Facilitated Adsorption of Mercury(II) and Chromium(VI) Ions over Functionalized Carbon Nanotubes.

By considering the importance of water and its purity, herein, a powerful adsorbent has been developed for the adsorption of two toxic contaminants that commonly exist in water, viz., divalent mercury and hexavalent chromium. The efficient adsorbent, CNTs-PLA-Pd, was prepared by covalent grafting polylactic acid to carbon nanotubes and subsequent deposition of palladium nanoparticles. The CNTs-PLA-Pd could adsorb Hg(II), and Cr(VI) entirely exists in water. The adsorption rate for Hg(II) and Cr(VI) was rapid at initial stage, followed by gradual decrease, and attained the equilibrium. The Hg(II) and Cr(VI) adsorption was perceived within 50 min and 80 min, respectively with CNTs-PLA-Pd,. Further, experimental data for Hg(II) and Cr(VI) adsorption was analyzed, and kinetic parameters were estimated using pseudo-first and second-order models. The adsorption process of Hg(II) and Cr(VI) followed the pseudo-second-order kinetics, and the rate-limiting step in the adsorption was chemisorption. The Weber-Morris intraparticle pore diffusion model revealed that the Hg(II) and Cr(VI) adsorption over CNTs-PLA-Pd occurs through multiple phases. The experimental equilibrium parameters for the Hg(II) and Cr(VI) adsorption were estimated by Langmuir, Freundlich, and Temkin isotherms models. All three models were well suited and demonstrated that Hg(II) and Cr(VI) adsorption over CNTs-PLA-Pd transpires through monolayer molecular covering and chemisorption.

The Cytotoxicity of Carbon Nanotubes and Hydroxyapatite, and Graphene and Hydroxyapatite Nanocomposites against Breast Cancer Cells.

Cancer is a current dreadful disease and the leading cause of death. Next to cardiovascular diseases, cancer is the most severe threat to human life and health. Breast cancer is the most common invasive cancer diagnosed in women. Each year about 2.3 million women are diagnosed with breast cancer. In consideration of the severity of breast cancer, herein we designed the biocompatible nanomaterials, CNTs-HAP and GR-HAP, through grafting of hydroxyapatite (HAP) to carbon nanotubes (CNTs) and graphene (GR) nanosheets. CNTs-HAP and GR-HAP have been tested for their cytotoxicity, growth and motility inhibitory effects, and their effects on the mesenchymal markers. All these demonstrated significant dose-dependent and time-dependent in vitro cytotoxicity against SUM-159 and MCF-7 breast cancer cell lines. The cell viability assay showed that the CNTs-HAP was more effective over SUM-159 cells than MCF-7 cells. It found that the increase in the concentration of GR-HAP has inhibited the clonogenic ability of breast cancer cells. The GR-HAP exhibited a substantial inhibitory effect on the cell motility of SUM-159 cell lines. It was investigated that the expression of vimentin (mesenchymal marker) was majorly reduced in SUM-159 cells by GR-HAP.

Elevated Adsorption of Lead and Arsenic over Silver Nanoparticles Deposited on Poly(amidoamine) Grafted Carbon Nanotubes.

An efficient adsorbent, CNTs-PAMAM-Ag, was prepared by grafting fourth-generation aromatic poly(amidoamine) (PAMAM) to carbon nanotubes (CNTs) and successive deposition of Ag nanoparticles. The FT-IR, XRD, TEM and XPS results confirmed the successful grafting of PAMAM onto CNTs and deposition of Ag nanoparticles. The absorption efficiency of CNTs-PAMAM-Ag was evaluated by estimating the adsorption of two toxic contaminants in water, viz., Pb(II) and As(III). Using CNTs-PAMAM-Ag, about 99 and 76% of Pb(II) and As(III) adsorption, respectively, were attained within 15 min. The controlling mechanisms for Pb(II) and As(III) adsorption dynamics were revealed by applying pseudo-first and second-order kinetic models. The pseudo-second-order kinetic model followed the adsorption of Pb(II) and As(III). Therefore, the incidence of chemisorption through sharing or exchanging electrons between Pb(II) or As(III) ions and CNTs-PAMAM-Ag could be the rate-controlling step in the adsorption process. Further, the Weber-Morris intraparticle pore diffusion model was employed to find the reaction pathways and the rate-controlling step in the adsorption. It revealed that intraparticle diffusion was not a rate-controlling step in the adsorption of Pb(II) and As(III); instead, it was controlled by both intraparticle diffusion and the boundary layer effect. The adsorption equilibrium was evaluated using the Langmuir, Freundlich, and Temkin isotherm models. The kinetic data of Pb(II) and As(III) adsorption was adequately fitted to the Langmuir isotherm model compared to the Freundlich and Temkin models.

