Size-tailored synthesis and luminescent properties of one-dimensional Gd2O3 : Eu3+ nanorods and microrods

Nearly monodisperse and well-defined one-dimensional (1D) Gd2O3:Eu3+ nanorods and microrods were successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent heat treatment process, without using any catalyst or template. X-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The size of the Gd2O3:Eu3+ rods could be modulated from micro- to nanoscale with the increase of pH value using ammonia solution. The as-formed product via the hydrothermal process, Gd(OH)(3):Eu3+, could transform to cubic Gd2O3:Eu3+ with the same morphology and a slight shrinking in size after a postannealing process.

Core Crosslinking of Biodegradable Block Copolymer Micelles Based on Poly(ester carbonate)

A biodegradable amphiphilic block copolymer, PEG-b-P(LA-co-MAC), was used to prepare spherical micelles consisting of a hydrophobic P(LA-co-MAC) core and a hydrophilic PEG shell. To improve their stability, the micelles were crosslinked by radical polymerization of the double bonds in the hydrophobic blocks. The crosslinked micelles had similar sizes and a narrow size distribution compared to their uncrosslinked precursor. The improved stability of the crosslinked micelles was confirmed by measurements of the CMC and a thermodynamic investigation. These micelles can internalize into Hela cells in vitro as demonstrated by inverted fluorescence microscopy and CLSM. These stabilized nanoscale micelles have potential use in biomedical applications such as drug delivery and disease diagnosis.

Facile synthesis of polyaniline nanofibers using pseudo-high dilution technique

A new approach for the synthesis of polyaniline nanofibers under pseudo-high dilute conditions in aqueous system has been developed. High yield nanoscale polyaniline fibers with 18-110 nm in diameter are readily prepared by a high aniline concentration 0.4 M oxidation polymerization using ammonium persulfate (APS) as an oxidant in the presence of hydrochloric acid (HCl), perchloric acid (HClO4), (1S)-(+)-10-camphorsulfonic acid (CSA), acidic phosphate PAEG120 (PA120) and sulfuric acid (H2SO4) as the dopants. The novel pathway always produces polyaniline nanofibers of tunable diameters, high conductivity (from 10(0) to 10(1) S/cm) and crystallinity.

Photoinduced DNA Cleavage by alpha-, beta-, and gamma-Cyclodextrin-Bicapped C-60 Supramolecular Complexes

Water-soluble supramolecular inclusion complexes of alpha-, beta-, and gamma-cyclodextrin-bicapped C-60 (CD/C-60) have been investigated for their photoinduced DNA cleavage activities, with the aim to assess the potential health risks of this class of compounds and to understand the effect of host cyclodextrins having different cavity dimensions. Factors such as incubation temperature, irradiation time, and concentration of NADH or CDs/C-60 supramolecular inclusion complexes have been examined. The results show that alpha-, beta-, and gamma-CDs/C-60 are all able to cleave double-stranded DNA under visible light irradiation in the presence of NADH. However, a difference in the photoinduced DNA cleavage efficiency is observed, where the cleavage efficiency increases in the order of alpha-, beta-, and gamma-CD/C-60. The difference is attributed to the different aggregation behavior of the inclusion complexes in aqueous solution, which is correlated to the cavity dimension of the host cyclodextrin molecules.

A facile synthesis and characterization of monodisperse spherical pigment particles with a core/shell structnre

In this paper, a facile sol-gel process for producing monodisperse, spherical, and nonaggregated pigment particles with a core/shell structure is reported. Spherical silica particles (245 and 385 nm in diameter) and Cr2O3, alpha-Fe2O3, ZnCo2O4, CuFeCrO4, MgFe2O4, and CoAl2O4 pigments are selected as cores and shells, respectively. The obtained core/shell-structured pigment samples, denoted as SiO2@Cr2O3 (green), SiO2@alpha-Fe2O3 (red), SiO2@MgFe2O4 (brown), SiO2@ZnCo2O4 (dark green), SiO2@CoAl2O4 (blue), and SiO2@CuFeCrO4 (black), are well characterized by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and UV-vis diffuse reflection, as well as by investigating the magnetic properties. The results of XRD and high-resolution TEM (HRTEM) demonstrate that the pigment shells crystallize well on the surface Of SiO2 Particles. The thickness of the pigment shell can be tuned by the number of coatings, to some extent. These pigment particles can be well dispersed in some solvents (such as glycol) to form relatively more stable suspensions than the commercial products.

