Photocatalytic reduction of o-chloronitrobenzene under visible light irradiation over CdS quantum dot sensitized TiO2.

The photocatalytic activity of CdS/P25 hybrid catalysts was studied under visible-light irradiation. The CdS quantum dots sensitized P25 (CdS QDs-P25) showed extremely enhanced activity in the reduction of o-chloronitrobenzene (o-CNB) by comparing to CdS-P25 prepared by the direct deposition-precipitation method in the presence of HCOOH. The synergistic effects between CdS QDs and P25 were beneficial for the separation of photogenerated carriers in space and thus the combination of photoelectrons and holes was prevented, and the CdS QDs could provide more photocharges than CdS due to the particle size effect. Furthermore, the process of photocatalytic reduction in the present system was investigated, under visible-light irradiation, the photogenerated electrons transferred from the valence band (VB) to the conduction band (CB) of CdS QDs, and injected into the CB of inactivated P25. Meanwhile, the holes generated in the VB of CdS QDs could oxidize HCOO(-) to give ˙CO2(-) and H(+). Then, o-CNB was reduced to o-chloroaniline (o-CAN) by the couple of e(-) and ˙CO2(-) with H(+). It is a significant method and a green process for hydrogenation of nitro compounds, which may have great potential applications in the reduction of various organic chemicals.

Glucose-sensitive colorimetric sensor based on peroxidase mimics activity of porphyrin-Fe3O4 nanocomposites.

5,10,15,20-Tetrakis(4-carboxyphenyl)-porphyrin-functionalized Fe3O4 nanocomposites (H2TCPP-Fe3O4) were successfully prepared by a simple two-step method. These nanocomposites exhibited ultra-high peroxidase-like activity compared with pure Fe3O4 nanoparticles. Colorless peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) was changed by H2O2 to its blue oxidized state. Kinetic studies indicated that the H2TCPP-Fe3O4 nanocomposites exhibited enhanced affinity toward H2O2 with a higher catalytic activity than Fe3O4 nanoparticles alone. Results of a fluorescent probe suggested that the catalase-mimic activity of the H2TCPP-Fe3O4 nanocomposites effectively catalyzed the decomposition of H2O2 into hydroxyl radicals. A simple, sensitive, and selective visual and colorimetric method with TMB as the substrate was designed to detect glucose when combined with glucose oxidase. This colorimetric method can be used for colorimetric detection of H2O2 with a minimum detection limit of 1.07×10(-6) M and a dynamic range of 5×10(-6) mol·L(-1) to 8×10(-5) mol·L(-1). This method can also be used to detect glucose at a minimum detection limit of 2.21×10(-6) M and a dynamic range of 25×10(-6) mol·L(-1) to 5×10(-6) mol·L(-1). Furthermore, the robustness of the nanocomposites makes them suitable for a wide range of applications in biomedicine and environmental chemistry fields.

Embedding NiCo2O4 nanoparticles into a 3DHPC assisted by CO2-expanded ethanol: a potential lithium-ion battery anode with high performance.

A high-performance anode material, NiCo2O4/3DHPC composite, for lithium-ion batteries was developed through direct nanoparticles nucleation on a three-dimensional hierarchical porous carbon (3DHPC) matrix and cation substitution of spinel Co3O4 nanoparticles. It was synthesized via a supercritical carbon dioxide (scCO2) expanded ethanol solution-assisted deposition method combined with a subsequent heat-treatment process. The NiCo2O4 nanoparticles were uniformly embedded into the porous carbon matrix and efficiently avoided free-growth in solution or aggregation in the pores even at a high content of 55.0 wt %. In particular, the 3DHPC was directly used without pretreatment or surfactant assistance. As an anode material for lithium-ion batteries, the NiCo2O4/3DHPC composite showed high reversible capacity and improved rate capability that outperformed those composites formed with single metal oxides (NiO/3DHPC, Co3O4/3DHPC), their physical mixture, and the composite prepared in pure ethanol (NiCo2O4/3DHPC-E). The superior performance is mainly contributed to the unique advantages of the scCO2-expanded ethanol medium, and the combination of high utilization efficiency and improved electrical conductivity of NiCo2O4 as well as the electronic and ionic transport advantages of 3DHPC.

