Polymer-Based Ion Trap Chemical Sensor

Ion traps are widely used in chemical analysis, and they are especially important in current attempts to miniaturize mass spectrometers to create portable instruments. The ultimate aim is to build a handheld device that would require a smaller mass analyzer. To accomplish this task, a robust precision fabrication procedure is desired. In this paper, the authors report a new approach to fabricating ion traps using stereolithography apparatus (SLA), which provides precision monolithic fabrication. An SLA-fabricated rectilinear ion trap, which employs a very simple electrode geometry, is shown to provide detection capabilities within a useful mass range encompassing that of interest in the detection of numerous volatile organic compounds, including those relevant to homeland security applications. Single small ion traps and integrated trap arrays can be made through this approach, which allows higher operating pressures and reduced power requirements     

Theory and implementation of path planning by negotiation for decentralized agents

This paper presents a cooperative decentralized path-planning algorithm for a group of autonomous agents that provides guaranteed collision-free trajectories in real-time. The algorithm is robust with respect to arbitrary delays in the wireless traffic, possible sources being transmission time and error correction. Agents move on reserved areas which are guaranteed not to intersect, therefore ensuring safety. A handshaking procedure guarantees recent information states for the agents. Conflicts between agents are resolved by a cost-based negotiation process. The basic algorithm is augmented by the introduction of waypoints, which increase performance at the cost of additional wireless traffic. An implementation of the algorithm is tested in simulation and successfully applied to a real system of autonomous robots. The results are presented and discussed.     

Linear matrix inequality conditions for robustness and control design

In this paper, well‐known stability conditions for linear, time‐invariant systems subject to structured uncertainty are extended to encompass matrix valued and affine integral constraints on the system inputs and outputs. Necessary and sufficient analysis conditions are derived in terms of linear matrix inequalities. For a large class of these problems, the synthesis question can also be expressed as a linear matrix inequality. Copyright © 2001 John Wiley & Sons, Ltd.     

Environmental estrogens and reproductive health: a discussion of the human and environmental data

Estrogenic activity of certain xenobiotics is an established mechanism of toxicity that can impair reproductive function in adults of either sex, lead to irreversible abnormalities when administered during development, or cause cancer. The concern has been raised that exposure to ambient levels of estrogenic xenobiotics may be having widespread adverse effects on reproductive health of humans and wildlife. The purpose of this review is to evaluate (a) the nature of the evidence supporting this concern, and (b) the adequacy of toxicity screening to detect, and risk assessment procedures to establish safe levels for, agents acting by this mechanism. Observations such as adverse developmental effects after maternal exposure to therapeutic levels of the potent estrogen diethylstilbestrol or male fertility problems after exposure to high levels of the weak estrogen chlordecone clearly demonstrate that estrogenicity is active as a toxic mechanism in humans. High level exposures to estrogenic compounds have also been shown to affect specific wildlife populations. However, there is little direct evidence to indicate that exposures to ambient levels of estrogenic xenobiotics are affecting reproductive health. Reports of historical trends showing decreasing reproductive capacity (e.g., decreased sperm production over the last 50 years) are either inconsistent with other data or have significant methodologic inadequacies that hinder interpretation. More reliable historical trend data show an increase in breast cancer rate, but the most comprehensive epidemiology study to data failed to show an association between exposure to persistent, estrogenic organochlorine compounds and breast cancer. Clearly, more work needs to be done to characterize historical trends in humans and background incidence of abnormalities in wildlife populations, and to test hypotheses about ambient exposure to environmental contaminants and toxic effects, before conclusions can be reached about the extent or possible causes of adverse effects. It is unlikely that current lab animal testing protocols are failing to detect agents with estrogenic activity, as a wide array of estrogen-responsive endpoints are measured in standard testing batteries. Routine testing for aquatic and wildlife toxicity is more limited in this respect, and work should be done to assess the validity of applying mammalian toxicology data for submammalian hazard identification. Current risk assessment methods appear to be valid for estrogenic agents, although the database for evaluating this is limited. In conclusion, estrogenicity is an important mechanism of reproductive and developmental toxicity; however, there is little evidence at this point that low level exposures constitute a human or ecologic health risk. Given the potential consequences of an undetected risk, more research is needed to investigate associations between exposures and effects, both in people and animals, and a number of research questions are identified herein. The lack of evidence demonstrating widespread xenobiotic-induced estrogenic risk suggests that far-reaching policy decisions can await these research findings.     

