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Showing papers in "Journal of the American Chemical Society in 2004"


Journal ArticleDOI
TL;DR: Arc-synthesized single-walled carbon nanotubes have been purified through preparative electrophoresis in agarose gel and glass bead matrixes and promise to be interesting nanomaterials in their own right.
Abstract: Arc-synthesized single-walled carbon nanotubes have been purified through preparative electrophoresis in agarose gel and glass bead matrixes. Two major impurities were isolated: fluorescent carbon and short tubular carbon. Analysis of these two classes of impurities was done. The methods described may be readily extended to the separation of other water-soluble nanoparticles. The separated fluorescent carbon and short tubule carbon species promise to be interesting nanomaterials in their own right.

3,357 citations


Journal ArticleDOI
Shouheng Sun1, Hao Zeng1, David B. Robinson1, Simone Raoux1, Philip M. Rice1, Shan X. Wang1, Guanxiong Li1 
TL;DR: As-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD and can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made.
Abstract: High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)3, with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe3O4) nanoparticles. Similarly, reaction of Fe(acac)3 and Co(acac)2 or Mn(acac)2 with the same diol results in monodisperse CoFe2O4 or MnFe2O4 nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe3O4 can be oxidized to Fe2O3, as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.

3,244 citations


Journal ArticleDOI
TL;DR: It is shown that the conductivity and viscosity of these liquids is controlled by ion mobility and the availability of voids of suitable dimensions, and this is consistent with the fluidity of other ionic liquids and molten salts.
Abstract: Deep Eutectic Solvents (DES) can be formed between a variety of quaternary ammonium salts and carboxylic acids. The physical properties are significantly affected by the structure of the carboxylic acid but the phase behavior of the mixtures can be simply modeled by taking account of the mole fraction of carboxylic acid in the mixture. The physical properties such as viscosity, conductivity, and surface tension of these DES are similar to ambient temperature ionic liquids and insight into the cause of these properties is gained using hole-theory. It is shown that the conductivity and viscosity of these liquids is controlled by ion mobility and the availability of voids of suitable dimensions, and this is consistent with the fluidity of other ionic liquids and molten salts. The DES are also shown to be good solvents for metal oxides, which could have potential application for metal extraction.

2,904 citations


Journal ArticleDOI
TL;DR: A strain-promoted [3 + 2] cycloaddition between cyclooctynes and azides that proceeds under physiological conditions without the need for a catalyst was demonstrated by selective modification of biomolecules in vitro and on living cells, with no apparent toxicity.
Abstract: Selective chemical reactions that are orthogonal to the diverse functionality of biological systems have become important tools in the field of chemical biology. Two notable examples are the Staudinger ligation of azides and phosphines and the Cu(I)-catalyzed [3 + 2] cycloaddition of azides and alkynes (“click chemistry”). The Staudinger ligation has sufficient biocompatibility for performance in living animals but suffers from phosphine oxidation and synthetic challenges. Click chemistry obviates the requirement of phosphines, but the Cu(I) catalyst is toxic to cells, thereby precluding in vivo applications. Here we present a strain-promoted [3 + 2] cycloaddition between cyclooctynes and azides that proceeds under physiological conditions without the need for a catalyst. The utility of the reaction was demonstrated by selective modification of biomolecules in vitro and on living cells, with no apparent toxicity.

2,202 citations


Journal ArticleDOI
TL;DR: The size-dependent shift in the apparent Fermi level of the TiO(2)-Au composite shows the ability of Au nanoparticles to influence the energetics by improving the photoinduced charge separation.
Abstract: Photoexcited semiconductor nanoparticles undergo charge equilibration when they are in contact with metal nanoparticles. Such a charge distribution has direct influence in dictating the energetics of the composite by shifting the Fermi level to more negative potentials. The transfer of electrons to Au nanoparticles has now been probed by exciting TiO2 nanoparticles under steady-state and laser pulse excitation. Equilibration with the C60/C60- redox couple provides a means to determine the apparent Fermi level of the TiO2−Au composite system. The size-dependent shift in the apparent Fermi level of the TiO2−Au composite (20 mV for 8-nm diameter and 40 mV for 5-nm and 60 mV for 3-nm gold nanoparticles) shows the ability of Au nanoparticles to influence the energetics by improving the photoinduced charge separation. Isolation of individual charge-transfer steps from UV-excited TiO2 → Au → C60 has provided mechanistic and kinetic information on the role of metal in semiconductor-assisted photocatalysis and siz...