Supercritical carbon dioxide assisted deposition of Fe(3)O(4) nanoparticles on hierarchical porous carbon and their lithium-storage performance.

A composite of highly dispersed Fe3 O4 nanoparticles (NPs) anchored in three-dimensional hierarchical porous carbon networks (Fe3 O4 /3DHPC) as an anode material for lithium-ion batteries (LIBs) was prepared by means of a deposition technique assisted by a supercritical carbon dioxide (scCO2 )-expanded ethanol solution. The as-synthesized Fe3 O4 /3DHPC composite exhibits a bimodal porous 3D architecture with mutually connected 3.7 nm mesopores defined in the macroporous wall on which a layer of small and uniform Fe3 O4 NPs was closely coated. As an anode material for LIBs, the Fe3 O4 /3DHPC composite with 79 wt % Fe3 O4 (Fe3 O4 /3DHPC-79) delivered a high reversible capacity of 1462 mA h g(-1) after 100 cycles at a current density of 100 mA g(-1) , and maintained good high-rate performance (728, 507, and 239 mA h g(-1) at 1, 2, and 5 C, respectively). Moreover, it showed excellent long-term cycling performance at high current densities, 1 and 2 A g(-1) . The enhanced lithium-storage behavior can be attributed to the synergistic effect of the porous support and the homogeneous Fe3 O4 NPs. More importantly, this straightforward, highly efficient, and green synthetic route will definitely enrich the methodologies for the fabrication of carbon-based transition-metal oxide composites, and provide great potential materials for additional applications in supercapacitors, sensors, and catalyses.

Self-assembly into temperature dependent micro-/nano-aggregates of 5,10,15,20-tetrakis(4-carboxyl phenyl)-porphyrin.

Various nanostructures of 5,10,15,20-tetrakis(4-carboxyl phenyl)-porphyrin (H2TCPP) can be easily synthesized by a surfactant-assisted self-assembly (SAS) method at different temperatures. When the DMF solution of porphyrin monomer was injected into cetyltimethylammonium bromide (CTAB) aqueous solution by a syringe, diverse H2TCPP nanostructures dependent on the different temperatures, including hollow nanospheres, solid nanospheres and nanospheres with holes, were successfully obtained. As a result, the suitable concentration of the CTAB aqueous solution used to form nanostructues of porphyrin ranges from 0.15 to 0.2 mM. The various morphologies of porphyrin nanostructures were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). UV-vis adsorption spectra showed that the micro-/nano-aggregate properties of porphyrin transformed from H-aggretates to J-aggregates during the process of self-assembly of porphyrin at different temperatures. Fluorescence spectra revealed a greater fluorescence quenching of various micro-/nano-aggregatess of porphyrin formed at different temperatures in aqueous solution, compared to the DMF solution of porphyrin monomer.

Trace amounts of water-induced distinct growth behaviors of NiO nanostructures on graphene in CO2-expanded ethanol and their applications in lithium-ion batteries.

In this work, we have developed a new method to grow NiO nanomaterials on the surface of graphene nanosheets (GNSs). The morphologies of NiO nanomaterials grown on GNSs could be tailored by trace amounts of water introduced into the mixed solvents of CO2-expanded ethanol (CE). Small and uniform Ni-salt nanoparticles (Ni-salt-NPs) were grown on the surface of graphene oxide (GO) through the decomposition of nickel nitrate directly in CE. However, when trace amounts of water were introduced into the mixed solvents, Ni-salt nanoflakes arrays (Ni-salt-NFAs) were grown on the surface of GO with almost perpendicular direction. After thermal treatment in N2 atmosphere, these Ni-salt @GO composites were converted to NiO@GNSs composites. The forming mechanisms of the NiO-NPs@GNSs and NiO-NFAs@GNSs were discussed by series comparative experiments. The presence of the trace amounts of water affected the chemical composition and structure of the precursors formed in CE and the growth behaviors on the surface of GNSs. When used as anode materials for lithium-ion batteries, the NiO-NPs@GNSs composite exhibited better cycle and rate performance compared with the NiO-NFAs@GNSs.