Photothermal effect and cytotoxicity of CuS nanoflowers deposited over folic acid conjugated nanographene oxide.

Herein, we present the rational synthesis of a multimode photothermal agent, NGO-FA-CuS, for the advancement of photothermal therapy of cancer. The hierarchical architecture created in NGO-FA-CuS was attained by the covalent conjugation of folic acid (FA) to nanographene oxide (NGO) through amide bonding, followed by the hydrothermal deposition of CuS nanoflowers. In this approach, instead of mere mixing or deposition, FA was covalently bonded to NGO, which helped in retaining their intrinsic properties after binding and allowed to access them in the resulting hybrid nanostructure. In this specifically designed photothermal agent, NGO-FA-CuS, each component has an explicit task, i.e., NGO, FA and CuS act as the quencher, cancer cell-targeting moiety and photothermal transduction agent, respectively. Prior to the grafting of FA molecules and the deposition of CuS nanoflowers, sulfonic acid groups were introduced into NGO to provide stability under physiological conditions. Under irradiation using a 980 nm laser, NGO-FA-CuS was able to attain a temperature of 63.1 °C within 5 min, which is far beyond the survival temperature for cancer cells. Therefore, the resulting temperature recorded for NGO-FA-CuS was sufficient to induce hyperthermia in cancer cells to cause their death. When coming into contact with cancer cells, NGO-FA-CuS can cause a rapid increase in the temperature of their nucleus, destroy the genetic substances, and ultimately lead to exhaustive apoptosis under illumination using a near-infrared (NIR) laser. An excellent photothermal efficiency of 46.2% under illumination using a 980 nm laser and outstanding cytotoxicity against HeLa, SKOV3 and KB cells were attained with NGO-FA-CuS. Moreover, NGO-FA-CuS displays exceptional persistent photo-stability without photo-corrosiveness. The photothermal effect of NGO-FA-CuS was found to be dependent on its concentration and the power density of the laser source. It was found that its cytotoxicity toward cancer cells was enhanced with an increase in the concentration of NGO-FA-CuS and the incubation period.

Cobalt Phthalocyanine-Sensitized Graphene-ZnO Composite: An Efficient Near-Infrared-Active Photothermal Agent.

Herein, a promising near-infrared-responsive photothermal agent was designed by anchoring of rice grain-shaped ZnO particles over graphene (GR) nanosheets and subsequent sensitization with cobalt phthalocyanine (CoPc). Thus, produced GR-ZnO-CoPc was able to attain the temperature of 68 °C by irradiating to 980 nm laser for 7 min, which is extremely higher than the endurance temperature of cancer cells. The linear fashioned progression in the photothermal effect of GR nanosheets was conquered by immobilization of ZnO particles and successive sensitization with CoPc. The excellence found in the photothermal effect of GR-ZnO-CoPc was verified by estimation of its photothermal conversion efficiency. The photothermal conversion efficiency assessed for GR-ZnO-CoPc was higher than those for the popular gold- and CuS-based photothermal agents. In addition, it possessed significant stability against photobleaching and structural rupture. It was found that the photothermal effect of GR-ZnO-CoPc is proportional to its concentration. However, by replacement of a 980 nm laser system with 808 nm, the photothermal effect of GR-ZnO-CoPc was reduced, which could be due to lower absorption of GR-ZnO-CoPc at 808 nm compared to 980 nm. On account of its significance and important properties, GR-ZnO-CoPc could be an interesting photothermal agent to employ in future photothermal therapy for cancer.

Ag2S nanocrystallites deposited over polyamidoamine grafted carbon nanotubes: An efficient NIR active photothermal agent.

