Substitutional Self-Assembly of Alkanethiol and Selenol SAMs from a Lying-Down Doubly Tethered Butanedithiol SAM on Gold

Substitutional self-assembly of thiol and selenol SAMs from a lying-down phase of butanedithiol (C4DT) (SAM) were investigated using thiols, disulfide, and diselenide molecules. The intent was to address the question if formation of a lying-down dithiol phase is an impediment to formation of standing-up dithiol phases as it has been assumed. It is demonstrated that this is not the case, and the C4DT SAM, where both the sulfur atoms are chemisorbed on gold, is removed and replaced in all cases. Differences in substitution kinetics are observed.

Hydrothermal preparation of Ba(Ti,Zr)O3 fine powders

Fine powders consisting of aggregated submicron crystallites of Ba(Ti,Zr)O3 in the complete range of Ti/Zr ratios are prepared at 85–130°C by hydrothermal method, starting from TiO2 + ZrO2 · xH2O mixed gel and Ba(OH)2 solution. The products obtained below 110°C incorporate considerable amounts of H2O and OH− within the lattice. As-prepared BaTiO3 is cubic and converts to tetragonal phase after the heat treatment at 1200°C, accompanied by the loss of residual hydroxyl ions. TEM investgations of the growth features show a transformation of the gel to the crystallite. Ba2+ ions entering the gel produce chemical changes within the gel, followed by dehydration, resulting in a cubic perovskite phase irrespective of Ti/Zr. The sintering properties of these powders to fine-grained, high density ceramics and their dielectric properties are presented.

System integration design in MEMS - A case study of micromachined load cell

One of the critical issues in large scale commercial exploitation of MEMS technology is its system integration. In MEMS, a system design approach requires integration of varied and disparate subsystems with one of a kind interface. The physical scales as well as the magnitude of signals of various subsystems vary widely. Known and proven integration techniques often lead to considerable loss in advantages the tiny MEMS sensors have to offer. Therefore, it becomes imperative to think of the entire system at the outset, at least in terms of the concept design. Such design entails various aspects of the system ranging from selection of material, transduction mechanism, structural configuration, interface electronics, and packaging. One way of handling this problem is the system-in-package approach that uses optimized technology for each function using the concurrent hybrid engineering approach. The main strength of this design approach is the fast time to prototype development. In the present work, we pursue this approach for a MEMS load cell to complete the process of system integration for high capacity load sensing. The system includes; a micromachined sensing gauge, interface electronics and a packaging module representing a system-in-package ready for end characterization. The various subsystems are presented in a modular stacked form using hybrid technologies. The micromachined sensing subsystem works on principles of piezo-resistive sensing and is fabricated using CMOS compatible processes. The structural configuration of the sensing layer is designed to reduce the offset, temperature drift, and residual stress effects of the piezo-resistive sensor. ANSYS simulations are carried out to study the effect of substrate coupling on sensor structure and its sensitivity. The load cell system has built-in electronics for signal conditioning, processing, and communication, taking into consideration the issues associated with resolution of minimum detectable signal. The packaged system represents a compact and low cost solution for high capacity load sensing in the category of compressive type load sensor.

Electrochemical Functionalization of a Gold Electrode with Redox-Active Self-Assembled Monolayer for Electroanalytical Application

The electrochemical functionalization of a Au electrode with a redox-active monolayer and the electroanalytical applications of the functionalized electrode are described. Reaction of the electrochemically derived o-quinone on the self-assembled monolayer (SAM) of 6-mercaptopurine (MPU) on a Au electrode gives a redox-active 4-(6-mercapto-purin-9-yl)benzene-1,2-diol (MPBD) self-assembly under optimized conditions. Electrochemical quartz crystal microbalance technique has been employed to follow the functionalization of the electrode in real time. Electrochemically derived o-quinone reacts at the N(9) position of the self-assembled MPU in neutral pH. Raman spectral measurement confirms the reaction of o-quinone on MPU self-assembly. MPBD shows a well-defined reversible redox response, characteristic of a surface-confined redox mediator at 0.21 V in neutral pH. The anodic peak potential (Epa) of MPBD shifts by −60 mV while changing the solution pH by 1 unit, indicating that the redox reaction involves two electrons and two protons. The surface coverage (Γ) of MPBD was 7.2 ± 0.3 × 10-12 mol/cm2. The apparent heterogeneous rate constant (ksapp) for MPBD was 268 ± 6 s-1. MPBD efficiently mediates the oxidation of nicotinamide adenine dinucleotide (NADH) and ascorbate (AA). A large decrease in the overpotential and significant increase in the peak current with respect to the unmodified electrode has been observed. Surface-confined MPBD has been successfully used for the amperometric sensing of NADH and AA in neutral pH at the nanomolar level.

