Bienzyme-based visual and spectrophotometric aptamer assay for quantitation of nanomolar levels of mercury(II)

The article describes a bienzyme visual system for aptamer-based assay of Hg(II) at nanomolar levels. The detection scheme is based on the finding that Hg(II) ions captured by aptamer-functionalized magnetic beads are capable of inhibiting the enzymatic activity of uricase and thus affect the formation of H₂O₂ and the blue product, i.e., oxidized tetramethylbenzidine. This strategy allows for a visual detection of Hg(II) at nanomolar levels without additional amplification procedure. Measuring the absorbance at 650 nm, the logarithmic calibration plot is linear in the concentration range of 0.5–50 nM and the limit of detection (LOD) is 0.15 nM. This is as low as the LOD obtained by atomic fluorescence spectrometry (AFS). The ions K⁺, Mg²⁺, Na⁺, Ca²⁺, Cu²⁺, Zn²⁺, Fe³⁺, Al³⁺, Co²⁺, AsO₂ ^?, Ni²⁺, Cd²⁺ and Pb²⁺ do not have a significant effect on color formation. The method was applied to the analysis of (spiked) river water, lake water, mineral water, tap water and certified reference water samples, and the results agreed well with those obtained by AFS or certified values, with recoveries ranging from 97% to 109%. The relative standard deviation for five parallel detections at a 10 nM Hg(II) level is 5.2%.

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Graphical abstract A bienzyme-based visual aptasensor was fabricated for label-free detection of nanomolar Hg²⁺ in water samples without any amplification or enrichment procedure.

     

A capillary coated with a metal-organic framework for the capillary electrochromatographic determination of cephalosporins

The authors have developed a rapid and reliable method for the capillary electrochromatographic determination of cephalosporin antibiotics in environmental waters. An open-tubular capillary column was modified with the complex [Cu(mal)(bpy)], a copper(II) complex with malic acid and 4,4′-bipyridyl, by an amide coupling method to act as the stationary phase. The simultaneous determination of the cephalosporins formulations, namely cefapirin (CP), ceftiofur (EFT) and cefixime (CFM) in environmental water samples was accomplished in buffer of pH 5.0 by applying a voltage of 8 kV and with DAD detection. Detection limits typically are 0.1 μg?mL^?1.The method was applied to the analysis of cephalosporins in spiked water samples from Kunming Lake to give recoveries betwen 88 and 106%.

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Graphical abstract A metal-organic framework (MOF) was synthesized from copper(II), malic acid and 4,4′-bipyridyl and used as stationary phase of capillary electrochromatography (CEC) by covalent immobilization on the capillary inner walls. Compared to an uncoated fused-silica capillary, improved separation of cephalosporin antibiotics can be accomplished.

     

Photometric determination of free cholesterol via cholesterol oxidase and carbon nanotube supported Prussian blue as a peroxidase mimic

Microchimica Acta - The authors describe a photometric method for the determination of free cholesterol based on the oxidation of cholesterol by the catalytic action of the enzyme...     

A Sodium-Ion-Conducting Direct Formate Fuel Cell: Generating Electricity and Producing Base

A barrier that limits the development of the conventional cation-exchange membrane direct liquid fuel cells (CEM-DLFCs) is that the CEM-DLFCs need additional base to offer both alkaline environment and charge carriers. Herein, we propose a Na⁺-conducting direct formate fuel cell (Na-DFFC) that is operated in the absence of added base. A proof-of-concept Na-DFFC yields a peak power density of 33 mW cm⁻² at 60 °C, mainly because the hydrolysis of sodium formate provides enough OH⁻ and Na⁺ ions, proving the conceptual feasibility. Moreover, contrary to the conventional chlor-alkali process, this Na-DFFC enables to generate electricity and produce NaOH simultaneously without polluting the environment. The Na-DFFC runs stably during 13 hours of continuous operation at a constant current of 10 mA, along with a theoretical production of 195 mg NaOH. This work presents a new type of electrochemical conversion device that possesses a wide range of potential applications.     

