Post-synthetic modification of nano-chitosan using gibberellic acid: Foliar application on sorghum under salt stress conditions and estimation of biochemical parameters.

The challenge of desert farming with a high salt level has become an ecological task due to salt stress negatively affecting plant growth and reproduction. The current study deals with the cultivation of sorghum under salt stress conditions to counteract the effect of chitosan and gibberellic acid (GA3). Here, the effects of chitosan, GA3 and nano-composite (GA3@chitosan) on biochemical contents, growth and seed yield of sorghum under salinity stress conditions were studied. The results showed that spraying with GA3@chitosan increased sorghum grain yield by 2.07, 1.81 and 1.64 fold higher than salinity stressed plants, chitosan treatment and GA3 treatment, respectively. Additionally, compared to the control of the same variety, the GA3@chitosan spraying treatment improved the concentration of microelements in the grains of the Shandweel-1 and Dorado by 24.51% and 18.39%, respectively for each variety. Furthermore, spraying GA3@chitosan on sorghum varieties increased the accumulation of the macroelements N, P, and K by 34.03%, 47.61%, and 8.67% higher than salt-stressed plants, respectively. On the other hand, the proline and glycinebetaine content in sorghum leaves sprayed with nano-composite were drop by 51.04% and 11.98% less than stressed plants, respectively. The results showed that, in Ras Sudr, the Shandweel-1 variety produced more grain per feddan than the Dorado variety. These findings suggest that GA3@chitosan improves the chemical and biochemical components leading to a decrease in the negative effect of salt stress on the plant which reflects in the high-yield production of cultivated sorghum plants in salt conditions.

Decoration of viscose fibers with silver nanoparticle-based titanium-organic framework for use in environmental applications.

To effectively remove pharmaceuticals, nitroaromatic compounds, and dyes from wastewater, an efficient multifunctional material was created based on silver nanoparticles (Ag) and MIL-125-NH2 (MOF) immobilized on viscose fibers (VF) as a support substrate. Firstly, silver nanoparticles (Ag) were immobilized on the surface of viscose fibers (VF) via in situ synthesis using trisodium citrate (TSC) as a reducing agent to create (VF-Ag). Then, VF and VF-Ag were decorated with the titanium metal-organic framework MIL-125-NH2 (MOF) to create VF-MOF and VF-Ag-MOF. The influence of VF-Ag, VF-MOF, and VF-Ag-MOF on the sonocatalytic or sonophotocatalytic degradation of sulfa drugs was investigated. The results show that VF-Ag-MOF showed excellent sonocatalytic and sonophotocatalytic activity towards the degradation of sulfa drugs compared to VF-Ag and VF-MOF. Furthermore, sonophotodegradation showed a dramatic enhancement in the efficiency of degradation of sulfa drugs compared to sonodegradation. The sonophotodegradation degradation percentage of sulfanilamide, sulfadiazine, and sulfamethazine drugs in the presence of VF-Ag-MOF was 65, 90, and 95 after 45 min of ultrasonic and visible light irradiation. The catalytic activity of VF-Ag, VF-MOF, and VF-Ag-MOF was evaluated through the conversion of p-nitrophenol (4-NP) to p-aminophenol (4-AP). The results demonstrate that VF-Ag-MOF had the highest catalytic activity, followed by VF-Ag and VF-MOF. The conversion percentage of 4-NP to 4-AP was 69%. The catalytic or photocatalytic effects of VF-Ag, VF-MOF, and VF-Ag-MOF on the elimination of methylene blue (MB) dye were investigated. The results demonstrate that VF-Ag-MOF showed high efficiency in removing the MB dye through the reduction (65%) or photodegradation (71%) after 60 min. VF-Ag-MOF composites structure-activity relationships represent that doping within silver NPs enhanced the photocatalytic activity of MIL-125-NH2, which could be explained as follows: (i) Due to the formation of a Schottky barrier at the junction between MIL-125-NH2 and Ag NPs, the photogenerated electrons in the conduction band of MIL-125-NH2 were supposed to be quickly transferred to the valence band of the Ag NPs, and subsequently, the electrons were transferred to the conduction band of Ag NPs. This considerable electron transferring process, which is reported as Z scheme heterojunction, can efficiently suppress the recombination of electron/hole pairs in VF-Ag-MIL-125-NH2 composites. (ii) Sufficient separation between the photogenerated charge carriers (holes and electrons) and avoiding their recombination enhanced the photocatalytic activity of composites.

