Prediction and optimizing of methylene blue sequestration to activated charcoal/magnetic nanocomposites using artificial neutral network and response surface methodology.

Green synthesized magnetic nanoparticles (MNPs) linked with activated charcoal (AC) (AC/Fe3O4 NCs) were exploited for methylene blue (MB) confiscation in this study. The AC/Fe3O4 NCs produced were characterized using TEM, FTIR, UV/Vis and XRD spectrometry. The Response-Surface-Methodology (RSM) was utilized to improve the experimental data for the MB sorption to AC/Fe3O4 NCs, with 20 experimental runs implemented through a central composite design (CCD) to assess the effect of sorption factors-initial MB concentration, pH and sorbent dosage effects on the response (removal-effectiveness). The quadratic model was discovered to ideally describe the sorption process, with an R2 value of 0.9857. The theoretical prediction of the experimental data using the Artificial-Neural-Network (ANN) model showed that the Levenberg-Marquardt (LM) had a better performance criterion. Comparison between the modelled experimental and predicted data showed also that the LM algorithm had a high R2 of 0.9922, which showed NN model applicability for defining the sorption of MB to AC/Fe3O4 NCs with practical precision. The results of the non-linear fitting (NLF) of both isotherm and kinetic models, showed that the sorption of MB to AC/Fe3O4 NCs was perfectly described using the pseudo-second-order (PSOM) and Freundlich (FRHM) models. The estimated optimum sorption capacity was 455 mg g-1. Thermodynamically, the sorption of MB to AC/Fe3O4 NCs was shown to be non-spontaneous and endothermic.

Porphyrin as a Cryoprotectant for Graphene Oxide-Coated Gold Nanorods to Produce Conjugated Product with Improved Stability and Opto-Phototherapeutic Properties.

Graphene oxide (GO) as a coating material for gold nanorods (AuNRs) has gained interest in reducing toxicity and improving the photothermal profiling of AuNRs. However, there is still a challenge regarding the storage of colloidal suspensions of GO-coated AuNRs (GO@AuNRs). Hence, the conjugation of GO@AuNRs to meso-tetra-(4-sulfonatophenyl)porphyrin (TPPS4), an anionic water-soluble porphyrin, has been reported to enhance their re-dispensability and improve their phototherapeutic properties. The AuNRs and GO were synthesised using seed-mediated and Hummers' methods, respectively. The GO@AuNRs were conjugated to TPPS4 and characterised using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, zeta analyser, dynamic light scattering (DLS), photoluminescence spectroscopy (PL), x-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FTIR) before freeze-drying. The results showed that the AuNRs were sandwiched between GO and TPPS4. After freeze-drying, the freeze-dried conjugate was dispensed in deionised water without adding cryoprotectants and its properties were compared to those of the unfreeze-dried conjugate. The results showed that the freeze-dried conjugate contained similar optical properties to the unfreeze-dried conjugate. However, the bare GO@AuNRs showed a change in the optical properties after freeze-drying. These results revealed that porphyrin is an excellent additive to reduce the freeze-drying stress tolerance of GO@AuNRs. The freeze-dried conjugate also showed both singlet oxygen and photothermal properties of GO@AuNRs and porphyrin. These results indicated that the freeze-dried conjugate is a promising dual photodynamic and photothermal agent, and porphyrin can act as a cryoprotectant.

Highly Toughened Nanostructured Self-Assembled Epoxy-Based Material-Correlation Study between Nanostructured Morphology and Fracture Toughness-Impact Characteristics.

We present an efficient and effective method for preparing a novel self-assembled nanostructured material with high toughness and impact strength from a blend of di-glycidyl ether of bisphenol-A (DGEBA) and epoxidized poly(styrene-block-butadiene-block-styrene) (eSBS55) tri-block copolymer. The field emission scanning electron microscopy and transmission electron microscope results show the nanostructured morphological characteristics of the blends. This study achieved the highest fracture toughness, with a fracture toughness in the form of critical stress intensity factors (KIC) value of 2.54 MPa m1/2, in epoxy/block copolymer blends compared to previous works in the field. The impact strength also increased by 116% compared to neat epoxy. This is a major advancement in epoxy toughening due to the use of a single secondary phase. The resulting highly tough and impact-resistant material is a promising candidate for coating applications in industries such as flooring, building, aerospace, and automobiles.

