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CuO/SiO2 heterogeneous hollow cubes have been successfully fabricated under hydrothermal conditions. XRD, SEM and EDX under TEM studies confirm that CuO nanoparticles deposit on the surface of SiO2 hollow cubic templates. In virtue of their heterogeneous and hollow structures as well as higher specific surface area, CuO/SiO2 heterogeneous hollow cubes exhibit enhanced photocatalytic properties compared to P25 TiO2, SiO2 hollow cubes and CuO hierarchical microflowers. [ABSTRACT FROM AUTHOR]

Fe2O3 nanosheets and nanoparticles are grown on graphene by simply varying reaction solvents in a facile solvothermal/hydrothermal preparation. Fe2O3 nanosheets are uniformly dispersed among graphene nanosheets, forming a unique sheet-on-sheet nanostructure. Due to the structure affinity between two types of two dimensional nanostructures, graphene nanosheets are separated better by Fe2O3 nanosheets compared to nanoparticles and their agglomeration is largely prevented. Alarge surface area of 173.9 m2 g-1 is observed for Fe2O3-graphene sheet-on-sheet composite, which is more than two times as large as that of Fe2O3-graphene particle-on-sheet composite (81.5 m2 g-1). The sheet-on-sheet composite is found to be better suitable as an anode for Li-ion battery. A high reversible capacity of 662.4 mAh g-1 can be observed after 100 cycles at 1000 mA g-1. The substantially improved cycling performance is ascribed to the unique structure affinity between Fe2O3 nanosheets and graphene nanosheets, thus offering complementary property improvement. [ABSTRACT FROM AUTHOR]

Engineering the topography of thin block copolymer (BCP) films by surface reconstruction associated with selective swelling of one of the blocks has been investigated intensively. Here we show that swelling-induced structural transitions in nanorods consisting of amphiphilic BCPs involve pronounced reshaping of the nonswollen glassy domains in the course of the transition from the equilibrium morphology of the molten BCP in cylindrical confinement to that of the BCP dissolved in the swelling agent. The reconstruction process can be quenched to retain intermediate nonequilibrium morphologies. The collapse of the swollen chains upon drying yields polymeric nanorods exhibiting complex nanoscopic architectures characterized by a variety of mesopore structures and surface topographies, including channels along the nanorods, bunches of partially interconnected strands, and strings of spheres. The complex BCP nanorods thus obtained can be used as soft templates for the rational arrangement of metal nanoparticles. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis of iron oxide nanoparticles using a freshly-made or recycled 1-butyl-3-methylimidazolium bis(triflylmethylsulfonyl)imide ([BMIM][Tf2N]) ionic liquid (IL). Iron pentacarbonyl (Fe(CO)5), which dissolves in [BMIM][Tf2N], thermally decomposed and subsequently oxidized to form iron oxide nanoparticles. These nanoparticles separated out automatically from the imidazolium-based ionic liquid mixtures. Multiple additional runs were tested in making iron oxide nanoparticles using recycled ionic liquid. The iron oxide nanoparticles made were characterized with transmission electron microscopy (TEM), high resolution TEM (HR-TEM) and powder X-ray diffraction (PXRD). The structure and thermal stability of the IL was examined using Fourier transform infrared (FT-IR) spectroscopy and thermal gravimetric analysis (TGA). We found that iron oxide nanoparticles with a narrow size distribution could be obtained. The [BMIM][Tf2N] ionic liquid showed no degradation based on the TGA and FT-IR study. The solvent-recyclable process of making size-controlled nanoparticles should have a broad impact on the application of imidazolium-based ionic liquids in the synthesis of nanomaterials. [ABSTRACT FROM AUTHOR]

1. Nanobiotechnologies have recently attracted significant attention from chemists, biologists, engineers and pharmaceutical scientists. In particular, they have been widely applied to improve drug, protein/peptide and gene delivery. 2. This review presents recent advances in the field of drug, protein/peptide and gene delivery using natural and synthetic polymer nanoparticles and explains how polymeric nanoparticles are specifically designed to suit the needs for targeted delivery of small molecular drugs, proteins/peptides and genes. In addition, some of the challenges and prospects for these technologies are discussed. [ABSTRACT FROM AUTHOR]

