Showing papers in "Journal of the American Chemical Society in 2005"
TL;DR: The ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction is analyzed and a necessary criterion for high catalytic activity is found: that the binding free energy of atomic hydrogen to the catalyst is close to zero.
Abstract: The electrochemical hydrogen evolution reaction is catalyzed most effectively by the Pt group metals. As H2 is considered as a future energy carrier, the need for these catalysts will increase and alternatives to the scarce and expensive Pt group catalysts will be needed. We analyze the ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction and find a necessary criterion for high catalytic activity. The necessary criterion is that the binding free energy of atomic hydrogen to the catalyst is close to zero. The criterion enables us to search for new catalysts, and inspired by the nitrogenase active site, we find that MoS2 nanoparticles supported on graphite are a promising catalyst. They catalyze electrochemical hydrogen evolution at a moderate overpotential of 0.1−0.2 V.
3,302 citations
TL;DR: The computed alignments of the molecular orbitals of the different complexes with the band edges of a model TiO(2) nanoparticle provide additional insights into the electronic factors governing the efficiency of dye-sensitized solar cell devices.
Abstract: We report a combined experimental and computational study of several ruthenium(II) sensitizers originated from the [Ru(dcbpyH2)2(NCS)2], N3, and [Ru(dcbpyH2)(tdbpy)(NCS)2], N621, (dcbpyH2 = 4,4‘-dicarboxy-2,2‘-bipyridine, tdbpy = 4,4‘-tridecyl-2,2‘-bipyridine) complexes. A purification procedure was developed to obtain pure N-bonded isomers of both types of sensitizers. The photovoltaic data of the purified N3 and N621 sensitizers adsorbed on TiO2 films in their monoprotonated and diprotonated state, exhibited remarkable power conversion efficiency at 1 sun, 11.18 and 9.57%, respectively. An extensive Density Functional Theory (DFT)−Time Dependent DFT study of these sensitizers in solution was performed, investigating the effect of protonation of the terminal carboxylic groups and of the counterions on the electronic structure and optical properties of the dyes. The calculated absorption spectra are in good agreement with the experiment, thus allowing a detailed assignment of the UV−vis spectral features ...
2,660 citations
TL;DR: The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
Abstract: The principal structure possibilities for packing infinite rod-shaped building blocks are described. Some basic nets derived from linking simple rods (helices and ladders) are then enumerated. We demonstrate the usefulness of the concept of rod secondary building units in the design and synthesis of metal-organic frameworks (MOFs). Accordingly, we present the preparation, characterization, and crystal structures of 14 new MOFs (named MOF-69A-C and MOF-70-80) of 12 different structure types, belonging to rod packing motifs, and show how their structures are related to basic nets. The MOFs reported herein are of polytopic carboxylates and contain one of Zn, Pb, Co, Cd, Mn, or Tb. The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
2,147 citations
TL;DR: The Au-TiO(2) can photoc atalytically oxidize ethanol and methanol at the expense of oxygen reduction under visible light; it is potentially applicable to a new class of photocatalysts and photovoltaic fuel cells.
Abstract: Plasmon-induced photoelectrochemistry in the visible region was studied at gold nanoparticle−nanoporous TiO2 composites (Au−TiO2) prepared by photocatalytic deposition of gold in a porous TiO2 film. Photoaction spectra for both the open-circuit potential and short-circuit current were in good agreement with the absorption spectrum of the gold nanoparticles in the TiO2 film. The gold nanoparticles are photoexcited due to plasmon resonance, and charge separation is accomplished by the transfer of photoexcited electrons from the gold particle to the TiO2 conduction band and the simultaneous transfer of compensative electrons from a donor in the solution to the gold particle. Besides its low-cost and facile preparation, a photovoltaic cell with the optimized electron mediator (Fe2+/3+) exhibits an optimum incident photon to current conversion efficiency (IPCE) of 26%. The Au−TiO2 can photocatalytically oxidize ethanol and methanol at the expense of oxygen reduction under visible light; it is potentially appli...
1,793 citations
TL;DR: Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.
Abstract: A homochiral porous noninterpenetrating metal−organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(μ-Cl)2]n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for the addition of diethyzinc to aromatic aldehydes to afford chiral secondary alcohols at up to 93% enantiomeric excess (ee). Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.