Formulating of the sustained release of Tebuconazole pesticide using chitosan aerogel reinforced NFC/CaCO3 nanocomposite.

Chitosan-based aerogels were fabricated through utilizing of nanofibrillated cellulose (NFC)/CaCO3 composites. Chitosan aerogel and extra three aerogels loaded different concentrations of NFC/CaCO3 were investigated to explore their release efficiency of Tebuconazole pesticides. Results obtained from ATR-FTIR showed a remarkable decline of the characterized chitosan hydroxyl group peak prolonging with appearance of new peaks assigned to the inclusion of inorganic calcium element. Also, SEM images showed chitosan aerogel with regular porous structure increased by incorporation with of NFC/CaCO3 nanocomposite, while EDS affirmed the presence of calcium element rather pristine chitosan aerogel. In addition to this, the physical characterizations showed significant improvement in swelling properties for aerogels incorporated NFC/CaCO3 nanocomposite at low ratios. Chitosan aerogel reinforced NFC/CaCO3 nanocomposite exhibited benefit on loading and release efficiency of Tebuconazole. All samples showed accessibility to column release method with fastest release at low slow rate 2 mL/min as giving chance for diffusion and solubility of ingredient, while release increase as heat increase as result of pore expansion. In conclusion, chitosan aerogels incorporated calcium carbonate showed better-sustained release of Tebuconazole pesticides than pristine chitosan aerogel. The produced aerogels loaded NFC/CaCO3 nanocomposite could be promising for controlled release of pesticides at water-streams in agriculture sector.

Selective separation of chlorophyll-a using recyclable hybrids based on Zn-MOF@cellulosic fibers.

Chlorophyll-a as pigments, exist in the green organelles for plants that act in photosynthesis. Different studies were considered with demonstration of an effective separation technique of Chlorophyll-a without decomposition; however, the reported methods were disadvantageous with expensiveness and low quantum yield. The current work uniquely represents an investigative method for the separation of Chlorophyll-a from spinach extract using cellulosic hybrids based on ZIF-8 @cellulosic fibers (Zn-zeolitic imidazolate frameworks@cellulosic fibers) as a cost effective and recyclable absorbents. To obtain hybrids, ZIF-8 was in-situ prepared over the cellulosic fibers (bamboo, modal and cotton). The untreated and treated fibers were well characterized via FTIR, SEM, EDX, XRD, in order to approve the successive impregnation of ZIF-8. Whereas, the microscopic images showed that, microcrystalline ZIF-8 rods with length of 1.3-4.4 µm were grown over the cellulosic fibers. The obtained hybrids and the untreated fibers were exploited in the separation of Chlorophyll-a via the adsorption/desorption process. The chlorophyll-adsorption was followed Langmuir isotherm and pseudo-second order model. The Langmuir maximum capacities of Chlorophyll-a onto hybrids were followed the order of ZIF-8@cotton (583.6 mg/g) > ZIF-8@modal (561.3 mg/g) > ZIF-8@bamboo (528.7 mg/g). After incorporation of ZIF-8, the maximum adsorption capacities of cellulosic fibers were enhanced by 1.4-1.9 times. Adsorption of chlorophyll onto the applied hybrids was lowered by 27-28%, after five repetitive washing cycles. The data summarized that; chlorophyll was effectively separated by the synthesized ZIF-8@cellulosic fibers hybrids, whereas, the prepared hybrids showed good reusability for application on wider scaled purposes.

A hybrid microcrystalline cellulose/metal-organic framework for dispersive solid phase microextraction of selected pharmaceuticals: A proof-of-concept.