A novel NIR (near infrared) active photothermal agent, CNTs-PAMAM-Ag2S has been synthesized by covalent grafting of polyamidoamine (PAMAM) to carbon nanotubes (CNTs) and subsequent deposition of Ag2S nanocrystallites. The potential of CNTs-PAMAM-Ag2S as a NIR active photothermal agent was preliminarily accessed by its electronic absorption spectrum measured in UV-vis-NIR region. The CNTs-PAMAM-Ag2S exhibited excellent photothermal effect and photothermal conversion efficiency of 26% under illumination with 980 nm laser, the efficiency was found to be higher than popular gold and copper based photothermal agents. Temperature attained by CNTs-PAMAM-Ag2S during measurement of its photothermal effect was 64.7 °C at 1 g/mL, which far exceeds the temperature tolerance level of cancer cells. So that CNTs-PAMAM-Ag2S could destroy the cancer cells in an effective manner. Furthermore, it was found the linear dependence of photothermal effect of CNTs-PAMAM-Ag2S over its concentration. CNTs-PAMAM-Ag2S possessed excellent stability against photo-bleaching and photo-corrosiveness. In consideration of its outstanding photothermal effect and photothermal conversion efficiency, CNTs-PAMAM-Ag2S could be a promising photothermal agent to employ in future photothermal therapy.

Nature engineered diatom biosilica as drug delivery systems.

Diatoms, unicellular photosynthetic algae covered with siliceous cell wall, are also called frustule. These are the most potential naturally available materials for the development of cost-effective drug delivery systems because of their excellent biocompatibility, high surface area, low cost and ease of surface modification. Mesoporous silica materials such as MCM-41 and SBA-15 have been extensively used in drug delivery area. Their synthesis is challenging, time consuming, requires toxic chemicals and are energy intensive, making the entire process expensive and non-viable. Therefore, it is necessary to explore alternative materials. Surprisingly, nature has provided some exciting materials called diatoms; biosilica is one such a material that can be potentially used as a drug delivery vehicle. The present review focuses on different types of diatom species used in drug delivery with respect to their structural properties, morphology, purification process and surface functionalization. In this review, recent advances along with their limitations as well as the future scope to develop them as potential drug delivery vehicles are discussed.

Advancement in Photothermal Effect of Carbon Nanotubes by Grafting of Poly(amidoamine) and Deposition of CdS Nanocrystallites.

A robust, near-infrared (NIR) active photothermal agent, CNTs-PAMAM/G4-CdS, is designed by covalent grafting of fourth generation poly(amidoamine) (PAMAM) to carbon nanotubes (CNTs) and successive deposition of cadmium sulfide (CdS) nanocrystallites. The systematic advancement in photothermal effect of CNTs was achieved by grafting of first, second, third, and fourth generation PAMAM through the repeated process of Michael's addition. The subsequent deposition of CdS nanocrystallites over fourth generation PAMAM grafted CNTs has further improved the photothermal effect (PTE) of CNTs. The photothermal effect of CNTs-PAMAM/G4-CdS was accessed by illuminating with 980 nm NIR laser. During measurement of PTE, maximum temperature attained by CNTs-PAMAM/G4-CdS was 64.1 °C which far exceeds the survival temperature of cancer cells. The photothermal conversion efficiency estimated for CNTs-PAMAM/G4-CdS was 32%, which is higher than the value reported for popular gold and copper based photothermal agents. Apart from its outstanding photothermal effect, CNTs-PAMAM/G4-CdS possessed excellence in both antiphoto-bleaching and antiphoto-corrosiveness.

Photothermal effect: an important aspect for the enhancement of photocatalytic activity under illumination by NIR radiation.