Photodynamic Therapy and Antibacterial Activities of a Novel Synthesized Quaternary Zn-Cu-In-S/ZnS QDs- mTHPP Porphyrin Conjugate.

Background: Photodynamic therapy (PDT) is a non-invasive treatment modality that destroys abnormally growing cells or microorganisms. Porphyrins are used as photosensitizers in PDT; however, their clinical application has been limited by their poor water solubility, resulting in aggregation and low quantum yields of reactive oxygen species (ROS). Methods: To overcome these limitations and improve PDT efficacy, we herein report the conjugation of ZnCuInS/ZnS (ZCIS/ZnS) quantum dots (QDs) to 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin (mTHPP). The optimal conditions for QDs porphyrin conjugation formation were systematically evaluated. Discussion: This study further assessed the PDT efficacy and antibacterial potency of the synthesized ZCIS/ZnS-mTHPP conjugates. The PDT efficacy of the QDs, mTHPP, and conjugate was evaluated against the murine metastatic melanoma (B16 F10 Nex2) cell line. This was performed with and without LED irradiation. Results: The conjugate exhibited the highest reduction in cell viability following LED irradiation (72%) compared to the bare QDs (19%) and mTHPP (1%). Antimicrobial studies conducted on E. coli showed that the conjugation exhibits a higher antibacterial effect than the bare QDs, even without light. Conclusion: The results suggest that conjugate is a promising class of materials for anti-cancer and antimicrobial PDT.

Thermal and Medium Stability Study of Polyvidone-Modified Graphene Oxide-Coated Gold Nanorods with High Photothermal Efficiency.

Coating gold nanorods (AuNRs) with different materials, such as polymers and graphene-based materials, has improved their biocompatibility. However, these materials have been shown to cause the instability of AuNRs in thermal and culture mediums. In addressing this issue, we herein report the synthesis, thermal and culture medium stability, and photothermal profiling of Polyvidone (PVP)-modified graphene oxide (GO)-coated AuNRs (mGO@AuNRs). The AuNRs, with a size of 40.70 nm × 9.16 nm and absorbing at 820 nm, were coated with PVP, GO, and mGO. The colloidal stability of the nanocomposites was tested in three commonly used cell culture mediums: the Roswell Park Memorial Institute 1640 (RPMI-1640), Dulbecco's Modified Eagle Medium, (DMEM) and Dulbecco's phosphate-buffered saline (PBS) using UV-Vis-NIR and dynamic light scattering. The GO-based nanocomposites were stable compared to PVP@AuNRs and AuNRs in all mediums. The photothermal profiling of mGO@AuNRs showed higher heat production, with the photothermal conversion efficiency of 54.8%, which is higher than the bare AuNRs, GO@AuNRs, and PVP@AuNRs. In addition, the mGO@AuNRs also showed good thermal stability at 70 °C for more than 24 h. These results present the dual coating of PVP and GO as excellent stabilising agents for AuNRs with good photothermal profiling.

Photothermal Conversion Profiling of Large-Scaled Synthesized Gold Nanorods Using Binary Surfactant with Hydroquinone as a Reducing Agent.