• Polymorphism of formed NiO nanoparticles with size in 25-50 nm was observed. • High toxicity of nanoparticles was witnessed against MG-63 cancer cells. • NiO nanoparticles revealed high biocompatibility on HEK293 normal cells. • Nanoparticles showed bactericidal activity on various human pathogenic bacteria. The green synthesis of metal oxide nanoparticles is interestingly becoming familiar as the reason of its non-toxicity, economical, eco-friendly, and commerciality. The secondary metabolites and bioactive molecules in biomaterial extract play an important role of reducing, capping, stabilizing and chelating activities to form the nanoparticles as a substitute of hazardous chemical surfactants. Hence this present work concentrated on the biogenic synthesis of NiO nanoparticles using grains extract of Oryza longistaminata (red rice), and their toxicity assessment as well as biomedical applications. The synthesized nanoparticles were widely characterized by using several analytical and biomedical techniques. The reduction mechanism of Ni2+ ions using major active phytocompound in red rice grains extract was stated. UV–visible spectroscopic analysis revealed the formation of NiO nanoparticles by emerging the sharp surface Plasmon resonance band at 326 nm. The absorption peaks of red rice grains extract at 206, 260, 330 and 410 nm stated the presence of phytocompounds in them. X-ray diffraction pattern explicated the high crystallinity of NiO nanoparticles and their average crystallite size was found to be at 36 nm. The diffraction pattern of red rice grains revealed the amorphous characteristic. Fourier transform infrared analysis displayed the different vibrational functional groups of nanoparticles and red rice grains. Dynamic light scattering analysis showed the particle size distribution was in between 30-65 nm. High-resolution transmission electron microscopic analysis showed the hexagonal, rectangular, oval and spherical shaped polymorphism of NiO nanoparticles and their size was in 25-50 nm. Energy dispersive X-ray spectrum and mapping analyses validated the formation of NiO nanoparticles by the major existence of Ni and O elements. The high toxicity of nanoparticles towards MG-63 osteosarcoma cancer cells was revealed at 94.69% in 100 μg/mL concentration. The nanoparticles showed no severe toxicity against HEK293 normal cells and red blood cells till higher concentration. The biomedical analyses such as antioxidant, anti-inflammatory and anti-diabetic activities exposed the potential bio-drug activity of NiO nanoparticles with maximum activity of 86.22, 84.23 and 85.18% in the high concentration of 80 μg/mL. The antibacterial activity divulged the good bactericidal drug nature of NiO nanoparticles against both Gram-positive (S. aureus and B. Subtilis) and Gram-negative (S. typhi and K. pneumonia) bacteria with low MBC/MIC ratio. As per the assessment of results, the biosynthesized NiO nanoparticles have non-carcinogenic, high biocompatible and potent nature and it suggests that they can be used as therapeutic candidates in biomedical, clinical and pharmaceutical fields for treating various diseases. [Display omitted] [ABSTRACT FROM AUTHOR]

The article measures the surface-enhanced Raman scattering (SERS) in colloidal nanoparticle dimers and trimers. It notes that SERS is strong in plasmon-coupled metal nanoparticles (NPs) gap. It points out that SERS enhacement factor (EF) relies on the specific hotspot which makes it difficult to compare different nanocluster results.

The article focuses on the separation of high-purity gold nanoparticle dimers and trimers. Study shows that CsCl solution's higher density and viscosity may slow down the nanoclusters and enhance sedimentation velocity's relative difference. It points out that its approach offers a fluent separation method without additional inconvenience as the structural intactness is vital for nanoassembly construction.

