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.

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.

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.

Thermal stability of functionalized carbon nanotubes studied by in-situ transmission electron microscopy.

The thermal stability of funtionalized carbon nanotubes (CNTs) has been studied experimentally by direct in-situ observations using a heating stage in a transmission electron microscope, from room temperature (RT) to about 1000 °C. It was found that the thermal stability of the functionalized CNTs was significantly reduced during the in-situ heating process. Their average diameter dramatically expanded from RT to about 500 °C, and then tended to be stable until about 1000 °C. The X-ray energy dispersive spectroscopy analysis suggested that the diameter expansion was associated with coalescence of the carbon structure instead of deposition with additional foreign elements during the heating process.

Deposition of silver nanoparticles on dendrimer functionalized multiwalled carbon nanotubes: synthesis, characterization and antimicrobial activity.

The nanohybrids composed of silver nanoparticles and aromatic polyamide functionalized multiwalled carbon nanotubes (MWCNTs) is successfully synthesized and tested for their antibacterial activity against different pathogens. Prior to deposition of silver nanoparticles, acid treated MWCNTs (MWCNTs-COOH) were successively reacted with p-phenylenediamine and methylmethacrylate to form series of NH2-terminated aromatic polyamide dendrimers on the surface of MWCNTs through Michael addition and amidation. Existence of high abundance of amine groups on the surface of functionalized MWCNTs (f-MWCNTs) provided sites for formation of silver nanoparticles by the reduction of aqueous solution of AgNO3. The silver nanoparticles formed in the resulted f-MWCNTs-Ag nanohybrids were determined to be face centered cubic (fcc) symmetry. The structure and nature of f-MWCNTs and f-MWCNTs-Ag nanohybrids were characterized by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction analysis (XRD), Raman spectroscopy and thermogravimetric analysis (TGA). The dispersion state of f-MWCNTs and immobilization of silver nanoparticles on the surface of f-MWCNTs were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Elemental composition of f-MWCNTs-Ag nanohybrids was determined by energy dispersive X-ray spectroscopy (EDS). The antimicrobial activity of f-MWCNTs-Ag nanohybrids were estimated against E. coli, P. aeruginosa and S. aureu and compared with MWCNTs-COOH and f-MWCNTs. The results indicate that functionalization of MWCNTs with aromatic polyamide dendrimers and successive deposition of Ag nanoparticles could play an important role in the enhancement of antimicrobial activity.

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.

Synthesis and characterization of chitosan-carbon nanotube composites.

Acid functionalized single walled carbon nanotubes were covalently grafted to chitosan by first reacting the oxidized carbon nanotubes with thionyl chloride to form acyl-chlorinated carbon nanotubes which are subsequently dispersed in chitosan and covalently grated to form composite material, CNT-chitosan, 1, which was washed several times to remove un-reacted materials. This composite has been characterized by FTIR, 13C NMR, TGA, SEM and TEM and has been shown to exhibit enhanced thermal stability. The reaction of 1, with poly lactic acid has also been accomplished to yield CNTchitosan-g-poly(LA), 2 and fully characterized by the above techniques. Results showed covalent attachment of chitosan and chitosan-poly lactic acid to the carbon nanotubes.

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.

Dispersion of aminoalkylsilyl ester or amine alkyl-phosphonic acid side wall functionalized carbon nanotubes in silica using sol-gel processing.

Aminopropyltriethoxysilane and aminopropyl-phosphonic ester modified carbon nanotubes were prepared by reacting fluorinated carbon nanotubes (F-CNTs) with the 3-aminopropyltriethoxysilane or 3-aminopropyl-phosphonic acid reagents at 120 °C temperature, using pyridine as the base catalyst. These functionalized carbon nanotubes, APTES-CNTs, 1, and APPA-CNTs, 2, were characterized by transmission electron microscopy (TEM), infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The homogeneous dispersion of these functionalized CNTs (0.1%) in silica were also accomplished by sol-gel processing. The TEM confirmed uniform dispersion of the functionalized CNT in silica.

Functionalization of single-walled carbon nanotubes with N-[3-(trimethoxysilyl)propyl]ethylenediamine and its cobalt complex.

The reaction of N-[3-(trimethoxysilyl)propyl]ethylenediamine with fluorinated carbon nanotubes (F-CNT) produced the corresponding aminoalkylalkoxysilane functionalized carbon nanotubes. Cobalt salt is then complexed to this functionalized carbon nanotubes by the addition of cobalt chloride to form cobalt complexed nanocomposite in high yield. This composite and precursors were characterized by using Fourier transform infra-red spectroscopy (FTIR), transmission electron microscopy (TEM), energy dispersive spectral (EDS) and thermal gravimetric analysis (TGA). The nanoparticulate metal complexes of functionalized carbon nanotubes generate new nanostructure with several practical applications. The reaction of N-[3-(trimethoxysilyl)propyl]ethylenediamine with cobalt (II) chloride salt afford the cobalt complex nanoparticles, with particle sizes less than 10 nm.

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.

Synthesis and characterization of Zinc/Chitosan-Folic acid complex.

Therapeutic drug delivery systems using polymeric materials is an emerging field of research. However, the use of certain polymers has gained much-needed attention by the researchers due to their low toxic nature. In recent years, chitosan has gained popularity as a potential biodegradable polymer that can be used as a component in drug delivery systems. In this study, we synthesized a chitosan derivative that is composed of both folic acid and zinc and may serve as a viable component of a drug delivery system. The results of Fourier Transform Infrared Spectroscopy (FTIR), solid-state 13C Nuclear Magnetic Resonance Spectroscopy (NMR) and UV-visible Spectroscopy demonstrated a substantial difference between chitosan and ZnS/Chitosan-Folic acid derivative. The results were also confirmed using Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM-EDS) techniques. The average particle size of the ZnS/Chitosan-Folic acid system was measured to be 463.67 ± 5.76 nm, showing that the product is within the nano-size range.

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.

Preparation and in vitro bioactivity of zinc containing sol-gel-derived bioglass materials.

Bioactive glass material of the type CaO--P(2)O(5)--SiO(2)--ZnO was obtained by the sol-gel processing method. This material was produced both in powder and in disks form by compression of the powder. The obtained material was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and surface electron micrograph (SEM). The bioactivity was examined in vitro with respect to the ability of hydroxyapatite layer to form on the surface as a result of contact with simulated body fluid (SBF). The XRD and FTIR studies were conducted before and after contact of the material with SBF. The gel-derived materials were amorphous as shown by XRD, but were able to crystallize calcium phosphates on their surfaces when exposed to SBF. We also examined the alkaline phosphatase (AP) activity of osteoblasts, using human fetal osteoblastic cells (hFOB 1.19) cultured on the zinc bioglass, and compared it with the polystyrene plates. The bone cells consistently expressed higher AP activity in the zinc bioglass materials compared with the polystyrene plates, which indicates the zinc containing composition stimulates bone cells production of AP.

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.

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.