A key auxiliary role of photothermal effect (PTE) in the enhancement of photocatalytic activity under illumination to near-infrared (NIR) radiations has been experimentally revealed. It was found that the photoexcitation of electrons, required for the process of photocatalysis does not occur in presence of NIR radiations alone without the support of both UV and visible radiations. Herein, a binary heterogeneous nanophotocatalyst, GR-ZnO was fabricated by a novel approach using hydrothermal process. In which ZnO nanotrapezoids were deposited over the surfaces of graphene nanosheets. In the reported unique approach, reduction of graphene oxide to graphene has been accomplished using water by an entirely alternative mechanism compared to traditional reduction processes those employ the hazardous reducing agents. Thus produced GR-ZnO photocatalyst has exhibited the excellence in rapid degradation of industrially voluntarily employing perilous dye, methyl orange. It is explored that PTE is mainly responsible for the rapid degradation of methyl orange transpired under illumination to NIR laser. Further, it has been established that PTE could not emerge with NIR radiations alone without the support of both UV and visible radiations. In consideration of its importance, PTE of GR-ZnO nanocatalyst has been revealed and compared with its individual components, viz., graphene and ZnO. Moreover, the photothermal conversion efficiency of GR-ZnO nanocatalyst was evaluated. Overall, the excellent catalytic activity found in GR-ZnO nanocatalyst was accounted for its decreased band gap, transpired by hybridization of ZnO with graphene could efficiently prevent the recombination of photo-generated charge carriers. In addition, admired catalytic activity of GR-ZnO nanocatalyst was attributed to improved optical absorption and enhancement in the adsorption affinity to methyl orange molecules.

Photothermal effect of Ag nanoparticles deposited over poly(amidoamine) grafted carbon nanotubes.

This paper illustrates the potential of Ag nanoparticles based nanocomposites to use as effective agents in photothermal therapy apart from their traditional employment as antimicrobial materials. Herein an Near- Infrared active photothermal agent was fabricated by deposition of Ag nanoparticles over aromatic poly(amidoamine) grafted carbon nanotubes. Thus prepared CNTs-PAMAM-Ag possessed strong photothermal effect under exposure to 980 nm laser system and prominent photothermal stability. The photothermal conversion efficiency of CNTs-PAMAM-Ag was found to be higher than readily used Au and CuS based photothermal agents. The photothermal effect of CNTs-PAMAM-Ag was substantial in presence of 980 nm laser compared to 808 nm laser and a linear dependence of photothermal effect on its concentration was identified. The maximum temperature attained by CNTs-PAMAM-Ag during assessment of its photothermal effect was about 66.0 °C, which is significantly higher than the survival temperature level of cancer cells. So CNTs-PAMAM-Ag could be a promising photothermal agent to apply in future photothermal hyperthermia therapy to treat cancer. Moreover CNTs-PAMAM-Ag can synchronous trigger by a single wavelength (980 nm) laser system, so it could simplify the future therapeutic process.

Graphene-Coupled ZnO: A Robust NIR-Induced Catalyst for Rapid Photo-Oxidation of Cyanide.

Herein, we report the modulation of ZnO for enhancement of its ability toward plasmonic absorption of near-infrared (NIR) photons through coupling of graphene (GR). The reported modification led GR-ZnO to be a promising photocatalyst by the complete removal of poisonous and nonvolatile potassium cyanide from water. The photocatalytic degradation of cyanide was revealed by exposing it to NIR laser and comparing with the rate of UV, visible, and sunlight using their apparent reaction rate constants derived from the Langmuir-Hinshelwood model. The heteronanostructured GR-ZnO promoted rapid photo-oxidation of cyanide under illumination with NIR laser rather than UV, visible, and sunlight. It was assessed that the photothermal effect (PTE) is the main cause for higher catalytic efficiency of GR-ZnO in the presence of NIR radiations. Except for the NIR radiations, GR-ZnO does not show any indication of PTE by irradiating with UV, visible, or sunlight. On account of its significance, the PTE of GR-ZnO in KCN solution was evaluated and compared with its individual components viz., GR and ZnO upon exposure to a 980 nm laser system. Furthermore, it has been revealed that the PTE of GR-ZnO was proportional to its concentration. In addition to its effectiveness in the degradation of cyanide, GR-ZnO retained its special structure and exhibited an outstanding photostability after its repeated use in three successive cycles.

Influence of carbon nanotubes and graphene nanosheets on photothermal effect of hydroxyapatite.