In this study, a novel intelligent nanoplatform to integrate multiple imaging and therapeutic functions for targeted cancer theranostics. The nanoplatform, DOX@Gd-MFe3O4 NPs, was constructed Gd-doped mesoporous Fe3O4 nanoparticles following with the doxorubicin (DOX) loading in the mesopores of the NPs. The DOX@Gd-MFe3O4 NPs exhibited good properties in colloidal dispersity, photothermal conversion, NIR triggered drug release, and high T1/T2 relaxicity rate (r1=9.64mM-1s-1, r2= 177.71mM-1s-1). Benefiting from the high MR contrast, DOX@Gd-MFe3O4 NPs enabled simultaneous T1/T2 dual-modal MR imagining on 4T1 bearing mice in vivo and the MR contrast effect was further strengthened by external magnetic field. In addition, the DOX@Gd-MFe3O4 NPs revealed the strongest inhibition to the growth of 4T1 in vitro and in vivo under NIR irradiation and guidance of external magnetic field. Moreover, biosafety was also validated by in vitro and in vivo tests. Thus, the prepared DOX@Gd-MFe3O4 NPs would provide a promising intelligent nanoplatform for dual-modal MR imagining guided synergistic therapy in cancer theranostics. [ABSTRACT FROM AUTHOR]

In this study, cationic nanoparticles self-assembled from the amphiphilic copolymer poly(N-methyldietheneamine sebacate)-co-[(cholesteryl oxocarbonylamido ethyl) methyl bis(ethylene) ammonium bromide] sebacate) (P(MDS-co-CES) were synthesized and used to deliver Bcl-2 targeted siRNA into HepG2, HeLa and MDA-MB-231 cell lines, and downregulate Bcl-2 mRNA expression levels. Confocal microscopic studies show that the nanoparticles were able to complex with siRNA and deliver it inside the cells efficiently, but siRNA was easily dissociated from the complexes in the cytoplasm for its biological functions. Bcl-2 mRNA expression levels as low as 10% were achieved after treatment with nanoparticle/siRNA complexes. The downregulation efficiency of Bcl-2 mRNA level was similar to that mediated by Lipofectamine but higher than that induced by PEI. PEG was also conjugated to siRNA via a cleavable disulfide bond, and nanoparticle/siRNA-PEG complexes showed no significant protein adsorption as compared with 26 and 17% for blank nanoparticles and nanoparticle/siRNA complexes, respectively. The presence of serum caused slight aggregation of nanoparticle/siRNA or nanoparticle/siRNA-PEG complexes. However, the size of the complexes was still below 250 nm after being incubated in PBS containing 10% serum for 4 h. On the other hand, PEGylated siRNA delivered by the nanoparticles downregulated Bcl-2 mRNA expression level in the cells as efficiently as unmodified siRNA. Bcl-2 protein was also downregulated efficiently by nanoparticle/siRNA complexes in all cell lines tested. The downregulation of Bcl-2 mRNA or Bcl-2 protein did not show significant cell death in the tested siRNA and polymer concentration range. However, the delivery of siRNA sensitized HeLa cells to paclitaxel treatment, yielding significant improvement over the untreated cells (p< 0.05). These cationic nanoparticles may be potentially employed to downregulate Bcl-2 expression and sensitize cancer cells to anticancer drugs for more efficient chemotherapy. [ABSTRACT FROM AUTHOR]

A new preparation process of the vanadium catalyst with nano-V2O5 particles was introduced in this paper. The inorganic sol-gel method is used to prepare the sols and gels with p nano-V2O5 particles. The morphology, size and distribution of the nano-V2O5 particles in the sols-gels and vanadium catalyst had been studied by TEM, SEM, XRD and DSC. The results show that with the w/v (the ratio of water and vanadium) declining, the morphology of the nano-V2O5 particles varies from needle to near-ball then to sphere; the better process parameter to prepare the sols and gels with nano-V2O5 particles is 800~860°C×10~15min; the sols and gels and catalyst with 30~60nm V2O5 particles had been obtained by this process. [ABSTRACT FROM AUTHOR]