1,720 citations
TL;DR: Structural studies of various 1.Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki-Miyaura coupling processes, and a comparison of the reactions is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type.
Abstract: Suzuki−Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl- and vinylboronic acids proceed in very good to excellent yield with the use of 2-(2‘,6‘-dimethoxybiphenyl)dicyclohexylphosphine, SPhos (1). This ligand confers unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, for reactions of aryl chlorides at room temperature. Additionally, structural studies of various 1·Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki−Miyaura coupling processes. Moreover, a comparison of the reactions with 1 and with 2-(2‘,4‘,6‘-triisopropylbiphenyl)diphenylphosphine (2) is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type. Further, when the aryl bromide becomes too hindered, an ...
1,562 citations
TL;DR: Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2, 3-triazoles and 3, 4-disubsided isoxazoles, respectively.
Abstract: Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.
1,486 citations
TL;DR: It is proposed that a series of the isolated Au:SG clusters corresponds to kinetically trapped intermediates of the growing Au cores, and it is revealed that the subnanometer-sized Au clusters thiolated constitute a distinct class of binary system which lies between the Au(I)-thiolate complexes and thiolate-protected Au NCs.
Abstract: Small gold clusters (∼1 nm) protected by molecules of a tripeptide, glutathione (GSH), were prepared by reductive decomposition of Au(I)−SG polymers at a low temperature and separated into a number of fractions by polyacrylamide gel electrophoresis (PAGE) Chemical compositions of the fractionated clusters determined previously by electrospray ionization (ESI) mass spectrometry (Negishi, Y et al J Am Chem Soc 2004, 126, 6518) were reassessed by taking advantage of freshly prepared samples, higher mass resolution, and more accurate mass calibration; the nine smallest components are reassigned to Au10(SG)10, Au15(SG)13, Au18(SG)14, Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, and Au39(SG)24 These assignments were further confirmed by measuring the mass spectra of the isolated Au:S(h-G) clusters, where h-GSH is a homoglutathione It is proposed that a series of the isolated Au:SG clusters corresponds to kinetically trapped intermediates of the growing Au cores The relative abundance of
1,406 citations
TL;DR: The ability of simple tailor-made monochemical surfaces to influence binding rates and conformation of bound proteins through protein-surface interactions is demonstrated, with the effect observed greatest for albumin.
Abstract: Protein adhesion plays a major role in determining the biocompatibility of materials. The first stage of implant integration is the adhesion of protein followed by cell attachment. Surface modification of implants (surface chemistry and topography) to induce and control protein and cell adhesion is currently of great interest. This communication presents data on protein adsorption (bovine serum albumin and fibrinogen) onto model hydrophobic (CH3) and hydrophilic (OH) surfaces, investigated using a quartz crystal microbalance (QCM) and grazing angle infrared spectroscopy. Our data suggest that albumin undergoes adsorption via a single step whereas fibrinogen adsorption is a more complex, multistage process. Albumin has a stronger affinity toward the CH3 compared to OH terminated surface. In contrast, fibrinogen adheres more rapidly to both surfaces, having a slightly higher affinity toward the hydrophobic surface. Conformational assessment of the adsorbed proteins by grazing angle infrared spectroscopy (GA...
1,324 citations
TL;DR: This is the first example of achieving overall water splitting by a photocatalyst with a band gap in the visible light region, which opens the possibility of new non-oxide-type photocatalysts for energy conversion.
Abstract: Photocatalytic overall water splitting has been studied extensively from the viewpoint of solar energy conversion Despite numerous attempts, none have yielded satisfactory results for the development of photocatalysts, which work under visible light irradiation to efficiently utilize solar energy We report here the first example of visible-light-driven overall water splitting on a novel oxynitride photocatalyst, a solid solution of GaN and ZnO with a band gap of 258-276 eV, modified with RuO2 nanoparticles In contrast to the conventional non-oxide photocatalysts, such as CdS, the solid solution is stable during the overall water splitting reaction This is the first example of achieving overall water splitting by a photocatalyst with a band gap in the visible light region, which opens the possibility of new non-oxide-type photocatalysts for energy conversion
1,280 citations
TL;DR: A new palladium-catalyzed arylation process based on C-H activation has been developed with utilization of pyridine-containing directing groups that allows the beta-arylation of carboxylic acid derivatives and gamma-ARYlation of amine derivatives.
