Synthesis of substantially monodispersed colloids

A method of forming ligated nanoparticles of the formula Y(Z).sub.x where Y is a nanoparticle selected from the group consisting of elemental metals having atomic numbers ranging from 21-34, 39-52, 57-83 and 89-102, all inclusive, the halides, oxides and sulfides of such metals, and the alkali metal and alkaline earth metal halides, and Z represents ligand moieties such as the alkyl thiols. In the method, a first colloidal dispersion is formed made up of nanoparticles solvated in a molar excess of a first solvent (preferably a ketone such as acetone), a second solvent different than the first solvent (preferably an organic aryl solvent such as toluene) and a quantity of ligand moieties; the first solvent is then removed under vacuum and the ligand moieties ligate to the nanoparticles to give a second colloidal dispersion of the ligated nanoparticles solvated in the second solvent. If substantially monodispersed nanoparticles are desired, the second dispersion is subjected to a digestive ripening process. Upon drying, the ligated nanoparticles may form a three-dimensional superlattice structure

Magnetism in small bimetallic Mn-Co clusters

Effects of alloying on the electronic and magnetic properties of Mn$_{x}$Co$_{y}$ ($x+y$=$n$=2-5; $x$=0-$n$) and Mn$_2$Co$_{11}$ nanoalloy clusters are investigated using the density functional theory (DFT). Unlike the bulk alloy, the Co-rich clusters are found to be ferromagnetic and the magnetic moment increases with Mn-concentration, and is larger than the moment of pure Co$_n$ clusters of same size. For a particular sized cluster the magnetic moment increases by 2 $\mu_B$/Mn-substitution, which is found to be independent of the size and composition. All these results are in good agreement with recent Stern-Gerlach (SG) experiments [Phys. Rev. B {\bf 75}, 014401 (2007) and Phys. Rev. Lett. {\bf 98}, 113401 (2007)]. Likewise in bulk Mn$_x$Co$_{1-x}$ alloy, the local Co-moment decreases with increasing Mn-concentration.Comment: 11 pages, 15 figures. To appear in Physical Review

Zinc-Silver, Zinc-Palladium, and Zinc-Gold as Bimetallic Systems for Carbon Tetrachloride Dechlorination in Water

Doping of zinc with silver, palladium, and gold was found to increase reactivity towards carbon tetrachloride in water. Commercial zinc dust, cryochemically prepared zinc metal particles (SMAD nanoparticles), and zinc dust pressed into pellets (mechanically activated zinc) were employed. Reduction products detected were methane, ethylene, acetylene, and other hydrocarbons along with products of partial dechlorination such as chloroform, methylene chloride, and methyl chloride. Dichloroethylenes (DCEs) and long-term reactions traces of trichloroethylene (TCE) were also detected. The use of zinc dust doped with palladium, gold, and silver resulted in 4-10 fold increases in carbon tetrachloride degradation rate and conversion into methane. Up to 30% of carbon tetrachloride was converted into methane by the Zn dust / 2 mol % Ag bimetallic system after the first six hours of reaction. Doping of activated forms of zinc, both cryoparticle and pellets, caused a further increase in methane formation and decrease in the concentration of methylene chloride. The data show that bimetallic enhancement with Pd, Ag, Au, as well as cryo and mechanical activation of zinc, enhances the metal surface reactivity and changes the priority of reaction pathways such that fully reduced products are favored. The “non-catalytic” gold metal was especially effective and this suggests that electron transfer, not catalytic hydrogenation, is rate determining

Ultrafine Zinc and Nickel, Palladium, Silver Coated Zinc Particles Used for Reductive Dehalogenation of Chlorinated Ethylenes in Aqueous Solution

Zero-valent zinc metal has been employed for the reductive dehalogenation of chlorinated ethylenes. In order to enhance this environmental remediation chemistry, ultrafine zinc particles and transition metal additives (coatings) have been employed. Indeed, activated zinc (cryozinc) significantly enhanced the reduction/dehalogenation process, especially in the presence of nickel and palladium coatings. These reagents were able to achieve rapid, deep reductive dehalogenation of trichloroethylene, trichloroethane, and dichloroethylenes at room temperature under neutral pH conditions. Highest reactivity was found for ultrafine Zn coated with small amounts of palladium. Products, reaction rates, and possible reaction mechanisms and intermediates are presented

