Hagenia abyssinica-Biomediated Synthesis of a Magnetic Fe3O4/NiO Nanoadsorbent for Adsorption of Lead from Wastewater.

Magnetic nanocomposite adsorbents are cost-effective, environmentally friendly, easy to use, and highly efficient at removing metals from large volumes of wastewater in a short time by using an external magnetic field. In this study, an Fe3O4/NiO composite nanoadsorbent was prepared by varying the mass percent ratios of NiO (50, 40, 30, 20%), which are denoted Fe3O4/50%NiO, Fe3O4/40%NiO, Fe3O4/30%NiO, and Fe3O4/20%NiO, respectively, using Hagenia abyssinica plant extract as the template/capping agent and a simple mechanical grinding technique. The nanocomposites were characterized using an X-ray diffractometer (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, nitrogen adsorption, and ζ-potential measurements. The adsorption performance of the nanoadsorbent was assessed for the removal of lead (Pb2+) ions from aqueous solutions. Among the composite adsorbents, Fe3O4/50%NiO demonstrated the best Pb(II) removal efficiency (96.65%) from aqueous solutions within 80 min at pH 8, at a 100 mg/L lead concentration and 0.09 g of adsorbent dose. However, with the same parameter, only 62.8% of Pb(II) was removed using Fe3O4 nanoparticles (NPs). The adsorptive performance indicated that the optimum amount of porous material (NiO) in the preparation of the Fe3O4/NiO composite nanoadsorbent, with the aid of H. abyssinica plant extract, enhances the removal of toxic heavy metals from aqueous solutions. Multiple isotherm and kinetic models were used to analyze the equilibrium data. Adsorption isotherm and kinetic studies were found to follow the Freundlich isotherm and pseudo-second-order kinetics, respectively.

Adsorptive removal of heavy metals from wastewater using Cobalt-diphenylamine (Co-DPA) complex.

Heavy metals like Cadmium, Lead, and Chromium are the pollutants emitted into the environment through industrial development. In this work, a new diphenylamine coordinated cobalt complex (Co-DPA) has been synthesized and tested for its efficiency in removing heavy metals from wastewater, and its adsorption capacity was investigated. The effectiveness of heavy metals removal by Co-DPA was evaluated by adjusting the adsorption parameters, such as adsorbent dose, pH, initial metals concentration, and adsorption period. Heavy metal concentrations in real sample were 0.267, 0.075, and 0.125 mg/L for Cd2+, Pb2+, and Cr3+ before using as-synthesized Co-DPA to treat wastewater. After being treated with synthesized Co-DPA the concentration of heavy metals was reduced to 0.0129, 0.00028, 0.00054 mg/L for Cd2+, Pb2+, and Cr3+, respectively, in 80 min. The removal efficiency was 95.6%, 99.5%, and 99.5% for the respective metals. The adsorption process fitted satisfactorily with Freundlich isotherm with R2(0.999, 0.997, 0.995) for Cd2+, Pb2+, and Cr3+, respectively. The kinetic data obeyed the pseudo-second order for Cd2+ and Cr2+ and the pseudo-first order for Pb2+. Based on the results obtained within the framework of this study, it is concluded that the as-synthesized Co-DPA is a good adsorbent to eliminate heavy metal ions like Cd2+, Pb2+, and Cr3+from wastewater solution. In general, Co-DPA is a promising new material for the removal of heavy metal ions from water.

Annealing Effect on Mechanical and Tribological Behaviors of Nanoscale Mechanics of Zr60Cu25Al5Ag5Ni5 Thin-Layer Metallic Glasses for Engineering Materials Applications.

