Tailoring Electrode Surface Charge to Achieve Discrimination and Quantification of Chemically Similar Small Molecules with Electrochemical Aptamers

Electrochemical biosensors based on structure-switching aptamers offer many advantages because they can operate directly in complex samples and offer the potential to integrate with miniaturized electronics. Unfortunately, these biosensors often suffer from cross-reactivity problems when measuring a target in samples containing other chemically similar molecules, such as precursors or metabolites. While some progress has been made in selecting highly specific aptamers, the discovery of these reagents remains slow and costly. In this work, a novel strategy is demonstrated to distinguish molecules with miniscule difference in chemical composition (such as a single hydroxyl group)—with cross reactive aptamer probes—by tuning the charge state of the surface on which the aptamer probes are immobilized. As an exemplar, it is shown that the strategy can distinguish between DOX and many structurally similar analytes, including its primary metabolite doxorubicinol (DOXol). Then the ability to accurately quantify mixtures of these two molecules based on their differential response to sensors with different surface-charge properties is demonstrated. It is believed that this methodology is general and can be extended to a broad range of applications.     

The Impact of Lattice Distortions on the Magnetic Stability of Single Atoms: Dy and Ho on BaO(100)

X-ray magnetic circular dichroism, atomic multiplet simulations, and density functional theory calculations are employed to identify criteria for the optimum combination of supporting alkaline earth oxide and adsorption site maximizing the spin lifetimes of lanthanide single-atom magnets. Dy and Ho atoms adsorbed on BaO(100) thin films on Pt(100) are characterized and compared with previous results for the same two elements on MgO/Ag(100). Dy shows hysteresis in magnetic fields up to ≈3.5 T and long spin lifetime, exceeding 300 s at 2.5 K and 0.5 T. Dy displays superior magnetic stability on the bridge site than on the top-O site. Surprisingly, Ho shows paramagnetism, as opposed to its long spin lifetime on MgO. These differences originate from the local surface distortions induced by the adatoms. On MgO, minimal distortions involve only the closest O atoms, while, on BaO, they affect both the closest anions and cations. This trend reflects the decrease of the lattice energy along the series of the alkaline earth oxides, going from MgO to BaO. This study represents a step ahead in the understanding of the factors determining the spin dynamics of surface-adsorbed single-atom magnets in order to achieve their operation as qubits and memories.     

A mixed-variable continuously deforming finite element method for parabolic evolution problems. Part III: Numerical implementation and computational results

In Part I of this paper,¹ the conceptual framework of a rate variational least squares formulation of a continuously deforming mixed-variable finite element method was presented for solving a single evolution equation. In Part II² a system of ordinary differential equations with respect to time was derived for solving a system of three coupled evolution equations by the deforming grid mixed-variable least squares rate variational finite element method. The system of evolution equations describes the coupled heat flow, fluid flow and trace species transport in porous media under conditions when the flow velocities and constituent phase transitions induce sharp fronts in the solution domain. In this paper, we present the method we have adopted to integrate with respect to time the resulting spatially discretized system of non-linear ordinary differential equations. Next, we present computational results obtained using the code in which this deforming mixed finite element method was implemented. Because several features of the formulation are novel and have not been previously attempted, the problems were selected to exercise these features with the objective of demonstrating that the formulation is correct and that the numerical procedures adopted converge to the correct solutions.     

Computational fluid dynamic simulations of coal-fired utility boilers: An engineering tool

The objective of this study was to develop an engineering tool by which the combustion behavior of coals in coal-fired utility boilers can be predicted. We presented in this paper that computational fluid dynamic (CFD) codes can successfully predict performance of- and emission from- full-scale pulverized-coal utility boilers of various types, provided that the model parameters required for the simulation are properly chosen and validated. For that purpose we developed a methodology combining measurements in a 50 kW pilot-scale test facility with CFD simulations using the same CFD code configured for both test and full-scale furnaces. In this method model parameters of the coal processes are extracted and validated. This paper presents the importance of the validation of the model parameters which are used in CFD codes. Our results show very good fit of CFD simulations with various parameters measured in a test furnace and several types of utility boilers. The results of this study demonstrate the viability of the present methodology as an effective tool for optimization coal burning in full-scale utility boilers.     

