Platinum-Iron(II) Oxide Sites Directly Responsible for Preferential Carbon Monoxide Oxidation at Ambient Temperature: An Operando X-ray Absorption Spectroscopy Study**

Operando X-ray absorption spectroscopy identified that the concentration of Fe²⁺ species in the working state-of-the-art Pt−FeO_x catalysts quantitatively correlates to their preferential carbon monoxide oxidation steady-state reaction rate at ambient temperature. Deactivation of such catalysts with time on stream originates from irreversible oxidation of active Fe²⁺ sites. The active Fe²⁺ species are presumably Fe⁺²O⁻² clusters in contact with platinum nanoparticles; they coexist with spectator trivalent oxidic iron (Fe³⁺) and metallic iron (Fe⁰) partially alloyed with platinum. The concentration of active sites and, therefore, the catalyst activity strongly depends on the pretreatment conditions. Fe²⁺ is the resting state of the active sites in the preferential carbon monoxide oxidation cycle.     

Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes

Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes with a limited array of substituents, are difficult to scale, or both. Herein, we disclose a new cyclopropane synthesis through the formal coupling of abundant carbon pronucleophiles and unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis of thianthrene in the presence of alkene substrates. We find that these dielectrophiles undergo cyclopropanation with methylene pronucleophiles via alkenyl thianthrenium intermediates. This protocol is scalable, proceeds with high diastereoselectivity, and tolerates diverse functional groups on both the alkene and pronucleophile coupling partners. To validate the utility of this new procedure, we prepared an array of substituted analogs of an established cyclopropane that is en route to multiple pharmaceuticals.     

Relations among complementary and supplementary pairings of Saalschützian $${}_4F_3(1)$$ series

We investigate sums \(J(\vec {x})\) and \(L(\vec {x})\) of pairs of normalized Saalschützian \({}_4F_3(1)\) hypergeometric series, and develop a theory of relations among these J and L functions. The function \(L(\vec {x})\) has been studied extensively in the literature and has been shown to satisfy a number of two-term and three-term relations with respect to the variable \(\vec {x}\). More recent works have framed these relations in terms of Coxeter group actions on \(\vec {x}\) and have developed a similar theory of two-term and three-term relations for \(J(\vec {x})\). In this article, we derive “mixed” three-term relations, wherein any one of the L (respectively, J) functions arising in the above context may be expressed as a linear combination of two of the above J (respectively, L) functions. We show that, under the appropriate Coxeter group action, the resulting set of three-term relations (mixed and otherwise) among J and L functions partitions into eighteen orbits. We provide an explicit example of a relation from each orbit. We further classify the eighteen orbits into five types, with each type uniquely determined by the distances (under a certain natural metric) between the J and L functions in the relation. We show that the type of a relation dictates the complexity (in terms of both number of summands and number of factors in each summand) of the coefficients of the J and L functions therein.     

Noise-resistant system of concealed information transfer on a chaotic delayed feedback oscillator with switchable delay time

We propose a system of concealed information transfer based on a delayed feedback oscillator with switchable chaotic regimes. The proposed system is analyzed numerically and experimentally. The dependences of the bit error rate during transmission of a binary information signal on the signal-to-noise ratio, attenuation of the signal in the communication channel, and the duration of the time interval during which a bit is transferred are constructed. The high stability of the system to noise and amplitude distortions of a signal in the communication channel is demonstrated.     

Designing ionic liquids with boron cluster anions: alkylpyridinium and imidazolium [nido-C(2)B(9)H(11)] and [closo-CB(11)H(12)] carborane salts

A range of new alkylpyridinium and imidazolium carborane salts with [nido-C(2)B(9)H(12)](-), [closo-CB(11)H(12)](-), and [RC(2)B(11)H(11)](-) (R = methyl or butyl) anions have been prepared and characterized by physical and thermal methods, including the solid state structures of five of the salts determined by single crystal X-ray diffraction. The tendency of the salts to form low-melting ionic liquids has been assessed; all the salts studied with [nido-C(2)B(9)H(12)](-) anions melted below 100 degrees C and, significantly, have melting points that are 25-85 degrees C lower than those of the corresponding [closo-CB(11)H(12)](-) analogs, demonstrating that a wider range of boron-rich ionic liquid materials can be readily accessed.     

On the Erdelyi-Magnus-Nevai Conjecture for Jacobi Polynomials

T. Erdelyi, A.P. Magnus and P. Nevai conjectured that for the orthonormal Jacobi polynomials satisfy the inequality

An asymmetric synthesis of L-pyrrolysine

An efficient asymmetric synthesis of the 22nd amino acid L-pyrrolysine has been accomplished. The key stereogenic centers were installed by an asymmetric conjugate addition reaction. A Staudinger/aza-Wittig cyclization was used to form the acid-sensitive pyrroline ring. Pyrrolysine was synthesized in 13 steps in 20% overall yield.     

Structure simulation into a lamellar supramolecular network and calculation of the metal ions/ligands ratio

Background

Biosensors have attracted increasing attention as reliable analytical instruments in in situ monitoring of public health and environmental pollution. For enzyme-based biosensors, the stabilization of enzymatic activity on the biological recognition element is of great importance. It is generally acknowledged that an effective immobilization technique is a key step to achieve the construction quality of biosensors.

Results

A novel disposable biosensor was constructed by immobilizing laccase (Lac) with silica spheres on the surface of multi-walled carbon nanotubes (MWCNTs)-doped screen-printed electrode (SPE). Then, it was characterized in morphology and electrochemical properties by scanning electron microscopy (SEM) and cyclic voltammetry (CV). The characterization results indicated that a high loading of Lac and a good electrocatalytic activity could be obtained, attributing to the porous structure, large specific area and good biocompatibility of silica spheres and MWCNTs. Furthermore, the electrochemical sensing properties of the constructed biosensor were investigated by choosing dopamine (DA) as the typical model of phenolic compounds. It was shown that the biosensor displays a good linearity in the range from 1.3 to 85.5 ??M with a detection limit of 0.42 ??M (S/N = 3), and the Michaelis-Menten constant (K_m ^app) was calculated to be 3.78 ??M.

Conclusion

The immobilization of Lac was successfully achieved with silica spheres to construct a disposable biosensor on the MWCNTs-doped SPE (MWCNTs/SPE). This biosensor could determine DA based on a non-oxidative mechanism in a rapid, selective and sensitive way. Besides, the developed biosensor could retain high enzymatic activity and possess good stability without cross-linking reagents. The proposed immobilization approach and the constructed biosensor offer a great potential for the fabrication of the enzyme-based biosensors and the analysis of phenolic compounds.     

Dichlorido{2‐[(3,5‐diphenyl‐1H‐pyrazol‐1‐yl‐κN2)methyl]pyridine‐κN}palladium(II)

The title compound, [PdCl₂(C₂₁H₁₇N₃)], is a member of a sequence of Pd, Pt and Co dichloride complexes bearing polysubstituted (pyrazol‐1‐ylmethyl)pyridine ligands. It is shown that there is a correlation between the steric bulkiness of the bidentate (pyrazol‐1‐ylmethyl)pyridine ligands and the Pd—N_pyrazole distances, i.e. the larger the ligand, the longer the bond. In contrast, no trend is observed between the steric properties of the ligand and the Pd—N_pyridine bond lengths.