One-pot synthesis optimization of thiol-capped SnS and SnS/ZnS QDs for photocatalytic degradation of Rhodamine 6G.

Interest in SnS-based quantum dots (QDs) has increased due to their low toxicity, widespread natural availability, and superior electro-optical characteristics suitable for photodegradation applications. Herein, we report the synthesis of SnS-based QDs using thiourea and tin (II)chloride as salt precursors. The study explored the impact of various synthetic parameters such as pH, capping ligand, Sn:S ratio, reaction solvent, and ZnS shell on the optical characteristics of the synthesized QDs. The optimal QDs properties were observed at pH = 3 and Sn:S ratio = 1:1. Transmission electron microscopy analysis showed spherical nanoparticles, while the Fourier Transform Infrared spectroscopy revealed QDs with thiol capping. Time-dependent studies revealed that when the QDs were synthesized using propylene glycol, the ultraviolet-visibile (UV-vis) spectrum exhibited an increase in absorbance over time and improved stability compared to aqueous synthesized QDs. SnS/ZnS QDs capped with 3-mercaptopropanoic acid exhibited improved photoluminscence (PL) emissions, stability, and aqueous dispersion compared to glutathione and l-Cysteine as thiol-capping agents. The photocatalytic activity of SnS/ZnS QDs was assessed against Rhodamine 6G and increased to 65 % when passivated with ZnS compared to 31 % for the core SnS QDs. With the given findings, this study supports the stability and effectiveness of the SnS/ZnS QDs as a viable dye degradant.

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.

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.

The Therapeutic Effect of Second Near-Infrared Absorbing Gold Nanorods on Metastatic Lymph Nodes via Lymphatic Delivery System.

Photothermal therapy has been established recently as a non-invasive treatment protocol for cancer metastatic lymph nodes. Although this treatment approach shows efficient tumour ablation towards lymph node metastasis, the monitoring and reporting of treatment progress using the lymphatic delivery channel still need to be explored. Herein, we investigated the anti-tumour effect of pegylated gold nanorods with a high aspect ratio (PAuNRs) delivered via the lymphatic route in a mouse model. In this study, breast carcinoma (FM3A-Luc) cells were inoculated in the subiliac lymph node (SiLN) to induce metastasis in the proper axillary lymph node (PALN). The treatment was initiated by injecting the PAuNRs into the accessory axillary lymph node (AALN) after tumour metastasis was confirmed in the PALN followed by external NIR laser irradiation under a temperature-controlled cooling system. The anti-tumour impact of the treatment was evaluated using an in vivo bioluminescence imaging system (IVIS). The results showed a time-dependent reduction in tumour activity with significant treatment response. Tumour growth was inhibited in all mice treated with PAuNRs under laser irradiation; results were statistically significant (** p < 0.01) even after treatment was concluded on day 3. We believe that this non-invasive technique would provide more information on the dynamics of tumour therapy using the lymphatically administered route in preclinical studies.

Diamond Nanoparticles-Porphyrin mTHPP Conjugate as Photosensitizing Platform: Cytotoxicity and Antibacterial Activity.

Conjugation of photosensitizers (PS) with nanoparticles has been largely used as a strategy to stabilize PS in the biological medium resulting in photosensitizing nanoparticles of enhanced photoactivity. Herein, (Meso-5, 10, 15, 20-tetrakis (3-hydroxyphenyl) phorphyryn (mTHPP) was conjugated with diamond nanoparticles (ND) by covalent bond. Nanoconjugate ND-mTHPP showed suitable stability in aqueous suspension with 58 nm of hydrodynamic diameter and Zeta potential of -23 mV. The antibacterial activity of ND-mTHPP was evaluated against Escherichia coli for different incubation times (0-24 h). The optimal activity was observed after 2 h of incubation and irradiation (660 nm; 51 J/cm2) performed right after the addition of ND-mTHPP (100 µg/mL) to the bacterial suspension. The inhibitory activity was 56% whereas ampicillin at the same conditions provided only 14% of bacterial growth inhibition. SEM images showed agglomerate of ND-mTHPP adsorbed on the bacterial cell wall, suggesting that the antimicrobial activity of ND-mTHPP was afforded by inducing membrane damage. Cytotoxicity against murine embryonic fibroblast cells (MEF) was also evaluated and ND-mTHPP was shown to be noncytotoxic since viability of cells cultured for 24 h in the presence of the nanoconjugate (100 µg/mL) was 78%. Considering the enhanced antibacterial activity and the absence of cytotoxic effect, it is possible to consider the ND-mTHPP nanoconjugate as promising platform for application in antimicrobial photodynamic therapy (aPDT).

