Application of synthesized metal-trimesic acid frameworks for the remediation of a multi-metal polluted soil and investigation of quinoa responses.

Metal-organic frameworks (MOFs) are structures with high surface area that can be used to remove heavy metals (HMs) efficiently from the environment. The effect of MOFs on HMs removal from contaminated soils has not been already investigated. Monometallic MOFs are easier to synthesize with high efficiency, and it is also important to compare their structures. In the present study, Zn-BTC, Cu-BTC, and Fe-BTC as three metal-trimesic acid MOFs were synthesized from the combination of zinc (Zn), copper (Cu), and iron (Fe) nitrates with benzene-1,3,5-tricarboxylic acid (H3BTC) by solvothermal method. BET analysis showed that the specific surface areas of the Zn-BTC, Cu-BTC, and Fe-BTC were 502.63, 768.39 and 92.4 m2g-1, respectively. The synthesized MOFs were added at the rates of 0.5 and 1% by weight to the soils contaminated with 100 mgkg-1 of Zn, nickel (Ni), lead (Pb), and cadmium (Cd). Then quinoa seeds were sown in the treated soils. According to the results, the uptakes of all four HMs by quinoa were the lowest in the Cu-BTC 1% treated pots and the lowest uptakes were observed for Pb in shoot and root (4.87 and 0.39, µgpot-1, respectively). The lowest concentration of metal extracted with EDTA in the post-harvest soils was for Pb (11.86 mgkg-1) in the Cu-BTC 1% treatment. The lowest metal pollution indices were observed after the application of Cu-BTC 1%, which were 20.29 and 11.53 for shoot and root, respectively. With equal molar ratios, highly porous and honeycomb-shaped structure, the most crystallized and the smallest constituent particle size (34.64 nm) were obtained only from the combination of Cu ions with H3BTC. The lowest porosity, crystallinity, and a semi-gel like feature was found for the Fe-BTC. The synthesized Cu-BTC showed the highest capacity of stabilizing HMs, especially Pb in the soil compared to the Zn-BTC and the Fe-BTC. The highly porous characteristic of the Cu-BTC can make the application of this MOF as a suitable environmental solution for the remediation of high Pb-contaminated soils.

Natural solution for the remediation of multi-metal contamination: application of natural amino acids, Pseudomonas fluorescens and Micrococcus yunnanensis to increase the phytoremediation efficiency.

Natural amino acids (NAA) have been rarely investigated as chelators, despite their ability to chelate heavy metals (HMs). In the present research, the effects of extracted natural amino acids, as a natural and environmentally friendly chelate agent and the inoculation of Pseudomonas fluorescens (PF) and Micrococcus yunnanensis (MY) bacteria were investigated on some responses of quinoa in a soil polluted with Pb, Ni, Cd, and Zn. Inoculation of PGPR bacteria enhanced plant growth and phytoremediation efficiency. Pb and Cd were higher in quinoa roots, while Ni and Zn were higher in the shoots. The highest efficiencies were observed with NAA treatment and simultaneous inoculation of PF and MY bacteria for Ni, Cd, Pb, and Zn. The highest values of phytoremediation efficiency and uptake efficiency of Ni, Cd, Pb, and Zn were 21.28, 19.11, 14.96 and 18.99 µg g-1, and 31.52, 60.78, 51.89, and 25.33 µg g-1, respectively. Results of present study well demonstrated NAA extracted from blood powder acted as strong chelate agent due to their diversity in size, solubilizing ability, abundant functional groups, and potential in the formation of stable complexes with Ni, Cd, Pb, and Zn, increasing metal availability in soil and improving phytoremediation efficiency in quinoa.

This study focused on an underexplored topic, the potential of natural amino acids (NAA) and plant growth-promoting rhizobacteria (PGPRs) to enhance phytoremediation efficiency of quinoa in a multi-metal contaminated soil with the waste recycling approach. Despite their chelating abilities, NAA have been rarely studied in this context. In the present study, the effects of extracted NAA, acting as environmentally friendly chelating agents, and the inoculation of Pseudomonas fluorescens (PF) and Micrococcus yunnanensis (MY) bacteria were examined on the responses of quinoa in a soil contaminated with Pb, Ni, Cd, and Zn.