A new and unique alloy formulation design strategy has been developed in order to fabricate thin-layered metallic glasses (TLMGs) with superior fracture resistance and low coefficient of friction (COF) during the nanoscratching test. Due to the outstanding properties, TFMG could be applied for different uses, such as for surface coating, biomedical, bioimprinting, electronic devices, spacecraft, and railway, all of which need surface fracture resistance. The fabricated Zr-based metallic glass was prepared from Zr, Al, Cu, Ni, and Ag above 99.9 Wt % in purity by arch melting techniques. TFMGs were coated on silicon wafer by sputtering the vapor deposition method from bulk metallic glass then annealed below glass transition temperature Tg ∼ 450 °C for 10, 30, and 60 min. Nanoindentation and nanoscratch tests were used to investigate nanomechanical and nanotribological properties, and atomic force microscopy (AFM) was used to examine the surface morphology and microstructures of TLMG. The nanoindentation data indicated that the average hardness of metallic glasses increased from 9.75 (as-cast MG) to 13.4 GPa (annealed for 60 min). Coefficients of friction for the cast sample, annealed for unannealed, 10, 30, and 60 min, were 0.062, 0.049, 0.039, and 0.03, respectively, as well as the wear depths were 201.56, 148.43, 37.32, and 25.27 nm, respectively. These studies show that the coefficient of friction and wear rate decreases when the annealing time increases as a result of atomic reordering and structural relaxation that occurred at longer annealing times. Furthermore, continuous wear process, wear depth, wear track volume, and contact area decrease with increasing annealing time. This study can be used to design protocols to prepare novel TLMGs, which have outstanding mechanical and tribological properties for engineering materials applications.

Highly efficient visible light active ZnO/Cu-DPA composite photocatalysts for the treatment of wastewater contaminated with organic dye.

Industrial effluents are a leading major threat for water contamination, subsequently which results in severe health associated risks. Hence, purifying wastewater before releasing into the water resources is essential to avoid contamination. In this study, ZnO/Cu-DPA nano-composites were prepared by altering the percentage of Cu-DPA (20%, 30%, 40%, and 50% which are denoted to be ZnO/20%Cu-DPA, ZnO/30%Cu-DPA, ZnO/40%Cu-DPA and ZnO/50%Cu-DPA) using a simple mechanical grinding process. Several spectroscopic studies were employed such as electron paramagnetic analysis (EPR), powdered X-ray diffractometer (PXRD), UV-Vis absorbance spectroscopy, Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscope to characterize these nano-composites. The photo-catalytic activities of the prepared nano-composites were studied by degrading MB under visible light irradiation. ZnO, ZnO/20%Cu-DPA, ZnO/30%Cu-DPA, ZnO/40%Cu-DPA and ZnO/50%Cu-DPA degradation efficiencies were determined to be 71.8, 78.5, 77.1, and 66.1%, respectively. Among the composite catalysts, the ZnO/20%Cu-DPA coupled system are demonstrated the best efficiency (87%) for photo-degradation of MB within 80 min when exposed to visible light. The ZnO/Cu-DPA nano-composites had a greater MB photodegradation efficiency than pristine ZnO owing to p-n heterojunction in the linked system. Under visible light irradiation, the ZnO/20%Cu-DPA catalysed the conversion of dissolved O2 to hydroxyl radicals (OH·), triggering the reduction of MB. This suggests that ·OH is the primary specific active radical involved in the photo-catalytic decomposition of MB. Furthermore, EPR analysis indicates the existence of ·OH in the photo-catalytic system. The proposed nano-composites (ZnO/20%Cu-DPA) reusability was investigated across three cycles as the most efficient photo-catalyst. The results show that, the ZnO/Cu-DPA nano-catalyst is a potential candidate for the remediation of dirty water.

Dodonaea angustifolia Extract-Assisted Green Synthesis of the Cu2O/Al2O3 Nanocomposite for Adsorption of Cd(II) from Water.

The enhanced worldwide concern for the protection and safety of the environment has made the scientific community focus their devotion on novel and highly effective approaches to heavy metals such as cadmium (Cd) pollutant removal. In this research, Dodonaea angustifolia plant extract-mediated Al2O3 and Cu2O nanoparticle (NP) syntheses were accomplished using the coprecipitation method, and the Cu2O/Al2O3 nanocomposite was prepared by simple mixing of Cu2O and Al2O3 NPs for the removal of Cd(II) ions from aqueous solution. Therefore, an efficient green, economical, facile, and eco-friendly synthesis method was employed, which improved the aggregation of individual metal oxide NPs. The chemical and physical properties of the nanocomposite were examined by different characterization techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Brunauer-Emmett-Teller (BET) surface area analysis. Furthermore, the performances of the nanoadsorbents for the adsorptive eradication of Cd2+ ions from water were investigated. The influence of pH, contact time, initial Cd quantity, and nanocomposite amount on adsorption effectiveness was carefully studied. The adsorption rates of the Cu2O/Al2O3 nanocomposite were rapid, and adsorption equilibrium was attained within 60 min for 97.36% removal of Cd(II) from water. The adsorption isotherm data were best fitted by the pseudo-second-order kinetic and Langmuir isotherm models with the highest adsorption ability of 4.48 mg/g. Therefore, the synthesized Cu2O/Al2O3 nanocomposite could be a potential candidate for a highly efficient adsorbent for heavy metal ion removal from aqueous solutions.