Photothermal application of gold nanorods (AuNRs) is widely increasing because of their good photothermal conversion efficiency (PCE) due to local surface plasmon resonance. However, the high concentration of hexadecyltrimethylammonium bromide used in the synthesis is a concern. Moreover, the mild and commonly used reducing agent-ascorbic acid does not reduce the Au(I) to A(0) entirely, resulting in a low yield of gold nanorods. Herein we report for the first time the PCE of large-scaled synthesized AuNRs using the binary surfactant seed-mediated method with hydroquinone (HQ) as the reducing agent. The temporal evolution of the optical properties and morphology was investigated by varying the Ag concentration, HQ concentration, HCl volumes, and seed solution volume. The results showed that the seed volume, HQ concentration, and HCl volume played a significant role in forming mini-AuNRs absorbing in the 800 nm region with a shape yield of 87.7%. The as-synthesized AuNRs were successfully up-scaled to a larger volume based on the optimum synthetic conditions followed by photothermal profiling. The photothermal profiling analysis showed a temperature increase of more than 54.2 °C at 2.55 W cm-2 at a low optical density (OD) of 0.160 after 630 s irradiation, with a PCE of approximately 21%, presenting it as an ideal photothermal agent.

Graphene Oxide-Gold Nanorods Nanocomposite-Porphyrin Conjugate as Promising Tool for Cancer Phototherapy Performance.

The cancer mortality rate has increased, and conventional cancer treatments are known for having many side effects. Therefore, it is imperative to find a new therapeutic agent or modify the existing therapeutic agents for better performance and efficiency. Herein, a synergetic phototherapeutic agent based on a combination of photothermal and photodynamic therapy is proposed. The phototherapeutic agent consists of water-soluble cationic porphyrin (5,10,15,20-tetrakis(N-methylpyridinium-3-yl)porphyrin, TMePyP), and gold nanorods (AuNRs) anchored on graphene-oxide (GO) sheet. The TMePyP was initially synthesized by Adler method, followed by methylation, while GO and AuNRs were synthesized using Hummer's and seed-mediated methods, respectively. The structural and optical properties of TMePyP were confirmed using UV-Vis, zeta analyzer, PL, FTIR and NMR. The formation of both GO and AuNRs was confirmed by UV-Vis-NIR, FTIR, TEM and zeta analyzer. TMePyP and AuNRs were anchored on GO to form GO@AuNRs-TMePyP nanocomposite. The as-synthesized nanocomposite was stable in RPMI and PBS medium, and, on irradiation, produced high heat than the bare AuNRs, with high photothermal efficiency. In addition, the nanocomposite produced higher singlet oxygen than TMePyP with high biocompatibility in the absence of light. These results indicated that the as-synthesized nanocomposite is a promising dual photodynamic and photothermal agent for cancer therapy.

Synthesis of NIR-II Absorbing Gelatin Stabilized Gold Nanorods and Its Photothermal Therapy Application against Fibroblast Histiocytoma Cells.

The excellent photothermal properties of gold nanorods (Au-NRs) make them one of the most researched plasmonic photothermal nanomaterials. However, their biological applications have been hampered greatly due to surfactant-induced cytotoxicity. We herein report a simple synthesis of highly biocompatible gelatin stabilized Au-NRs (gelatin@Au-NRs) to address this issue. The optical and structural properties of the as-synthesized gelatin@Au-NRs were investigated by Zetasizer, Ultraviolet-Visible-Near Infrared (UV-Vis-NIR) spectroscopy, high-resolution transmission electron microscopy (HR-TEM), and Fourier transform infrared spectroscopy (FTIR). The as-synthesized gelatin@Au-NRs were highly crystalline and rod-like in shape with an average length and diameter of 66.2 ± 2.3 nm and 10 ± 1.6 nm, respectively. The as-synthesized gelatin@Au-NRs showed high stability in common biological media (phosphate buffer saline and Dulbecco's Modified Eagle's Medium) compared to CTAB capped Au-NRs. Similarly, the gelatin@Au-NRs showed an improved heat production and outstanding cell viability against two different cancer cell lines; KM-Luc/GFP (mouse fibroblast histiocytoma cell line) and FM3A-Luc (breast carcinoma cell line) compared to CTAB capped Au-NRs and PEG@Au-NRs. An in vitro photothermal therapy study against KM-Luc/GFP showed that gelatin@Au-NRs effectively destroys the cancer cells.