On the mechanism of metal nanoparticle synthesis in the brust-schiffrin method

Brust-Schiffrin synthesis (BSS) of metal nanoparticles has emerged as a major breakthrough in the field for its ability to produce highly stable thiol functionalized nanoparticles. In this work, we use a detailed population balance model to conclude that particle formation in BSS is controlled by a new synthesis route: continuous nucleation, growth, and capping of particles throughout the synthesis process. The new mechanism, quite different from the others known in the literature (classical LaMer mechanism, sequential nucleation-growth-capping, and thermodynamic mechanism), successfully explains key features of BSS, including size tuning by varying the amount of capping agent instead of the widely used approach of varying the amount of reducing agent. The new mechanism captures a large body of experimental observations quantitatively, including size tuning and only a marginal effect of the parameters otherwise known to affect particle synthesis sensitively. The new mechanism predicts that, in a constant synthesis environment, continuous nucleation-growth-capping mechanism leads to complete capping of particles (no more growth) at the same size, while the new ones are born continuously, in principle leading to synthesis of more monodisperse particles. This prediction is validated through new experimental measurements.

MECHANISM OF CELL LYSIS IN MICROFLUIDIC CHANNEL WITH INTEGRATED NANOCOMPOSITE ELECTRODES

This paper reports on the characterization of an integrated micro-fluidic platform for controlled electrical lysis of biological cells and subsequent extraction of intracellular biomolecules. The proposed methodology is capable of high throughput electrical cell lysis facilitated by nano-composite coated electrodes. The nano-composites are synthesized using Carbon Nanotube and ZnO nanorod dispersion in polymer. Bacterial cells are used to demonstrate the lysis performance of these nanocomposite electrodes. Investigation of electrical lysis in the microchannel is carried out under different parameters, one with continuous DC application and the other under DC biased AC electric field. Lysis in DC field is dependent on optimal field strength and governed by the cell type. By introducing the AC electrical field, the electrokinetics is controlled to prevent cell clogging in the micro-channel and ensure uniform cell dispersion and lysis. Lysis mechanism is analyzed with time-resolved fluorescence imaging which reveal the time scale of electrical lysis and explain the dynamic behavior of GFP-expressing E. coli cells under the electric field induced by nanocomposite electrodes. The DNA and protein samples extracted after lysis are compared with those obtained from a conventional chemical lysis method by using a UV-Visible spectroscopy and fluorimetry. The paper also focuses on the mechanistic understanding of the nano-composite coating material and the film thickness on the leakage charge densities which lead to differential lysis efficiency.

Metal based photosensitizers of tetradentate Schiff base: Promising role in anti-tumor activity through singlet oxygen generation mechanism

In the present investigation, a Schiff base N'(1),N'(3)-bis(Z)-(2-hydroxynapthyl)methylidene]benzene-1,3-dicarbod ihydrazide (L-1) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized as novel photosensitizing agents for photodynamic therapy (PDT). The interaction of these complexes with calf thymus DNA (CT DNA) has been explored using absorption, thermal denaturation and viscometric studies. The experimental results revealed that Co(II) and Ni(II) complexes on binding to CT DNA imply a covalent mode, most possibly involving guanine N7 nitrogen of DNA, with an intrinsic binding constant K-b of 4.5 x 10(4) M-1 and 4.2 x 10(4) M-1, respectively. However, interestingly, the Cu(II) complex is involved in the surface binding to minor groove via phosphate backbone of DNA double helix with an intrinsic binding constant K-b of 5.7 x 10(4) M-1. The Co(II), Ni(II) and Cu(II) complexes are active in cleaving supercoiled (SC) pUC19 DNA on photoexposure to UV-visible light of 365 nm, through O-1(2) generation with quantum yields of 0.28, 0.25 and 0.30, respectively. Further, these complexes are cytotoxic in A549 lung cancer cells, showing an enhancement of cytotoxicity upon light irradiation. (C) 2013 Elsevier B.V. All rights reserved.