Efficient Immobilization of heavy metals using newly synthesized magnetic nanoparticles and some bacteria in a multi-metal contaminated soil.

Simultaneous application of modified Fe3O4 with biological treatments in remediating multi-metal polluted soils, has rarely been investigated. Thus, a pioneering approach towards sustainable environmental remediation strategies is crucial. In this study, we aimed to improve the efficiency of Fe3O4 as adsorbents for heavy metals (HMs) by applying protective coatings. We synthesized core-shell magnetite nanoparticles coated with modified nanocellulose, nanohydrochar, and nanobiochar, and investigated their effectiveness in conjunction with bacteria (Pseudomonas putida and Bacillus megaterium) for remediating a multi-metal contamination soil. The results showed that the coatings significantly enhanced the immobilization of heavy metals in the soil, even at low doses (0.5%). The coating of nanocellulose had the highest efficiency in stabilizing metals due to the greater variety of surface functional groups and higher specific surface area (63.86 m2 g-1) than the other two coatings. Interestingly, uncoated Fe3O4 had lower performance (113.6 m2 g-1) due to their susceptibility to deformation and oxidation. The use of bacteria as a biological treatment led to an increase in the stabilization of metals in soil. In fact, Pseudomonas putida and Bacillus megaterium increased immobilization of HMs in soil successfully because of extracellular polymeric substances and intensive negative charges. Analysis of metal concentrations in plants revealed that Ni and Zn accumulated in the roots, while Pb and Cd were transferred from the roots to the shoots. Treatment Fe3O4 coated with modified nanocellulose at rates of 0.5 and 1% along with Pseudomonas putida showed the highest effect in stabilizing metals. Application of coated Fe3O4 for in-situ immobilization of HMs in contamination soils is recommendable due to their high metal stabilization efficiency and suitability to apply in large quantities.

Heavy metals immobilization and bioavailability in multi-metal contaminated soil under ryegrass cultivation as affected by ZnO and MnO2 nanoparticle-modified biochar.

Pollution by heavy metals (HMs) has become a global problem for agriculture and the environment. In this study, the effects of pristine biochar and biochar modified with manganese dioxide (BC@MnO2) and zinc oxide (BC@ZnO) nanoparticles on the immobilization and bioavailability of Pb, Cd, Zn, and Ni in soil under ryegrass (Lolium perenne L.) cultivation were investigated. The results of SEM-EDX, FTIR, and XRD showed that ZnO and MnO2 nanoparticles were successfully loaded onto biochar. The results showed that BC, BC@MnO2 and BC@ZnO treatments significantly increased shoots and roots dry weight of ryegrass compared to the control. The maximum dry weight of root and shoot (1.365 g pot-1 and 4.163 g pot-1, respectively) was reached at 1% BC@MnO2. The HMs uptake by ryegrass roots and shoots decreased significantly after addition of amendments. The lowest Pb, Cd, Zn and Ni uptake in the plant shoot (13.176, 24.92, 32.407, and 53.88 µg pot-1, respectively) was obtained in the 1% BC@MnO2 treatment. Modified biochar was more successful in reducing HMs uptake by ryegrass and improving plant growth than pristine biochar and can therefore be used as an efficient and cost effective amendment for the remediation of HMs contaminated soils. The lowest HMs translocation (TF) and bioconcentration factors were related to the 1% BC@MnO2 treatment. Therefore, BC@MnO2 was the most successful treatment for HMs immobilization in soil. Also, a comparison of the TF values of plant showed that ryegrass had a good ability to accumulate all studied HMs in its roots, and it is a suitable plant for HMs phytostabilization.

Functionalization of ß-cyclodextrin metal-organic frameworks with gelatin and glutamine for drug delivery of curcumin to cancerous cells.