Graphene supported plasmonic photocatalyst for hydrogen evolution in photocatalytic water splitting

It is well known that the noble metal nanoparticles show active absorption in the visible region because of the existence of the unique feature known as surface plasmon resonance (SPR). Here we report the effect of plasmonic Au nanoparticles on the enhancement of the renewable hydrogen (H2) evolution through photocatalytic water splitting. The plasmonic Au/graphene/TiO2 photocatalyst was synthesized in two steps: first the graphene/TiO2 nanocomposites were developed by the hydrothermal decomposition process; then the Au was loaded by photodeposition. The plasmonic Au and the graphene as co-catalyst effectively prolong the recombination of the photogenerated charges. This plasmonic photocatalyst displayed enhanced photocatalytic H2 evolution for water splitting in the presence of methanol as a sacrificial reagent. The H2 evolution rate from the Au/graphene co-catalyst was about 9 times higher than that of a pure graphene catalyst. The optimal graphene content was found to be 1.0 wt %, giving a H2 evolution of 1.34 mmol (i.e., 26 μmolhˉ¹), which exceeded the value of 0.56 mmol (i.e., 112 μmolhˉ¹) observed in pure TiO2. This high photocatalytic H2 evolution activity results from the deposition of TiO2 on graphene sheets, which act as an electron acceptors to efficiently separate the photogenerated charge carriers. However, the Au loading enhanced the H2 evolution dramatically and achieved a maximum value of 12 mmol (i.e., 2.4 mmolhˉ¹) with optimal loading of 2.0 wt% Au on graphene/TiO2 composites. The enhancement of H2 evolution in the presence of Au results from the SPR effect induced by visible light irradiation, which boosts the energy intensity of the trapped electron as well as active sites for photocatalytic activity

On the hierarchical classification of G Protein-Coupled Receptors

Motivation: G protein-coupled receptors (GPCRs) play an important role in many physiological systems by transducing an extracellular signal into an intracellular response. Over 50% of all marketed drugs are targeted towards a GPCR. There is considerable interest in developing an algorithm that could effectively predict the function of a GPCR from its primary sequence. Such an algorithm is useful not only in identifying novel GPCR sequences but in characterizing the interrelationships between known GPCRs. Results: An alignment-free approach to GPCR classification has been developed using techniques drawn from data mining and proteochemometrics. A dataset of over 8000 sequences was constructed to train the algorithm. This represents one of the largest GPCR datasets currently available. A predictive algorithm was developed based upon the simplest reasonable numerical representation of the protein's physicochemical properties. A selective top-down approach was developed, which used a hierarchical classifier to assign sequences to subdivisions within the GPCR hierarchy. The predictive performance of the algorithm was assessed against several standard data mining classifiers and further validated against Support Vector Machine-based GPCR prediction servers. The selective top-down approach achieves significantly higher accuracy than standard data mining methods in almost all cases

Early Detection of Critical Pulmonary Shunts in Infants

This paper aims to improve the design of modern Medical Cyber Physical Systems through the addition of supplemental noninvasive monitors. Specifically, we focus on monitoring the arterial blood oxygen content (CaO2), one of the most closely observed vital signs in operating rooms, currently measured by a proxy - peripheral hemoglobin oxygen saturation (SpO2). While SpO2 is a good estimate of O2 content in the finger where it is measured, it is a delayed measure of its content in the arteries. In addition, it does not incorporate system dynamics and is a poor predictor of future CaO2 values. Therefore, as a first step towards supplementing the usage of SpO2, this work introduces a predictive monitor designed to provide early detection of critical drops in CaO2 caused by a pulmonary shunt in infants. To this end, we develop a formal model of the circulation of oxygen and carbon dioxide in the body, characterized by unknown patient-unique parameters. Employing the model, we design a matched subspace detector to provide a near constant false alarm rate invariant to these parameters and modeling uncertainties. Finally, we validate our approach on real-patient data from lung lobectomy surgeries performed at the Children\u27s Hospital of Philadelphia. Given 198 infants, the detector predicted 81% of the critical drops in CaO2 at an average of about 65 seconds earlier than the SpO2-based monitor, while achieving a 0:9% false alarm rate (representing about 2 false alarms per hour)