Spectral and kinetic characterization of 7,8-diaminopelargonic acid synthase from Mycobacterium tuberculosis

The indispensability of biotin for crucial processes like lipid biosynthesis coupled to the absence of the biotin biosynthesis pathway in humans make the enzymes of this pathway, attractive targets for development of novel drugs against numerous pathogens including M. tuberculosis. We report the spectral and kinetic characterization of the Mycobacterium tuberculosis 7,8-Diamino-pelargonic acid (DAPA) synthase, the second enzyme of the biotin biosynthesis pathway. In contrast to the E. coli enzyme, no quinonoid intermediate was detected during the steady state reaction between the enzyme and S-adenosyl-L-methionine (SAM). The second order rate constant for this half of the reaction was determined to be 1.75 +/- 0.11 M-1 s(-1). The K-m values for 7-keto-8-aminopelargonic acid (KAPA) and SAM are 2.83 mu M and 308.28 mu M, respectively whereas the V-max and k(cat) values for the enzyme are 0.02074 mu moles/min/ml and 0.003 s(-1), respectively. Our initial studies pave the way for further detailed mechanistic and kinetic characterization of the enzyme.

The top 100 questions of importance to the future of global agriculture

Despite a significant growth in food production over the past half-century, one of the most important challenges facing society today is how to feed an expected population of some nine billion by the middle of the 20th century. To meet the expected demand for food without significant increases in prices, it has been estimated that we need to produce 70-100 per cent more food, in light of the growing impacts of climate change, concerns over energy security, regional dietary shifts and the Millennium Development target of halving world poverty and hunger by 2015. The goal for the agricultural sector is no longer simply to maximize productivity, but to optimize across a far more complex landscape of production, rural development, environmental, social justice and food consumption outcomes. However, there remain significant challenges to developing national and international policies that support the wide emergence of more sustainable forms of land use and efficient agricultural production. The lack of information flow between scientists, practitioners and policy makers is known to exacerbate the difficulties, despite increased emphasis upon evidence-based policy. In this paper, we seek to improve dialogue and understanding between agricultural research and policy by identifying the 100 most important questions for global agriculture. These have been compiled using a horizon-scanning approach with leading experts and representatives of major agricultural organizations worldwide. The aim is to use sound scientific evidence to inform decision making and guide policy makers in the future direction of agricultural research priorities and policy support. If addressed, we anticipate that these questions will have a significant impact on global agricultural practices worldwide, while improving the synergy between agricultural policy, practice and research. This research forms part of the UK Government's Foresight Global Food and Farming Futures project.

Crystallization of SrCO3 on a self-assembled monolayer substrate: an in-situ synchrotron X-ray study

Self-assembled monolayers (SAMs) of alkanethiols on gold surfaces show great promise in controlling the nucleation and growth of inorganic minerals from solution. In doing so, they mimic the role of some biogenic macromolecules in natural biomineralisation processes. Crystallization on SAM surfaces is usually monitored ex-situ; by allowing the process to commence and to evolve for some time, removing the substrate from the mother solution, and then examining it using microscopy, diffraction etc. We present here for the first time, the use of high energy monochromatic synchrotron X-radiation in conjunction with a two dimensional detector to monitor in situ, in a time resolved fashion, the growth of SrCO3 (strontianite) crystals on a SAM substrate.