Electrochemical oxidation of stabilized landfill leachate on DSA electrodes

The electrochemical oxidation of stabilized landfill leachate with 2960 mg L(-1) chemical oxygen demand (COD) over a Ti/IrO(2)-RuO(2) anode was investigated in the presence of HClO(4) as the supporting electrolyte. Emphasis was given on the effect of electrolysis time (up to 240 min) and temperature (30, 60 and 80°C), current density (8, 16 and 32 mA cm(-2)), initial effluent's pH (0.25, 3, 5 and 6), HClO(4) concentration (0.25 and 1M) and the addition of NaCl (20 and 100mM) or Na(2)SO(4) (20mM) as source of extra electrogenerated oxidants on performance; the latter was evaluated regarding COD, total carbon (TC), total phenols (TPh) and color removal. Moreover, the anode was studied by scanning electron microscopy and cyclic voltammetry. The main parameters affecting the process were the effluent's pH and the addition of salts. Treatment for 240 min at 32 mA cm(-2) current density, 80°C and the pH adjusted from its inherent value of 0.25 (i.e. after the addition of HClO(4)) to 3 yielded 90% COD, 65% TC and complete color and TPh removal at an electricity consumption of 35 kWh kg(-1) COD removed. Comparable performance (i.e. 75% COD reduction) could be achieved without pH adjustment but with the addition of 100mM NaCl consuming 20 kWh kg(-1) COD removed.     

Stereochemistry and Circular Dichroism of Chiral Internal Olefin-Platinum(II) Complexes

A series of cis- and trans-dichloro(benzylamine) (chiral olefin) platinum(II) complexes, containing (Z) and (E) isomers of the internal chiral olefins R-CH=CH-R', has been prepared by ethylene displacement from the corresponding ethylene containing complexes. The particular stereochemical features of the complexes allow one to interpret the CD on the basis of the individual contributions coming from the chiral centres already present in the free olefin and from the chiral centres formed in the complexation of the double bond. Evidence is reported showing that the aforementioned contributions are additive and that the chiral centre(s) bound to the metal dominates the CD at about 400 nm, its chirality type being reflected in the sign and its chirality prevalence in the Δϵ value.     

Using Quick‐Start to enhance TCP‐friendly rate control performance in bidirectional satellite networks

In the not so distant future, we envisage an Internet where the biggest share of capacity is used by streaming applications. To avoid congestion collapse from unresponsive flows calls for a robust and ubiquitous end‐to‐end multimedia congestion control mechanism, such as TCP‐friendly rate control (TFRC), which provides fair sharing with the other Internet traffic. This paper therefore analyses the implications of using rate‐adaptive congestion control over satellite links that utilize demand allocation multiple access (DAMA) to maximize satellite transponder utilization. The interaction between TFRC and DAMA is explored using simulations supported by fluidic flow models. The analysis shows that DAMA reduces the start‐up phase of TFRC, causing non‐negligible delays. To mitigate this problem, we propose a new cross‐layer method based on the Quick‐Start mechanism. This can accelerate the start‐up of multimedia flows by a judicious allocation of additional capacity derived from cross‐layer signalling. Copyright © 2009 John Wiley & Sons, Ltd.     

Reduced graphene oxide-ZnO hybrid composites as photocatalysts: The role of nature of the molecular target in catalytic performance

Spurred by controversial literature findings, we enwrapped reduced graphene oxide (rGO) in ZnO hierarchical microstructures (rGO loadings spanning from 0.01 to 2 wt%) using an in situ synthetic procedure. The obtained hybrid composites were carefully characterized, aiming at shining light on the possible role of rGO on the claimed increased performance as photocatalysts. Several characterization tools were exploited to unveil the effect exerted by rGO, including steady state and time resolved photoluminescence, electron microscopies and electrochemical techniques, in order to evaluate the physical, optical and electrical features involved in determining the catalytic degradation of rhodamine B and phenol in water.Several properties of native ZnO structures were found changed upon the rGO enwrapping (including optical absorbance, concentration of native defects in the ZnO matrix and double-layer capacitance), which are all involved in determining the photocatalytic performance of the hybrid composites. The findings discussed in the present work highlight the high complexity of the field of application of graphene-derivatives as supporters of semiconducting metal oxides functionality, which has to be analyzed through a multi-parametric approach.     

Miniaturization and geometry optimization of a polymer-based rectilinear ion trap

The fabrication, operation, and characterization of a polymer-based rectilinear ion trap mass analyzer is discussed. A novel, fast prototyping technique, stereolithography (SLA)-based fabrication, traditionally reserved for end use production parts and to fabricate master molds for rubber products, is applied here as a tool to create precise, arbitrary geometries. Taking full advantage of the SLA methodology, an open corner, polymer-based ion trap has been fabricated and tested. The use of a custom resin, Nanoform 15120 (DSM Somos, New Castle, DE), has resulted in a polymer with high heat deflection temperature and greater structural stability at higher temperatures and lower capacitance. The mass analyzer was mounted in a polymer holder and tested in a custom vacuum system using modified LCQ Duo (Thermo Fisher Corp.) electronics. The resolution, mass/charge range, and MS/MS capabilities were examined using electrospray ionization as well as atmospheric pressure chemical ionization. In the course of this study, three traps of different sizes were fabricated, beginning with a "full size" device measuring 10 x 8 x 50 mm. The next two traps were scaled down by linear factors of a half and a third. SLA is shown to allow fabrication of light, small rectilinear ion traps, which are less expensive and have the same performance as traditional machined devices of the same size. In addition, smaller traps can be built just as easily, and they show unit mass resolution to mass 300, tandem mass spectrometry capabilities, and low power consumption.