Direct sunlight induced room temperature synthesis of anticancer and catalytic silver nanoparticles by shrimp shell waste derived chitosan.

The use of marine waste derived chitosan (CS) for the synthesis of nanomaterials is considered as one of the effective routes for bio-waste management and recovering functional products. Herein, CS capped silver nanoparticles (Ag NPs-CS) with potential anticancer and dye pollutants adoption properties have been synthesized photochemically under direct sunlight. To obtain, CS, shrimp shell waste was subjected to a serious of standard demineralization, deproteinization and deacetylation processes. The electronic absorption peak (400 nm) denoting surface plasmonic resonance of Ag NPs and infrared peaks relevant to CS (3364 cm-1 of OH/NH2, 2932 cm-1 of CH, and 1647 cm-1 of -CO) exhibited peaks confirmed the formation of CS-Ag NPs. Ag NPs-CS exhibited anticancer activity against Human lung adenocarcinoma cell lines (A549), the maximum cell death noticed at the concentration of 20 µg/mL and 70 µg/mL was 20 and 52 %, respectively. An aqueous Ag NPs-CS (100 µg/mL) was degraded ≥95 % of mixed dye target solution (25 mg/mL) containing equal volume of cationic dye (Methylene blue and Rhodamine B) and anionic dye (methyl orange). Therefore, these findings suggest that the shrimp shell waste derived CS can be used for the synthesis of CS-Ag NPs with potential biomedical and environmental applications.

Facile synthesis of carbon/titanium oxide quantum dots from lignocellulose-rich mandarin orange peel extract via microwave irradiation: Synthesis, characterization and bio-imaging application.

A nanohybrid prepared from the lignocellulosic residue is a feasible approach to synthesize blue light emitting fluorescent doped TiO2 quantum dot nanocomposite (C-TiO2 QDs) by microwave techniques using Mandarin orange (Citrus reticulata) peel powder with titanium isopropoxide precursors. With a greater orange peel colloidal medium, the structure of the TiO2-NPs changed from a mixture of rutile and anatase phases to exclusively the anatase phase. The optical and morphological properties of as-prepared C-TiO2 QDs were characterized by HR-TEM, XRD, FT-IR, UV-visible, PL spectra, DLS, and Zeta potential techniques. The reaction condition was optimized by changing substrate composition, pH, and reaction time. C-TiO2 QDs exhibit outstanding stability at pH 7 and remain sustained for at least 180 days without aggregation. As prepared C-TiO2 QDs have distinct emission and excitation activities with an average particle size of 2.8 nm. Cell viability was performed on normal L929 cells, where it showed excellent biocompatibility (<90 %) even at the concentration of 200 µg/mL after 24 h treatment. Additionally, the synthesized C-TiO2 QDs were used with L929 cells as a fluorescent probe for bio-imaging applications. The results revealed that neither of the cell lines' morphologies had significantly changed, proving the biocompatibility of the synthetic C-TiO2 QDs.

N-Cholyl d-Penicilamine Micelles Templated Red Light-Emitting Silver Nanoclusters: Fluorometric Sensor for S2- Ions and Bioimaging Application Using Zebrafish Model.

Red-light-emitting silver nanoclusters (AgNCs) are recently emerged as a promising nanoprobe in the field of biomedical applications, because of their attractive properties, including brightness, luminescence stability, and better biocompatibility. In this report, we have developed highly water-soluble red-light-emitting AgNCs by using N-cholyl d-penicilamine (NCPA) as a biosurfactant at above the critical micelle concentration (CMC) at room temperature. Moreover, the NCPA was initially synthesized by demonstrating the reaction between cholic acid and d-penicilamine via a simple coupling reaction strategy. The primary and secondary critical micellar concentration (CMC) of NCPA surfactant was measured using pyrene (1 × 10-6 M) as a fluorescent probe, and the values were found to be 3.18 and 10.6 mM, respectively. Steady-state fluorescence measurements reveal that the prepared AgNCs shows the excitation and emission maxima at 365 and 672 nm, respectively, with a large Stokes shift (307 nm). The average lifetime measurements and quantum yield of the AgNCs were calculated to be 143.43 ns and 16.34%, respectively. Also, the red luminescent NCPA-templated AgNCs was synthesized in various protic and aprotic polar solvents, among which DMF and DMSO exhibit bright emission at longer wavelength as synthesized in aqueous medium. At higher concentration of AgNO3, bright luminescent and highly stable solid AgNCs was obtained with excitation and emission maxima at 607 and 711 nm, respectively. Furthermore, the synthesized AgNCs has been successfully utilized as a fluorescent probe for selective and sensitive detection of S2- ions at nanomolar level in water samples, showing its potential applicability for the detection of S2- ions in drinking, river, and tap water samples. Finally, toxicity and bioimaging studies of NCPA-templated AgNCs was demonstrated using zebrafish as in vivo model, showing no significant toxicity up to 200 µL/mL. The AgNCs-stained embryos exhibited red fluorescence with high intensity, which shows that AgNCs are stable in a living system.