A highly selective and sensitive nanoprobe for detection and imaging of the superoxide anion radical in living cells.

A novel fluorescent nanoprobe with high sensitivity and selectivity for detection and imaging of the superoxide anion radical O(2)(·-) in living cells was designed and synthesized by a simple self-assembly method based on 2-chloro-1,3-dibenzothiazoline-cyclohexene (DBZTC) and Ag@SiO(2) core-shell nanoparticles.

Simultaneous detection of intracellular tumor mRNA with bi-color imaging based on a gold nanoparticle/molecular beacon.

The successful treatment of most cancers depends on early detection. Tumor mRNA as a specific marker provides new avenues to monitor tumor progression in the early stages and assesses response to treatment. However, single tumor mRNA testing usually yields "false positive" results because cancer is associated with multiple tumor mRNA. It is indispensable to develop simple and effective approaches for the detection of multiple tumor mRNA. In this study, we used a combination of tumor-specific mRNA markers to avoid the inherent limitations associated with the single-marker technique. A gold nanoparticle (AuNP) was assembled with a bi-molecular beacon (bi-MB), and termed AuNP/bi-MB, which simultaneously targeted to two types of tumor mRNA in breast cancer cells. This imaging agent could prevent effectively false positive results and provide comprehensive and dependable information for the early detection of cancer. It would be beneficial to identify the stage of tumor progression and assess treatment decisions with the real-time detection of the relative expression levels of tumor mRNA in cancer cells. This strategy would offer an appealing approach toward the early detection of cancer by using multianalysis of tumor mRNA.

Study on the photoluminescence character of water-soluble CdSe nanocrystals under ambient conditions.

Water soluble, thioglycolic acid (TGA) modified CdSe nanocrystals (NCs) have been prepared in aqueous media by the reaction between Cd2+ and NaHSe. Although initially these quantum dots (QDs) display photoluminescence (PL) with very low quantum yields (QY), upon prolonged exposure to ambient light, a strong PL enhancement by illumination is observed which leads to water soluble QDs with high luminescence. This result may have important application potential in biological or other fields. The primary reason for the luminescence enhancement is concluded to be the incorporation of sulfide ions from TGA into the lattice of CdSe NCs and the subsequent formation of alloy structures. Moreover, the CdSe/CdS core-shell structured QDs synthesized in aqueous solutions also consolidate this conclusion.

A tumor mRNA-dependent gold nanoparticle-molecular beacon carrier for controlled drug release and intracellular imaging.

We demonstrate a tumor mRNA-dependent drug carrier for controlled release of doxorubicin (Dox) and intracellular imaging based on gold nanoparticle-molecular beacon. Fluorescent Dox is released effectively and induces apoptosis in breast cancer cells but not in normal cells. Significantly, the release of Dox is correlated positively with the quantities of tumor mRNA, which is according to various stages of tumor progression, and so can decrease effectively side effects of Dox.

A highly selective, cell-permeable fluorescent nanoprobe for ratiometric detection and imaging of peroxynitrite in living cells.

Peroxynitrite (ONOO(-)) is a highly reactive species implicated in the pathology of numerous diseases and there is currently great interest in developing fluorescent probes that can selectively detect ONOO(-) in living cells. Herein, a polymeric micelle-based and cell-penetrating peptide-coated fluorescent nanoprobe that incorporates ONOO(-) indicator dye and reference dye for the ratiometric detection and imaging of ONOO(-) has been developed. The nanoprobe effectively avoids the influences from enzymatic reaction and high-concentration ·OH and ClO(-). The improved ONOO(-) selectivity of the nanoprobe is achieved by a delicate complementarity of properties between the nanomatrix and the embedded molecular probe (BzSe-Cy). This nanoprobe also has other attractive properties, such as good water solubility, photostability, biocompatibility, and near-infrared excitation and emission. Fluorescence imaging experiments by confocal microscopy show that this nanoprobe is capable of visualizing ONOO(-) produced in living cells and it exhibits very low toxicity and good membrane permeability. We anticipate that this technique will be a potential tool for the precise pathological understanding and diagnosis of ONOO(-)-related human diseases.

A tumor mRNA-mediated bi-photosensitizer molecular beacon as an efficient imaging and photosensitizing agent.