Decomposition of Fe5C2 catalyst particles in carbon nanofibers during TEM observation

The effect of an electron beam on nanoparticles of two Fe carbide catalysts inside a carbon nanofiber was investigated in a transmission electron microscope. Electron beam exposure does not result in significant changes for cementite (θ-Fe₃C). However, for Hägg carbide nanoparticles (χ-Fe₅C₂), explosive decay is observed after exposure for 5–10 s. This produces small particles of cementite and γ-Fe, each covered with a multilayer carbon shell, and significantly modifies the carbon-fiber structure. It is considered that the decomposition of Hägg carbide is mostly due to the damage induced by high-energy electron collisions with the crystal lattice, accompanied by the heating of the particle and by mechanical stress provided by the carbon layers of the nanofiber.     

Estimating Internet Users' Demand Characteristics

We investigate two parametric approaches and one non-parametric approach toestimating Internet users' value-of-time, an important characteristic ofdemand for Internet services. The advantages of these approaches are madeclear and their limitations discussed. The models are tested with datagenerated from our similation model of the Internet economy. Given thecharacteristics of the data, we investigate parametric count-data modelsfirst. While reasonably good results are obtained on all medium- andlarge-sized jobs, the method fails on small-sized ones. Second, we develop anonparametric quasi-Bayesian update algorithm for retrieving the underlyingdistribution function of Internet users' value-of-time purely fromobservations on their choices. Compared with the parametric count-data models,good results are obtained in every case.     

The Effect of an Fe-doped GaN Buffer on off-State Breakdown Characteristics in AlGaN/GaN HEMTs on Si Substrate

An Fe-doped GaN buffer layer was employed in the growth of AlGaN/GaN high-electron mobility transistors (HEMTs) on Si substrates. In order to investigate the effects of an Fe-doped GaN buffer on OFF-state breakdown characteristics, HEMT devices with an Fe-doped GaN buffer on Si substrates were fabricated along with conventional devices utilizing an unintentionally doped GaN buffer on Si substrates. The device characteristics were compared. While HEMT devices with the conventional structure showed an extremely unstable OFF-state breakdown behavior due to punchthrough to the Si substrate, it was demonstrated that an Fe-doped GaN buffer layer on a Si substrate successfully suppressed the premature failure caused by Si-induced breakdown. As a result, the AlGaN/GaN HEMTs with an Fe-doped GaN buffer on Si substrates exhibited much more consistent and enhanced breakdown voltages, when compared with the conventional devices. Consequently, it is highly desirable that AlGaN/GaN HEMTs on Si substrates have an Fe-doped GaN buffer layer in order to achieve stable and robust OFF-state breakdown characteristics     

Discrete thermodynamics of chemical equilibria and classical limit in thermodynamic simulation

This article sets forth comprehensive basic concepts of the discrete thermodynamics of chemical equilibrium as balance between internal and external thermodynamic forces. Conditions of chemical equilibrium in the open chemical system are obtained in the form of a logistic map, containing only one new parameter that defines the chemical system's resistance to external impact and its deviation from thermodynamic equilibrium. Solutions to the basic map are bifurcation diagrams that have quite traditional shape but the diagram areas feature specific meanings for chemical systems and constitute the system's domain of states. The article is focused on two such areas: the area of “true” thermodynamic equilibrium and the area of open chemical equilibrium. The border between them represents the classical limit, a transition point between the classical and newly formulated equilibrium conditions. This limit also separates regions of the system ideality, typical for isolated classical systems, and non-ideality due to the limitations imposed on the open system from outside. Numerical examples illustrating the difference between results of classical and discrete thermodynamic simulation methods are presented. The article offers an analytical formula to find the classical limit, compares analytical results with these obtained by simulation, and shows the classical limit dependence upon the chemical reaction stoichiometry and robustness.