• The structure–activity relationship of Fe nanoparticles in the CO activation process was investigated. • Structures includes four aspects: morphologies, sizes, defects, and hetero atoms. • Line dislocation and vacancies suggest an effective way to tune the CO dissociation rate. • CO 2 formation: Eley–Rideal vs. Langmuir–Hinshelwood mechanism. The structure–activity relationship is crucial in catalytic performance and material design but still largely obscure due to the complexity of heterogeneous catalytic systems. CO activation occurs widely in Fischer–Tropsch reactions and pyrometallurgy, and it is a key to understanding carburization. Here, we investigate the structure–activity relationship in Fe nanoparticles by reactive molecular dynamics simulations. We focus on two activities, the adsorption and dissociation of CO, and four structural characteristics, morphologies, sizes, defects, and heteroatoms. The results show that CO adsorption and dissociation varies with the change of nanoparticles. Line dislocation and vacancies can strikingly boost CO dissociation, suggesting an effective way to tune the CO dissociation rate. Further analysis shows that the Eley–Rideal mechanism possibly works in the early periods, followed by the Langmuir–Hinshelwood mechanism in the later periods for CO 2 formation. Our results shed light on the mechanism and possible optimization of the carburization of iron. [ABSTRACT FROM AUTHOR]

Atomically precise metal clusters have attracted increasing interest owing to their unique size-dependent properties; however, little has been known about the effect of size on the catalytic properties of metal clusters at the single-cluster level. Here, by real-time monitoring with single-molecule fluorescence microscopy the size-dependent catalytic process of individual Au clusters at single-turnover resolution, we study the size-dependent catalytic behaviors of gold (Au) clusters at the single-cluster level, and then observe the strong size effect on the catalytic properties of individual Au clusters, in both catalytic product formation and dissociation processes. Surprisingly, indicated by both experiments and density functional theory (DFT) calculations, due to such a unique size effect, besides observing the different product dissociation behaviors on different-sized Au clusters, we also observe that small Au clusters [i.e., Au15(MPA)13; here, MPA denotes 3-mercaptopropionic acid] catalyze the product formation through a competitive Langmuir-Hinshelwood mechanism, while those relatively larger Au clusters [e.g., Au18(MPA)14 and Au25(MPA)18] or nanoparticles catalyze the same process through a noncompetitive Langmuir-Hinshelwood mechanism. Such a size effect on the nanocatalysis could be attributed intrinsically to the size-dependent electronic structure of Au clusters. Further analysis of dynamic activity fluctuation of Au clusters reveals more different catalytic properties between Au clusters and traditional Au nanoparticles due to their different size-dependent structures. [ABSTRACT FROM AUTHOR]

Incorporation of guest materials inside single-crystalline hosts leads to single-crystal composites that have become more and more frequently seen in both biogenic and synthetic crystals. The unique composite structure together with long-range ordering promises special properties that are, however, less often demonstrated. Here, we examine the fluorescent properties of quantum dots (QDs) and polymer dots (Pdots) encapsulated inside the hosts of calcite single-crystals. Two CdTe QDs and two Pdots are incorporated into growing calcite crystals, as the QDs and Pdots are dispersed in the crystallization media of agarose gels. As a result, enhanced fluorescent properties are obtained from the QDs and Pdots inside calcite single-crystals with greatly improved photostability and significantly prolonged fluorescence lifetime, compared to those in solutions and gels. Particularly, the fluorescence lifetime increases by 0.5-1.6 times after the QDs or Pdots are incorporated. The enhanced fluorescent properties indicate the advantages of encapsulation by single-crystal hosts that provide dense shells to isolate the fluorescent nanoparticles from atmosphere. As such, this work has implications for advancing the research of single-crystal composites toward their functional design. [ABSTRACT FROM AUTHOR]