1,896 citations


Journal ArticleDOI
TL;DR: By solving the convection-diffusion equation in the frame of the moving rod, it was found that the interfacial tension force scales approximately as SR(2)gamma/muDL, where S is the area-normalized oxygen evolution rate, gamma is the liquid-vapor interfacial pressure, R is the rod radius, mu is the viscosity, D is the diffusion coefficient of oxygen, and L is the length of the rod.
Abstract: Rod-shaped particles, 370 nm in diameter and consisting of 1 μm long Pt and Au segments, move autonomously in aqueous hydrogen peroxide solutions by catalyzing the formation of oxygen at the Pt end. In 2−3% hydrogen peroxide solution, these rods move predominantly along their axis in the direction of the Pt end at speeds of up to 10 body lengths per second. The dimensions of the rods and their speeds are similar to those of multiflagellar bacteria. The force along the rod axis, which is on the order of 10-14 N, is generated by the oxygen concentration gradient, which in turn produces an interfacial tension force that balances the drag force at steady state. By solving the convection-diffusion equation in the frame of the moving rod, it was found that the interfacial tension force scales approximately as SR2γ/μDL, where S is the area-normalized oxygen evolution rate, γ is the liquid−vapor interfacial tension, R is the rod radius, μ is the viscosity, D is the diffusion coefficient of oxygen, and L is the le...

1,786 citations


Journal ArticleDOI
TL;DR: A practical approach is proposed which combines the benefits of TDDFT and configuration interaction singles (CIS) and which does not suffer from electron-transfer self-interaction.
Abstract: It is well-known that time-dependent density functional theory (TDDFT) yields substantial errors for the excitation energies of charge-transfer (CT) excited states, when approximate standard exchange-correlation (xc) functionals are used, for example, SVWN, BLYP, or B3LYP. Also, the correct 1/R asymptotic behavior of CT states with respect to a distance coordinate R between the separated charges of the CT state is not reproduced by TDDFT employing these xc-functionals. Here, we demonstrate by analysis of the TDDFT equations that the first failure is due to the self-interaction error in the orbital energies from the ground-state DFT calculation, while the latter is a similar self-interaction error in TDDFT arising through the electron transfer in the CT state. Possible correction schemes, such as inclusion of exact Hartree−Fock or exact Kohn−Sham exchange, as well as aspects of the exact xc-functional are discussed in this context. Furthermore, a practical approach is proposed which combines the benefits o...

1,598 citations


Journal ArticleDOI
TL;DR: A seed-mediated growth method was used to control the morphology and dimensions of Au nanocrystals by the manipulation of the experimental parameters in aqueous solution in the presence of a single surfactant, cetyltrimethylammonium bromide.
Abstract: A seed-mediated growth method was used to control the morphology and dimensions of Au nanocrystals by the manipulation of the experimental parameters in aqueous solution at room temperature. This chemical route produces various structural architectures with rod-, rectangle-, hexagon-, cube-, triangle-, and starlike profiles and branched (such as bi-, tri-, tetra-, and multipod) Au nanocrystals of various dimensions in high yield in the presence of a single surfactant, cetyltrimethylammonium bromide.

1,495 citations


Journal ArticleDOI
TL;DR: Experimental and molecular modeling studies are conducted to investigate the underlying mechanisms for the high solubility of CO2 in imidazolium-based ionic liquids and it is found that the bis(trifluoromethylsulfonyl)imide anion has the greatest affinity for CO2, while there is little difference in CO2solubility between ionsic liquids having the tetrafluoroborate or hexafluorophosphate anion.
Abstract: Experimental and molecular modeling studies are conducted to investigate the underlying mechanisms for the high solubility of CO2 in imidazolium-based ionic liquids. CO2 absorption isotherms at 10, 25, and 50 °C are reported for six different ionic liquids formed by pairing three different anions with two cations that differ only in the nature of the “acidic” site at the 2-position on the imidazolium ring. Molecular dynamics simulations of these two cations paired with hexafluorophosphate in the pure state and mixed with CO2 are also described. Both the experimental and the simulation results indicate that the anion has the greatest impact on the solubility of CO2. Experimentally, it is found that the bis(trifluoromethylsulfonyl)imide anion has the greatest affinity for CO2, while there is little difference in CO2 solubility between ionic liquids having the tetrafluoroborate or hexafluorophosphate anion. The simulations show strong organization of CO2 about hexafluorophosphate anions, but only small diffe...