Herein we present a successful strategy for enhancement of photothermal efficiency of hydroxyapatite (HAP) by its conjugation with carbon nanotubes (CNTs) and graphene nanosheets (GR). Owing to excellent biocompatibility with human body and its non-toxicity, implementation of HAP based nanomaterials in photothermal therapy (PTT) provides non-replaceable benefits over PTE agents. Therefore, in this report, it has been experimentally exploited that the photothermal effect (PTE) of HAP has significantly improved by its assembly with CNTs and GR. It is found that the type of carbon nanomaterial used to conjugate with HAP has influence on its PTE in such a way that the photothermal efficiency of GR-HAP was higher than CNTs-COOH-HAP under exposure to 980nm near-infrared (NIR) laser. The temperature attained by aqueous dispersions of both CNTs-COOH-HAP and GR-HAP after illuminating to NIR radiations for 7min was found to be above 50°C, which is beyond the temperature tolerance of cancer cells. So that the rise in temperature shown by both CNTs-COOH-HAP and GR-HAP is enough to induce the death of tumoral or cancerous cells. Overall, this approach in modality of HAP with CNTs and GR provide a great potential for development of future nontoxic PTE agents.

Photocatalytic activity and NIR laser response of polyaniline conjugated graphene nanocomposite prepared by a novel acid-less method.

Herein, we present a novel acid-less synthetic approach for in-situ polymerization of aniline synchronized with reduction of graphene oxide to graphene. This method provides uniform deposition of ordered polyaniline nanotubes over the surface of graphene nanosheets. The synthesized graphene-polyaniline nanocomposite has the ability of complete removal of harmful dyes commonly used in industry: such as methyl orange, methylene blue, and rhoadmine B from the waste water under the exposure to natural sunlight. The system can be used as an efficient solar energy operated photocatalyst due to effective suppression of recombination of the charge carriers. The unique spatial structure of the graphene-polyaniline nanocomposite has high chemical stability, can be recycled after photolysis, and allows using in multiple cycles without reduction in its photocatalytic activity. In addition, the graphene-polyaniline nanocomposite exhibits strong near-infrared (NIR) absorption, good photothermal stability, as well as shows substantial thermal energy generation under exposure to 808 or 980 nm NIR lasers. The electrical conductivity of polyaniline nanotubes is improved as a result of their conjugation with graphene nanosheets in the nanocomposite. Owing to its outstanding photocatalytic activity and chemical stability, the reported graphene-polyaniline nanocomposite has a great potential in purification of industrially generated waste water.

Synthesis and characterization of reduced graphite oxide-polymer composites and their application in adsorption of lead.

Herein, we report the in situ polymerization of 1,5-diaminonaphthalene (15DAN) and 1,4-diaminoanthraquinone (14DAA) on the surface of reduced graphite oxide (RGO). Synthesized RGO-P15DAN and RGO-P14DAA were characterized by FTIR, Raman, SEM, TGA and XRD. The adsorption capacity and adsorptivity of the synthesized composites were investigated by Atomic Absorption Spectroscopy (AAS) using 100 ppm aqueous solution of Pb(2+) ions. Further, we compared the results of the composites with those of poly 1,5-(diaminonaphthalene) (P15DAN), poly 1,4-(diaminoanthraquinone) (P14DAA), RGO, graphite oxide (GO) and graphite. Among the tested adsorbents, RGO-P15DAN demonstrated the high adsorptivity.

ZnO and cobalt phthalocyanine hybridized graphene: efficient photocatalysts for degradation of rhodamine B.

A novel method has been developed to synthesize graphene-ZnO composite as a highly efficient catalyst by reduction of graphite oxide and in situ deposition of ZnO nanoparticles by chemical reduction reaction. The graphene-ZnO catalyst is capable of complete degradation of rhodamine B under exposure to natural sunlight. Further, the catalytic efficiency of graphene-ZnO catalyst was enhanced by sensitizing with cobalt phthalocyanine. The formation of graphene-ZnO photocatalyst and its further sensitization with cobalt phthalocyanine was characterized using UV-vis, ATR-IR and Raman spectroscopy, powder XRD and thermogravimetric analysis. The morphology of both graphene-ZnO and graphene-ZnO-CoPC catalysts was analyzed using scanning and transmission electron microscopes.

Hydroxyapatite grafted carbon nanotubes and graphene nanosheets: promising bone implant materials.