Biofunctionalization of CeF3 : Tb3+ nanoparticles

CeF3: Tb3+ nanoparticles (short pillar-like morphology with an average length and width of 11 and 5 nm, respectively) were successfully prepared by a polyol process using diethyleneglycol (DEG) as solvent. After being functionalized with a SiO2-NH2 layer, these CeF3: Tb3+ nanoparticles can be conjugated with biotin molecules (activated by thionyl chloride) and further with avidin. The as-formed CeF3: Tb3+ nanoparticles, CeF3: Tb3+ nanoparticles functionalized with amino groups, biotin conjugated amino-functionalized CeF3: Tb3+ nanoparticles and biotinylated CeF3: Tb3+ nanoparticles bonded with avidin were characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), UV/vis absorption spectra and luminescence spectra, respectively. The biofunctionalization of the CeF3: Tb3+ nanoparticles has less effect on their luminescence properties, i.e. they still show strong green emission (from Tb3+, with D-5(4) - F-7(5) at 543 nm as the most prominent group), indicative of the great potential for these CeF3: Tb3+ nanoparticles to be used as biological fluorescence probes.

Nanoelectrode ensembles based on semi-interpenetrating network of carbon nanotubes

A method for preparing nanoelectrode ensembles based on semi-interpenetrating network (SIN) of multi-walled carbon nanotubes (MWNTs) on gold electrode through phase-separation method is initially proposed. Individual nanoelectrode owns irregular three-dimensional MWNTs networks, which is denoted as SIN-MWNTs. On the as-prepared SIN-MWNTs nanoelectrode ensembles, the assembled MWNTs clusters in nanoscale serve as individual nanoelectrode and the electroinactive lipid networks located on the top of alkanethiol monolayer are used as a shielding layer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy (SEM) were used to characterize the as-prepared SIN-MWNT nanoelectrode ensembles. Experimental results indicate that the well-defined nanoelectrode ensembles were prepared through self-assembly technology. Meantime, sigmoid curves in a wide scanning range can be obtained in CV experiments. This study may pave the way for the construction of truly nanoscopic nanoelectrode arrays by bottom-up strategy.

Toward high-performance polymer solar cells: The importance of morphology control

Polymer solar cells have the potential to become a major electrical power generating tool in the 21st century. R&D endeavors are focusing on continuous roll-to-roll printing of polymeric or organic compounds from solution-like newspapers-to produce flexible and lightweight devices at low cost. It is recognized, though, that besides the functional properties of the compounds the organization of structures on the nanometer level-forced and controlled mainly by the processing conditions applied-determines the performance of state-of-the-art polymer solar cells. In such devices the photoactive layer is composed of at least two functional materials that form nanoscale interpenetrating phases with specific functionalities, a so-called bulk heterojunction. In this perspective article, our current knowledge on the main factors determining the morphology formation and evolution is introduced, and gaps of our understanding on nanoscale structure-property relations in the field of high-performance polymer solar cells are addressed. Finally, promising routes toward formation of tailored morphologies are presented.

Facile transformation of hydrophilic cellulose into superhydrophobic cellulose

Superhydrophobic cellulose-based materials coupled with transparent, stable and nanoscale polymethylsiloxane coating have been successfully achieved by a simple process via chemical vapor deposition, followed by hydrolyzation and polymerization.

Enantiomeric PLA-PEG block copolymers and their stereocomplex micelles used as rifampin delivery

A novelty approach to self-assembling stereocomplex micelles by enantiomeric PLA-PEG block copolymers as a drug delivery carrier was described. The particles were encapsulated by enantiomeric PLA-PEG stereocomplex to form nanoscale micelles different from the microspheres or the single micelles by PLLA or PDLA in the reported literatures. First, the block copolymers of enantiomeric poly(L-lactide)-poly(ethylene-glycol) (PLLA-PEG) and poly(D-lactide)-poly(ethylene-glycol) (PDLA-PEG) were synthesized by the ring-opening polymerization of L-lactide and D-lactide in the presence of monomethoxy PEG, respectively. Second, the stereocomplex block copolymer micelles were obtained by the self-assembly of the equimolar mixtures of enantiomeric PLA-PEG copolymers in water. These micelles possessed partially the crystallized hydrophobic cores with the critical micelle concentrations (cmc) in the range of 0.8-4.8 mg/l and the mean hydrodynamic diameters ranging from 40 to 120 nm. The micelle sizes and cmc values obviously depended on the hydrophobic block PLA content in the copolymer.Compared with the single PLLA-PEG or PDLA PEG micelles, the cmc values of the stereocomplex micelles became lower and the sizes of the stereocomplex micelles formed smaller. And lastly, the stereocomplex micelles encapsulated with rifampin were tested for the controlled release application.