In oil industry, wax deposition is one of the frequently encountered problems that causes severe issues during the production, storage, and transportation of crude oil. Recently, it is found that addition of nanohybrids to crude oil is an effective method to solve this problem. However, the mechanism of how nanoparticles affect the wax crystallization and rheological behavior of crude oil has not been clearly understood. Here we reported the influence of SiO2 nanoparticles on crystallization and rheological behavior of model oils with and without asphaltene and resin. It was demonstrated that the wax appearance temperature increased upon the addition of SiO2 nanoparticles of model oil without asphaltenes and resin, while the rheological behavior was less affected. When in the presence of asphaltenes and resin, the amount of wax crystals, wax appearance temperature, and rheological parameter of model oils were found to decrease while SiO2 nanofluid was added, resulting in the improvement of flowability. [ABSTRACT FROM AUTHOR]

Despite being promising substitutes for noble metal catalysts used in hydrogen evolution reaction (HER), the nonprecious metal catalysts (NPMCs) based on inexpensive and earth-abundant 3d transition metals (TMs) are still practically unfeasible due mainly to unsatisfactory activity and durability. Herein, a highly active and stable catalyst for HER has been developed on the basis of molybdenum-carbide-modified N-doped carbon vesicle encapsulating Ni nanoparticles (MoxC-Ni@NCV). This Mox-CN@NCV material was synthesized simply by the solid-state thermolysis of melamine-related composites of oxalate and molybdate with uniform Ni ions doping (Ni@MOM-com). Notably, the prepared MoxC-Ni@NCV was almost the most efficient NPMCs for HER in acidic electrolyte to date. Besides good long-term stability, MoxC-Ni(o)NCV exhibited a quiet low overpotential that was comparable to Pt/C. Thus, this work opens a new avenue toward the development of highly efficient, inexpensive HER catalysts. [ABSTRACT FROM AUTHOR]

• The mechanism for eliminating adsorbed oxygen by the reduction with H and CO on χ-Fe 5 C 2 surfaces was investigated. • The removal mechanism shows diversity over different facets. • Carbon-rich surface exhibits higher barriers to direct CO 2 formation, like (110) and (111). The removal of surface oxygen adsorbed on iron carbides is essential to protect the nanoparticle from oxidation in heterogeneous catalysis. Herein, we explored the removal of pre-adsorbed oxygen on seven facets of χ-Fe 5 C 2, and four pathways including both direct and indirect routes for generating H 2 O and CO 2 were investigated. The removal mechanism shows diversity over different facets. On (010), the formation of CO 2 through the reaction between surface oxygen and adsorbed CO is more favorable. While on (510), (001), (110), (11-1) and (-411), the elimination in the form of H 2 O through OH disproportionation dominates. In particular, surface oxygen can be removed facilely either in H 2 O or CO 2 on (111) surface. What's more, surface with more carbons exhibits higher barriers to direct CO 2 formation, like (110) and (111). Our work provides knowledge about mechanism of O removal and CO 2 formation, which may be helpful in protecting the nanoparticle from further oxidation. Graphical Abstract [Display omitted]. [ABSTRACT FROM AUTHOR]

Multimodal imaging probes represent an extraordinary tool for accurate diagnosis of diseases due to the complementary advantages of multiple imaging modalities. The purpose of the work was to fabricate a simple dual-modality MR/CT probe for osteosarcoma visualization in vivo. Protein-directed synthesis methods offer a suitable alternative to MR/CT probe produced by synthetic chemistry. Bovine serum albumin (BSA) bound to gadolinium nanoparticles (GdNPs) was first prepared via a biomimetic synthesis method and was subsequently iodinated by chloramine-T method. The final iodinated BSA-GdNPs (1-BSA-GdNPs) showed excellent chemical stability and biocompatibility, intense X-ray attenuation coefficient, and good MR imaging ability. However, an iodinated protein nanoparticles synthesis for MR/CT imaging, as well as its useful application, has not been reported yet. Intravenous injection of I-BSA-GdNPs into orthotopic osteosarcoma-bearing rats led to its accumulation and retention by the tumor, allowing for a noninvasive tumor dual-modality imaging through the intact thigh. The long-circulating dual-model I-BSA-GdNPs probes possess potential application for image-guided drug delivery and image-guided surgery. Our study is therefore highlighting the properties of albumin in this field combined with its useful use in dual-model MR/CT osteosarcoma visualization, underlining its potential use as a drug carrier for a future therapy on cancer. [ABSTRACT FROM AUTHOR]