Cytotoxicity, fluorescence tagging and gene-expression study of CuInS/ZnS QDS - meso (hydroxyphenyl) porphyrin conjugate against human monocytic leukemia cells.

The toxicity of heavy metals present in binary semiconductor nanoparticles also known as quantum dots (QDs) has hindered their wide applications hence the advent of non-toxic ternary quantum dots. These new group of quantum dots have been shown to possess some therapeutic action against cancer cell lines but not significant enough to be referred to as an ideal therapeutic agent. In this report, we address this problem by conjugating red emitting CuInS/ZnS QDs to a 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin -photosensitizer for improved bioactivities. The glutathione capped CuInS/ZnS QDs were synthesized in an aqueous medium using a kitchen pressure cooker at different Cu: In ratios (1:4 and 1:8) and at varied temperatures (95 °C, 190 °C and 235 °C). Optical properties show that the as-synthesized CuInS/ZnS QDs become red-shifted compared to the core (CuInS) after passivation with emission in the red region while the cytotoxicity study revealed excellent cell viability against normal kidney fibroblasts (BHK21). The highly fluorescent, water-soluble QDs were conjugated to 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin (mTHPP) via esterification reactions at room temperature. The resultant water-soluble conjugate was then used for the cytotoxicity, fluorescent imaging and gene expression study against human monocytic leukemia cells (THP-1). Our result showed that the conjugate possessed high cytotoxicity against THP-1 cells with enhanced localized cell uptake compared to the bare QDs. In addition, the gene expression study revealed that the conjugate induced inflammation compared to the QDs as NFKB gene was over-expressed upon cell inflammation while the singlet oxygen (1O2) study showed the conjugate possessed large amount of 1O2, three times than the bare porphyrin. Thus, the as-synthesized conjugate looks promising as a therapeutic agent for cancer therapy.

Facile, large scale synthesis of water soluble AgInSe2/ZnSe quantum dots and its cell viability assessment on different cell lines.

I-III-VI chalcopyrite ternary quantum dots have emerged as a good alternative over the conventional II-VI and IV-VI chalcogenide binary QDs that usually consist of heavy metals such as Cd and Pb which has limited their bioapplications. Among the chalcopyrite QDs, AgInSe2 QDs has been the least developed due to the imbalanced cation reactivity, unwanted impurities, broad size distribution and resultant large particle sizes. In addition, the cell viability of these QDs still needs to be investigated on different cell lines both normal and cancerous ones. Herein, large-scale synthesis of water-soluble thioglycolic acid (TGA) capped and gelatin-stabilized AgInSe2 (AISe) core and AgInSe2/ZnSe (AISe/ZnSe) core/shell QDs in the absence of an inert atmosphere and their cell viability against different cell lines are reported. The optical and structural characteristics of the as-synthesized QDs were investigated by UV-visible (vis) absorption, photoluminescence (PL) and Fourier-transmission infrared (FTIR) spectroscopies, dynamic light scattering (DLS), X-ray diffraction (XRD), and high-resolution transmission electron microscope (HRTEM) techniques. Growth of ZnSe shell on the core AISe resulted in the blue shifting of the emission maximum position with the increased PL intensity. The QDs are small and spherical in shape with an average particle diameter of 2.8 nm and 3.2 nm for AISe and AISe/ZnSe QDs respectively. The in vitro cell viability assay revealed that the as-synthesized AISe/ZnSe QDs are not toxic towards cancerous (HeLa -cervical cancer and A549-lung cancer) and normal (BHK21 -Kidney) cell lines.

