Fe-Bi-O, and Ni-Zn-Fe-Bi-O catalysts supported on γ-Al2O3 were synthesized, characterized, and evaluated in a packed bed flow reactor at different temperatures and O2/n-butane molar ratios. Substituting 50 wt.% of Ni with one or both promoters were found to enhance both the butadiene selectivity. Among the synthesized catalysts, Ni-Zn-Fe-Bi-O/γ-Al2O3 (10 wt.% Ni-5 wt.% Zn-5 wt.% Fe-30 wt.% Bi) showed the highest butadiene selectivity of 49.0% with 18.6% n-butane conversion at 450 °C and a molar feed ratio of O2/n-butane = 2.0. This enhanced performance was attributed to the synergetic effects of Ni, which simultaneously improved the first-step dehydrogenation selectivity via a promotion with Zn and the second-step dehydrogenation selectivity by the incorporation of Fe. Moreover, Zn allowed the surface reduction to occur at lower temperatures, while Fe balanced the densities of strong basic sites with weak and moderate acid sites (0.183 mmol CO2/g-cat and 0.188 mmol NH3/g-cat, respectively). The aforementioned results were confirmed with CO2/NH3 temperature-programmed desorption and H2 temperature-programmed reduction experiments. Under this reaction condition, the catalyst maintains good stability over 15 h of time-on-stream.

Uptake and speciation of Zn and Pb by Miscanthus grown in contaminated soils.

The uptake by and distribution of Zn and Pb within a novel seed-based Miscanthus hybrid grown in contaminated soil was assessed. Results from juvenile plants in a pot-trial was compared with data for mature biomass of the same species harvested during a field-trial. Both Zn and Pb uptake by juvenile plants were observed to increase in proportion to the soil concentrations. Both Zn and Pb accumulation differed between leaf and stem structures, and both were different in the mature biomass compared with juvenile plants. Analysis of X-Ray Absorption Fine Structures (XAFS) revealed different Zn speciation in stems and leaves, and differences in Zn speciation with plant maturity. Sulfur ligands consistent with the presence of cysteine rich metallothioneins (MT) and phytochelatin (PC) complexes were the dominant Zn species in juvenile plant leaves, together with octahedral O/N species typified by Zn-malate. Sulfur ligands were also prevalent in stems from juvenile plants, but predominant O/N speciation shifted towards tetrahedral coordination. In contrast, tetrahedral Zn coordination with O/N species predominated in the mature biomass crop. The XAFS spectra for the mature biomass were consistent with Zn being retained within cell walls as pectin and/or phosphate complexes.

Transformation of zinc oxide nanoparticles in the presence of aluminum oxide with pre-sorbed phosphorus ligands

Naturally occurring oxides could react with zinc oxide (ZnO) nanoparticles (NPs) and then change its transformation and toxicity to ecological receptors. The reaction may be affected by a variety of environmental factors, yet the relevant processes and mechanisms are limitedly investigated. Natural prevalent ligands, as an important factor, can sorb on natural oxide minerals and change its surface property, finally affecting ZnO NP transformation. This study investigated the interactions of ZnO NPs with phosphorus ligands (i.e., phytate and orthophosphate) pre-sorbed γ-alumina (γ-Al2O3) via batch experiments and multi-technique analyses. A limited amount of aqueous Zn2+ is observed when the concentration of ZnO NPs is relatively low (<64.8 mg L−1) in the presence of phytate pre-sorbed γ-Al2O3. Solid Zn(II) species includes binary/ternary surface Zn(II) complexes on γ-Al2O3 with minor amounts of zinc phytate precipitates. As the concentration of ZnO NPs increases, surface Zn(II) complexes gradually transform into zinc phytate and Zn−Al layered double hydroxide (Zn−Al LDH) precipitates. The quantitative analysis indicates that, as the concentration of ZnO NPs increases from 32.4 to 388.8 mg L−1, the proportion of Zn(II) species as binary/ternary surface complexes decreases from 81.9 to 30.2%; and the proportion as zinc phytate and Zn−Al LDH increases from 17.9 to 27.6% and 0 to 43.8%, respectively. The pre-sorption of orthophosphate can also inhibit ZnO NP transformation into Zn−Al LDH precipitates on γ-Al2O3. This study suggests that natural ligands pre-existed on natural oxide minerals could greatly influence the solubility, stability, transformation, and fate of easily dissoluble metal oxides (e.g., ZnO) in the environments.

Folic-acid adorned alginate-polydopamine modified paclitaxel/Zn-CuO nanocomplex for pH triggered drug release and synergistic antitumor efficacy

Targeted chemotherapy is a prominent cancer treatment research trend that intends to boost the efficacy of drug delivery to cancer cells. The present work aimed to design, a folate-decorated biologically inspired alginate-polydopamine capped zinc doped copper oxide nanoparticles (Zn-CuO) loaded with paclitaxel (Zn-CuO@PTX/AlgPDA-FA) as a simple, efficient, and versatile nanoplatform. Interestingly, Zn species doped in CuO frameworks significantly improved paclitaxel (PTX) molecule loading efficiency without requiring any additional functionalization and fostered the increased antitumor efficacy by precisely delivering them in tumor's acidic microenvironment by obliterating the formed coordination connections between the host as well as guest species. According to DLS, average size of nanocomplex was 196 ± 5.01 nm with ȥ-potential −31.4 ± 1.54 mV. PTX encapsulation and loading efficiencies were 75.2 ± 1.54 % and 18.54 ± 2.31 %, respectively. Furthermore, nanocomplex demonstrates high stability and biocompatibility in vitro. Under an acidic environment (pH 5.0), there was greater PTX release compared to normal physiological conditions. Moreover, Zn-CuO@PTX/AlgPDA-FA NPs showed remarkable internalization efficiency in MCF-7 cells and demonstrated strong cytotoxicity with IC50 (150 ± 2.58 μg/mL) along with improved ROS generation and changed mitochondrial membrane potential level. Therefore, our approach could suggest excellent potential for tumor targeting in cancer therapy with reduced off-target toxicity, and desirable therapeutic effects.