Green Chemical Synthesis of N-Cholyl-L-Cysteine Encapsulated Gold Nanoclusters for Fluorometric Detection of Mercury Ions.

Herein we report a simple, single-step, cost-effective, environmentally friendly, and biocompatible approach using sodium salt of N-cholyl-L-cysteine (NaCysC) capped gold nanoclusters (AuNCs) with green emission properties at above the CMC in aqueous medium under UV-light irradiation. The primary and secondary CMC of NaCysC was found to be 4.6 and 10.7 mM respectively using pyrene as fluorescent probe. The synthesized AuNCs exhibit strong emission maxima at 520 nm upon excitation at 375 nm with a large Stokes shift of 145 nm. The surface functionality and morphology of NCs are studied by fourier transform infrared spectroscopy, dymanic light scattering studies and transmission electron microscopy. The formation of AuNCs was completed within 5 h and exhibit high stability for more than 6 months. The NaCysC templated AuNCs selectively quenches the Hg2+ ions with higher sensitivity in aqueous solution over the other metal ions. The fluorescence analysis of Hg2+ showed a wide linear range from 15 to 120 µM and a detection limit was found to be 15 nM.

Role of Surface Hydrophobicity of Dicationic Amphiphile-Stabilized Gold Nanoparticles on A549 Lung Cancer Cells.

Herein, we report the surface functionality of dicationic cysteamine conjugated cholic acid (DCaC), dicationic cysteamine conjugated deoxycholic acid (DCaDC), and dicationic cysteamine conjugated lithocholic acid (DCaLC) templated gold nanoparticles (AuNPs) on mammalian cells. The haemocompatibility of the synthesized NPs was evaluated by in vitro hemolysis and erythrocyte sedimentation rate using human red blood cells (RBCs). In all of the systems, no toxicity was observed on human erythrocytes (RBCs) up to the concentration of 120 µg/mL. The anticancer activity of these dicationic amphiphile-stabilized AuNPs on A549 lung cancer cells was demonstrated by in vitro cell viability assay, intracellular reactive oxygen species estimation by DCFH-DA, apoptosis analysis using AO-EtBr fluorescence staining, DNA fragmentation analysis by agarose gel electrophoresis, and western blot analysis of caspase-3 expression. These results suggest that the cytotoxicity of AuNPs to A549 cells increase with the dose and hydrophobicity of amphiphiles and were found to be in the order: DCaLC-AuNPs > DCaDC-AuNPs > DCaC-AuNPs.

Auric Chloride Induced Micellization on Fractal Patterned Dicationic Amphiphiles and Stabilization of Gold Nanoparticles.

The present article reports the development of sunlight-mediated rapid synthesis of bile acid derived dicationic amphiphiles, namely, dicationic cysteamine-conjugated cholic acid (DCaC), dicationic cysteamine-conjugated deoxycholic acid (DCaDC), and dicationic cysteamine-conjugated lithocholic acid (DCaLC) by adopting thiol-yne click chemistry approach. The auric chloride (AuHCl4) induced micellization of amphiphiles from fractal pattern to chainlike aggregates was examined by critical micelle concentration measurements, quenching studies, field emission scanning electron microscopy, and optical microscopy techniques. The micelles thus formed act as ideal templates for the stabilization of gold nanoparticles (AuNPs) and exhibit good stability for more than 6 months. The synthesized AuNPs were characterized using UV-visible spectroscopy, high-resolution transmission electron microscopy, DLS, zeta potential, and contact angle measurements. These NPs showed high salt tolerance, and the levels were found to be 420, 460, and 580 mM for DCaC-, DCaDC-, and DCaLC-capped AuNPs, respectively.