A bi-photosensitizer molecular beacon (bi-PS MB) is assembled by coupling two PS molecules, respectively, onto the opposite ends of a single MB. The MB can be triggered by a tumor marker-survivin mRNA. Fluorescence and cytotoxic (1)O(2) generation occur effectively in breast cancer cells, but not in normal cells. Compared with a single-PS MB, a bi-PS MB exhibits much-enhanced properties in the signal-to-background ratio and (1)O(2) generation simultaneously.

Hierarchically nanoporous ceria nanoparticles with a high-surface area: synthesis, characterization, and their catalytic activity.

A redox route based on ethylene glycol mediated process was developed to synthesize hierarchically nanoporpous ceria nanoparticles (ceria HNPNPs). The synthesized ceria HNPNPs are composed of building blocks fabricated with cubic ceria nanocrystals of several nanometers in diameter. Scanning electron microscopy was performed to investigate the evolution process of ceria precursor, and a two-step growth process was suggested for the morphology evolution. The synthesized ceria HNPNPs exhibit high surface area, which lead to high catalytic activity for CO oxidation.

Microcrystalline sodium tungsten bronze nanowire bundles as efficient visible light-responsive photocatalysts.

Microcrystalline sodium tungsten bronze nanowire bundles were obtained via a facile hydrothermal synthesis, and were applied in water purification as visible-light-driven photocatalysts for the first time.

Direct electrochemistry of horseradish peroxidase immobilized on the layered calcium carbonate-gold nanoparticles inorganic hybrid composite.

A mediator-free hydrogen peroxide (H(2)O(2)) biosensor was fabricated based on immobilization of horseradish peroxidase (HRP) on layered calcium carbonate-gold nanoparticles (CaCO(3)-AuNPs) inorganic hybrid composite. The proposed biosensor showed a strong electrocatalytic activity toward the reduction of H(2)O(2), which could be attributed to the favored orientation of HRP in the well-confined surface as well as the high electrical conductivity of the resulting CaCO(3)-AuNPs inorganic hybrid composite. The hybrid composite was obtained by the adsorption of AuNPs onto the surfaces of layered CaCO(3) through electrostatic interaction. The key analytical parameters relative to the biosensor performance such as pH and applied potential were optimized. The developed biosensor also exhibited a fast amperometric response (3s), a good linear response toward H(2)O(2) over a wide range of concentration from 5.0x10(-7) to 5.2x10(-3)M, and a low detection limit of 1.0x10(-7)M. The facile, inexpensive and reliable sensing platform based on layered CaCO(3)-AuNPs inorganic hybrid composite should hold a huge potential for the fabrication of more other biosensors.

A novel assembly of Au NPs-beta-CDs-FL for the fluorescent probing of cholesterol and its application in blood serum.

A novel assembly of Au NPs-beta-CDs-FL for the fluorescent probing of cholesterol (Cho) is provided. Gold nanoparticles (Au NPs) possessing a high extinction coefficient function can be used as excellent fluorescent quenchers in Au NP-fluorophore composites. Inclusion of fluorescein (FL) into beta-cyclodextrin (beta-CD) makes fluorescence resonance energy transfer (FRET) occur through the donor and quencher nearby. FRET switches off because of the cholesterol-induced release of FL from beta-CD cavity, which results in the fluorescence recovery of the quenched dye. Spectral analysis supported the idea that the signal enhancement was attributed to the formation of an inclusion complex of the cholesterol moiety in beta-CD, resulting in separation of FL from the Au NPs. This phenomenon is explained by the guest-induced location change of the FL from inside to outside the cavity, suggesting that the assembly of Au NPs-beta-CDs-FL is effective as a fluorescent probe for cholesterol recognition. The fluorescence increase is proportional to the concentration of cholesterol in the range of approx. 30 nM to 15 muM. A concentration of cholesterol as low as 9 nM would be readily detected. The precision of the method applied to the determination of quantities of cholesterol present in human blood serum were satisfactory.

A new nanobiosensor for glucose with high sensitivity and selectivity in serum based on fluorescence resonance Energy transfer (FRET) between CdTe quantum dots and Au nanoparticles.