Synthesis and properties of a novel isomeric polyimide/SiO2 hybrid material

A novel isomeric polyimide/SiO2 hybrid material was successfully prepared through sol-gel technique, and its structure, thermal properties and nano-indenter properties were investigated. First, 3-[(4-phenylethynyl)phthalimide]propyl triethoxysilane (PEIPTES) was successfully synthesized, its structure was characterized by elemental analysis, FT-IR and C-13 NMR. The researches on solubility and thermal properties of PEIPTES show that it can be used for modifying nano-SiO2 precursor. Nano-SiO2 precursor was synthesized by tetraethoxysilane (TECS) through sol-gel technique. Then the PEIPTES solution and the nano-SiO2 precursor were mixed for 6 h to let the PEIPTES molecules react with the nano-SiO2 precursor, and modified nano-SiO2 precursor was obtained. The modified reaction was confirmed by the analyses of FT-IR. At last, isomeric polyimide/SiO2 hybrid material was produced by using isomeric polyimide resin solution and the modified nano-SiO2 precursor after heat treatment process. The structure analysis by SEM indicated that SiO2 particles dispersed in isomeric polyimide matrix homogeneously with nanoscale. Thermogravimetric analyzer, dynamic mechanical thermal analyzer and nano-indenter XP was employed to detect the properties of the materials, the results demonstrated that isomeric polyimide/SiO2 hybrid material has much better thermal properties and nano-indenter properties than those of isomeric polyimide.

Manipulations of atoms and molecules by scanning probe microscopyk

Scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), has become a powerful tool in building nanoscale structures required by modern industry. In this article, the use of SPM for the manipulation of atoms and molecules for patterning nanostructures for opt-electronic and biomedical applications is reviewed. The principles and procedures of manipulation using STM and AFM-based technologies are presented with an emphasis on their ability to create a wide variety of nanostructures for different applications. The interaction among the atoms/molecules, surface, and tip are discussed. The approaches for positioning the atom/molecule from and to the desired locations and for precisely controlling its movement are elaborated for each specific manipulation technique. As an AFM-based technique, the dip-pen nanolithography is also included. Finally, concluding remarks on technological improvement and future research is provided.

Solvent-induced microphase separation in diblock copolymer thin films with reversibly switchable morphology

We have studied the surface morphology of symmetric poly(styrene)-block-poly(methyl methacrylate) diblock copolymer thin films after solvent vapor treatment selective for poly(methyl methacrylate). Highly ordered nanoscale depressions or striped morphologies are obtained by varying the solvent annealing time. The resulting nanostructured films turn out to be sensitive to the surrounding medium, that is, their morphologies and surface properties can be reversibly switchable upon exposure to different block-selective solvents.

Direct patterning of rhodamine 6G molecules on mica by dip-pen nanolithography

Dip-pen nanolithography (DPN) has been developed to pattern monolayer film of various molecules on suitable substrate through the controlled movement of ink-coated atomic force microscopy (AFM) tip, which makes DPN a potentially powerful tool for making the functional nanoscale devices. In this paper, the direct patterning of rhodamine 6G on mica by dip-pen nanolithography was demonstrated. R6G features patterned on the mica was successfully achieved with different tip movement which can be programmed by Nanoscript(TM) language. From the AFM image of R6G patterns, we know that R6G molecule is flatly binding to the mica surface through electrostatic interaction, thus stable R6G nanostructures could be formed on mica. The influence of translation speed and contact time on DPN was discussed. The method can be extended to direct patterning of many other organic molecules, and should open many opportunities for miniaturized optical device and site-specific biological staining.

The influence of tip performance on scanning probe lithography

Scanning probe lithography (SPL), employing the tip of an atomic force microscope to mechanically pattern various materials in nanoscale region has provided a simple but significant method for making nanostructures. We use this technique for the lithography of several kinds of substrate surfaces. The tip performance has been found to be a crucial factor in the lithographic process. Four types of cantilevers are employed in nanolithography, including standard silicon nitride (DNP), tapping mode(TM) etched silicon (TESP(W)), uncoated silicon cantilever (NSC21/50) and conductive platinum/iridium-coated probe. Results demonstrate that tips with smaller spring constants can not be used for physically scribing and nanomanipulating in our experiment. The possible mechanism of our experiment is discussed.