Abstract: A new palladium-catalyzed arylation process based on C−H activation has been developed. The utilization of pyridine-containing directing groups allows the β-arylation of carboxylic acid derivatives and γ-arylation of amine derivatives. Both primary and secondary sp3 C−H bonds, as well as sp2 C−H bonds, are reactive.
TL;DR: Analysis of solvent isotope effects and of the changes in LCST with ion concentration and identity showed multiple mechanisms were at work, and in solutions containing sufficient concentrations of strongly hydrated anions, the phase transition of PNIPAM was directly correlated with the hydration entropy of the anion.
Abstract: Aqueous processes ranging from protein folding and enzyme turnover to colloidal ordering and macromolecular precipitation are sensitive to the nature and concentration of the ions present in solution. Herein, the effect of a series of sodium salts on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide), PNIPAM, was investigated with a temperature gradient microfluidic device under a dark-field microscope. While the ability of a particular anion to lower the LCST generally followed the Hofmeister series, analysis of solvent isotope effects and of the changes in LCST with ion concentration and identity showed multiple mechanisms were at work. In solutions containing sufficient concentrations of strongly hydrated anions, the phase transition of PNIPAM was directly correlated with the hydration entropy of the anion. On the other hand, weakly hydrated anions were salted-out through surface tension effects and displayed improved hydration by direct ion binding.
TL;DR: Single-crystal PbSe nanowires are synthesized in solution through oriented attachment of nanocrystal building blocks, resulting in a nearly defect-free crystal lattice and high uniformity of nanowire diameter along the entire length.
Abstract: Single-crystal PbSe nanowires are synthesized in solution through oriented attachment of nanocrystal building blocks. Reaction temperatures of 190-250 degrees C and multicomponent surfactant mixtures result in a nearly defect-free crystal lattice and high uniformity of nanowire diameter along the entire length. The wires' dimensions are tuned by tailoring reaction conditions in a range from approximately 4 to approximately 20 nm in diameter with wire lengths up to approximately 30 microm. PbSe nanocrystals bind to each other on either {100}, {110}, or {111} faces, depending on the surfactant molecules present in the reaction solution. While PbSe nanocrystals have the centrosymmetric rocksalt lattice, they can lack central symmetry due to a noncentrosymmetric arrangement of Pb- and Se-terminated {111} facets and possess dipole driving one-dimensional oriented attachment of nanocrystals to form nanowires. In addition to straight nanowires, zigzag, helical, branched, and tapered nanowires as well as single-crystal nanorings can be controllably prepared in one-pot reactions by careful adjustment of the reaction conditions.
TL;DR: The development of a synthetically controlled magnetic nanocrystal model system that correlates the nanoscale tunabilities in terms of size, magnetism, and induced nuclear spin relaxation processes led to the development of high-performance Nanocrystal-antibody probe systems for the diagnosis of breast cancer cells via magnetic resonance imaging.
Abstract: Since the use of magnetic nanocrystals as probes for biomedical system is attractive, it is important to develop optimal synthetic protocols for high-quality magnetic nanocrystals and to have the systematic understanding of their nanoscale properties. Here we present the development of a synthetically controlled magnetic nanocrystal model system that correlates the nanoscale tunabilities in terms of size, magnetism, and induced nuclear spin relaxation processes. This system further led to the development of high-performance nanocrystal−antibody probe systems for the diagnosis of breast cancer cells via magnetic resonance imaging.
TL;DR: Amino acid ionic liquids dissolved native amino acids, despite water-free conditions, and are soluble in various organic solvents, such as chloroform.
Abstract: We first succeeded in synthesizing ionic liquids from 20 natural amino acids. Amino acid ionic liquids dissolved native amino acids, despite water-free conditions. Furthermore, these ionic liquids are soluble in various organic solvents, such as chloroform. Effects of acidity, hydrogen bonding ability, and steric factors on the properties of these ionic liquids were analyzed as the function of side groups.
TL;DR: Charge equilibration with redox couple such as C60/C60*- shows the ability of these core shell structures to carry out photocatalytic reduction reactions.