Scalar transport in diffusion flame wrapped up by an air and fuel side vortex

The present work involves a computational study of soot (chosen as a scalar which is a primary pollutant source) formation and transport in a laminar acetylene diffusion flame perturbed by a convecting line vortex. The topology of soot contours resulting from flame vortex interactions has been investigated. More soot was produced when vortex was introduced from the air side in comparison to the fuel side. Also, the soot topography was spatially more diffuse in the case of air side vortex. The computational model was found to be in good agreement with the experimental work previously reported in the literature. The computational simulation enabled a study of various parameters like temperature, equivalence ratio and temperature gradient affecting the soot production and transport. Temperatures were found to be higher in the case of air side vortex in contrast to the fuel side one. In case of fuel side vortex, abundance of fuel in the vortex core resulted in fuel-rich combustion zone in the core and a more discrete soot topography. Besides, the overall soot production was observed to be low in the fuel side vortex. However, for the air side vortex, air abundance in the core resulted in higher temperatures and greater soot production. Probability density functions (PDFs) have been introduced to investigate the spatiotemporal variation of soot yield and transport and their dependence on temperature and acetylene concentration from statistical view point. In addition, the effect of flame curvature on soot production is also studied. The regions convex to fuel stream side witnessed thicker soot layer. All numerical simulations have been carried out on Fluent 6.3.26. (C) 2013 Elsevier Ltd. All rights reserved.

Mechanism design for time critical and cost critical task execution via crowdsourcing

An exciting application of crowdsourcing is to use social networks in complex task execution. In this paper, we address the problem of a planner who needs to incentivize agents within a network in order to seek their help in executing an atomic task as well as in recruiting other agents to execute the task. We study this mechanism design problem under two natural resource optimization settings: (1) cost critical tasks, where the planner's goal is to minimize the total cost, and (2) time critical tasks, where the goal is to minimize the total time elapsed before the task is executed. We identify a set of desirable properties that should ideally be satisfied by a crowdsourcing mechanism. In particular, sybil-proofness and collapse-proofness are two complementary properties in our desiderata. We prove that no mechanism can satisfy all the desirable properties simultaneously. This leads us naturally to explore approximate versions of the critical properties. We focus our attention on approximate sybil-proofness and our exploration leads to a parametrized family of payment mechanisms which satisfy collapse-proofness. We characterize the approximate versions of the desirable properties in cost critical and time critical domain.

A strategy-proof and budget-balanced mechanism for carbon footprint reduction by global companies

The problem addressed in this paper is concerned with an important issue faced by any green aware global company to keep its emissions within a prescribed cap. The specific problem is to allocate carbon reductions to its different divisions and supply chain partners in achieving a required target of reductions in its carbon reduction program. The problem becomes a challenging one since the divisions and supply chain partners, being autonomous, may exhibit strategic behavior. We use a standard mechanism design approach to solve this problem. While designing a mechanism for the emission reduction allocation problem, the key properties that need to be satisfied are dominant strategy incentive compatibility (DSIC) (also called strategy-proofness), strict budget balance (SBB), and allocative efficiency (AE). Mechanism design theory has shown that it is not possible to achieve the above three properties simultaneously. In the literature, a mechanism that satisfies DSIC and AE has recently been proposed in this context, keeping the budget imbalance minimal. Motivated by the observation that SBB is an important requirement, in this paper, we propose a mechanism that satisfies DSIC and SBB with slight compromise in allocative efficiency. Our experimentation with a stylized case study shows that the proposed mechanism performs satisfactorily and provides an attractive alternative mechanism for carbon footprint reduction by global companies.

Mechanism design for green, truthful procurement auctions

Auction based mechanisms have become popular in industrial procurement settings. These mechanisms minimize the cost of procurement and at the same time achieve desirable properties such as truthful bidding by the suppliers. In this paper, we investigate the design of truthful procurement auctions taking into account an additional important issue namely carbon emissions. In particular, we focus on the following procurement problem: A buyer wishes to source multiple units of a homogeneous item from several competing suppliers who offer volume discount bids and who also provide emission curves that specify the cost of emissions as a function of volume of supply. We assume that emission curves are reported truthfully since that information is easily verifiable through standard sources. First we formulate the volume discount procurement auction problem with emission constraints under the assumption that the suppliers are honest (that is they report production costs truthfully). Next we describe a mechanism design formulation for green procurement with strategic suppliers. Our numerical experimentation shows that emission constraints can significantly alter sourcing decisions and affect the procurement costs dramatically. To the best of our knowledge, this is the first effort in explicitly taking into account carbon emissions in planning procurement auctions.

Mechanism design for cost optimal PAC learning in the presence of strategic noisy annotators

We consider the problem of Probably Ap-proximate Correct (PAC) learning of a bi-nary classifier from noisy labeled exam-ples acquired from multiple annotators(each characterized by a respective clas-sification noise rate). First, we consider the complete information scenario, where the learner knows the noise rates of all the annotators. For this scenario, we derive sample complexity bound for the Mini-mum Disagreement Algorithm (MDA) on the number of labeled examples to be ob-tained from each annotator. Next, we consider the incomplete information sce-nario, where each annotator is strategic and holds the respective noise rate as a private information. For this scenario, we design a cost optimal procurement auc-tion mechanism along the lines of Myer-son’s optimal auction design framework in a non-trivial manner. This mechanism satisfies incentive compatibility property,thereby facilitating the learner to elicit true noise rates of all the annotators.

