Melamine-Formaldehyde Polymer-Based Nanocomposite for Sunlight-Driven Photodegradation of Multiple Dyes and Their Mixture.

Cadmium sulfide (CdS)-decorated, cross-linked melamine-formaldehyde polymer-based nanocomposite (MFP-CdS) has been synthesized. MFP-CdS is utilized here as a photoactive material for the photodegradation of six model organic dyes and their mixture in an aqueous medium in the presence of sunlight. The half-life values from the kinetic study of multiple dyes strongly support the importance of sunlight on the fast degradation of all six dyes compared to bulb light and control (dark) conditions. A comparative 1H NMR analysis of the dyes and their degraded products has been performed to support the breakdown of the aromatic framework of organic dyes using MFP-CdS in sunlight. The mechanisms involved in the photodegradation of dyes have been investigated based on radical trapping studies that support the significant involvement of superoxide radicals along with holes. Moreover, the dye removal efficiency using MFP-CdS from real industrial wastewater samples is evaluated via the external spiking of organic dyes and their mixture in unknown industrial effluents where they showed similar photodegradation results. Based on the high recyclability of MFP-CdS, these are used for multiple cycles.

Fluorescent Carbon Nano-onion as Bioimaging Probe.

Concentrically arranged multilayered fullerenes exhibiting onion-like morphology are popularly known as carbon nano-onion (CNO) and are useful in bioimaging application. On the basis of the origin of the fluorescence, the CNO-based nanoprobes are classified into type I and type II. The type I CNO-based nanoprobe needs a secondary moiety such as organic dyes or an amine functionalization at its surface to induce the fluorescence. On the other hand, the emission in type II does not originate from such an external surface passivating agent. The CNO-based system not only shows structural similarity to the well-known multiwalled carbon nanotube but is also a bit more advantageous because of its low cytotoxicity. These features enable their prolonged use in the biological system for imaging purposes. In particular, we have covered the aspects of synthesis, surface functionalization, the origin of fluorescence, and biocompatibility. In addition, recent developments directed toward in vitro and in vivo imaging studies by utilizing CNO-based nanoprobes are summarized here.

N, S-codoped Carbon Dots for Nontoxic Cell Imaging and As a Sunlight-Active Photocatalytic Material for the Removal of Chromium.

Nitrogen-sulfur codoped carbon dots (NSCD) were synthesized via a single-step microwave-assisted method having a fluorescence quantum yield of ∼12%. The NSCD has been proven to be nontoxic and utilized as a fluorescent imaging nanoprobe for cancer cells (HeLa cells) under UV and blue light excitation (in vitro environment). In addition to the long-known cell imaging application, these NSCD have been used as a sunlight active photomaterial for the removal of toxic hexavalent chromium as Cr(VI). The experimental results reveal that the sunlight active NSCD shows good potential toward the photocatalytic removal of Cr(VI) ions from the wastewater. For the environment and water purification purpose, three different wastewater samples were tested that are synthetic wastewater (up to 100 ppm), laboratory wastewater, and Cr(VI) ion-spiked industrial wastewater for the photocatalytic removal of Cr(VI). The biocompatible NSCD as a fluorescent imaging probe of cancer cells along with its fruitful utilization in photocatalysis under sunlight (compared to the dark condition) demonstrates the overall sustainability of the presented process.

Pollutant-Soot-Based Nontoxic Water-Soluble Onion-like Nanocarbons for Cell Imaging and Selective Sensing of Toxic Cr(VI).