Solid phase microextraction (SPME) is considered simple, ecofriendly, sustainable, cost-effective and timesaving sample preparation mode in comparison with other sample preparation procedures. The researchers always try to develop new sorbents with higher surface area in comparison with other conventional sorbents aiming to enhance the extraction efficiency. In this work for the first time, a comparative study was performed between Ca-BTC MOF (1,3,5-benzenetricarboxylic acid, BTC; metal-organic framework, MOF) and a hybrid Ca-BTC-MCC MOF (microcrystalline cellulose, MCC) by using as model compounds seven drugs with different physicochemical properties. The evaluation of the extraction efficiency of both sorbents were obtained by means of an HPLC/DAD instrument configuration in reversed phase mode under isocratic elution mode. The results indicate that Ca-BTC MOF showed superior extraction efficiency than Ca-BTC-MCC MOF in the case of all analytes except nirmatrelvir and ritonavir. The results highlight that not only the surface area of adsorbents controlled the adsorption capacity, but also other factors have a role in extraction efficiency including morphology of adsorbent and physico-chemical properties of the analytes. It is worth mentioning that this is the first time that a comparative study was performed between Ca-BTC MOF and Ca-BTC-MCC MOF hybrid material.

Use of titanium dioxide doped multi-wall carbon nanotubes as promoter for the growth, biochemical indices of Sesamum indicum L. under heat stress conditions.

The behavior of multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanoparticles (TiO2 NPs) as plant growth enhancers was still unclear; however, in this study, the effects of MWCNTs, TiO2NPs, 5%TiO2@MWCNTs, 10%TiO2@MWCNTs and 15%TiO2@MWCNTs on physical and biochemical contents in Sesamum indicum L. under heat stress conditions were studied. The content of malondialdehyde (MDA) and hydrogen peroxide (H2O2) concentrations were reduced by the spraying MWCNTs and TiO2 NPs on plants. The hydrogen peroxide (H2O2) content was reduced by 49.02% in plants treated with 15%TiO2@MWCNTs while 42.14% reduction was found in plants treated with 10%TiO2@MWCNTs. The proportion of oil and the peroxidase enzyme activity in plants treated with 15%TiO2@MWCNTs were increased by 48.99%, for the oil content, and 2.39 times for POD activity respected to the stressed plants. The proportion of unsaturated fatty acids increased in plants treated with 15%TiO2@MWCNTs, 10%TiO2@MWCNTs and TiO2 NPs by 2.7, 2.52, and 2.09 times, respectively, greater than the control of the Shandweel-3 variety. Finally, plants treated with 15%TiO2@MWCNTs showed increases in seed yield and weight 1000-seeds by 4.42 and 1.67 times, respectively. These findings suggest that TiO2@MWCNTs more effective than separated MWCNTs and TiO2 NPs in improve plant growth. In addition, the cultivar Shandweel-3 showed an improvement in growth indicators more than the Giza-32 cultivar.

Application of honeybee venom loaded nanoparticles for the treatment of chronic toxoplasmosis: parasitological, histopathological, and immunohistochemical studies.

Toxoplasma gondii is an opportunistic intracellular protozoon which may cause severe disease in the immunocompromised patients. Unfortunately, the majority of treatments on the market work against tachyzoites in the acute infection but can't affect tissue cysts in the chronic phase. So, this study aimed to evaluate the effect of bee venom (BV) loaded metal organic frameworks (MOFs) nanoparticles (NPs) for the treatment of chronic murine toxoplasmosis. Ninety laboratory Swiss Albino mice were divided into 9 groups (10 mice each); GI (negative control), GII (infected control), GIII-GXI (infected with Me49 strain of Toxoplasma and treated); GIII (MOFs-NPs), GIV and GV (BV alone and loaded on MOFs-NPs), GVI and GVII (spiramycin alone and loaded on MOFs-NPs), GVIII and GIX (ciprofloxacin alone and loaded on MOFs-NPs). Parasitological examination of brain cyst count, histopathological study of brain, retina, liver, and kidney tissue sections and immunohistochemical (IHC) evaluation of liver was performed. Counting of Toxoplasma brain cysts showed high statistically significant difference between the infected treated groups and GII. GV showed the least count of brain cysts; mean ± SD (281 ± 29.5). Histopathological examination revealed a marked ameliorative effect of BV administration when used alone or loaded MOFs-NPs. It significantly reduced tissue inflammation, degeneration, and fibrosis. IHC examination of liver sections revealed high density CD8+ infiltration in GII, low density CD8+ infiltration in GIII, GVI, GVII, GVIII, and GIX while GIV and GV showed intermediate density CD8+ infiltration. BV is a promising Apitherapy against chronic toxoplasmosis. This effect is markedly enhanced by MOFs-NPs.