1,352 citations


Journal ArticleDOI
TL;DR: In this paper, the interactions between various functionalized carbon nanotubes and several types of human cancer cells are explored. And they have shown that these can be derivatized in a way that enables attachment of small molecules and of proteins, the latter through a novel noncovalent association.
Abstract: The interactions between various functionalized carbon nanotubes and several types of human cancer cells are explored. We have prepared modified nanotubes and have shown that these can be derivatized in a way that enables attachment of small molecules and of proteins, the latter through a novel noncovalent association. The functionalized carbon nanotubes enter nonadherent human cancer cells as well as adherent cell lines (CHO and 3T3) and by themselves are not toxic. While the fluoresceinated protein streptavidin (MW approximately 60 kD) by itself does not enter cells, it readily enters cells when complexed to a nanotube-biotin transporter and exhibits dose-dependent cytotoxicity. The uptake pathway is consistent with adsorption-mediated endocytosis. The use of carbon nanotubes as molecular transporters could be exploited for various cargos. The biocompatibility and unique physical, electrical, optical, and mechanical properties of nanotubes provide the basis for new classes of materials for drug, protein, and gene delivery applications.

1,326 citations


Journal ArticleDOI
TL;DR: Interfacial polymerization is shown to be readily scalable to produce bulk quantities of nanofibers and the measured Brunauer-Emmett-Teller surface area of the nan ofibers increases as the average diameter decreases.
Abstract: Uniform polyaniline nanofibers readily form using interfacial polymerization without the need for templates or functional dopants. The average diameter of the nanofibers can be tuned from 30 nm using hydrochloric acid to 120 nm using perchloric acid as observed via both scanning and transmission electron microscopy. When camphorsulfonic acid is employed, 50 nm average diameter fibers form. The measured Brunauer-Emmett-Teller surface area of the nanofibers increases as the average diameter decreases. Further characterization including molecular weight, optical spectroscopy, and electrical conductivity are presented. Interfacial polymerization is shown to be readily scalable to produce bulk quantities of nanofibers.

Journal ArticleDOI
TL;DR: Results showed a clear dependence of the efficiency on the spectral overlap between the QD donor and dye acceptor and a good model system to explore FRET phenomena in QD-protein-dye conjugates.
Abstract: We used luminescent CdSe−ZnS core−shell quantum dots (QDs) as energy donors in fluorescent resonance energy transfer (FRET) assays. Engineered maltose binding protein (MBP) appended with an oligohistidine tail and labeled with an acceptor dye (Cy3) was immobilized on the nanocrystals via a noncovalent self-assembly scheme. This configuration allowed accurate control of the donor−acceptor separation distance to a range smaller than 100 A and provided a good model system to explore FRET phenomena in QD−protein−dye conjugates. This QD−MBP conjugate presents two advantages: (1) it permits one to tune the degree of spectral overlap between donor and acceptor and (2) provides a unique configuration where a single donor can interact with several acceptors simultaneously. The FRET signal was measured for these complexes as a function of both degree of spectral overlap and fraction of dye-labeled proteins in the QD conjugate. Data showed that substantial acceptor signals were measured upon conjugate formation, in...

Journal ArticleDOI
TL;DR: Five porous metal-organic frameworks based on linking zinc oxide clusters with benzene-1,4-dicarboxylate, naphthalene-2,6-dICarboxyate, 4,5,9,10-tetrahydropyrene- 2,7-divellyate, 2,3,5-6-Tetramethylbenzene-3,3-tris(4-benzoate) or benzene
Abstract: Five porous metal−organic frameworks based on linking zinc oxide clusters with benzene-1,4-dicarboxylate, naphthalene-2,6-dicarboxylate, 4,5,9,10-tetrahydropyrene-2,7-dicarboxylate, 2,3,5,6-tetramethylbenzene-1,4-dicarboxylate, or benzene-1,3,5-tris(4-benzoate) were synthesized in gram-scale quantities to measure their hydrogen uptake properties. Hydrogen adsorption isotherms measured at 77 K show a distinct dependence of uptake on the nature of the link. At 1 atm, the materials sorb between 4.2 and 9.3 molecules of H2 per formula unit. The results imply a trend in hydrogen uptake with the number of rings in the organic moiety.