Green synthesis of multi-functional carbon dots from medicinal plant leaves for antimicrobial, antioxidant, and bioimaging applications.

In this research work, carbon dots (CDs) were synthesized from the renewable leaves of an indigenous medicinal plant by the one-pot sand bath method, Azadirachta indica. The synthesized CDs were characterized for its optical properties using UV-Vis, Fluorescence and Fourier transform infrared (FT-IR) spectrophotometry and for structural properties using dynamic light scattering (DLS), X-ray Diffraction (XRD) and high resolution Transmission electron microscopy (HR-TEM). The synthesized CDs exhibited concentration dependent biocompatibility when tested in mouse fibroblast L929 cell line. The EC50 values of biomedical studies, free radical scavenging activity (13.87 µgmL-1), and total antioxidant capacity (38 µgmL-1) proved CDs were exceptionally good. These CDs showed an appreciable zone of inhibition when examined on four bacterial (two gram-positive and gram-negative) and two fungal strains at minimum concentrations. Cellular internalisation studies performed on human breast cancer cells (MCF 7- bioimaging) revealed the applicability of CDs in bioimaging, wherein the inherent fluorescence of CDs were utilised. Thus, the CDs developed are potential as bioimaging, antioxidants and antimicrobial agents.

Synthesis of Carbon-Encapsulated Magnetic Iron Oxide Nanocomposites for Bioapplication.

Carbon-encapsulated Fe3O4 nanoparticles (NPs) were successfully synthesized from a single precursor using one-step solvothermal methods. X-ray diffraction and transmission electron microscopy were used to characterize the as-prepared NPs, and UV-visible absorbance spectroscopy was used to check their optical properties. The morphological results revealed that Fe3O4@C, quasi-spherical Fe3O4 particles encapsulated by carbon. In addition, the carbon-encapsulated Fe3O4 NPs were conjugated with folic acid (FA) to be used as biomarkers in the diagnosis and treatment of tumour cells. Fourier transform infrared spectroscopy and UV-visible spectroscopic techniques were used to confirm the conjugation process.

Heteroatom doped carbon dots with nanoenzyme like properties as theranostic platforms for free radical scavenging, imaging, and chemotherapy.

Carbon-based artificial nanoenzymes have gained increasing interest as emerging and promising nanotheranostic agents due to their biocompatibility, low cost, and straightforward production. Herein, a multifunctional Mn, N, and S incorporated carbon dots (MnNS:CDs) nanoenzyme exhibiting scavenging activity against reactive oxygen species (ROS) and reactive nitrogen species (RNS), photoluminescence quantum yield of 17.7%, and magnetic resonance imaging (MRI) contrast was explored. The optical, magnetic, and antioxidant properties of MnNS:CDs were then regulated by control over Mn incorporation to achieve higher photostability and antioxidant properties. Furthermore, conjugation of MnNS:CDs with hyaluronic acid (HA) (denoted as MnNS:CDs@HA) endowed them with high biocompatibility, which is validated by in vivo studies on zebrafish, and the ability to specifically target cluster determinant 44 (CD44)-overexpressing B16F1 cells, as verified by in vitro confocal and MRI studies. The MnNS:CDs@HA probe with therapeutic antioxidant and dual-modal imaging capability was further assessed for non-covalent binding of doxorubicin (DOX) as a model chemotherapeutic cancer drug. Results showed that targeted delivery and pH-dependent release of DOX elicited apparent cell toxicity (90%) toward B16F1 cancer cells when compared to free DOX treatment group (60%). Benefiting from their intrinsic antioxidant properties, and dual-modal imaging ability, the MnNS:CDs@HA nanocarrier is projected to improve non-invasive targeted diagnosis and therapy. STATEMENT OF SIGNIFICANCE: Carbon dots (CDs) have gained increasing interest as emerging and promising artificial functional nanomaterials that mimic the structures and functions of natural enzymes. In this work, Mn, N, and S incorporated CDs (MnNS:CDs) were synthesized using a one-pot microwave hydrothermal method to serve as fluorescent and magnetic resonance imaging probes, and catalase mimics in the reduction of the oxidative-stress related damage. Further conjugation of the probes with hyaluronic acid endows them with a good in vitro and in vivo biocompatibility as well as the capability to selectively target CD44-overexpressing cancer cells, as investigated by in vitro fluorescence, and magnetic resonance imaging. The dual-modal nanoprobe was then used to carry on doxorubicin through a non-covalent association. Favorably, targeted delivery, and pH-responsive release of doxorubicin enhanced cell killing efficiency by 50% as opposed to the free doxorubicin treatment group. The presented theranostic heteroatom doped CDs hold great promise for dual-modal imaging enabling accurate diagnosis coupled with therapeutic effect through free radical scavenging and chemotherapy.