Synthesis of meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS4) - CuInS/ZnS quantum dots conjugate as an improved photosensitizer.

BACKGROUND:  Metal-free, water-soluble and highly stable meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS4) has been studied for their singlet oxygen quantum yield. However, TPPS4 suffers from inherent shortcomings. To address these, TPPS4 was conjugated to ternary copper indium sulphide/ zinc sulphide (CuInS2/ZnS) quantum dots (QDs). PURPOSE:  We herein report for the first time the synthesis of TPPS4-CuInS/ZnS QDs conjugate as an improved photosensitizer. METHODS:  Water-soluble TPPS4 was synthesized from tetraphenylporphyrin (TPPH2) after silica-gel purification. The CuInS/ZnS QDs were synthesized by hydrothermal method at a Cu:In ratio of 1:4. The porphyrin-QDs conjugate was formed via the daggling sulfonyl bond of the porphyrin and amine bond of the QDs. The effect of pH on the optical properties of TPPS4 was evaluated. The effect of Zn:Cu + In ratio on the ZnS shell passivation was examined to reduce structural defects on the as-synthesized QDs. RESULTS: Various spectroscopic techniques were used to confirm the successful conversion of the organic TPPH2 to water-soluble TPPS4. The singlet oxygen generation evaluation shows an improved singlet oxygen quantum yield from 0.19 for the porphyrin (TPPS4) alone to 0.69 after conjugation (CuInS/ZnS-TPPS4) with an increase in the reaction rate constant (k (s-1)).

Porphyrin as Diagnostic and Therapeutic Agent.

The synthesis and application of porphyrins has seen a huge shift towards research in porphyrin bio-molecular based systems in the past decade. The preferential localization of porphyrins in tumors, as well as their ability to generate reactive singlet oxygen and low dark toxicities has resulted in their use in therapeutic applications such as photodynamic therapy. However, their inherent lack of bio-distribution due to water insolubility has shifted research into porphyrin-nanomaterial conjugated systems to address this challenge. This has broadened their bio-applications, viz. bio-sensors, fluorescence tracking, in vivo magnetic resonance imaging (MRI), and positron emission tomography (PET)/CT imaging to photo-immuno-therapy just to highlight a few. This paper reviews the unique theranostic role of porphyrins in disease diagnosis and therapy. The review highlights porphyrin conjugated systems and their applications. The review ends by bringing current challenges and future perspectives of porphyrin based conjugated systems and their respective applications into light.

Applications of functionalized nanomaterials in photodynamic therapy.

Specially designed functionalized nanomaterials such as superparamagnetic iron oxide, gold, quantum dots and up- and down-conversion lanthanide series nanoparticles have consistently and completely revolutionized the biomedical environment over the past few years due to their specially inferring properties, such as specific drug delivery, plasmonic effect, optical and imaging properties, therapeutic thermal energy productionand excellent irresistible cellular penetration. These properties have been used to improve many existing disease treatment modalities and have led to the development of better therapeutic approaches for the advancement of the treatment of critical human diseases, such as cancers and related malaise. In photodynamic therapy, for example, where the delivery of therapeutic agents should ideally avoid toxicity on nearby healthy cells, superparamagnetic iron oxide nanoparticles have been shown to be capable of making photodynamic therapy (PDT) prodrugs and their associative targeting moieties tumor-specific via their unique response to an external magnetic fields. In this review, the nanomaterials commonly employed for the enhancement of photodynamic therapy are discussed. The review further describes the various methods of synthesis and characterization of these nanomaterials and highlights challenges for improving the efficacy of PDT in the future.