Continuous and uniform carbon nanofilms (CNFs) are prepared by pyrolysis of polyimide films which are produced by molecular layer deposition (MLD). The film thickness can be easily controlled at nanometer scale by altering the cycle numbers. During the annealing process at 600 °C, the polyimide film is subject to shrinkage of 70% in thickness. The obtained CNFs do not exhibit a well-graphitized structure due to the low calcination temperature. No clear pore structures are observed in the produced films. CNFs grown on a glass substrate with a thickness of about 1.4 nm shows almost 98% optical transmittance in the visible spectrum range. Au nanoparticles coated with CNFs are produced by this method. Carbon nanotubes with uniform wall thickness are obtained using anodic aluminum oxide as a template by depositing polyimide films into its pores. Our results demonstrate that this method is very effective to coat conformal and uniform CNFs on various substrates, such as nanoparticles and porous templates, to produce functional composite nanomaterials. [ABSTRACT FROM AUTHOR]

We report a catalyst made of Pd nanoparticles (NPs) supported on mesoporous N-doped carbon, Pd@CN0132, which was shown to be highly active in promoting biomass refining. The use of a task-specific ionic liquid (3-methyl-1-butylpyridine dicyanamide) as a precursor and silica NPs as a hard template afforded a high-nitrogen-content (12 wt %) mesoporous carbon material that showed high activity in stabilizing Pd NPs. The resulting Pd@CN0.132 catalyst showed very high catalytic activity in hydrodeoxygenation of vanillin (a typical model compound of lignin) at low H2 pressure under mild conditions in aqueous media. Excellent catalytic results (100% conversion of vanillin and 100% selectivity for 2-methoxy-4-methylphenol) were achieved, and no loss of catalytic activity was observed after six recycles. [ABSTRACT FROM AUTHOR]

Metal and metal oxide nanoparticles supported on high surface area materials are widely used in industry for fuel and chemical production and for environmental pollution control, but preventing nanosized particle sintering has remained a great challenge. In this paper, we report that Ni−Cu alloy nanoparticles can be effectively stabilized in cubic mesostructured silica (SBA-16) following a conventional impregnation and thermal treatment process. The three-dimensional interconnected cage structure of the mesoporous SBA-16 allows good accessibility of reactant gas molecules to the metal nanoparticles and confines these particles within its nanosized cages. This confinement hinders metal nanoparticle migration and sintering under harsh conditions. A new class of regenerable metal-based adsorbents which can remove sulfur impurities from warm syngas stream down to less than 60 parts per billion by volume (ppbv) is described. This same confinement strategy is expected to have impact for minimizing sintering or particle coarsening of nanosized materials employed in other applications. [ABSTRACT FROM AUTHOR]

Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H3PW12O40 (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1 -butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including 31P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support. [ABSTRACT FROM AUTHOR]

In this work, we reported an approach for the site-selective growth of nanoparticle onto the tip apex of an atomic force microscopy (AFM) probe. The silicon AFM probe was first coated with a self-assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) through a chemical vapor deposition (CVD) method. Subsequently, COOH groups were selectively generated at the tip apex of silicon AFM probes by applying an appropriate bias voltage between the tip and a flat gold electrode. The transformation of methyl to carboxylic groups at the tip apex of the AFM probe was investigated through measuring the capillary force before and after electrochemical oxidation. To prepare the nanoparticle terminated AFM probe, the oxidized AFM probe was then immersed in an aqueous solution containing positive metal ions, for example, Ag +, to bind positive metal ions to the oxidized area (COOH terminated area), followed by chemical reduction with aqueous NaBH 4and further development (if desired) to give a metal nanoparticle-modified AFM probe. The formation of a metal nanoparticle at the tip apex of the AFM probe was confirmed by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA). [ABSTRACT FROM AUTHOR]