Albumin-functionalized CuFeS2/photosensitizer nanohybrid for single-laser-induced folate receptor-targeted photothermal and photodynamic therapy.

Multimodal therapy is an emerging medical intervention to overcome the current limitation in cancer therapy combining treatment modalities with different mechanisms of action to eradicate tumors. This study demonstrates a targeted multifunctional bovine serum albumin (BSA)-functionalized CuFeS2/chlorin e6 (Ce6) for synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) effects. The CuFeS2 nanocrystals were synthesized through a simple heating-up approach and transferred into an aqueous phase using BSA in an ultrasonic-assisted microemulsion method. The as-prepared CuFeS2@BSA nanoparticles further conjugated with folic acid (FA) followed by attachment of Ce6 to form the Ce6:CuFeS2@BSA-FA nanohybrid with improved solubility and strong near-infrared (NIR) absorbance and fluorescence. It is the first report to fabricate the targeted Ce6:CuFeS2@BSA-FA hybrid and evaluates their synergistic PTT/PDT effect using a single laser. The Ce6:CuFeS2@BSA-FA hybrid showed lower toxicity in vitro (HeLa and HepG2 cells) and in vivo (zebrafish embryos), while they are selectively recognized and internalized by HeLa cells that over-express folate receptors. Compared to each modality applied separately, the combined single-laser-induced PTT and PDT treatment showed the enhanced generation of heat and reactive oxygen species (ROS) with synergistic cancer killing under 671 nm laser irradiation (10 min, 1 W/cm2). As a biocompatible targeted nanoprobe, the multifunctional nanohybrid holds promise in combined PDT/PTT synergistic therapy to achieve better efficacy.

Synthesis of Cisplatin(IV) Prodrug-Tethered CuFeS2 Nanoparticles in Tumor-Targeted Chemotherapy and Photothermal Therapy.

In this study, for the first time, CuFeS2 nanocrystals were successfully prepared through a facile noninjection-based synthetic strategy, by reacting Cu and Fe precursors with dodecanethiol in a 1-octadecene solvent. This one-pot noninjection strategy features easy handling, large-scale production, and high synthetic reproducibility. Following hyaluronic acid (HA) encapsulation, CuFeS2 nanocrystals coated with HA (CuFeS2@HA) not only readily dispersed in water and showed improved biocompatibility but also possessed a tumor-specific targeting ability of cancer cells bearing the cluster determinant 44 (CD44) receptors. The encapsulated CuFeS2@HA showed broad optical absorbance from the visible to the near-infrared (NIR) region and high photothermal conversion efficiencies of about 74.2%. They can, therefore, be utilized for the photothermal ablation of cancer cells with NIR light irradiation. In addition, toxicity studies in vitro (B16F1 and HeLa) and in vivo (zebrafish embryos), as well as in vitro blood compatibility studies, indicated that CuFeS2@HA show low cytotoxicity at the doses required for photothermal therapy. More importantly, CuFeS2@HA can be used as delivery vehicles for chemotherapy cisplatin(IV) prodrug forming CuFeS2@HA-Pt(IV). Their release profile revealed pH- and glutathione-mediated drug release from CuFeS2@HA-Pt(IV), which may minimize the side effects of the drug to normal tissues during therapy. Subsequent in vitro experiments confirmed that the use of CuFeS2@HA-Pt(IV) provides an enhanced and synergistic therapeutic effect compared to that from the use of either chemotherapy or photothermal therapy alone.

Magnetofluorescent Carbon Dots Derived from Crab Shell for Targeted Dual-Modality Bioimaging and Drug Delivery.