Beta-cyclodextrin Metal-Organic Framework (ß-CD-MOF) is a unique class of porous materials that merges the inherent properties of cyclodextrins with the structural advantages of metal-organic frameworks (MOFs). When combined with the concept of MOFs, which are crystalline structures composed of metal ions or clusters linked by organic ligands, the resulting ß-CD-MOF holds immense potential for various applications, especially in the field of drug delivery. In this study, biocompatible metal-organic frameworks (MOFs) synthesized using ß-Cyclodextrin (ß-CD) and potassium enabled drug delivery of curcumin (CCM) to cancerous cells. Functionalizing ß-CD-MOF with l-glutamine (glutamine-ß-CD-MOF) enhanced cancer cell-specific targeting due to glutamine's essential role in cancer cell proliferation and energy pathways. Amino group functionalization provided further functionalization opportunities. Gelatin coating (gelatin@ß-CD-MOF) facilitated controlled drug release in an acidic medium. High drug loading capacities (52.38-55.63 %) were achieved for ß-CD-MOF@CCM and glutamine-ß-CD-MOF@CCM, leveraging the high porosity and affinity of amine and phenol groups of curcumin. The MTT assay highlighted the specificity and differentiation of glutamine-ß-CD-MOF in targeting cancerous over normal cells. These functionalized ß-CD MOFs efficiently encapsulate curcumin, ensuring controlled drug release and enhanced therapeutic efficacy, particularly in cancer therapy.

Highly Rapid and Sensitive Formaldehyde Detection at Room Temperature Using a ZIF-8/MWCNT Nanocomposite.

Formaldehyde is a volatile organic compound (VOC) with extensive applications, volatility, and toxicity, which have made it an important risk to human health even at low concentrations. Therefore, rapid detection of formaldehyde vapors in the environment is a necessity. Herein, we introduce a resistive gas sensor based on zeolitic imidazolate framework-8/multiwalled carbon nanotube (ZIF-8/MWCNT) for detection of formaldehyde vapors at room temperature. In this sensor, a low amount of MWCNTs was used in order to improve the electrical conductivity of the porous nanoparticles of ZIF-8. The sensor was fabricated by deposition of a thin layer of the nanocomposite onto interdigitated electrodes, and its sensing ability was investigated on exposure to formaldehyde vapors. The obtained sensor showed sensitive and fast responses to different concentrations of formaldehyde, and the sensor response to formaldehyde was higher than toward some other VOCs, including methanol, ethanol, acetone, and acetonitrile. Furthermore, because of the hydrophobic nature of ZIF-8, the effect of relative humidity on the gas-sensing performance was insignificant, which proves that this sensor is suitable for use under humid conditions.

Nanoporous MIL-101(Cr) as a sensing layer coated on a quartz crystal microbalance (QCM) nanosensor to detect volatile organic compounds (VOCs).

The application of metal-organic frameworks (MOFs) as a sensing layer has been attracting great interest over the last decade, due to their high porosity and tunability, which provides a large surface area and active sites for trapping or binding target molecules. MIL-101(Cr) is selected as a good candidate from the MOFs family to fabricate a quartz crystal microbalance (QCM) nanosensor for the detection of volatile organic compound (VOC) vapors. The structural and chemical properties of synthesized MIL-101(Cr) are investigated by X-ray diffraction (XRD), Fourier-transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) and so on. A stable and uniform layer of MOF is coated onto the surface of a QCM sensor by the drop casting method. The frequency of the QCM crystal is changed during exposure to different concentrations of target gas molecules. Here, the sensor response to some VOCs with different functional groups and polarities, such as methanol, ethanol, isopropanol, n-hexane, acetone, dichloromethane, chloroform, tetrahydrofuran (THF), and pyridine under N2 atmosphere at ambient conditions is studied. Sensing properties such as sensitivity, reversibility, stability, response time, recovery time, and limit of detection (LOD) of the sensor are investigated. The best sensor response is observed for pyridine detection with sensitivity of 2.793 Hz ppm-1. The sensor shows short response/recovery time (less than two minutes), complete reversibility and repeatability which are attributed to the physisorption of the gases into the MOF pores and high stability of the device.

The enzyme-sensitive release of prodigiosin grafted ß-cyclodextrin and chitosan magnetic nanoparticles as an anticancer drug delivery system: Synthesis, characterization and cytotoxicity studies.