Identification of key amino acid residues in the catalytic mechanism of diaminopropionate ammonialyase from Salmonella typhimurium

Diaminopropionate ammonialyase (DAPAL), a fold-typeII pyridoxal 5-phosphate-dependent enzyme, catalyzes the ,-elimination of diaminopropionate (DAP) to pyruvate and ammonia. DAPAL was able to utilize both d- and l-DAP as substrates with almost equal efficiency. Mutational analysis of functionally important residues such as Thr385, Asp125 and Asp194 was carried out to understand the mechanism by which the isomers are hydrolyzed. Further, the putative residues involved in the formation of disulfide bond Cys271 and Cys299 were also mutated. T385S, T385D sDAPAL were as active with dl-DAP as substrate as sDAPAL, whereas the later exhibited a threefold increase in catalytic efficiency with d-Ser as substrate. Further analysis of these mutants suggested that DAPAL might follow an anti-E-2 mechanism of catalysis that does not involve the formation of a quinonoid intermediate. Of the two mutants of Asp125, D125E showed complete loss of activity with d-DAP as substrate, whereas the reaction with l-DAP was not affected significantly, demonstrating that Asp125 was essential for abstraction of protons from the d-isomer. By contrast, mutational analysis of Asp194 showed that the residue may not be directly involved in proton abstraction from l-DAP. sDAPAL does not form a disulfide bond in solution, although the position of Cys299 and Cys271 in the modeled structure of sDAPAL favored the formation of a disulfide bond. Further, unlike eDAPAL, sDAPAL could be activated by monovalent cations. Mutation of the cysteine residues showed that Cys271 may be involved in coordinating the monovalent cation, as observed in the case of other fold-typeII enzymes.

Particle size, morphology and color tunable ZnO:Eu3+ nanophosphors via plant latex mediated green combustion synthesis

Efficient ZnO:Eu3+ (1-11 mol%) nanophosphors were prepared for the first time by green synthesis route using Euphorbia tirucalli plant latex. The final products were well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), etc. The average particle size of ZnO:Eu3+ (7 mol%) was found to be in the range 27-47 nm. With increase of plant latex, the particle size was reduced and porous structure was converted to spherical shaped particles. Photoluminescence (PL) spectra indicated that the peaks situated at similar to 590, 615, 648 and 702 nm were attributed to the D-5(0) -> F-7(j(j=1,2,3,4)) transitions of Eu3+ ions. The highest PL intensity was recorded for 7 mol% with Eu3+ ions and 26 ml plant latex concentration. The PL intensity increases with increase of plant latex concentration up to 30 ml and there after it decreases. The phosphor prepared by this method show spherical shaped particles, excellent chromaticity co-ordinates in the white light region which was highly useful for WLED's. Further, present method was reliable, environmentally friendly and alternative to economical routes. (c) 2013 Elsevier B.V. All rights reserved.

Growth mechanism of ZnO nanostructures for ultra-high piezoelectric d(33) coefficient

A comparative morphological study of different ZnO nanostructures was carried out with different varying process parameters for energy harvesting. Molarity, temperature, growth duration and seed layer were such fundamental controlling parameters. The study brings out an outstanding piezoelectric coefficient (d(33)) of 44.33 pm/V for vertically aligned ZnO nanorod structures, considered as the highest reported d(33) value for any kind of ZnO nanostructures. XRD analysis confirms wurtzite nature of this nanorod structure with 0001] as preferential growth direction. Semiconducting characteristic of nanorods was determined with temperature induced I/V characterization.

Antithyroid drugs and their analogues: synthesis, structure, and mechanism of action