Journal ArticleDOI
TL;DR: It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines and functions as an excellent catalyst.
Abstract: It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines. The beneficial effects of the 3,3‘-bisaryl substituents of the catalysts on the enantioselectivity are greatly appreciated, and thus 1d functions as an excellent catalyst. The Bronsted acid-catalyzed direct Mannich reactions presented herein provide an attractive way to construct β-aminoketones under extremely mild conditions. The stereochemical course of this reaction was established through the synthesis of Boc-(S)-phenylglycine methylester. The transformation thus demonstrated is applicable to a useful method for the synthesis of various phenylglycine derivatives.

Journal ArticleDOI
TL;DR: The new indoline dye was optimized for the amount of 4-tert-butyl pyridine in the electrolyte and cholic acid as a coadsorbent and the solar energy to current conversion efficiencies reached 8.00%, which was the highest obtained efficiency for dye-sensitized solar cells based on metal-free organic dyes without an antireflection layer.
Abstract: We now report metal-free organic dyes having a new type of indoline structure, which exhibits high efficiencies in dye-sensitized solar cells. The solar energy to current conversion efficiencies with the new indoline dye was 6.51%. Under the same conditions, the N3 dye was 7.89% and the N719 dye was 8.26%. The new indoline dye was optimized for the amount of 4-tert-butyl pyridine in the electrolyte and cholic acid as a coadsorbent. Subsequently, the solar energy to current conversion efficiencies reached 8.00%. This value was the highest obtained efficiency for dye-sensitized solar cells based on metal-free organic dyes without an antireflection layer.

Journal ArticleDOI
Xinjian Feng1, Lin Feng1, Meihua Jin1, Jin Zhai1, Lei Jiang1, Daoben Zhu1 
TL;DR: Remarkable surface wettability transition occurs with an inducement of ultraviolet (UV) for aligned ZnO nanorod films and this reversible effect is ascribed to the cooperation of the surface photosensitivity and the aligned nanostructure.
Abstract: Remarkable surface wettability transition occurs with an inducement of ultraviolet (UV) for aligned ZnO nanorod films. The inorganic oxide films, which show super-hydrophobicity (left), become super-hydrophilic (right) when exposed to UV illumination. After the films are placed in the dark, the wettability evolves back to super-hydrophobicity. This reversible effect is ascribed to the cooperation of the surface photosensitivity and the aligned nanostructure. Such special property will greatly extend the applications of ZnO films.

Journal ArticleDOI
TL;DR: The study demonstrates that the modification of TiO2 both to extend its spectral response to the visible region and to improve its catalytic efficiency can be achieved by doping with boron, a nonmetal, and Ni2O3, a metal oxide.
Abstract: To promote efficient use of solar energy, many studies have focused on the modification of TiO2 to extend its spectral response to visible region. Here we report a combined modification of TiO2 by two components: the nonmetal element boron and the metal oxide Ni2O3. The photocatalyst presents high photocatalytic activity in the visible region, which can efficiently degrade and mineralize toxic organic pollutants such as trichlorophenol (TCP), 2,4-dichlorophenol (2,4-DCP), and sodium benzoate. The dechlorination and mineralization results indicate the photocatalytic pathway via visible light excitation. The study demonstrates that the modification of TiO2 both to extend its spectral response to the visible region and to improve its catalytic efficiency can be achieved by doping with boron, a nonmetal, and Ni2O3, a metal oxide.