A novel assembled nanobiosensor QDs-ConA-beta-CDs-AuNPs was designed for the direct determination of glucose in serum with high sensitivity and selectivity. The sensing approach is based on fluorescence resonance energy transfer (FRET) between CdTe quantum dots (QDs) as an energy donor and gold nanoparticles (AuNPs) as an energy acceptor. The specific combination of concanavalin A (ConA)-conjugated QDs and thiolated beta-cyclodextrins (beta-SH-CDs)-modified AuNPs assembles a hyperefficient FRET nanobiosensor. In the presence of glucose, the AuNPs-beta-CDs segment of the nanobiosensor is displaced by glucose which competes with beta-CDs on the binding sites of ConA, resulting in the fluorescence recovery of the quenched QDs. Experimental results show that the increase in fluorescence intensity is proportional to the concentration of glucose within the range of 0.10-50 muM under the optimized experimental conditions. In addition, the nanobiosensor has high sensitivity with a detection limit as low as 50 nM, and has excellent selectivity for glucose over other sugars and most biological species present in serum. The nanobiosensor was applied directly to determine glucose in normal adult human serum, and the recovery and precision of the method were satisfactory. The unique combination of high sensitivity and good selectivity of this biosensor indicates its potential for the clinical determination of glucose directly and simply in serum, and provides the possibility to detect low levels of glucose in single cells or bacterial cultures. Moreover, the designed nanobiosensor achieves direct detection in biological samples, suggesting the use of nanobiotechnology-based assembled sensors for direct analytical applications in vivo or in vitro.

Probing hydroxyl radicals and their imaging in living cells by use of FAM-DNA-Au nanoparticles.

The incorporation of gold nanoparticles (Au NPs) as quencher modules in fluorescent probes for DNA damage caused by intracellular hydroxyl radicals (HO*) is reported. Au NPs of 15 nm diameter were decorated with DNA oligomers terminating in thiol functions in their 3' positions and possessing 5' fluorophore modifications. The Au NPs, which have high extinction coefficients, functioned as excellent fluorescent quenchers in the fluorophore-Au NP composites. FRET is switched off as a factor of HO*-induced strand breakage in the single-stranded DNAs, restoring the fluorescence of the quenched fluorophores, which can be followed by spectrofluorimetry. In vitro assays with HO*-generating Fenton reagent demonstrated increases in fluorescence intensity with a linear range from 8.0 nM to 1.0 microM and a detection limit as low as 2.4 nM. Confocal microscopic imaging of macrophages and HepG2 revealed that the probe is cell-permeable and intracellular HO*-responsive. The unique combination of good selectivity and high sensitivity establishes the potential value of the probe for facilitating investigations of HO*-mediated cellular homeostasis and injury.

One-dimensional hierarchical layered KxMnO2 (x < 0.3) nanoarchitectures: synthesis, characterization, and their magnetic properties.

One-dimensional (1D) hierarchical nanostructures of ultralong layered K(x)MnO(2) (x < 0.3) bundles with diameters 50-100 nm and lengths up to 50-100 microm have been successfully prepared by a PEG-assisted hydrothermal method based on the reaction of KMnO(4) with 2-ethylhexanol. The obtained samples ascribe to the monoclinic phase and exhibit ferromagnetic behaviors below 32 K and paramagnetic behaviors above 32 K, which may make this system a promising base material for magnetic devices. A series of contrastive experiments have illustrated that 2-ethylhexanol, PEG 400, KOH, and reaction time play an important role in the synthesis of the nanobundles. A possible growth mechanism has been proposed.

Facile route to alpha-FeOOH and alpha-Fe2O3 nanorods and magnetic property of alpha-Fe2O3 nanorods.

alpha-FeOOH nanorods with diameters of 15-25 nm and lengths up to 170-300 nm were synthesized in high yield via a facile and template-free hydrothermal method at low temperature. After calcining the as-synthesized alpha-FeOOH at 250 degrees C for 2 h, we could obtain alpha-Fe2O3 nanorods. Interestingly, the as-obtained alpha-Fe2O3 nanorods exhibited weakly ferromagnetic characteristics at low temperature and superparamagnetic property at room temperature, which is different from the behavior of the corresponding bulk material.