Thyroid hormones are essential for the development and differentiation of all cells of the human body. They regulate protein, fat, and carbohydrate metabolism. In this Account, we discuss the synthesis, structure, and mechanism of action of thyroid hormones and their analogues. The prohormone thyroxine (14) is synthesized on thyroglobulin by thyroid peroxidase (TPO), a heme enzyme that uses iodide and hydrogen peroxide to perform iodination and phenolic coupling reactions. The monodeiodination of T4 to 3,3',5-triiodothyronine (13) by selenium-containing deiodinases (ID-1, ID-2) is a key step in the activation of thyroid hormones. The type 3 deiodinase (ID-3) catalyzes the deactivation of thyroid hormone in a process that removes iodine selectively from the tyrosyl ring of T4 to produce 3,3',5'-triiodothyronine (rT3). Several physiological and pathological stimuli influence thyroid hormone synthesis. The overproduction of thyroid hormones leads to hyperthyroidism, which is treated by antithyroid drugs that either inhibit the thyroid hormone biosynthesis and/or decrease the conversion of T4 to T3. Antithyroid drugs are thiourea-based compounds, which indude propylthiouracil (PTU), methimazole (MM I), and carbimazole (CBZ). The thyroid gland actively concentrates these heterocyclic compounds against a concentration gradient Recently, the selenium analogues of PTU, MMI, and CBZ attracted significant attention because the selenium moiety in these compounds has a higher nucleophilicity than that of the sulfur moiety. Researchers have developed new methods for the synthesis of the selenium compounds. Several experimental and theoretical investigations revealed that the selone (C=Se) in the selenium analogues is more polarized than the thione (C=S) in the sulfur compounds, and the selones exist predominantly in their zwitterionic forms. Although the thionamide-based antithyroid drugs have been used for almost 70 years, the mechanism of their action is not completely understood. Most investigations have revealed that MMI and PTU irreversibly inhibit TPO. PTU, MTU, and their selenium analogues also inhibit ID-1, most likely by reacting with the selenenyl iodide intermediate. The good ID-1 inhibitory activity of Pill and its analogues can be ascribed to the presence of the -N(H)-C(=O)- functionality that can form hydrogen bonds with nearby amino add residues in the selenenyl sulfide state. In addition to the TPO and ID-1 inhibition, the selenium analogues are very good antioxidants. In the presence of cellular reducing agents such as GSH, these compounds catalytically reduce hydrogen peroxide. They can also efficiently scavenge peroxynitrite, a potent biological oxidant and nitrating agent.

Low temperature combustion synthesis and magnetostructural properties of Co-Mn nanoferrites

In the present work, Co1-xMnxFe2O4 nanoparticles were synthesized by the low-temperature auto-combustion method. The thermal decomposition process was investigated by means of differential and thermal gravimetric analysis (TG-DTA) that showed the precursor yield the final product above 450 degrees C. The phase purity and crystal lattice symmetry were estimated from X-ray diffraction (XRD). Microstructural features observed by scanning electron microscopy (SEM) demonstrates that the fine clustered particles were formed with an increase in average grain size with Mn2+ content. Fourier transform infrared spectroscopy (FTIR) study confirms the formation of spinel ferrite. Room temperature magnetization measurements showed that the magnetization M-s increases from 29 to 60 emu/g and H-c increases from 13 to 28 Oe with increase in Mn2+ content, which implies that these materials may be applicable for magnetic data storage and recording media. (C) 2013 Elsevier B.V. All rights reserved.

Gas sensing response analysis of p-type porous chromium oxide thin films

The ethanol sensing properties of porous Cr2O3 thin films deposited by the ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture is reported. The impact of the precursor selection and various deposition parameters on the film crystallinity, surface morphology and stoichiometry are studied using thermo-gravimetric analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy techniques. The film morphology exhibits a highly porous nature, as a result of the exothermic combustion reaction during film deposition. The gas sensing properties of these films are investigated in the temperature range of 200-375 degrees C for ethanol. The films show two different regions of response for ethanol above and below 300 degrees C. A good relationship between the response and the ethanol concentration is observed, and is modeled using an empirical relation. The possible mechanism and the surface chemical reactions of ethanol over the chromium oxide surface are discussed.

On the Mechanism of Phase Transfer Catalysis in Brust-Schiffrin Synthesis of Metal Nanoparticles

The two-phase Brust-Schiffrin method (BSM) is used to synthesize highly stable nanoparticles of noble metals. A phase transfer catalyst (PTC) is used to bring in aqueous phase soluble precursors into the organic phase to enable particle synthesis there. Two different mechanisms for phase transfer are advanced in the literature. The first mechanism considers PTC to bring in an aqueous phase soluble precursor by complexing with it. The second mechanism considers the ionic species to be contained in inverse micelles of PTC, with a water core inside. A comprehensive experimental study involving measurement of interfacial tension, viscosity, water content by Karl-Fischer titration, static light scattering, H-1 NMR, and small-angle X-ray scattering is reported in this work to establish that the phase transfer catalyst tetraoctylammonium bromide transfers ions by complexing with them, instead of encapsulating them in inverse micelles. The findings have implications for particle synthesis in two-phase methods such as BSM and their modification to produce more monodispersed particles.