Abstract: Photocatalytic properties of Ag@TiO2 composite clusters have been investigated using steady state and laser pulse excitations. Photoexcitation of TiO2 shell results in accumulation of the electrons in the Ag core as evidenced from the shift in the surface plasmon band from 460 to 420 nm. The stored electrons are discharged when an electron acceptor such as O2, thionine, or C60 is introduced into the system. Charge equilibration with redox couple such as C60/C60•- shows the ability of these core shell structures to carry out photocatalytic reduction reactions. The charge separation, charge storage, and interfacial charge-transfer steps that follow excitation of the TiO2 shell are discussed.
TL;DR: A distinct step in the isotherm occurs during the adsorption of CO2 on MIL-53 at 304 K and it is suggested that a breathing behavior is induced in MIL- 53 during CO2 adsorptive activity.
Abstract: A distinct step in the isotherm occurs during the adsorption of CO2 on MIL-53 at 304 K. Such behavior is neither observed during the adsorption of CH4 on MIL-53 nor during the adsorption on the isostructural MIL-47. This phenomenon seems to be due to a different mechanism than that of previous adsorption steps on MOF samples. It is suggested that a breathing behavior is induced in MIL-53 during CO2 adsorption.
TL;DR: Carbon nanotubes represent a new class of molecular transporters potentially useful for future in vitro and in vivo protein delivery applications.
Abstract: Various proteins adsorb spontaneously on the sidewalls of acid-oxidized single-walled carbon nanotubes. This simple nonspecific binding scheme can be used to afford noncovalent protein-nanotube conjugates. The proteins are found to be readily transported inside various mammalian cells with nanotubes acting as the transporter via the endocytosis pathway. Once released from the endosomes, the internalized protein-nanotube conjugates can enter into the cytoplasm of cells and perform biological functions, evidenced by apoptosis induction by transported cytochrome c. Carbon nanotubes represent a new class of molecular transporters potentially useful for future in vitro and in vivo protein delivery applications.
TL;DR: The selectivity of this rhodamine-based fluorescent and colorimetric chemodosimeter for Hg2+ over other metal ions is remarkably high, and its sensitivity is below 2 ppb in aqueous solutions.
Abstract: A rhodamine-based fluorescent and colorimetric chemodosimeter for the rapid detection of Hg2+ ions in aqueous media was developed. The system, which utilizes an irreversible Hg2+-promoted oxadiazole forming reaction, responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Hg2+. The selectivity of this system for Hg2+ over other metal ions is remarkably high, and its sensitivity is below 2 ppb in aqueous solutions.
TL;DR: The fluorescent nanodiamonds (FND) show no sign of photobleaching and can be taken up by mammalian cells with minimal cytotoxicity and the nanomaterial can have far-reaching biological applications.
Abstract: Diamond nanocrystals emit bright fluorescence at 600−800 nm after irradiation by a 3 MeV proton beam (5 × 1015 ions/cm2) and annealing at 800 °C (2 h) in vacuum. The irradiation/annealing process yields high concentrations of nitrogen-vacancy defect centers (∼107 centers/μm3), making possible visualization of the individual 100 nm diamond crystallites using a fluorescence microscope. The fluorescent nanodiamonds (FND) show no sign of photobleaching and can be taken up by mammalian cells with minimal cytotoxicity. The nanomaterial can have far-reaching biological applications.
TL;DR: In this paper, density functional theory was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H(+) + 2e(-) --> H(2)).