Carboxymethyl cellulose/sulfur-functionalized Ti-based MOF composite: synthesis, characterization, antimicrobial, antiviral and anticancer potentiality.

Microbial resistance is the first morbidity and mortality cause for patients as usually a secondary infection. Additionally, the MOF is a promising material that shows a nice activity in this field. However, these materials need a good formulation to enhance biocompatibility and sustainability. Cellulose and its derivatives are well as filers for this gap. In this presented work, a novel green active system based on carboxymethyl cellulose and Ti-MOF (MIL-125-NH2@CMC) modified with thiophene (Thio@MIL-125-NH2@CMC) was prepared by a post-synthetic modification (PSM) route based. FTIR, SEM and PXRD were utilized to characterize nanocomposites. In addition, transmission electron microscopy (TEM) was used to corroborate the nanocomposites' particle size and diffraction pattern as well as the DLS affirmed the size as 50 and 35 nm for MIL-125-NH2@CMC and Thio@MIL-125-NH2@CMC, respectively. The formulation of the nanocomposites was validated by physicochemical characterization techniques, while morphological analysis confirmed the nanoform of the prepared composites. The antimicrobial, antiviral and antitumor properties of MIL-125-NH2@CMC and Thio@MIL-125-NH2@CMC were assessed. Antimicrobial testing revealed that Thio@MIL-125-NH2@CMC possesses greater antimicrobial activity than MIL-125-NH2@CMC. Additionally, Thio@MIL-125-NH2@CMC demonstrated promising antifungal activity against C. albicans and A. niger where MICs were 31.25 and 0.97 µg/mL, respectively. Also, Thio@MIL-125-NH2@CMC exhibited antibacterial activity against E. coli and S. aureus where MICs were 1000 and 250 µg/mL, respectively. In addition, the results demonstrated that Thio@MIL-125-NH2@CMC displayed promising antiviral activity against both HSV1 and COX B4, with antiviral activities of 68.89% and 39.60%, respectively. Furthermore, Thio@MIL-125-NH2@CMC exhibited potential anticancer activity against MCF7 and PC3 cancerous cell lines, where IC50 was 93.16 and 88.45%, respectively. In conclusion, carboxymethyl cellulose/sulfur-functionalized Ti-based MOF composite was successfully synthesized which had antimicrobial, antiviral and anticancer activities.

Efficient phenolic compounds adsorption by immobilization of copper-based metal-organic framework anchored polyacrylonitrile/chitosan beads.

The application of newly formulated beads from copper-benzenetricarboxylate (Cu-BTC), polyacrylonitrile (PAN), and chitosan (C), Cu-BTC@C-PAN, C-PAN, and PAN, for the removal of phenolic chemicals from water, is described in the current paper. Phenolic compounds (4-chlorophenol (4-CP) and 4-nitrophenol (4-NP)) were adsorbed using beads and the adsorption optimization looked at the effects of several experimental factors. The Langmuir and Freundlich models were used to explain the adsorption isotherms in the system. A pseudo-first and second-order equation is performed for describing the kinetics of adsorption. The obtained data fit (R2 = 0.999) supports the suitability of the Langmuir model and pseudo-second-order kinetic equation for the adsorption mechanism. Cu-BTC@C-PAN, C-PAN, and PAN beads' morphology and structure were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transforms infrared spectroscopy (FT-IR). According to the findings, Cu-BTC@C-PAN has very high adsorption capacities of 277.02, and 324.74 mg g-1, for 4-CP and 4-NP, respectively. The Cu-BTC@C-PAN beads showed 2.55 times higher adsorption capacity than PAN in the case of 4-NP, but in the case of 4-CP, it was higher by 2.64 times.