Two copper(II)-bbtz modified Keggin and β-octamolybdate compounds captured in one-pot under hydrothermal conditions

Under hydrothermal conditions two compounds based on Keggin and β-octamolybdate, respectively, [Cu₂(bbtz)₄(SiMo₁₂O₄₀)] (1) and [Cu₂(bbtz)₄(Mo₈O₂₆)]_1/2·H₂O (2) (bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), were synthesized in one-pot and characterized by single-crystal X-ray diffraction, elemental analyses, and IR spectroscopy. In compound 1, two adjacent wave-like Cu^II-bbtz lines are connected by SiMo₁₂ anions and bbtz to generate a ladder-like chain. Adjacent chains share the same Cu^II ions to build a three-dimensional (3-D) framework. In compound 2, the β-Mo₈ anions link Cu₃(bbtz)₂ subunits alternately to form a one-dimensional (1-D) chain. These chains connect each other through sharing Cu^II ions and a 3-D network is constructed. Moreover, we studied the electrocatalytic and photocatalytic activities of these two compounds. The results indicate that 1 and 2 show good electrocatalytic performance for the reduction of nitrite and bromate; they also exhibit photocatalytic properties for degradation of MB and RhB.     

Template-directed syntheses of two 3D metal oxalates: in situ N-methylation and crystal structures

Two isomorphic organically templated zinc/cobalt oxalates, (dmdabco)[Zn₂(C₂O₄)₃]·4H₂O (1), and (dmdabco)[Co₂(C₂O₄)₃]·4H₂O (2) (C₂O₄^2? = oxalate; dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane), have been prepared under solvothermal conditions and characterized by X-ray structural analyses. The dmdabco²⁺ templating agent was derived from simple in situ N-alkylation between methanol and 1,4-diazabicyclo[2,2,2]octane (dabco). Distinct from conventional Eschweiler-Clarke methylation containing excess formic acid and formaldehyde, such one-step methylation from methanol molecules is convenient. Both 1 and 2 exhibit a uninodal 3-connected 3-D interrupted open-framework, in which oxalate ligands have in-plane and out-of-plane connection modes.     

Determination of Protonation Constants of O-Phospho-<Emphasis Type="SmallCaps">l</Emphasis>-serine in Aqueous Solution: Potentiometry,Microcalorimetry, NMR Spectroscopy and Quantum Chemical Calculations

O-Phospho-l-serine is one of the naturally occurring phosphorylated amino acids, having important pharmacological activity and bioactivity. The protonation constants of O-phospho-l-serine were determined by means of potentiometric titrations at 25 °C and ionic strength of 0.5 mol·L^?1 (NaCl). The heat effects of the protonation reaction of the O-phospho-l-serine were measured by direct calorimetry. NMR spectroscopy has demonstrated that the first protonation site occurs at the nitrogen atom in the amino group, followed by one of the oxygen atoms in the phosphono group, and finally the carboxyl oxygen atom. This trend is in good agreement with the enthalpy of protonation and quantum chemical calculations. These data will help to predict the speciation of O-phospho-l-serine in physiological systems.     

Voltammetric Anion Sensors based on Redox‐active Ferrocene‐bearing Macrocyclic Amides

Reactions between 5‐ferrocenylisophthalic dichloride and 1,2‐bis(o‐aminophenoxy)ethane yield 1:1‐ and 2:2‐cyclization products with amide linkages, which are marked as L1 and L2 , respectively. The crystal structure of the 2:2‐macrocycle L2 is determined by X‐ray single crystal structure analysis. Interestingly, L2 affords a folded conformation due to the intermolecular π–π interaction between two isophthaloyl groups, so as to stabilize the marcocylic conformation. The electrochemical anion sensing studies of L1 and L2 show that they have a good ability to recognize H₂PO₄^–, and the 2:2‐cyclization products ( L2 ) with two ferrocene groups, more anion binding sites, and larger cavities, give better electrochemical anion recognition results than L1 .     

Geometry of spacelike generalized constant ratio surfaces in Minkowski 3-space

Generalized constant ratio surfaces are defined by the property that the tangential component of the position vector is a principal direction on the surfaces. In this work, we study these class of surfaces in the 3-dimensional Minkowski space L³. We achieve a complete classification of spacelike generalized constant ratio surfaces in L³.     

Multi-recurrence and van der Waerden systems

We explore recurrence properties arising from dynamical approach to the van der Waerden theorem and similar combinatorial problems. We describe relations between these properties and study their consequences for dynamics. In particular, we present a measure-theoretical analog of a result of Glasner on multi-transitivity of topologically weakly mixing minimal maps. We also obtain a dynamical proof of the existence of a C-set with zero Banach density.