Highly sensitive photoelectrochemical immunosensor based on anatase/rutile TiO2 and Bi2S3 for the zero-biased detection of PSA

Journal of Solid State Electrochemistry - A novel label-free photoelectrochemical immunosensor was developed for the determination of prostate-specific antigen (PSA) based on fluorine-doped tin...     

Formation of oxysulfide LnO<Subscript>2</Subscript>S<Subscript>2</Subscript> and oxysulfate LnO<Subscript>2</Subscript>SO<Subscript>4</Subscript> phases in the thermal decomposition process of lanthanide sulfonates (Ln = La,Sm)

This study investigates two lanthanide compounds (La³⁺ and Sm³⁺) obtained in water/ethyl alcohol solutions employing the anionic surfactant diphenyl-4-amine sulfonate (DAS) as ligand. Both sulfonates were characterized through IR, TG/DTG (O₂ and N₂). The thermal treatment of both compounds at 1273 K under air leaves residues containing variable percentages of lanthanide oxysulfide/oxysulfate phases shown by synchrotron high-resolution XRD pattern including the Rietveld analysis. The phase distributions found in the residues evidence the differences in the relative stability of the precursors.     

Insights on spin polarization through the spin density source function

Understanding how spin information is transmitted from paramagnetic to non-magnetic centers is crucial in advanced materials research and calls for novel interpretive tools. Herein, we show that the spin density at a point may be seen as determined by a local source function for such density, operating at all other points of space. Integration of the local source over Bader''s quantum atoms measures their contribution in determining the spin polarization at any system''s location. Each contribution may be then conveniently decomposed in a magnetic term due to the magnetic natural orbital(s) density and in a reaction or relaxation term due to the remaining orbitals density. A simple test case, ³B₁ water, is chosen to exemplify whether an atom or group of atoms concur or oppose the paramagnetic center in determining a given local spin polarization. Discriminating magnetic from reaction or relaxation contributions to such behaviour strongly enhances chemical insight, though care needs to be paid to the large sensitivity of the latter contributions to the level of the computational approach and to the difficulty of singling out the magnetic orbitals in the case of highly correlated systems. Comparison of source function atomic contributions to the spin density with those reconstructing the electron density at a system''s position, enlightens how the mechanisms which determine the two densities may in general differ and how diverse may be the role played by each system''s atom in determining each of the two densities. These mechanisms reflect the quite diverse portraits of the electron density and electron spin density Laplacians, hence the different local concentration/dilution of the total and (α–β) electron densities throughout the system. Being defined in terms of an observable, the source function for the spin density is also potentially amenable to experimental determination, as customarily performed for its electron density analogue.     

Laplace equation in a domain with a rectilinear crack: higher order derivatives of the energy with respect to the crack length

We consider the weak solution of the Laplace equation in a planar domain with a straight crack, prescribing a homogeneous Neumann condition on the crack and a nonhomogeneous Dirichlet condition on the rest of the boundary. For every k we express the k-th derivative of the energy with respect to the crack length in terms of a finite number of coefficients of the asymptotic expansion of the solution near the crack tip and of a finite number of other parameters, which only depend on the shape of the domain.     

Thermodynamic performance vs. dynamic stability in an enzymatic reaction model

Previous studies on thermal engine models and energy-converting biological systems have shown that some of the parameters affecting their thermodynamic performance also affect their dynamic stability. In some cases, such parameters represent a tradeoff between these two generic properties. In the present work we carry out a similar analysis on a simple model for an enzymatic reaction. Despite its simplicity, this model captures the essential characteristics of numerous biochemical reactions where an endothermic reaction is made possible by coupling it (via an enzyme) with an exothermic reaction. Our results indicate that the global reaction chemical potential gap () affects both the thermodynamic properties and stability of the steady state. Larger values imply a higher power output and a higher efficiency, but also a less strongly stable steady state.     

Simultaneous Differential Pulse Voltammetric Determination of Sulfamethoxazole and Trimethoprim on a Boron‐Doped Diamond Electrode

The performance of hydrogen‐ (HT) and oxygen‐terminated (OT) boron‐doped diamond (BDD) electrodes (electrochemically pretreated) on the simultaneous differential pulse voltammetric determination of sulfamethoxazole and trimethoprim in pharmaceutical products is presented. Under the optimum analytical experimental conditions, the HT‐BDD electrode presented two well‐defined oxidation peaks at 920 and 1100 mV vs. Ag/AgCl for sulfamethoxazole and trimethoprim, respectively. On the other hand, when the OT‐BDD electrode was used, the sulfamethoxazole oxidation current peak was decreased twenty fold. The calculated LOD values for sulfamethoxazole and trimethoprim using the HT‐BDD electrode were 3.65 μg L^?1 and 3.92 μg L^?1, respectively. The results obtained in the simultaneous determination of sulfamethoxazole and trimethoprim in three different commercial formulations were similar to those obtained using a standard HPLC method at 95% confidence level.     