Efficiency and selectivity of cost-effective Zn-MOF for dye removal, kinetic and thermodynamic approach.

Green synthesis of metal-organic frameworks (MOFs) has attracted a lot of attention as a crucial step for practical industrial applications. In this work, green synthesis of zinc(II) metal-organic framework (Zn-MOF) has been carried out at room temperature. The Zn metal (node) was extracted from spent domestic batteries, and the linker was benzene di-carboxylic acid (BDC). The characterization of the as-prepared Zn-MOF was accomplished by PXRD, FT-IR spectroscopy, SEM, TEM, TGA, and nitrogen adsorption at 77 K. All the characterization techniques strongly supported that as-synthesized Zn-MOF using metallic solid waste Zn is similar to that was reported in the literature. The as-prepared Zn-MOF was stable in water for 24 h without any changes in its functional groups and framework. The prepared Zn-MOF was tested for the adsorption of three dyes, two anionic dyes, aniline blue (AB), and orange II (O(II)) as well as methylene blue (MB), an example of cationic dye from aqueous solution. AB has the highest equilibrium adsorbed amount, qe, of value 55.34 mg g-1 at pH = 7 and 25 °C within 40 min. Investigation of the adsorption kinetics indicated that these adsorption processes could be described as a pseudo-second-order kinetic model. Furthermore, the adsorption process of the three dyes was described well by the Freundlich isotherm model. According to the thermodynamic parameters, the adsorption of AB on the prepared Zn-MOF was an endothermic and spontaneous process. In contrast, it was non-spontaneous and exothermic for the uptake of O(II) and MB. This study complements the business case development model of "solid waste to value-added MOFs."

Boosting vegetation, biochemical constituents, grain yield and anti-cancer performance of cultivated oat (Avena sativa L) in calcareous soil using oat extracts coated inside nanocarriers.

Calcareous soil contains many problems such as the lack of sources of major and minor elements that are useful for plant growth and development. Plant extracts and nanoparticles are very popular as biostimulants in plant production. Here, the effect of aqueous, non-aqueous and alcoholic oat extracts on the growth, biochemical response of oats leaves and grains grown in experimental fields under new reclamation lands were studied. Moreover, different oat extracts were a pathway through the copper-dependent metal-organic framework (MOFs) to separate bioactive molecules from extracts such as salicylic acid, anthraquinone, and triacylglycerol. Additionally, the separated molecules incorporated in Cu-BTC MOFs and oats extracts missed active molecules were spray applied on oat plants. The results showed that the treated plants showed stimulatory responses in growth and physiology. The treatments improved plant growth and biomass, enhanced total protein, water-soluble carbohydrates, free phenolic compounds content in oat leaves, photosynthesis, and chlorophyll contents. The treatments also improved the level of vitamins E and K, phenolic compounds, and avenanthramides C in the oat grains. Moreover, the treatments showed an improvement in the yield of oats (grain and straw) using water and alcoholic oat extracts in which the active molecules were missed. Our findings demonstrate that Cu-BTC and oats extracts can act as a biostimulant to enhance the biological and chemical properties of oats and increase the yield in calcareous soils. The cytotoxicity study of oats (produced from AE, c@Cu-BTC, and AE-c treatments) was conducted using Vero Cell lines. The anticancer activities of different oat grains were carried out using MCF 7cell lines. The results show that the grains produced from the AE, c@Cu-BTC, and AE-c treatments possessed 94.3, 72.3, and 100% activity towards the cancer cell line. Removal of growth inhibitors from spray solutions increases grain yield and anticancer activity.

Novel allyl-hydrazones including 2,4-dinitrophenyl and 1,2,3-triazole moieties as optical sensor for ammonia and chromium ions in water.