Comparative assessment of the heavy metal phytoextraction potential of vegetables from agricultural soils: A field experiment

A field study was established to determine the phytoextraction potential of six vegetable species, namely Amaranthus viridis L., Basella alba L., Brassica chinensis var. Parachinensis, Brassica rapa L., Capsicum frutescens L., and Ocimum tenuiflorum L.. These edible plants were selected for their short growth cycles and high biomass production, which are some traits for efficient phytoremediation. Following acid digestion of the soil and vegetable samples using the USEPA 3050B acid digestion method, the extracts were analyzed for Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn using ICP-OES. Results in soil samples showed that the concentrations of both beneficial and essential heavy metals, and non-essential heavy metals are below the WHO, USEPA, and CCME soil quality guidelines. Al is one of the highest concentrations found in the soil samples but it tends to accumulate in the root part of all vegetable species compared to the aboveground parts. In general, B. rapa L. accumulated the highest level of Cd (0.4 mg/kg) and Pb (5.71 mg/kg), while B. alba L. accumulated the highest Cr (2.62 mg/kg) in all plant parts. The findings in this study indicated that Co, Cu, Fe, Mn and Zn were mostly accumulated in leaves of A. viridis L. (Co, Cu, Fe, Mn and Zn), B. alba L. (Co, Fe and Mn), B. chinensis (Mn and Zn) and O. tenuiflorum L. (Mn), and roots of C. frutescens L. (Co, Cu, Fe and Mn), B. alba L. (Co, Cu and Zn), A. viridis L. and B. chinensis (Cu and Fe) and B. rapa L. (Fe). Cr, Pb and Ni were significantly greater in B. alba L. (Cr) And B. rapa L. (Ni and Pb) roots. MTF >1 was observed in the roots of all species for Co, Cd, Zn, and Ni. BTC values varied between the different vegetable species with A. viridis L. having the greatest heavy metal mobility between its plant parts and the best heavy metal phytoextraction potential among other species. The PCA biplots showed that heavy metals were partitioned differently between various plant parts of the vegetable species and can be explained by the first two components (PC1 and PC2) which were associated with the root and/or leaf parts for most vegetable species.

Developing Superior Hydrophobic 3D Hierarchical Electrocatalysts Embedding Abundant Catalytic Species for High Power Density Zn-Air Battery.

It is essential but still challenging to design and construct inexpensive, highly active bifunctional oxygen electrocatalysts for the development of high power density zinc-air batteries (ZABs). Herein, a CoFe-S@3D-S-NCNT electrocatalyst with a 3D hierarchical structure of carbon nanotubes growing on leaf-like carbon microplates is designed and prepared through chemical vapour deposition pyrolysis of CoFe-MOF and subsequent hydrothermal sulfurization. Its 3D hierarchical structure shows excellent hydrophobicity, which facilitates the diffusion of oxygen and thus accelerates the oxygen reduction reaction (ORR) kinetic process. Alloying and sulfurization strategies obviously enrich the catalytic species in the catalyst, including cobalt or cobalt ferroalloy sulfides, their heterojunction, core-shell structure, and S, N-doped carbon, which simultaneously improve the ORR/OER catalytic activity with a small potential gap (ΔE= 0.71V). Benefiting from these characteristics, the corresponding liquid ZABs show high peak power density (223mW cm-2 ), superior specific capacity (815mA h gZn -1 ), and excellent stability at 5mA cm-2 for ≈900 h. The quasi-solid-state ZABs also exhibit a very high peak power density of 490mW cm-2 and an excellent voltage round-trip efficiency of more than 64%. This work highlights that simultaneous composition optimization and microstructure design of catalysts can effectively improve the performance of ZABs.

Zn-ethylenediaminetetraacetic acid complex derived N-doped porous carbon for high-performance supercapacitor

The development of N-doped porous carbon is an effective strategy to improve supercapacitor performance such as energy density and rate capability. The synthesis of N-doped porous carbon with high surface area by a simple method remains a challenge since it usually requires an additional chemical activation. In this work, we developed Zn-ethylenediaminetetraacetic acid (EDTA) coordination complexes, and then synthesized N-doped porous carbon with high surface area through pyrolysis of Zn-EDTA complexes based on the high nitrogen content of EDTA and the activation ability of Zn species. The morphology and surface area of the obtained porous carbon significantly depend on the morphology of the Zn-EDTA complexes, which can be easily controlled by adjusting the amount of Zn salt. The porous carbon exhibited a specific capacitance of 251.9 F g−1 at 1 A g−1 and 194.4 F g−1 at 20 A g−1 in a two-electrode system. Furthermore, the assembled supercapacitor device displayed an energy density of 8.7 Wh kg−1 at a power density of 248.7 W kg−1 at 1 A g−1 and good cycling performance with capacitance retention of 100 % over 10,000 cycles at the current density of 10 A g−1. The excellent supercapacitive performance should be mainly ascribed to the large surface area and abundant micro-, meso-, and macropores, which offer large electrode/electrolyte interfaces and fast ion diffusion. In addition, the high-level and uniformly distributed N atoms endow the porous carbon with both a high concentration of active sites and good wettability.