p-d Orbital Hybridization-Engineered PdSn Nanozymes for a Sensitive Immunoassay.

Nanozymes with peroxidase-like activity have been extensively studied for colorimetric biosensing. However, their catalytic activity and specificity still lag far behind those of natural enzymes, which significantly affects the accuracy and sensitivity of colorimetric biosensing. To address this issue, we design PdSn nanozymes with selectively enhanced peroxidase-like activity, which improves the sensitivity and accuracy of a colorimetric immunoassay. The peroxidase-like activity of PdSn nanozymes is significantly higher than that of Pd nanozymes. Theoretical calculations reveal that the p-d orbital hybridization of Pd and Sn not only results in an upward shift of the d-band center to enhance hydrogen peroxide (H2O2) adsorption but also regulates the O-O bonding strength of H2O2 to achieve selective H2O2 activation. Ultimately, the nanozyme-linked immunosorbent assay has been successfully developed to sensitively and accurately detect the prostate-specific antigen (PSA), achieving a low detection limit of 1.696 pg mL-1. This work demonstrates a promising approach for detecting PSA in a clinical diagnosis.

Glycerol Oligomerization over Titania-Based Catalyst Compositions.

The possibility of using TiO2 -based compositions: individual and sulfated titania, and their composites with carbon nanotubes as catalysts for glycerol oligomerization has been displayed. The effect of modification of TiO2 with sulfur and carbon nanotubes on acid-base and catalytic characteristics in the glycerol conversion was investigated. The activation of glycerol on the catalysts has been studied using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Only the samples based on sulfated titania are active over glycerol transformation, showing up to 58.7 % conversion. This is explained by the presence of strong base sites. Glycerides up to pentaglycerides, both linear and nonlinear structure are formed by glycerol oligomerization over TiO2 -S. The addition of nanotubes to the catalyst reduces both the glycerol conversion (up to 10.5 %) and the yield of glycerides. However, the spectrum of the resulting products is significantly narrowed, increasing the selectivity for short-chain glycerides: the portion of diglycerides reaches 72 %, and triglycerides 21 %. Herewith, glycerides of a linear structure only formed.

Yttria-Stabilized Zirconia as a High-Performance Catalyst for Ethanol to n-Butanol Guerbet Coupling.

It has been shown that yttria-stabilized zirconia is an effective catalyst for ethanol to n-butanol Guerbet coupling. The variation of the calcination temperature allows an improvement in the catalytic characteristics of this material via stabilization of the tetragonal phase of zirconia, having higher basicity than the monoclinic one. The treatment of yttria-stabilized zirconia at an optimal calcination temperature of 500 °C induces the increase in surface basicity required for the aldol condensation step, along with a decrease in surface acidity, which is responsible for the side reaction such as ethylene formation. The catalyst obtained significantly exceeds in selectivity and n-butanol yield than individual zirconia and other oxide systems which have been studied in this reaction.

Insight into the active site nature of zeolite H-BEA for liquid phase etherification of isobutylene with ethanol.

The nature of active acid sites of zeolite H-BEA with different Si/Al ratios (15-407) in liquid phase etherification of isobutylene with ethanol in a continuous flow reactor in the temperature range 80-180 °C has been explored. We describe and discuss data concerning the strength and concentration of acid sites of H-BEA obtained by techniques of stepwise (quasi-equilibrium) thermal desorption of ammonia, X-ray diffraction, low-temperature adsorption of nitrogen, FTIR spectroscopy of adsorbed pyridine and solid-state 27Al MAS NMR. The average values of the adsorption energy of NH3 on H-BEA were experimentally determined as 63.7; 91.3 and 121.9 mmol g-1 (weak, medium, and strong, respectively). In agreement with this, a correlation between the rate of ethyl-tert-butyl ether synthesis and the concentration of weak acid sites (E NH3 = 61.6-68.9 kJ mol-1) has been observed. It was concluded that the active sites of H-BEA for this reaction are Brønsted hydroxyls representing internal silanol groups associated with octahedrally coordinated aluminum in the second coordination sphere.

Temporal and spatial organization of chemical and hydrodynamic processes. The system Pb(2+)-chlorite-thiourea.