In present investigation, two glucose based smart tumor-targeted drug delivery systems coupled with enzyme-sensitive release strategy are introduced. Magnetic nanoparticles (Fe3O4) were grafted with carboxymethyl chitosan (CS) and ß-cyclodextrin (ß-CD) as carriers. Prodigiosin (PG) was used as the model anti-tumor drug, targeting aggressive tumor cells. The morphology, properties and composition and grafting process were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), vibration sample magnetometer (VSM), X-ray diffraction (XRD) analysis. The results revealed that the core crystal size of the nanoparticles synthesized were 14.2±2.1 and 9.8±1.4nm for ß-CD and CS-MNPs respectively when measured using TEM; while dynamic light scattering (DLS) gave diameters of 121.1 and 38.2nm. The saturation magnetization (Ms) of bare magnetic nanoparticles is 50.10emucm-3, while modification with ß-CD and CS gave values of 37.48 and 65.01emucm-3, respectively. The anticancer compound, prodigiosin (PG) was loaded into the NPs with an encapsulation efficiency of approximately 81% for the ß-CD-MNPs, and 92% for the CS-MNPs. This translates to a drug loading capacity of 56.17 and 59.17mg/100mg MNPs, respectively. Measurement of in vitro release of prodigiosin from the loaded nanocarriers in the presence of the hydrolytic enzymes, alpha-amylase and chitosanase showed that 58.1 and 44.6% of the drug was released after one-hour of incubation. Cytotoxicity studies of PG-loaded nanocarriers on two cancer cell lines, MCF-7 and HepG2, and on a non-cancerous control, NIH/3T3 cells, revealed that the drug loaded nanoparticles had greater efficacy on the cancer cell lines. The selective index (SI) for free PG on MCF-7 and HepG2 cells was 1.54 and 4.42 respectively. This parameter was reduced for PG-loaded ß-CD-MNPs to 1.27 and 1.85, while the SI for CS-MNPs improved considerably to 7.03 on MCF-7 cells. Complementary studies by fluorescence and confocal microscopy and flow cytometry confirm specific targeting of the nanocarriers to the cancer cells. The results suggest that CS-MNPs have higher potency and are better able to target the prodigiosin toxicity effect on cancerous cells than ß-CD-MNPs.

Interaction of prodigiosin with HSA and ß-Lg: Spectroscopic and molecular docking studies.

Human serum albumin (HSA) and bovine ß-lactoglobulin (ß-Lg) are both introduced as blood and oral carrier scaffolds with high affinity for a wide range of pharmaceutical compounds. Prodigiosin, a natural three pyrrolic compound produced by Serratia marcescens, exhibits many pharmaceutical properties associated with health benefits. In the present study, the interaction of prodigiosin with HSA and ß-Lg was investigated using fluorescence spectroscopy, circular dichroism (CD) and computational docking. Prodigiosin interacts with the Sudlow's site I of HSA and the calyx of ß-Lg with association constant of 4.41 × 10(4) and 1.99 × 10(4) M(-1) to form 1:1 and 2:3 complexes at 300K, respectively. The results indicated that binding of prodigiosin to HSA and ß-Lg caused strong fluorescence quenching of both proteins through static quenching mechanism. Electrostatic and hydrophobic interactions are the major forces in the stability of PG-HSA complex with enthalpy- and entropy-driving mode, although the formation of prodigiosin-ß-Lg complex is entropy-driven hydrophobic associations. CD spectra showed slight conformational changes in both proteins due to the binding of prodigiosin. Moreover, the ligand displacement assay, pH-dependent interaction and protein-ligand docking study confirmed that the prodigiosin binds to residues located in the subdomain IIA and IIIA of HSA and central calyx of ß-Lg.

Synthesis of biologically stable gold nanoparticles using imidazolium-based amino acid ionic liquids.

A novel double-step reduction procedure for the synthesis of gold nanoparticles (AuNPs) using amino acid ionic liquids has been employed. 1-Dodecyl-3-methyl imidazolium tryptophan ([C(12)mim]Trp) and 1-ethyl-3-methyl imidazolium tryptophan ([C(2)mim]Trp) were used for this synthesis. The synthesized AuNPs were characterized by UV-vis spectroscopy, transmission electron microscopy and dynamic light scattering. The behavior of these AuNPs were also probed in a biological media. It was proven that AuNPs synthesized at [C(12)mim]Trp have more stability than AuNPs synthesized at [C(2)mim]Trp due to the longer alkyl chain of the imidazolium moiety. The solubility test shows that the resultant AuNPs have a hydrophilic nature. Finally, it was seen that due to the presence of a biomolecule, namely Trp, in the structure of AuNPs protecting shell, higher stability and biocompatibility was achieved in the biological media.