Design and synthesis of a Cu(II)-complex-based carbazole-hemicyanine hybrid for fluorescent sensing of H2S in SDS micellar solution

A novel fluorescent chemosensor HACBA with carbazole-hemicyanine fluorophore as signal reporter and N,N,N'-tri(2-pyridylmethyl)ethylenediamine (TPEA) as binding sites was designed and synthesized. Its assemblies with anionic surfactant sodium dodecyl sulfate (SDS) show improved fluorescence emission stability and enhanced fluorescence intensity. HACBA/SDS system can selectively recognize Cu²⁺, which led to a dramatic fluorescence quenching. The in situ resultant HACBA-Cu(II)/SDS ensemble functioned as a highly selective and sensitive sensor for H₂S with a turn-on fluorescent response. Our results show that the “on-off-on” molecular switch occured through the reversible formation-dissociation reaction between HACBA-Cu(II) complex and HACBA/CuS in the SDS micellar solution, and at least 3 cycles of on-off-on switches were observed.     

Synthesis of polysubstituted 5-hydroxyhydantoins via ring-opening of isatins

A simple and efficient tandem reaction approach was developed for the synthesis of 5-hydroxyhydantoins from one-pot reaction of isatins, phthalic anhydride or succinic anhydride, and 1,3-dimethylurea (1,3-diethylurea). The products were gained through the ring-opening of isatins process. The advantages of this report are simple operation, mild reaction conditions, good yields and easily available raw materials. It was very important for us to obtain the intermediate product and that provided a solid basis for the correct interpretation of the reaction mechanism.     

E-Stilbene derivatives synthesized by stereoselective reductive coupling of benzylic gem-dibromide promoted by Cu/polyamine

Stereoselective reductive coupling reaction of benzylic gem-dibromide promoted by Cu/polyamine produces E-stilbene derivatives with high yield under mild conditions. It provides a short pathway to synthesize symmetrical and asymmetrical E-stilbene derivatives using cheap reagents and alkenyl-free starting material together with easy workup.     

Lateral flow test for visual detection of silver(I) based on cytosine-Ag(I)-cytosine interaction in C-rich oligonucleotides

The authors describe an oligonucleotide-based lateral flow test for visual detection of Ag(I). The assay is based on cytosine-Ag(I)-cytosine [C-Ag(I)-C] coordination chemistry to capture gold nanoparticle (AuNP) tags in the test zone. A thiolated C-rich oligonucleotide probe was immobilized on the AuNPs via gold-thiol chemistry, and a biotinylated C-rich oligonucleotide probe was immobilized on the test zone. The AuNPs labelled with C-rich oligonucleotides are captured by Ag(I) ions in the test zone through the C-Ag(I)-C coordination. The resulting accumulation of AuNPs produces a readily visible red band in the test zone. Under optimized conditions, the test is capable of visually detecting 1.0 ppb of Ag(I) which is 50 times lower than the maximum allowable concentration as defined by the US Environmental Protection Agency for drinking water. Hence, the test is inexpensive and highly sensitive. It was applied to the detection of Ag(I) in spiked samples of tap water and river water. In our perception, the test is a particularly valuable tool in limited resource settings.

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Graphical abstract Graphical Abstract

     

Ultrasensitive amperometric determination of PSA based on a signal amplification strategy using nanoflowers composed of single-strand DNA modified fullerene and Methylene Blue,and an improved surface-initiated enzymatic polymerization

The authors describe a signal amplification strategy for highly sensitive detection of the prostate-specific antigen (PSA). This is accomplished by a combination of two methods, viz. (a) improved surface-initiated enzymatic polymerization (SIEP), and (b) the use of nanoflowers prepared from C₆₀ fullerene and Methylene Blue (C₆₀/MB) modified with a long single-strand DNA. C₆₀/MB acts as a novel electrochemical indicator. The C₆₀/MB nanoflowers improve the load of MB and promote the electron transfer. The integration of the SIEP technique and the C₆₀/MB nanomaterial also results in improved loading of MB on the nucleic acid. Ultimately, dual cascade signal amplification is accomplished. The biosensor was constructed as follows: (a) Gold nanospheres were modified with antibody 2 (Ab₂) and a thiolated oligonucleotide (referred to as S₀). (2) S₀ is then extended by the SIEP reaction. (3) The redox indicator C₆₀/MB is then connected to the extended guanine-rich ssDNA which then yields the amperometric signal. (4) A sandwich immunoassay is performed by capturing the nanoprobe oy type Ab₂-Au-S₀ on the gold electrode modified with multi-walled carbon nanotubes (MWCNTs) and protein A. Current is measured by using differential pulse voltammetry (DPV). The synergic effect of the biofunctional nanomaterial and the signal amplification strategy greatly improves the performance of this immunoassay. Under optimized conditions and at a working voltage of typically ?0.18 V (vs Ag/AgCl), the assay has a linear range that extends from 15 pg·mL^?1 to 8 ng·mL^?1 of PSA. The detection limit is as low as 1.7 pg·mL^?1 (at an S/N ratio of 3). In our perception, this dual amplification scheme has a wide scope in that it may become applicable to numerous other immunoassays.

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Graphical abstract C₆₀/Methylene blue nanoflowers, a novel electrochemical indicator, connect with the long single-stranded DNA (ssDNA) extended by the improved surface-initiated enzymatic polymerization method. This amplification strategy is utilized to construct a sandwich prostate-specific antigen (PSA) immunosensor.

     

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.

     

Synthesis of a Novel Double Salt: Ammonium 3,4‐Diamino‐1,2,4‐triazolium Styphnate

Nitrogen‐rich double salt ammonium 3,4‐diamino‐1,2,4‐triazoliumstyphnate (NH₄ · DATr · TNR) ( 2 ) with good thermal stability was successfully synthesized by reacting 3,4‐diamino‐1,2,4‐triazolium chloride aqueous solution with styphnic acid methanol solution under the reaction medium of aqueous ammonia. The title double salt was characterized by elemental analysis (EA), Fourier transformation infrared spectrum (FT‐IR), and X‐ray single‐crystal diffraction. It crystallizes in the monoclinic crystal system with space group P2₁/n. Its density is 1.780 g · cm^–3. Compound 2 is thermal stable below 200 °C by the differential scanning calorimetry (DSC) test. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa‐Doyle's method, respectively. In addition, compound 2 showed low friction and impact sensitivities.     

Plutonium concentration and <Superscript>240</Superscript>Pu/<Superscript>239</Superscript>Pu isotopic ratio in the surface soils from the Jiuquan region in northwestern China

Surface soil samples collected in the Jiuquan region in the downwind area of the Chinese nuclear test site (CNTs) were analyzed for Pu isotopes. The ^239+240Pu activities ranged from 0.025 ± 0.009 to 0.89 ± 0.16 mBq g^?1, varying significantly with different sampling sites. The Dunhuang city that is located in the southwestern part of the Jiuquan region received the heaviest Pu deposition (^239+240Pu activities, 0.23–0.89 mBq g^?1). Most of the ²⁴⁰Pu/²³⁹Pu isotopic ratios were similar with that of the global fallout. However, the low values (0.080–0.147) observed in three sampling sites further supported the finding of Pu originated from CNTs in that region.     

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.