Presently, the technologies associated with using waste materials for the fabrication of newer useful materials have been greatly advanced. For the same purpose, a possible sustainable approach is described for the utilization of globally available dirty dangerous material, known as black carbon (BC), in the form of particulate diesel soot. From the black diesel particulate matter, onion-like nanocarbons (ONC) have been isolated followed by their surface functionalization to yield their amine-functionalized water-soluble version as ONC-NH2, which exhibits a high quantum yield value of ∼20%. Concerning the synthetic protocol, the potential associated with the presented report reveals that these ONC were used without being explicitly synthesized. These were just isolated from the diesel soot, which on amine functionalization have been converted to an efficient, biocompatible fluorescent probe for the imaging of cancer (HeLa) cells and selective sensing of toxic chromium Cr(VI) in water. The detailed surface functionalization by the amine molecules in ONC-NH2, which make them readily soluble in aqueous media, is investigated using several spectroscopic techniques such as XPS, NMR, and FTIR.

Riboflavin-Terminated, Multivalent Quantum Dot as Fluorescent Cell Imaging Probe.

Bioconjugated nanoparticles are commonly used for targeting cellular/subcellular components, and labeling performance is known to depend on multivalency, i.e., the number of attached biomolecule per particle. However, these multivalency effects are largely unexplored. Here, we show that multivalency of nanoparticle-bound riboflavin controls the cellular interaction, cellular entry/exit mechanism, and subcellular trafficking property. We have synthesized riboflavin-functionalized quantum dot (QD) of 15-25 nm hydrodynamic size with average riboflavin multivalencies of 15, 30, and 70 [designated as QD(RF)15, QD(RF)30, and QD(RF)70, respectively] and investigated their uptake mechanism in riboflavin receptor overexpressed KB cells. We found that increased multivalency from 15 to 70 increases the cellular interaction with QD, shifts the cell uptake mechanism from caveolae-clathrin to exclusive clathrin-mediated endocytosis, and enhances lysosomal trafficking. This work demonstrates the importance of multivalency of bioconjugated molecule at the nanoparticle surface toward biolabeling performance and should be optimized for best performance of designed nanobioconjugate.

Arginine-Terminated, Chemically Designed Nanoparticle for Direct Cell Translocation.

Direct cell translocation of nanomaterials is preferred over the endocytotic uptake for various subcellular targeting applications that can bypass the lysosomal trafficking/degradation. Although arginine-rich cell-penetrating peptides are routinely used for cell transfection of wider range materials from molecule to nanoparticle, the direct cell translocation of nanoparticle is not a routine approach, particularly because of the predominate endocytotic uptake. Here we report arginine-terminated, designed nanoparticle of 15-30 nm hydrodynamic size that enters into cell via direct translocation. We found that direct cell translocation of nanoparticle is very efficient without localization at any specific subcellular compartment for 12-24 h. This study shows that nanomaterial can be chemically designed for direct cell translocation and for cytosolic delivery without any biomembrane-coated endosome that can be employed for subcellular targeting applications.

Colloidal Nanobioconjugate with Complementary Surface Chemistry for Cellular and Subcellular Targeting.

Chemically and biochemically functionalized colloidal nanoparticles with appropriate surface chemistry are essential for various biomedical applications. Although a variety of approaches are now available in making such functional nanoparticles and nanobioconjugates, the lack of complementary surface chemistry often leads to poor performance with respect to intended biomedical applications. This feature article will focus on our efforts to make colloidal nanobioconjugates with appropriate/complementary surface chemistry for better performance of a designed nanoprobe with respect to cellular and subcellular targeting applications. In particular, we emphasize polyacrylate-based coating chemistry followed by a conjugation strategy for transforming <10 nm inorganic nanoparticle to colloidal nanoprobe of 20-50 nm hydrodynamic size. We show that a colloidal nanoprobe can be chemically designed to control the cell-nanoparticle interaction, cellular endocytosis, and targeting/labeling of subcellular compartments. Further study should be directed to adapt this surface chemistry to different nanoparticles, fine tune the surface chemistry for targeting/imaging on the subcellular/molecular length scale, and develop a delivery nanocarrier for subcellular compartments.

Multivalency Effect of TAT-Peptide-Functionalized Nanoparticle in Cellular Endocytosis and Subcellular Trafficking.