It is critical to take safety action if carcinogenic heavy metals and ammonia can be detected quickly, cheaply, and selectively in an environmental sample. As a result, compound 4a [4-(1-(2-(2,4-Dinitrophenyl)hydrazineylidene)-3-(naphthalen-2-yl)allyl)-5-methyl-1-phenyl-1 H-1,2,3-triazole] and compound 4b [4-(1-(2-(2,4-Dinitrophenyl)hydrazineylidene)-3-(naphthalen-2-yl)allyl)-1-(4-fluorophenyl)-5-methyl-1 H-1,2,3-triazole] were prepared. The aldol condensation process of 4-acetyl-1,2,3-triazoles 1a,b (Ar = C6H4; 4-FC6H4) with 2-naphthaldehyde yields 1-acetyl-1,2,3-triazoles 1a,b (Ar = C6H4; 4-FC6H4) (5-methyl-1-aryl-1 H-1,2,3-triazol-4-yl) -3-(naphthalen-2-yl)prop-2-en-1-ones 3a,b with a yield of around 95%. The target compounds 4a,b are obtained in around 88% yield by condensation of 3a,b with (2,4-dinitrophenyl)hydrazine in a refluxing acidic medium. Compounds 4a,b exhibited possible colorimetric detection for chromium ion in the range of 0-14 ppm and ammonia in the range of 0-20 ppm. As a result, this research suggests that strong electron-withdraw groups in related probes can improve anion detection ability, while the conjugation effect should also be considered while building structures.

Controlled release of drug molecules by pillararene-modified nanosystems.

Stimuli-responsive nanosystems have attracted the interest of researchers due to their intelligent function of controlled release regulated by a variety of external stimuli and have been applied in biomedical fields. Pillar[n]arenes with the advantages of a rigid structure, electron holes and easy functionalization are considered as excellent candidates for the construction of host-guest nanosystems. In recent years, many pillararene modified nanosystems have been reported in response to different stimuli. In this feature article, we summarize the advance of stimuli-responsive pillararene modified nanosystems for controlled release of drugs from the perspectives of decomposition release and gated release, focusing on the control principles of these nanosystems. We expect that this review can enlighten and guide investigators in the field of stimuli-responsive controlled release.

Size-tunable effect of CaCO3/nanocellulose hybrid composites on the removal of paracetamol from aqueous solution.

Paracetamol is a ubiquitous drug used by animals and humans but is not fully metabolized within their bodies, and thus often finds its way into raw wastewater. This study represents a new class of adsorbent nanocomposite with high adsorption capacity towards paracetamol removal. Herein, both the kinetic study and the removal of paracetamol from aqueous solutions were investigated in terms of diverse CaCO3/nanocellulose composites with different surface charges and different particle sizes. To fine-tune these parameters, the latter was hydrothermally synthesized by manipulating of three nanocelluloses types. Precisely, micro-crystalline cellulose (MCC), nano-crystalline cellulose (CNC), and nano-fibrillated cellulose (NFC) were used as templates for precipitating CaCO3 particles from CaCl2 solution with the aid of Na2CO3. Results revealed the successful in situ deposition of calcite form of CaCO3 with size varied relying on the base of nanocellulose. For MCC, CNC, and NFC, the size of CaCO3 was disclosed in the range of 850-1200 nm, 350-600 nm, and 150-200 nm, respectively, regarding their surface charge. While the process of paracetamol adsorption was described by Freundlich and Langmuir isotherms, it was observed that, for MCC, the best fit of the experimental data was achieved with the Freundlich model, while the Langmuir model was the most appropriate for CNC and NFC. Also, the highest max adsorption capacities of paracetamol varied respectively to both size and surface charge of hybrid composite used. Among them, MCC/CaCO3 composite exhibited the highest max adsorption capacity at 428 mg g-1, clarifying that the low surface zeta potential of the latter hybrid nanocomposite is responsible for the accumulation of CaCO3 at a bigger size with a higher affinity to adsorb paracetamol with the highest capacity due to its weak repulsion. Results also demonstrated that the material is highly effective and economical for removal of paracetamol and reusability with marginal diminishing in adsorption capacity up to 10% after five reuse cycles.

Affinity of carbon quantum dots anchored within metal organic framework matrix as enhancer of plant nourishment.