Abstract: Density functional theory (DFT) was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H(+) + 2e(-) --> H(2)). The kinetics of the HER was studied on the [NiFe] hydrogenase, the [Ni(PS3*)(CO)](1)(-) and [Ni(PNP)(2)](2+) complexes, and surfaces such as Ni(111), Pt(111), or Ni(2)P(001). Our results show that the [NiFe] hydrogenase exhibits the highest activity toward the HER, followed by [Ni(PNP)(2)](2+) > Ni(2)P > [Ni(PS3*)(CO)](1)(-) > Pt > Ni in a decreasing sequence. The slow kinetics of the HER on the surfaces is due to the fact that the metal hollow sites bond hydrogen too strongly to allow the facile removal of H(2). In fact, the strong H-Ni interaction on Ni(2)P(001) can lead to poisoning of the highly active sites of the surface, which enhances the rate of the HER and makes it comparable to that of the [NiFe] hydrogenase. In contrast, the promotional effect of H-poisoning on the HER on Pt and Ni surfaces is relatively small. Our calculations suggest that among all of the systems investigated, Ni(2)P should be the best practical catalyst for the HER, combining the high thermostability of the surfaces and high catalytic activity of the [NiFe] hydrogenase. The good behavior of Ni(2)P(001) toward the HER is found to be associated with an ensemble effect, where the number of active Ni sites is decreased due to presence of P, which leads to moderate bonding of the intermediates and products with the surface. In addition, the P sites are not simple spectators and directly participate in the HER.
TL;DR: The strong resistance of zwitterionic phosphorylcholine (PC) self-assembled monolayers (SAMs) to protein adsorption is shown and key factors leading to their nonfouling behavior are examined using both experimental and molecular simulation techniques.
Abstract: In this work, we show the strong resistance of zwitterionic phosphorylcholine (PC) self-assembled monolayers (SAMs) to protein adsorption and examine key factors leading to their nonfouling behavior using both experimental and molecular simulation techniques. Zwitterions with a balanced charge and minimized dipole are excellent candidates as nonfouling materials due to their strong hydration capacity via electrostatic interactions.
TL;DR: A multiscale coarse-graining model for ionic liquids has been extended and it has been found that, with sufficiently long side chains, the tail groups of cations aggregate to form spatially heterogeneous domains, while headgroups of the cations and the anions distribute as uniformly as possible.
Abstract: A multiscale coarse-graining model for ionic liquids has been extended to investigate the unique aggregation of cations in ionic liquids through computer simulation. It has been found that, with sufficiently long side chains, the tail groups of cations aggregate to form spatially heterogeneous domains, while headgroups of the cations and the anions distribute as uniformly as possible. This is understood as the result of competition between the charged electrostatic interactions between headgroups and anions and the collective short-range interactions between the neutral tail groups. This aggregation can help to explain a number of experimentally observed physical phenomena in ionic liquids.
TL;DR: Experimental results that substantiate the superior photochemical and colloidal stability of the multishell particles are presented.
Abstract: We report on the preparation and structural characterization of CdSe nanocrystals, which are covered by a multishell structure from CdS and ZnS. By using the newly developed successive ion layer adhesion and reaction (SILAR) technique, we could gradually change the shell composition from CdS to ZnS in the radial direction. Because of the stepwise adjustment of the lattice parameters in the radial direction, the resulting nanocrystals show a high crystallinity and are almost perfectly spherical, as was investigated by X-ray diffraction and electron microscopy. Also, due to the radial increase of the respective valence- and conduction-band offsets, the nanocrystals are well electronically passivated. This leads to a high fluorescence quantum yield of 70-85% for the amine terminated multishell particles in organic solvents and a quantum yield of up to 50% for mercapto propionic acid-covered particles in water. Finally, we present experimental results that substantiate the superior photochemical and colloidal stability of the multishell particles.
TL;DR: A new class of bifunctional catalysts bearing a thiourea moiety and an amino group on a chiral scaffold bearing 3,5-bis(trifluoromethyl)benzene and dimethylamino groups was revealed to be highly efficient for the asymmetric Michael reaction of 1,3-dicarbonyl compounds to nitroolefins.
Abstract: We synthesized a new class of bifunctional catalysts bearing a thiourea moiety and an amino group on a chiral scaffold. Among them, thiourea 1e bearing 3,5-bis(trifluoromethyl)benzene and dimethylamino groups was revealed to be highly efficient for the asymmetric Michael reaction of 1,3-dicarbonyl compounds to nitroolefins. Furthermore, we have developed a new synthetic route for (R)-(-)-baclofen and a chiral quaternary carbon center with high enantioselectivity by Michael reaction. In these reactions, we assumed that a thiourea moiety and an amino group of the catalyst activates a nitroolefin and a 1,3-dicarbonyl compound, respectively, to afford the Michael adduct with high enantio- and diastereoselectivity.
TL;DR: Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films.
Abstract: To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named "ion gels", decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10(-2) S cm(-1). Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI(-) anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself.