Correlation of Calcification on Excised Aortic Valves by Micro-Computed Tomography with Severity of Aortic Stenosis

Background and aim of the study: The quantification of incidentally found aortic valve calcification on computed tomography (CT) is not performed routinely, as data relating to the accuracy of aortic valve calcium for estimating the severity of aortic stenosis (AS) is neither consistent nor validated. As aortic valve calcium quantification by CT is confounded by wall and coronary ostial calcification, as well as motion artifact, the ex-vivo micro-computed tomography (micro-CT) of stenotic aortic valves allows a precise measurement of the amounts of calcium present. The study aim, using excised aortic valves from patients with confirmed AS, was to determine if the amount of calcium on micro-CT correlated with the severity of AS. Methods: Each of 35 aortic valves that had been excised from patients during surgical valve replacement were examined using micro-CT imaging. The amount of calcium present was determined by absolute and proportional values of calcium volume in the specimen. Subsequently, the correlation between calcium volume and preoperative mean aortic valve gradient (MAVG), peak transaortic velocity (V-max), and aortic valve area (AVA) on echocardiography, was evaluated. Results: The mean calcium volume across all valves was 603.2 +/- 398.5 mm(3), and the mean ratio of calcium volume to total valve volume was 0.36 +/- 0.16. The mean aortic valve gradient correlated positively with both calcium volume and ratio (r = 0.72, p <0.001). V-max also correlated positively with the calcium volume and ratio (r = 0.69 and 0.76 respectively; p <0.001). A logarithmic curvilinear model proved to be the best fit to the correlation. A calcium volume of 480 mm(3) showed sensitivity and specificity of 0.76 and 0.83, respectively, for a diagnosis of severe AS, while a calcium ratio of 0.37 yielded sensitivity and specificity of 0.82 and 0.94, respectively. Conclusion: A radiological estimation of calcium amount by volume, and its proportion to the total valve volume, were shown to serve as good predictive parameters for severe AS. An estimation of the calcium volume may serve as a complementary measure for determining the severity of AS when aortic valve calcification is identified on CT imaging. The Journal of Heart Valve Disease 2012;21:320-327

Structural, electrical and dielectric properties of sputtered TiO2 films for Al/TiO2/Si capacitors

Metal-oxide semiconductor capacitors based on titanium dioxide (TiO2) gate dielectrics were prepared by RF magnetron sputtering technique. The deposited films were post-annealed at temperatures in the range 773-1173 K in air for 1 hour. The effect of annealing temperature on the structural properties of TiO2 films was investigated by X-ray diffraction and Raman spectroscopy, the surface morphology was studied by atomic force microscopy (AFM) and the electrical properties of Al/TiO2/p-Si structure were measured recording capacitance-voltage and current-voltage characteristics. The as-deposited films and the films annealed at temperatures lower than 773 K formed in the anatase phase, while those annealed at temperatures higher than 973 K were made of mixtures of the rutile and anatase phases. FTIR analysis revealed that, in the case of films annealed at 1173 K, an interfacial layer had formed, thereby reducing the dielectric constant. The dielectric constant of the as-deposited films was 14 and increased from 25 to 50 with increases in the annealing temperature from 773 to 973 K. The leakage current density of as-deposited films was 1.7 x 10(-5) and decreased from 4.7 X 10(-6) to 3.5 x 10(-9) A/cm(2) with increases in the annealing temperature from 773 to 1173 K. The electrical conduction in the Al/TiO2/p-Si structures was studied on the basis of the plots of Schottky emission, Poole-Frenkel emission and Fowler-Nordheim tunnelling. The effect of structural changes on the current-voltage and capacitance-voltage characteristics of Al/TiO2/p-Si capacitors was also discussed.