Nano-fertilizers were ascribed to be significantly advantageous with minimizing the negative effects of requiring excessive contents in the soil and reducing the number of times for fertilization. Herein, the superior affinity of carbon quantum dots (CQDs) anchored within metal organic framework (Cu-BTC) matrix was investigated for the first time as a fertilizer for sunflower. CQDs were nucleated from alkali-hydrolyzed carboxymethyl cellulose (CMC) via the hydrothermal technique. The synthesized CQDs (6.8 ± 3.7 nm) were anchored within Cu-BTC (crystalline rod-like structure) matrix, to produce CQDs@Cu-BTC composite. The obtained CQDs and CQDs@Cu-BTC were applied as nutrients for the sunflower plant. The chlorophyll a and carotenoids contents were 0.465 & 0.497 and 0.350 & 0.364 mg/g after treatment with CQDs & CQDs@Cu-BTC, respectively. The shoot length of sunflower sample was increased after feeding with CQDs and CQDs@Cu-BTC to be 38.7 and 46.5 cm, respectively. The obtained results confirmed that, the synthesized CQDs@Cu-BTC showed superiority as nutrient material via enhancing the growth and physiological properties of sunflower and consequently could be used as fertilizer for plants instead of the commercial nutrient.

High adsorption of sodium diclofenac on post-synthetic modified zirconium-based metal-organic frameworks: Experimental and theoretical studies.

Water pollution by pharmaceuticals is currently a great concern due to their ecological risks. In this study, zirconium-based metal-organic frameworks (UiO-66-(COOH)2) were used for removal of the nonsteroidal anti-inflammatory drug (NSAID) diclofenac sodium (DCF). They have been synthesized using a hydrothermal method. Copper and iron metal ions were incorporated in the framework using post-synthetic modification techniques to produce UiO-66-(COOCu)2 and UiO-66-(COOFe)2. The resulted MOFs were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning/transmission electron microscopy, and Brunauer-Emmett-Teller. The effects of the pH, initial concentration, and adsorption time on the adsorption process of diclofenac were studied. The maximum adsorption capacities obtained on UiO-66-(COOH)2, UiO-66-(COOCu)2, and UiO-66-(COOFe)2 were 480.5, 624.3, and 769.1 mg/g, respectively. The adsorption of diclofenac was found to be better fitted with Langmuir isotherm and pseudo-second-order kinetic models. The adsorption mechanism was investigated using XRD, FT-IR, density functional theory and Monte Carlo simulation, in which the latter method was used to calculate the adsorption energies and determine the possible interactions between diclofenac and the adsorbents. UiO-66-(COOH)2, UiO-66-(COOCu)2, and UiO-66-(COOFe)2 exhibited good recyclability for diclofenac removal, which confirms the sustainability of these materials.

In-situ construction of Zr-based metal-organic framework core-shell heterostructure for photocatalytic degradation of organic pollutants.

Photocatalysis is an eco-friendly promising approach to the degradation of textile dyes. The majority of reported studies involved remediation of dyes with an initial concentration ≤50 mg/L, which was away from the existing values in textile wastewater. Herein, a simple solvothermal route was utilized to synthesize CoFe2O4@UiO-66 core-shell heterojunction photocatalyst for the first time. The photocatalytic performance of the as-synthesized catalysts was assessed through the photodegradation of methylene blue (MB) and methyl orange (MO) dyes at an initial concentration (100 mg/L). Under simulated solar irradiation, improved photocatalytic performance was accomplished by as-obtained CoFe2O4@UiO-66 heterojunction compared to bare UiO-66 and CoFe2O4. The overall removal efficiency of dyes (100 mg/L) over CoFe2O4@UiO-66 (50 mg/L) reached >60% within 180 min. The optical and photoelectrochemical measurements showed an enhanced visible light absorption capacity as well as effective interfacial charge separation and transfer over CoFe2O4@UiO-66, emphasizing the successful construction of heterojunction. The degradation mechanism was further explored, which revealed the contribution of holes (h+), superoxide (•O2 -), and hydroxyl (•OH) radicals in the degradation process, however, h+ were the predominant reactive species. This work might open up new insights for designing MOF-based core-shell heterostructured photocatalysts for the remediation of industrial organic pollutants.

Anti-inflammatory and antioxidant effects of nanoformulations composed of metal-organic frameworks delivering rutin and/or piperine natural agents.