We propose a one-pot microwave-assisted pyrolysis method for fabrication of magnetofluorescent carbon quantum dots (MFCQDs), using a combination of waste crab shell and three different transition-metal ions, Gd3+, Mn2+, and Eu3+, referred to as Gd@CQDs, Mn@CQDs, and Eu@CQDs, respectively. Chitin from waste crab shell acted not only as a carbon source but also as a chelating ligand to form complexes with transition-metal ions. Gd@CQDs exhibited a high r1 relaxivity of 4.78 mM-1·s-1 and a low r2/r1 ratio of 1.33, suggesting that they show excellent potential as a T1 contrast agent. Mn@CQDs and Eu@CQDs showed high r2 relaxivity values of 140.7 and 28.32 mM-1·s-1, respectively, suggesting their potential for use as T2 contrast agents. Further conjugation of Gd@CQDs with folic acid (FA) enabled specific targeting to folate receptor-positive HeLa cells, as confirmed via in vitro magnetic resonance and fluorescence imaging. Doxorubicin (DOX) was selected as a model drug for conjugation with FA-Gd@CQDs. The as-prepared nanocomposites showed significantly higher cytotoxicity toward HeLa cells than free DOX. No apparent cytotoxicity was observed in vivo (zebrafish embryos) or in vitro (cell viability), suggesting that MFCQDs show potential for development as diagnostic probes or theranostic agents.

Synthetic strategies and biomedical applications of I-III-VI ternary quantum dots.

Surface modified and bioconjugated quantum dots (QDs) are of central importance in biomedical applications. In this regard, particularly I-III-VI QDs are of specific interest for biosensors, multimodal imaging, chemotherapy and for phototherapy in theranostic applications. Surface modification allows management of the physico-chemical properties, biocompatibility, and pharmacological properties. This review is anticipated to provide an introduction to new researchers about I-III-VI type QDs relating to their synthesis, optical properties, surface modification, bioconjugation, and their applications in biosensors, biological imaging, drug delivery, photothermal therapy and photodynamic therapy. We also highlight introducing magnetic metals and nanoparticles to these QDs for multimodal imaging applications and have addressed toxicity related issues. Finally, we summarize the results obtained and give a short outlook on future directions of I-III-VI based QDs for biomedical applications.

Rapid fabrication of carbon quantum dots as multifunctional nanovehicles for dual-modal targeted imaging and chemotherapy.

Herein, we synthesized an S, N, and Gd tri-element doped magnetofluorescent carbon quantum dots (GdNS@CQDs) within 10min by using a one-pot microwave method. Our results showed that these magnetofluorescent GdNS@CQDs have excellent fluorescent and magnetic properties. Moreover, GdNS@CQDs exhibited high stability at physiological conditions and ionic strength. These magnetofluorescent GdNS@CQDs were conjugated with a folic acid, denoted as FA-GdNS@CQDs, for targeting dual modal fluorescence/magnetic resonance (MR) imaging. The in vitro and in vivo studies confirmed the high biocompatibility and low toxicity of FA-GdNS@CQDs. FA-GdNS@CQDs enhanced the MR response as compared to that for commercial Gd-DTPA. The targeting capabilities of FA-GdNS@CQDs were confirmed in HeLa and HepG2 cells using in vitro fluorescence and MR dual modality imaging. Additionally, an anticancer drug, doxorubicin, was incorporated into the FA-GdNS@CQDs forming FA-GdNS@CQDs-DOX, which enables targeted drug delivery. Importantly, the prepared FA-GdNS@CQDs-DOX showed a high quantity of doxorubicin loading capacity (about 80%) and pH-sensitive drug release. The uptake into cancer cells and the intracellular location of the FA-GdNS@CQDs were observed by confocal laser scanning microscopy. We also successfully demonstrated in vivo fluorescence bio imaging of the FA-GdNS@CQDs, using zebrafish as an animal model. STATEMENT OF SIGNIFICANCE: In this manuscript, we reported a facial, rapid, and environmental friendly method to fabricate hetero atoms including gadolinium, nitrogen, and sulfur doped multi-functional magnetofluorescent carbon quantum dots (GdNS@CQDs) nanocomposite. These multifunctional GdNS@CQDs were conjugated with a folic acid for targeting dual modal fluorescence/magnetic resonance imaging. Additionally, an anticancer drug, doxorubicin, was incorporated into the nanocomposite forming FA-GdNS@CQDs-DOX, which enables targeted drug delivery. We have developed GdNS@CQDs with integrated functions for simultaneous in vitro cell imaging, targeting, and pH-sensitive controlled drug release in HeLa cells. Furthermore, we successfully demonstrated the use of this material for in vivo fluorescence imaging, using zebrafish as an animal model.