Hierarchical Self-Assembly of Bile-Acid-Derived Dicationic Amphiphiles and Their Toxicity Assessment on Microbial and Mammalian Systems.

A thiol-yne click chemistry approach was adopted for the first time to prepare highly water-soluble bile acid derived dicationic amphiphiles. The synthesized amphiphiles dicationic cysteamine conjugated cholic acid (DCaC), dicationic cysteamine conjugated deoxycholic acid (DCaDC), and dicationic cysteamine conjugated lithocholic acid (DCaLC) exhibited hierarchically self-assembled microstructures at various concentrations in an aqueous medium. Interestingly at below critical micellar concentration (CMC) the amphiphiles showed distinct fractal patterns such as fractal grass, microdendrites and fern leaf like fractals for DCaC, DCaDC and DCaLC respectively. The fractal dimension (Df) analysis indicated that the formation of fractal like aggregates is a diffusion limited aggregation (DLA) process. The preliminary aggregation studies such as determination of CMC, fluorescence quenching, wettability and contact angle measurements were elaborately investigated. The morphology of the aggregates were analyzed by SEM and OPM techniques. Further, we demonstrated the antimicrobial and hemolytic activity for the cationic amphiphiles. DCaC had potent antimicrobial activity and showed no toxicity on human RBCs indicating that DCaC could be used in biomedical applications, in addition to their industrial and laboratory applications such as detergency, surface cleaning, and disinfection agent.

Sodium cholate-templated blue light-emitting Ag subnanoclusters: in vivo toxicity and imaging in zebrafish embryos.

We report a novel green chemical approach for the synthesis of blue light-emitting and water-soluble Ag subnanoclusters, using sodium cholate (NaC) as a template at a concentration higher than the critical micelle concentration (CMC) at room temperature. However, under photochemical irradiation, small anisotropic and spherically shaped Ag nanoparticles (3-11 nm) were obtained upon changing the concentration of NaC from below to above the CMC. The matrix-assisted laser desorption ionization time-of-flight and electrospray ionization mass spectra showed that the cluster sample was composed of Ag4 and Ag6. The optical properties of the clusters were studied by UV-visible and luminescence spectroscopy. The lifetime of the synthesized fluorescent Ag nanoclusters (AgNCs) was measured using a time-correlated single-photon counting technique. High-resolution transmission electron microscopy was used to assess the size of clusters and nanoparticles. A protocol for transferring nanoclusters to organic solvents is also described. Toxicity and bioimaging studies of NaC templated AgNCs were conducted using developmental stage zebrafish embryos. From the survival and hatching experiment, no significant toxic effect was observed at AgNC concentrations of up to 200 µL/mL, and the NC-stained embryos exhibited blue fluorescence with high intensity for a long period of time, which shows that AgNCs are more stable in living system.

Label free fluorometric characterization of DNA interaction with cholate capped gold nanoparticles using ethidium bromide as a fluorescent probe.

We demonstrated label free ethidium bromide assisted characterization of DNA interaction with cholate capped AuNPs. Interactions between ss/ds DNA and AuNPs with two different lengths (0.5 and 0.85 kb) were analyzed through fluorescence spectrophotometer and agrose gel electrophoresis analysis. Further results were confirmed by UV-globally visible spectrophotometer, DLS and TEM. As 0.5 and 0.85 kb of ssDNA effectively interacted with AuNPs through the van der Waals interaction which consequently led to the prevention of salt induced aggregation, EtBr intercalations as well as fluorescence shift with less binding constant 0.098 and 0.108 µM, respectively. On the contrary, the same length of dsDNA (0.5 and 0.85 kb) not interacted with AuNPs which led to the NPs aggregation, EtBr intercalation as well as fluorescence shift with increased binding constant 0.166 and 0.599 µM, respectively. This approach helped to understand the mode of interactions of DNA with cholate capped AuNPs without any modifications in a simple method and the results could be readout through the naked eye under the UV transilluminator.