In the present study, hydroxyapatite (HA) was successfully grafted to carboxylated carbon nanotubes (CNTs) and graphene nanosheets. The HA grafted CNTs and HA-graphene nanosheets were characterized using FT-IR, TGA, SEM and X-ray diffraction. The HA grafted CNTs and graphene nanosheets (CNTs-HA and Gr-HA) were further used to examine the proliferation and differentiation rate of temperature-sensitive human fetal osteoblastic cell line (hFOB 1.19). Total protein assays and western blot analysis of osteocalcin expression were used as indicators of cell proliferation and differentiation. Results indicated that hFOB 1.19 cells proliferate and differentiate well in treatment media containing CNTs-HA and graphene-HA. Both CNTs-HA and graphene-HA could be promising nanomaterials for use as scaffolds in bone tissue engineering.

Adsorption of lead over graphite oxide.

The adsorption efficiency and kinetics of removal of lead in presence of graphite oxide (GO) was determined using the Atomic Absorption Spectrophotometer (AAS). The GO was prepared by the chemical oxidation of graphite and characterized using FTIR, SEM, TGA and XRD. The adsorption efficiency of GO for the solution containing 50, 100 and 150 ppm of Pb(2+) was found to be 98%, 91% and 71% respectively. The adsorption ability of GO was found to be higher than graphite. Therefore, the oxidation of activated carbon in removal of heavy metals may be a viable option to reduce pollution in portable water.

In-situ deposition of hydroxyapatite on graphene nanosheets.

Graphene nanosheets were effectively functionalized by in-situ deposition of hydroxyaptite through a facile chemical precipitation method. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. The resulting hydroxyapatite functionalized graphene nanosheets were characterized by attenuated total reflection IR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, Raman spectroscopy and thermogravimetric analysis. These characterization techniques revealed the successful grafting of hydroxyapatite over well exfoliated graphene nanosheets without destroying their structure.

Antimicrobial activity of CdS and Ag2S quantum dots immobilized on poly(amidoamine) grafted carbon nanotubes.

Herein we report the design of antimicrobial nanohybrids, f-MWCNTs-CdS and f-MWCNTs-Ag(2)S developed by covalent grafting of cationic hyperbranched dendritic polyamidoamine (PAMAM) onto multiwalled carbon nanotubes (MWCNTs) and successive deposition of CdS and Ag(2)S quantum dots (QDs). The CdS and Ag(2)S QDs were in situ deposited on PAMAM grafted MWCNTs instead of anchoring the pre-synthesized QDs. The fourth generation, amine terminated hyperbranched PAMAM was grafted on MWCNTs, which was achieved through repetitive reactions of Michael addition of methylmethacrylate to the surface amino groups and amidation of terminal ester groups with ethylenediamine. The covalent grafting of PAMAM onto MWCNTs and the consecutive conjugation of CdS and Ag(2)S QDs were characterized using Fourier transform infrared spectroscopy, elemental analysis, powder X-ray diffraction, Raman spectroscopy, transmission electron microscopy and energy dispersive spectroscopy. The antibacterial activity of f-MWCNTs-CdS and f-MWCNTs-Ag(2)S nanohybrids was evaluated against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus and the results were compared with the activity of carboxylated MWCNTs, PAMAM grafted MWCNTs, PAMAM dendrimer, and CdS and Ag(2)S QDs. It was found that the germicidal action of MWCNTs was enhanced by grafting of PAMAM, which was further improved with immobilization of CdS and Ag(2)S QDs.

Synthesis, characterization and stability of chitosan and poly(methyl methacrylate) grafted carbon nanotubes.

The single walled carbon nanotubes (CNTs) were effectively functionalized through grafting with chitosan (CTS) and poly(methyl methacrylate) (PMMA). Prior to grafting reaction, the carboxylated SWNCTs (SWNCTs-COOH) were obtained by treating pristine CNTs with a mixture of 3:1 (v/v) H(2)SO(4) and HNO(3), and the successive treatment of SWNCTs-COOH with SOCl(2) yielded the acylated CNTs (CNTs-COCl). The functionalized derivatives of CNTs were characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, atomic force microscopy, scanning electron microscopy and transmission electron microscopy. Both CTS and PMMA grafted CNTs showed better dispersability in acetic acid and tetrahydrofuran, in addition to higher stability in solution.