TL;DR: This work has developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O, and confirmed the thin layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size.
Abstract: It is well-known that inorganic nanocrystals are a benchmark model for nanotechnology, given that the tunability of optical properties and the stabilization of specific phases are uniquely possible at the nanoscale. Copper (I) oxide (Cu(2)O) is a metal oxide semiconductor with promising applications in solar energy conversion and catalysis. To understand the Cu/Cu(2)O/CuO system at the nanoscale, we have developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O. The procedure also serves to demonstrate our development of a generalized method for the synthesis of transition metal oxide nanocrystals. Cu nanocrystals are initially formed and subsequently oxidized to form highly crystalline Cu(2)O. The volume change during phase transformation can induce crystal twinning. Absorption in the visible region of the spectrum gave evidence for the presence of a thin, epitaxial layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size. XPS confirmed the thin layer of CuO, calculated to have a thickness of approximately 5 A. We note that the copper (I) oxide phase is surprisingly well-stabilized at this length scale.
TL;DR: To provide for water solubility and biocompatibility, QDs and MPs were encapsulated within a silica shell using a reverse microemulsion synthesis to present a unique combination of magnetic and optical properties.
Abstract: Quantum dots (QDs) and magnetic nanoparticles (MPs) are of interest for biological imaging, drug targeting, and bioconjugation because of their unique optoelectronic and magnetic properties, respectively. To provide for water solubility and biocompatibility, QDs and MPs were encapsulated within a silica shell using a reverse microemulsion synthesis. The resulting SiO2/MP-QD nanocomposite particles present a unique combination of magnetic and optical properties. Their nonporous silica shell allows them to be surface modified for bioconjugation in various biomedical applications.
TL;DR: The analysis of human brain extract and cerebrospinal fluid samples from control and Alzheimer's disease patients reveals that the LSPR nanosensor provides new information relevant to the understanding and possible diagnosis of Alzheimer’s disease.
Abstract: A nanoscale optical biosensor based on localized surface plasmon resonance (LSPR) spectroscopy has been developed to monitor the interaction between the antigen, amyloid-β derived diffusible ligands (ADDLs), and specific anti-ADDL antibodies. Using the sandwich assay format, this nanosensor provides quantitative binding information for both antigen and second antibody detection that permits the determination of ADDL concentration and offers the unique analysis of the aggregation mechanisms of this putative Alzheimer's disease pathogen at physiologically relevant monomer concentrations. Monitoring the LSPR-induced shifts from both ADDLs and a second polyclonal anti-ADDL antibody as a function of ADDL concentration reveals two ADDL epitopes that have binding constants to the specific anti-ADDL antibodies of 7.3 × 1012 M-1 and 9.5 × 108 M-1. The analysis of human brain extract and cerebrospinal fluid samples from control and Alzheimer's disease patients reveals that the LSPR nanosensor provides new informati...
TL;DR: Particle Replication In Nonwetting Templates affords the simple, straightforward encapsulation of a variety of important bioactive agents, including proteins, DNA, and small-molecule therapeutics, which indicates that PRINT can be used to fabricate next-generation particulate drug-delivery agents.
Abstract: A versatile "top-down" method for the fabrication of particles, Particle Replication In Nonwetting Templates (PRINT), is described which affords absolute control over particle size, shape, and composition. This technique is versatile and general enough to fabricate particles with a variety of chemical structures, yet delicate enough to be compatible with sophisticated biological agents. Using PRINT, we have fabricated monodisperse particles of poly(ethylene glycol diacrylate), triacrylate resin, poly(lactic acid), and poly(pyrrole). Monodisperse particle populations, ranging from sub-200 nm nanoparticles to complex micron-scale objects, have been fabricated and harvested. PRINT uses low-surface energy, chemically resistant fluoropolymers as molding materials, which eliminates the formation of a residual interconnecting film between molded objects. Until now, the presence of this film has largely prevented particle fabrication using soft lithography. Importantly, we have demonstrated that PRINT affords the simple, straightforward encapsulation of a variety of important bioactive agents, including proteins, DNA, and small-molecule therapeutics, which indicates that PRINT can be used to fabricate next-generation particulate drug-delivery agents.