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.

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.

Biosynthesis of Smaller-Sized Platinum Nanoparticles Using the Leaf Extract of Combretum erythrophyllum and Its Antibacterial Activities.

Nanobiotechnology is a promising field in the development of safe antibiotics to combat the increasing trend of antibiotic resistance. Nature is a vast reservoir for green materials used in the synthesis of non-toxic and environmentally friendly nano-antibiotics. We present for the first time a facile, green, cost-effective, plant-mediated synthesis of platinum nanoparticles (PtNPs) using the extract of Combretum erythrophyllum (CE) plant leaves. The extract of CE served as both a bio-reductant and a stabilizing agent. The as-synthesized PtNPs were characterized using ultraviolet-visible (UV-Vis) absorption spectroscopy, high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and dynamic light scattering (DLS) techniques. The HR-TEM image confirmed that the PtNPs are ultrasmall, spherical, and well dispersed with an average particle diameter of 1.04 ± 0.26 nm. The PtNPs showed strong antibacterial activities against pathogenic Gram-positive Staphylococcus epidermidis (ATCC 14990) at a minimum inhibitory concentration (MIC) of 3.125 µg/mL and Gram-negative Klebsiella oxytoca (ATCC 8724) and Klebsiella aerogenes (ATCC 27853) at an MIC value of 1.56 µg/mL. The CE-stabilized PtNPs was mostly effective in Klebsiella species that are causative organisms in nosocomial infections.

Diagnosis of Prostate Cancer and Prostatitis Using near Infra-Red Fluorescent AgInSe/ZnS Quantum Dots.

The link between the microbiome and cancer has led researchers to search for a potential probe for intracellular targeting of bacteria and cancer. Herein, we developed near infrared-emitting ternary AgInSe/ZnS quantum dots (QDs) for dual bacterial and cancer imaging. Briefly, water-soluble AgInSe/ZnS QDs were synthesized in a commercial kitchen pressure cooker. The as-synthesized QDs exhibited a spherical shape with a particle diameter of 4.5 ± 0.5 nm, and they were brightly fluorescent with a photoluminescence maximum at 705 nm. The QDs showed low toxicity against mouse mammary carcinoma (FM3A-Luc), mouse colon carcinoma (C26), malignant fibrous histiocytoma-like (KM-Luc/GFP) and prostate cancer cells, a greater number of accumulations in Staphylococcus aureus, and good cellular uptake in prostate cancer cells. This work is an excellent step towards using ternary QDs for diagnostic and guided therapy for prostate cancer.

Facile Green, Room-Temperature Synthesis of Gold Nanoparticles Using Combretum erythrophyllum Leaf Extract: Antibacterial and Cell Viability Studies against Normal and Cancerous Cells.

We herein report a facile, green, cost-effective, plant-mediated synthesis of gold nanoparticles (AuNPs) for the first time using Combretum erythrophyllum (CE) plant leaves. The synthesis was conducted at room temperature using CE leaf extract serving as a reducing and capping agent. The as-synthesized AuNPs were found to be crystalline, well dispersed, and spherical in shape with an average diameter of 13.20 nm and an excellent stability of over 60 days. The AuNPs showed broad-spectrum antibacterial activities against both pathogenic Gram-positive (Staphylococcus epidermidis (ATCC14990), Staphylococcus aureus (ATCC 25923), Mycobacterium smegmatis (MC 215)) and Gram-negative bacteria (Proteus mirabilis (ATCC 7002), Escherichia coli (ATCC 25922), Klebsiella pneumoniae (ATCC 13822), Klebsiella oxytoca (ATCC 8724)), with a minimum inhibition concentration of 62.5 µg/mL. In addition, the as-synthesized AuNPs were highly stable with exceptional cell viability towards normal cells (BHK- 21) and cancerous cancer cell lines (cervical and lung cancer).

Preparation of Graphene oxide- CuInS2/ZnS Quantum dots Nanocomposite as "Turn-On" Fluorescent Probe for the Detection of Polycyclic Aromatic Hydrocarbons in Aqueous Medium.

Graphene oxide is well known for its adsorption properties with aromatic compounds. In this study, graphene oxide and eco-friendly ternary CuInS2/ZnS QDs were used to prepare graphene oxide-qunatum dots (GO-QDs) nanocomposite via in-situ method. The composite was characterized using ultraviolet-visible (UV-Vis) spectroscopy, photoluminescence (PL) spectroscopy, transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) spectroscopy. The effect of the polycyclic aromatic hydrocarbons (PAHs) on the PL properties of the nanocomposite was investigated. The results showed that the addition of PAHs increased the PL intensity of the nanocomposite. This "turn-on" fluorescence approach can be used for the successful detection of PAHs in aqueous media.

Green Synthesis of Sodium Alginate Capped -CuInS2 Quantum Dots with Improved Fluorescence Properties.

CuInS2 (CIS) quantum dots (QDs) are known to be ideal fluorophores based on their low toxicity and tunable emission. However, due to low quantum yield (QY) and photostability, the surface is usually passivated by a higher bandgap shell (e.g. ZnS). This always resulted in a blue-shifted emission position which is not usually favourable for biological imaging. To address this problem, we herein report the passivation of green synthesized near infra-red emitting glutathione (GSH) capped CuInS2 QDs using different concentration of sodium alginate (SA) at different temperatures. The as-synthesized QDs are small (~ 3.2 nm), highly crystalline and emitted in the near infra-red region. The optical results showed a 36% increase in photostability and a 2-fold increase in quantum yield at ratio 1:8 (SA: CIS) which is suitable for prolonged biological imaging applications. Transmission electron microscope and X-ray diffraction (XRD) analyses showed that the materials are highly crystalline without any change in shape and size after passivation with the biopolymer. Graphical Abstract.

Sodium alginate passivated CuInS2/ZnS QDs encapsulated in the mesoporous channels of amine modified SBA 15 with excellent photostability and biocompatibility.

We herein report the synthesis of CuInS2/ZnS (CIS/ZnS) quantum dots (QDs) via a greener method followed by sodium alginate (SA) passivation and encapsulation into mesoporous channels of amine modified silica (SBA15-NH2) for improved photostability and biocompatibility. The as-synthesized CIS/ZnS QDs exhibited near infrared emission even after SA passivation and silica encapsulation. Transmission electron microscopy (TEM) and Small angle X-ray diffraction (XRD) revealed the mesoporous nature of the SBA-15 remained stable after loading with the SA-CIS/ZnS QDs. The effective encapsulation of SA-CIS/ZnS QDs inside the pores of SBA15-NH2 matrix was confirmed by Brunauer-Emmett-Teller (BET) pore volume analysis while the interaction between the QDs and SBA15-NH2 was confirmed using Fourier transform infrared (FTIR) spectroscopy. The photostability of the QDs was greatly enhanced after these modifications. The resultant SA-CIS/ZnS-SBA15-NH2 (QDs-silica) composite possessed remarkable biocompatibility towards lung cancer (A549) and kidney (HEK 293) cell lines making it a versatile material for theranostic applications.