Minimum cycle cover and Chinese postman problems on mixed graphs with bounded tree-width

Let M=(V,E,A) be a mixed graph with vertex set V, edge set E and arc set A. A cycle cover of M is a family C={C₁,…,C_k} of cycles of M such that each edge/arc of M belongs to at least one cycle in C. The weight of C is . The minimum cycle cover problem is the following: given a strongly connected mixed graph M without bridges, find a cycle cover of M with weight as small as possible. The Chinese postman problem is: given a strongly connected mixed graph M, find a minimum length closed walk using all edges and arcs of M. These problems are NP-hard. We show that they can be solved in polynomial time if M has bounded tree-width.     

Low-energy electron stimulated desorption of neutrals from multilayers of SiCl4 on Si(111)

The interaction of low-energy electrons with multilayers of SiCl(4) adsorbed on Si(111) leads to production and desorption of Cl((2)P(32)), Cl((2)P(12)), Si, and SiCl. Resonant structure in the yield versus incident electron energy (E(i)) between 6 and 12 eV was seen in all neutral channels and assigned to dissociative electron attachment (DEA), unimolecular decay of excited products produced via autodetachment and direct dissociation. These processes yield Cl((2)P(32)) and Cl((2)P(12)) with nonthermal kinetic energies of 425 and 608 meV, respectively. The Cl((2)P(12)) is produced solely at the vacuum surface interface, whereas the formation of Cl((2)P(32)) likely involves subsurface dissociation, off-normal trajectories, and collisions with neighbors. Structure in the Cl((2)P(32)) yield near 14 and 25 eV can originate from excitation of electrons in the 2e, 7t(2) and 6t(2), 6a(1) levels, respectively. Although the 14 eV feature was not present in the Cl((2)P(12)) yield, the broad 25 eV feature, which involves complex Auger filling of holes in the 6t(2) and 6a(1) levels of SiCl(4), is observed. Direct ionization, exciton decay, and DEA from secondary electron scattering all occur at E(i)>14 eV. Si and SiCl were detected via nonresonant ionization of SiCl(x) precursors that are produced via the same states and mechanisms that yield Cl. The Si retains the kinetic energy profile of the desorbed precursors.     

Medium effects on the decarboxylation of a biotin model in pure and mixed solvents from QM/MM simulations

The decarboxylation of imidazolidin-2-one-1-carboxylate anion 2 has been investigated via combined quantum and statistical mechanics methodology. Monte Carlo statistical mechanics simulations utilizing free-energy perturbation theory and PDDG/PM3 for the QM method yielded free-energy profiles for the reaction in water, methanol, acetonitrile, and mixed solvents. The results for free energies of activation are uniformly in close accord with experimental data and reflect large rate accelerations in progressing from protic to dipolar aprotic media. Structural and energetic analyses confirm that the rate retardation in protic solvents comes from loss of hydrogen bonding in progressing from the carboxylate anion 2 to the more charge-delocalized transition state (TS). The structure of the TS is found to be significantly affected by the reaction medium; it occurs at a 0.2-A shorter C-N separation in protic solvents than in acetonitrile. Characterization of the hydrogen bonding for 2 and the TS also provided insights for design of decarboxylase catalysts, namely, it is desirable to have three hydrogen-bond donating groups positioned to interact with the ureido oxygen along with two hydrogen-bond donors positioned to interact with the ureido nitrogen of the breaking C-N bond.     

The effect of chemical composition on microfibrillar cellulose films from wood pulps: water interactions and physical properties for packaging applications

The interactions with water and the physical properties of microfibrillated celluloses (MFCs) and associated films generated from wood pulps of different yields (containing extractives, lignin, and hemicelluloses) have been investigated. MFCs were produced by combining mechanical refining and a high pressure treatment using a homogenizer. The produced MFCs were characterized by morphology analysis, water retention, hard-to-remove water content, and specific surface area. Regardless of chemical composition, processing to convert macrofibrils to microfibrils resulted in a decrease in water adsorption and water vapor transmission rate, both important properties for food packaging applications. After homogenization, MFCs with high lignin content had a higher water vapor transmission rate, even with a higher initial contact angle, hypothesized to be due to large hydrophobic pores in the film. A small amount of paraffin wax, less than 10%, reduced the WVTR to a similar value as low density polyethylene. Hard-to-remove water content correlated with specific surface area up to approximately 50 m²/g, but not with water retention value. The drying rate of the MFCs increased with the specific surface area. Hornified fibers from recycled paper also have the potential to be used as starting materials for MFC production as the physical and optical properties of the films were similar to the films from virgin fibers. In summary, the utilization of lignin containing MFCs resulted in unique properties and should reduce MFC production costs by reducing wood, chemical, and energy requirements.