Plant-derived natural medicines have been extensively studied for anti-inflammatory or antioxidant properties, but challenges to their clinical use include low bioavailability, poor solubility in water, and difficult-to-control release kinetics. Nanomedicine may offer innovative solutions that can enhance the therapeutic activity and control release kinetics of these agents, opening the way to translating them into the clinic. Two agents of particular interest are rutin (Ru), a flavonoid, and piperine (Pip), an alkaloid, which exhibit a range of pharmacological activities that include antioxidant and anti-inflammatory effects. In this work, nanoformulations were developed consisting of two metal-organic frameworks (MOFs) with surface modifications, Ti-MOF and Zr-MOF, each of them loaded with Ru and/or Pip. Both MOFs and nanoformulations were characterized and evaluated in vivo for anti-inflammatory and antioxidant effects. Loadings of ∼17 wt.% for a single pro-drug and ∼27 wt.% for dual loading were achieved. The release patterns for Ru and or Pip followed two stages: a zero-order for the first 12-hour stage, and a second stage of stable sustained release. At pH 7.4, the release patterns best fit to zero-order and Korsmeyer-Peppas kinetic models. The nanoformulations had enhanced anti-inflammatory and antioxidant effects than any of their elements singly, and those with Ru or Pip alone showed stronger effects than those with both agents. Results of assays using a paw edema model, leukocyte migration, and plasma antioxidant capacity were in agreement. Our preliminary findings indicate that nanoformulations with these agents exert better anti-inflammatory and antioxidant effects than the agents in their free form.

Melt intercalation technique for synthesis of hetero-metallic@chitin bio-composite as recyclable catalyst for prothiofos hydrolysis.

The compatibility of homo-metallic and hetero-metallic bio-composite was promisingly investigated as recyclable catalyst for prothiofos hydrolysis. Chitin as water insoluble biopolymer was functionalized as a template for generation of homo-metallic (Ag@chitin, Au@chitin and Pd@chitin) and hetero-metallic (Au@Ag@chitin, Pd@Ag@chitin and Pd@Au@Ag@chitin) composites, by using melt intercalation technique. Investigation of the compatibility of the synthesized homo-metallic and hetero-metallic bio-composites in hydrolysis of prothiofos was performed and affirmed via HPLC results. Immobilization of Pd in the composites showed perfection in the catalytic performance for prothiofos hydrolysis. Pd@Au@Ag@chitin exhibited the highest hydrolysis result of 99% for prothiofos was hydrolyzed within 150 min with rate constant (k1) of 24.48 min-1. After five recycles for Pd@Au@Ag@chitin, the hydrolysis of prothiofos was lowered from 346 mg/g to 269 mg/g with reduction percentage of 22%. The synthesized bio-composite was highly effective as recyclable catalyst and can be easily served in the remediation of pesticides.

Observable removal of pharmaceutical residues by highly porous photoactive cellulose acetate@MIL-MOF film.

Pharmaceutical products are used tremendously worldwide and subsequently released into wastewater even at very low concentration caused serious environmental problem due to their high activity. Therefore, the present work focuses on remarkable removal of paracetamol as one from the most used pharmaceutical intermediates, by using porous film based on cellulose acetate@metal organic framework (CA@Ti-MIL-NH2). The film was designed to achieve extreme removal of paracetamol by action of both of adsorption and degradation. Metal organic frame work was directly synthesized and inserted within the pre-prepared porous CA film to obtain porous CA@Ti-MIL-NH2 film. The synthesized films were applied in adsorption and photo-degradation of paracetamol separately and together. Due to the photocatalytic activity of Ti-MIL-NH2, the photo-degradation of paracetamol in visible-light was much effective and considerably high degradation of paracetamol was observed (k1 = 760.0 m-1) comparing to the adsorption (k1 = 160.0 m-1). The overall removal of paracetamol was significantly enlarged from 82.7 mg/g for CA film to 519.1 mg/g for porous CA@Ti-MIL-NH2 film. The used film exhibited quite good reusability and the removal of paracetamol was lowered from 96% to 85% after 5 regeneration cycles. Results of total organic carbon confirmed that paracetamol was fully degraded to CO2 and water.