Interstitial Defects Induced Ferroelectricity in Undoped ZnO Nanorods at Room Temperature

A simple approach for obtaining room temperature ferroelectricity in ZnO rod structures at the nanoscale is reported. A systematic comparative study between two kinds of nanorods prepared by different processes reveals the physics behind it. It is observed that ZnO nanorods grown (in-situ) by a sol gel method on platinum substrate show ferroelectric behaviour. On the contrary, ZnO nanorods first grown by a sol gel method and then spin-coated on a platinum substrate (ex-situ) do not demonstrate this kind of feature. X-ray diffraction analysis confirms partially (002) and (100) plane oriented growth of both samples. From photoluminescence (PL) spectral analysis it is interpreted that oxygen vacancies/zinc interstitial defects, which arises from the large lattice mismatch between the Pt substrate and the ZnO nanorods grown thereon, and preferential ZnO growth along 002], can be causes of this type of phenomena. C-V characterization, P-E hysteresis loop along with piezoelectric force microscopy support this observation.

Characteristics of Photo Electrodes Based on TiO2 Nanoparticles, Nanotubes and Microspheres for Dye Solar Cell

We have analyzed the characteristics of electrodes made of TiO2 nanotubes, microspheres and commercially available nanoparticles for dye sensitized solar cell. The morphology of the electrodes and the formation of aggregates have been analyzed by scanning electron microscopy and surface profiling technique. The concentration of Ti3+ type impurity state on the surface of these electrodes is quantified by X-ray photoelectron spectroscopy. Micro structural properties have been characterized by Brunauer, Emmett and Teller method The optical properties of the electrodes such as band gap energy, the type of band formation and the diffuse reflectance are evaluated by UV-Visible spectroscopy. The photovoltaic characteristics of dye solar cell made of these electrodes have been evaluated and it is found that the characteristics of the TiO2 film alone can alter the overall conversion efficiency to a great extent. Additional analysis using electrochemical impedance spectroscopy has been carried out to probe the electron transport properties and charge collection efficiency of these electrodes.

Preparation of Self Assembled Sodium Oleate Monolayer on Mild Steel and Its Corrosion Inhibition Behavior in Saline water

A self assembled monolayer (SAM) of sodium oleate was generated on mild steel by the dip coating method. Formation of the SAM on mild steel was examined using Infrared Reflection Absorption Spectroscopy (IRRAS) and contact angle measurements. The chemical and anticorrosive properties of the SAM were analyzed using different techniques. IRRAS and water contact angle data revealed the crystallinity and chemical stability of the SAM modified mild steel. The electrochemical measurements showed that the mild steel with the sodium oleate derived SAM exhibited better corrosion resistance in saline water. The effect of temperature and pH on the SAM formation and its anti corrosion ability was explored.

Positive temperature coefficient and structural relaxations in selectively localized MWNTs in PE/PEO blends

The dispersion state of multiwall carbon nanotubes (MWNTs) in melt mixed polyethylene/polyethylene oxide (PE/PEO) blends has been assessed by both surface and volume electrical conductivity measurements and the structural relaxations have been assessed by broadband dielectric spectroscopy. The selective localization of MWNTs in the blends was controlled by the flow characteristics of the components, which led to their localization in the energetically less favored phase (PE). The electrical conductivity and positive temperature co-efficient (PTC) measurements were carried out on hot pressed samples. The neat blends exhibited only a negative temperature coefficient (NTC) effect while the blends with MWNTs exhibited both a PTC and a NTC at the melting temperatures of PE and PEO respectively. These phenomenal changes were corroborated with the different crystalline morphology in the blends. It was deduced that during compression molding, the more viscous PEO phase spreads less in contrast to the less viscous PE phase. This has further resulted in a gradient in morphology as well as the distribution state of the MWNTs in the samples and was supported by scanning electron and scanning acoustic microscopy (SAM) studies and contact angle measurements. SAM from different depths of the samples revealed a gradient in the microstructure in the PE/PEO blends which is contingent upon the flow characteristics of the components. Interestingly, the surface and volume electrical conductivity was different due to the different dispersion state of the MWNTs at the surface and bulk. The observed surface and volume electrical conductivity measurements were corroborated with the evolved morphology during processing. The structural relaxations in both PE and PEO were discerned from broadband dielectric spectroscopy. The segmental dynamics below and above the melting temperature of PEO were significantly different in the presence of MWNTs.