Journal ArticleDOI
TL;DR: This work has enabled us to prepare metal nanostructures with controllable geometric shapes and structures, and thus optical properties (for example, the surface plasmon resonance peaks could be readily shifted from 500 to 1200 nm by controlling the ratio between Ag and HAuCl(4)).
Abstract: The replacement reaction between silver nanostructures and an aqueous HAuCl4 solution has recently been demonstrated as a versatile method for generating metal nanostructures with hollow interiors Here we describe the results of a systematic study detailing the morphological, structural, compositional, and spectral changes involved in such a heterogeneous reaction on the nanoscale Two distinctive steps have been resolved through a combination of microscopic and spectroscopic methods In the first step, silver nanostructure (ie, the template) is dissolved to generate gold atoms that are deposited epitaxially on the surface of each template Silver atoms also diffuse into the gold shell (or sheath) to form a seamless, hollow nanostructure with its wall made of Au−Ag alloys The second step involves dealloying, a process that selectively removes silver atoms from the alloyed wall, induces morphological reconstruction, and finally leads to the formation of pinholes in the walls Reaction temperature was f

Journal ArticleDOI
TL;DR: A class of liquid crystalline regioregular polythiophenes, PQTs, that possess sufficient air stability to enable achievement of excellent TFT properties under ambient conditions and will help bring the long-standing concept of low-cost organic/polymer transistor circuits closer to commercial reality.
Abstract: Conjugated polymers have been widely studied as potential semiconductor materials for organic thin-film transistors (TFTs). However, they have provided functionally poor transistor properties when the TFTs are fabricated in air. We have developed a class of liquid crystalline regioregular polythiophenes, PQTs, that possess sufficient air stability to enable achievement of excellent TFT properties under ambient conditions. These polythiophenes exhibit unique self-assembly ability and form highly structured thin films when deposited from solution under appropriate conditions. TFTs fabricated in air with PQT channel layers have provided high field-effect mobility to 0.14 cm2 V-1 s-1 and high current modulation to over 107, together with other desirable transistor properties. These high-performance polythiophenes will therefore help bring the long-standing concept of low-cost organic/polymer transistor circuits closer to commercial reality.

Journal ArticleDOI
TL;DR: Fluorescence, absorption, mass, and NMR spectra all indicate that multiple species are present, but that their creation is both nucleotide- and time-dependent, and that the nanoclusters are associated with the chiral ss-DNA template.
Abstract: The high affinity of Ag+ for DNA bases has enabled creation of short oligonucleotide-encapsulated Ag nanoclusters without formation of large nanoparticles. Time-dependent formation of cluster sizes ranging from Ag1 to Ag4/oligonucleotide were observed with strong, characteristic electronic transitions between 400 and 600 nm. The slow nanocluster formation kinetics enables observation of specific aqueous nanocluster absorptions that evolve over a period of 12 h. Induced circular dichroism bands confirm that the nanoclusters are associated with the chiral ss-DNA template. Fluorescence, absorption, mass, and NMR spectra all indicate that multiple species are present, but that their creation is both nucleotide- and time-dependent.

Journal ArticleDOI
TL;DR: The results of this study provide an important structural characterization of self-assembled phospholipid bilayers and establish a framework for the design of soluble amphiphilic nanoparticles of controlled size.
Abstract: Using a recently described self-assembly process (Bayburt, T. H.; Grinkova, Y. V.; Sligar, S. G. Nano Letters 2002, 2, 853−856), we prepared soluble monodisperse discoidal lipid/protein particles with controlled size and composition, termed Nanodiscs, in which the fragment of dipalmitoylphosphatidylcholine (DPPC) bilayer is surrounded by a helical protein belt. We have customized the size of these particles by changing the length of the amphipathic helical part of this belt, termed membrane scaffold protein (MSP). Herein we describe the design of extended and truncated MSPs, the optimization of self-assembly for each of these proteins, and the structure and composition of the resulting Nanodiscs. We show that the length of the protein helix surrounding the lipid part of a Nanodisc determines the particle diameter, as measured by HPLC and small-angle X-ray scattering (SAXS). Using different scaffold proteins, we obtained Nanodiscs with the average size from 9.5 to 12.8 nm with a very narrow size distributi...