Precise spatio-temporal organization of chemical, hydrodynamic, and mechanical processes is typical for biological systems where particular chemical reactions have to accrue in precisely assignment place and time. It is rarely studied and observed in chemical systems. We report unusual precipitation pattern formation of PbSO(4) in chemical media (Pb(2+)-Chlorite-Thiourea System). We have found that there is a region in a plane of initial concentrations of chlorite ions and thiourea where precipitation of lead sulfate appears in a form of ring if a pellet of lead nitrate is placed into the system. The whole process may be divided into three stages: movement of first circular front of lead containing solution, formation of a ringlike pattern of lead sulfate, and finally, propagation of this pattern resulting in a formation of ring with final inside diameter. Our experiments indicate that the following values are reproducible and quantify the PbSO(4) ring evolution: induction time, radius of the ring birth, speed of ring propagation toward the center, and final inside radius of the ring. Numerical solution of kinetic equations allowed us to give a qualitative explanation for the phenomenon observed. Formation and evolution of the PbSO(4) rings are caused by interplay of concentration gradients in the system and chemical reactions that occur in excitable chlorite-thiourea system. Chemical reactions and hydrodynamic processes form a complex causal network that made morphogenesis of this unusual pattern possible.

The effect of oxygen on time-dependent bifurcations in the Belousov-Zhabotinsky oscillating chemical reaction in a batch.

We have studied the effect of oxygen on the time-dependent bifurcations of transient oscillations in the Belousov-Zhabotinsky oscillating chemical reaction in a closed system. Experiments show that oscillations disappear through different bifurcations depending on the oxygen concentration in gas phase above the reaction solution. Oscillations disappear through the time-delayed Hopf bifurcation at low oxygen concentrations, whereas at high oxygen concentrations they disappear through the time-dependent SNIPER (saddle-node infinite period) bifurcation. We propose a kinetic scheme that describes the effects observed in experiments. Good agreement between the experimental data and simulations is obtained.

Scalings of mixed-mode regimes in a simple polynomial three-variable model of nonlinear dynamical systems.

We describe scaling laws for a control parameter for various sequences of bifurcations of the LSn mixed-mode regimes consisting of single large amplitude maximum followed by n small amplitude peaks. These regimes are obtained in a normalized version of a simple three-variable polynomial model that contains only one nonlinear cubic term. The period adding bifurcations for LSn patterns scales as 1/n at low n and as 1/n2 at sufficiently large values of n. Similar scaling laws 1/k at low k and 1/k2 at sufficiently high values of k describe the period adding bifurcations for complex k(LSn)(LS(n + 1)) patterns. A finite number of basic LSn patterns and infinite sequences of complex k(LSn)(LS(n + 1)) patterns exist in the model. Each periodic pattern loses its stability by the period doubling bifurcations scaled by the Feigenbaum law. Also an infinite number of the broken Farey trees exists between complex periodic orbits. A family of 1D return maps constructed from appropriate Poincaré sections is a very fruitful tool in studies of the dynamical system. Analysis of this family of maps supports the scaling laws found using the numerical integration of the model.

Complex mixed-mode periodic and chaotic oscillations in a simple three-variable model of nonlinear system.

A detailed study of a generic model exhibiting new type of mixed-mode oscillations is presented. Period doubling and various period adding sequences of bifurcations are observed. New type of a family of 1D (one-dimensional) return maps is found. The maps are discontinuous at three points and consist of four branches. They are not invertible. The model describes in a qualitative way mixed-mode oscillations with two types of small amplitude oscillations at local maxima and local minima of large amplitude oscillations, which have been observed recently in the Belousov-Zhabotinsky system. (c) 2000 American Institute of Physics.

Infinite period and Hopf bifurcations for the pH-regulated oscillations in a semibatch reactor (H(2)O(2)-Cu(2+)-S(2)O(2-) (3)-NaOH system).

Dynamic behavior of the pH-regulated oscillations has been studied for the hydrogen peroxide oxidation of thiosulfate ions in the presence of trace amounts of copper(II) ions in a semibatch reactor. A solution of 0.08 M Na(2)S(2)O(3) and 0.112 M NaOH was flowed at 0.160 mL/min into 300 mL of solution containing the H(2)O(2) and Cu(2+) in a vessel. There exists a critical value of the H(2)O(2) or Cu(2+) concentrations below which the system does not oscillate. The oscillations appear due to an infinite period bifurcation at low initial concentrations of the H(2)O(2). The initial concentration of Cu(2+) may be considered as a bifurcation parameter in this case. Increase of the initial hydrogen peroxide concentration causes the pH-regulated oscillations through a nondegenerate supercritical Hopf bifurcation. The classification of bifurcations is based on the analysis of the behavior of oscillation amplitude and period at different initial concentrations of the H(2)O(2) and Cu(2+). Our results show a possibility to distinguish different scenarios for the appearance of transient oscillations in semibatch experiments. (c) 1996 American Institute of Physics.