Although trans-activating transcription (TAT) peptide-functionalized nanoparticle/polymer/liposome is widely used for cellular transfection applications, the multivalency (number of attached peptide per particle) effect on cell uptake mechanism and subcellular targeting performance is largely unexplored. Here we show that multivalency of nanoparticle controls the cellular interaction, cellular entry/exit mechanism, and subcellular targeting performance. We have synthesized TAT-peptide functionalized quantum dot (QD) of 30-35 nm hydrodynamic diameter with varied multivalency from 10 to 75 (e.g., QD(TAT)10, QD(TAT)20, QD(TAT)40, QD(TAT)75) and studied the role of multivalency in endocytosis and subcellular trafficking. We found that both low and high multivalent nanoparticles enter into cell predominantly via lipid-raft mediated endocytosis but the higher multivalency of 40 and 75 induces vesicular trapping followed by exocytosis within 12 h. In contrast, lower multivalency of 10 and 20 offers efficient trafficking toward perinuclear region and Golgi apparatus. This work shows the functional role of nanoparticle multivalency in cellular uptake mechanism and importance of lower multivalency for efficient subcellular targeting.

Ion-pair coordination driven stimuli-responsive one-dimensional supramolecular helicate.

Formation of an ion-pair i.e. Fe2+ and [Cl2(H2O)2]2- coordination driven one dimensional (1D) smart supramolecular helical assembly of a new heteroditopic ligand was achieved. Moreover, thermo- and chemo-responsive transformation/disassembly/reassembly of the helical superstructure was also demonstrated.

Supramolecular Host-Guest Chemistry-Based Folate/Riboflavin Functionalization and Cancer Cell Labeling of Nanoparticles.

Nanoparticle-based cellular probes are commonly designed via covalent conjugation with affinity biomolecules. Those nanobioconjugates selectively interact with cell surface receptors and induce endocytosis followed by intracellular trafficking. However, this approach requires functional modification of biomolecules that may alter their biochemical activity. Here, we show that supramolecular host-guest chemistry can be utilized as an alternative approach in nanoparticle functionalization and selective cell labeling. We have used cyclodextrin-conjugated quantum dots (QDs) for supramolecular host-guest interaction-based functionalization with folate (QD-folate) and riboflavin (QD-riboflavin), where cyclodextrin acts as a host for the folate/riboflavin guest. We demonstrate that QD-folate and QD-riboflavin selectively label cells that have over-expressed folate/riboflavin receptors and induce the endocytosis pathway similar to covalently conjugated folate-/riboflavin-based nanoprobes. However, labeling is highly sensitive to the molar ratio of folate/riboflavin to cyclodextrin and incubation time. The presented functionalization/labeling approach is unique as it does not require covalent conjugation and may be extended for in vivo targeting application via simultaneous delivery of host and guest molecules.

Red Fluorescent Carbon Nanoparticle-Based Cell Imaging Probe.

Fluorescent carbon nanoparticle-based probes with tunable visible emission are biocompatible, environment friendly and most suitable for various biomedical applications. However, synthesis of red fluorescent carbon nanoparticles and their transformation into functional nanoparticles are very challenging. Here we report red fluorescent carbon nanoparticle-based nanobioconjugates of <25 nm hydrodynamic size and their application as fluorescent cell labels. Hydrophobic carbon nanoparticles are synthesized via high temperature colloid-chemical approach and transformed into water-soluble functional nanoparticles via coating with amphiphilic polymer followed by covalent linking with desired biomolecules. Following this approach, carbon nanoparticles are functionalized with polyethylene glycol, primary amine, glucose, arginine, histidine, biotin and folic acid. These functional nanoparticles can be excited with blue/green light (i.e., 400-550 nm) to capture their emission spanning from 550 to 750 nm. Arginine and folic acid functionalized nanoparticles have been demonstrated as fluorescent cell labels where blue and green excitation has been used for imaging of labeled cells. The presented method can be extended for the development of carbon nanoparticle-based other bioimaging probes.