Journal ArticleDOI
TL;DR: Novel microporous metal-organic framework material composed of Mn(II) and formate ions displays permanent porosity, high thermal stability, and size-selective gas sorption behavior and may find useful applications in gas separation and sensor.
Abstract: Novel microporous metal−organic framework material composed of Mn(II) and formate ions displays permanent porosity, high thermal stability, and size-selective gas sorption behavior. The framework is stable enough to maintain single crystallinity after the complete guest removal at 150 °C under a reduced pressure. Most importantly, it selectively adsorbs H2 and CO2 but not N2 and other gases with larger kinetic diameters, which appears to be due to the small aperture of the channels. Despite a moderate H2 storage capacity, which is however still higher than that of any zeolite, its H2 surface coverage is one of the highest among the known microporous materials. Thus this new zeolite-like material made of a simple organic building block may find useful applications in gas separation and sensor.

Journal ArticleDOI
TL;DR: A new and highly practical Pd(II)-catalyzed method for the regio- and chemoselective oxidative functionalization of arenes and alkanes and a preliminary catalytic cycle is proposed.
Abstract: This communication describes a new and highly practical Pd(II)-catalyzed method for the regio- and chemoselective oxidative functionalization of arenes and alkanes. Carbon−hydrogen bonds of substrates that contain a variety of directing groups (e.g., pyridine, azobenzene, pyrazole, and imine derivatives) are selectively transformed into esters, ethers, and aryl-halides under mild conditions. The scope of this reaction in terms of substrate, directing group, and oxidant is described, and a preliminary catalytic cycle is proposed.

Journal ArticleDOI
TL;DR: Inclusion of this correction with the CHARMM22 all-atom protein force field is shown to lead to significant improvement in the treatment of the conformational energies of both the peptide model compound, the alanine dipeptide, and of proteins in their crystal environment.
Abstract: Empirical force field-based calculations of proteins, including protein-folding studies, have improved our understanding of the relationship of their structure to their biological function. However, limitations in the accuracy of empirical force fields in the treatment of the peptide backbone exist. Presented is a grid correction approach to improve the treatment of the peptide backbone φ/ψ conformational energies. Inclusion of this correction with the CHARMM22 all-atom protein force field is shown to lead to significant improvement in the treatment of the conformational energies of both the peptide model compound, the alanine dipeptide, and of proteins in their crystal environment. The developed approach is suggested to lead to significant improvements in the accuracy of empirical force fields to treat peptides and proteins.

Journal ArticleDOI
TL;DR: The present Pd catalyst does not require additives to complete the catalytic cycle, and the diameters of the generated Pd nanoclusters can be controlled upon acting on the alcohol substrates used.
Abstract: Treatment of a stoichiometric hydroxyapatite (HAP), Ca10(PO4)6(OH)2, with PdCl2(PhCN)2 gives a new type of palladium-grafted hydroxyapatite. Analysis by means of powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX), IR, and Pd K-edge X-ray absorption fine structure (XAFS) proves that a monomeric PdCl2 species is chemisorbed on the HAP surface, which is readily transformed into Pd nanoclusters with a narrow size distribution in the presence of alcohol. Nanoclustered Pd0 species can effectively promote the alcohol oxidation under an atmospheric O2 pressure, giving a remarkably high turnover number (TON) of up to 236,000 with an excellent turnover frequency (TOF) of approximately 9800 h(-1) for a 250-mmol-scale oxidation of 1-phenylethanol under solvent-free conditions. In addition to advantages such as a simple workup procedure and the ability to recycle the catalyst, the present Pd catalyst does not require additives to complete the catalytic cycle. The diameters of the generated Pd nanoclusters can be controlled upon acting on the alcohol substrates used. Oxidation of alcohols is proposed to occur primarily on low-coordination sites within a regular arrangement of the Pd nanocluster by performing calculations on the palladium crystallites.

Journal ArticleDOI
TL;DR: A combination of electron lifetime measurement in nanoparticles as a function of the Fermi level position at high resolution in the potential scale with a new model to describe this dependence provides a powerful tool to study the microscopic processes and parameters governing recombination in dye-sensitized solar cells.
Abstract: A combination of electron lifetime measurement in nanoparticles as a function of the Fermi level position at high resolution in the potential scale with a new model to describe this dependence provides a powerful tool to study the microscopic processes and parameters governing recombination in dye-sensitized solar cells. This model predicts a behavior divided in three domains for the electron lifetime dependence on open-circuit voltage that is in excellent agreement with the experimental results: a constant lifetime at high photovoltage, related to free electrons; an exponential increase due to internal trapping and detrapping and an inverted parabolla at low photovoltage that corresponds to the density of levels of acceptor electrolyte species, including the Marcus inverted region.

Journal ArticleDOI
TL;DR: Using nitrilotriacetic acid as the functional molecule, an M/Fe2O3-DA-NTA (M = Co or SmCo5.2) nanostructure is created, which possesses high stability and specificity for separating histidine-tagged proteins.
Abstract: We report on the use of dopamine (DA) as a robust molecular anchor to link functional molecules to the iron oxide shell of magnetic nanoparticles. Using nitrilotriacetic acid (NTA) as the functional molecule, we created a system with an M/Fe2O3-DA-NTA (M = Co or SmCo5.2) nanostructure, which possesses high stability and specificity for separating histidine-tagged proteins. The well-established biocompatibility of iron oxide and the robust covalent bonds between DA and Fe2O3 render this strategy attractive for constructing biofunctional magnetic nanoparticles containing iron oxide.

Journal ArticleDOI
TL;DR: In this study, single-crystal-like anatase TiO(2) nanowires were formed in a network structure by surfactant-assisted self-assembling processes at low temperature by applying the titania nanomaterials with network structure as the Titania thin film of dye-sensitized solar cells.
Abstract: In this study, single-crystal-like anatase TiO(2) nanowires were formed in a network structure by surfactant-assisted self-assembling processes at low temperature. The crystal lattice planes of the nanowires and networks of such wires composed of many nanoparticles were almost perfectly aligned with each other due to the "oriented attachment" mechanism, resulting in the high rate of electron transfer through the TiO(2) nanonetwork with single-crystal-like anatase nanowires. The direction of crystal growth of oriented attachment was controlled by changing the mole ratio of acetylacetone to Ti, that is, regulating both the adsorption of surfactant molecules via control of the reaction rate and the surface energy. A single-crystalline anatase exposing mainly the [101] plane has been prepared, which adsorbed ruthenium dye over 4 times higher as compared to P-25. A high light-to-electricity conversion yield of 9.3% was achieved by applying the titania nanomaterials with network structure as the titania thin film of dye-sensitized solar cells.

Journal ArticleDOI
TL;DR: Two 3d-4f heterometallic coordination polymers synthesized under hydrothermal conditions increased significantly upon addition of Zn2+, while the introduction of other metal ions caused the intensity to be either unchanged or weakened.
Abstract: Two 3d-4f heterometallic coordination polymers {[Ln(PDA)3Mn1.5(H2O)3].3.25H2O}infinity with 1D channels were synthesized under hydrothermal conditions (PDA = pyridine-2,6-dicarboxylic acid; Ln = Eu (1); Ln = Tb (2)). The emission intensities of 1 and 2 increased significantly upon addition of Zn2+, while the introduction of other metal ions caused the intensity to be either unchanged or weakened. The case implies that 1 and 2 may be used as luminescent probes of Zn2+.

Journal ArticleDOI
TL;DR: The G2-PAMAM-capped MSN material (G2-MSN) was used to complex with a plasmid DNA (pEGFP-C1) that encodes for an enhanced green fluorescence protein that renders the possibility to serve as a universal transmembrane carrier for intracellular drug delivery and imaging applications.
Abstract: We synthesized a MCM-41-type mesoporous silica nanosphere (MSN)-based gene transfection system, where second generation (G2) polyamidoamines (PAMAMs) were covalently attached to the surface of MSN The G2-PAMAM-capped MSN material (G2-MSN) was used to complex with a plasmid DNA (pEGFP-C1) that encodes for an enhanced green fluorescence protein The gene transfection efficacy, uptake mechanism, and biocompatibility of the G2-MSN system with various cell types, such as neural glia (astrocytes), human cervical cancer (HeLa), and Chinese hamster ovarian (CHO) cells, were investigated The mesoporous structure of the MSN material allows membrane-impermeable molecules, such as pharmaceutical drugs and fluorescent dyes, to be encapsulated inside the MSN channels The system renders the possibility to serve as a universal transmembrane carrier for intracellular drug delivery and imaging applications