Discrimination and ultrasensitive detection of β 2-agonists using copper nanoclusters as a fluorescent probe

Microchimica Acta - The authors describe a rapid method for the determination of 11 β 2-agonists by exploiting the color changes and fluorescence intensity changes of copper nanoclusters...     

The synthesis and study of the fluorescent probe for sensing Cu2＋ based on a novel coumarin Schiff-base

A novel, fluorescent probe was synthesized from 2,4-dihydroxybenzaldehyde and 8-hydroxyquinoline for sensing Cu2+by the naked eye. The structure was confirmed by IR, MS,1H NMR,13 C NMR and the spectral properties of the probe were investigated. It exhibited strong fluorescence responses toward Cu2+and high selectivity over other metal ions. The binding constant between the probe and Cu2+was calculated using Benesi–Hildebrand equation.     

Synthesis of Au13(glutathionato)8@β-cyclodextrin nanoclusters and their use as a fluorescent probe for silver ions

Heating and drying of the mixture of glutathione-etched gold nanoparticles (Au-SG) and β-cyclodextrin (β-CD) results in the formation of β-CD-capped and glutathionate-protected Au₁₃ nanoclusters (Au₁₃(SG)₈@β-CD). Their particle size, composition, and number of gold atoms and the capping molecules were characterized by scanning electron microscopy, fluorescence, UV–vis absorption, FT-IR spectroscopy and mass spectrometry. The fluorescence of these nanoclusters is specifically enhanced by the addition of Ag(I) ions to the aqueous solution. This effect was exploited to develop a selective and sensitive method for the fluorometric determination of Ag(I) in water in the concentration range between 0.5 nM and 0.1 μM, with a detection limit at 0.3 nM (at a signal-to-noise ratio of 3). Graphical Abstract

β-CD-capped Au₁₃ nanoclusters has been synthesized by heating and drying the mixture of glutathione-etched gold nanoparticles and β-CD. A simple, sensitive and selective FL sensing method for Ag⁺ in environmental water has developed using the Au nanoclusters.     

Preparation and application of rifamycin-capped (3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica particles as chiral stationary phase for high-performance liquid chromatography

Rifamycin-capped (3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica particles (RCD-HPS), a new type of substituted β-cyclodextrin-bonded chiral stationary phase (CSP) for high-performance liquid chromatography (HPLC), have been synthesized by the treatment of bromoacetate-substituted-(3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)-propylsilyl-appended silica particles (BACD-HPS) with rifamycin SV in anhydrous acetonitrile. The stationary phase is characterized by means of elemental analysis and Fourier-transform infrared spectroscopy. This new CSP has a chiral selector with two recognition sites: rifamycin and β-cyclodextrin (β-CD). The chromatographic behavior of RCD-HPS was studied with several disubstituted benzenes and some chiral drug compounds under reversed-phase HPLC mobile phase conditions. The results show that RCD-HPS has excellent selectivity for the separation of aromatic positional isomers and enantiomers of chiral compounds due to the cooperative functioning of rifamycin and β-CD.     

Quantum-chemical studies of catalysts immobilized on silica. The complex Cu(OSiH3)2·2H2O as a model of catalytically active polycopperphenylsiloxanes

The structures of the complexes CuX₂·2L (X=0H, OSiH₃, or Cl; L=H₂O, NH₃, H₂S, or PH₃) were calculated and their electron affinities were estimated by the MP2//HF/SBK(6–31) method. The [CuX₂·2L]⁻ anions are unstable and decompose to chlorocuprite anions and free ligands. Based on the results of calculations for the complex Cu(OSiH₃)₂·2H₂O (the simplest model of the structural unit of polycopperphenylsiloxane) and possible products of its conversions, the catalytic properties of polycopperphenylsiloxanes in the reactions of chloroorganic synthesis are discussed. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1499–1503, September, 2000.     

Inclusion of (aminostyryl)-1-methylpyridinium dyes byβ-cyclodextrin and its use for fluorescent-probe studies on association of cationic and neutral molecules withβ-cyclodextrin

An inclusion complex between TRIMEB and (S)-naproxen has been crystallised and characterised by physicochemical methods including X-ray analysis. The complex crystallises in the orthorhombic crystal system, space groupP2₁2₁2₁, witha=15.179(4),b=21.407(5),c=27.67(1) Å andZ=4. The structure was solved using published coordinates for the skeleton atoms of TRIMEB in an isomorphous complex. Refinement by full-matrix least-squares analysis yieldedR=0.0571 for 6573 unique observed reflections. Hydrophobic forces are responsible for the inclusion of the drug, which has its methoxy group buried in the cavity of the host and its propionic acid moiety protruding from the O(2), O(3) side of the TRIMEB molecule. Both host and guest undergo conformational changes on complexation relative to their conformations observed in the TRIMEB monohydrate and naproxen crystal structures respectively. Complex units pack in a screw-channel mode in a head-to-tail fashion with their axes almost parallel to theb-axis.     

Simple and efficient method for aromatization of tetrahydro-β-carbolines by using K2S2O8 as a catalyst and its antimicrobial activity comparison with molecular docking studies

Russian Journal of General Chemistry - A novel and efficient aromatization of tetrahydro-β-carbolines under mild conditions using K2S2O8 as a catalyst was developed. The method is applicable...     

Preparation and chiral recognition of a novel chiral stationary phase for HPLC,based on mono（6A-N- 1-（2-hydroxyl）- phenylethylimino-6A-deoxy）-β-cyclodextrin and covalently bonded silica gel

A novel chiral stationary phase （CSP） was prepared by immobilizing mono（6A-N-1-（2-hydroxyl）-phenylethylimino-6A- deoxy）-β-cyclodextrin onto the surface of silica gel via a longer spacer. This chiral stationary phase exhibited good enantioselectivity for a variety of chiral compounds under reversed-phase conditions.     

Preconcentration of Pb2+ by iron oxide/amino-functionalized silica core–shell magnetic nanoparticles as a novel solid-phase extraction adsorbent and its determination by flame atomic absorption spectrometry

The use of iron oxide/amino-functionalized silica core–shell magnetic nanoparticles for preconcentration of Pb²⁺ followed by its consecutive atomic absorption spectrometry determination is described. Effects of various operating variables, namely, solution pH, initial Pb²⁺ concentration, contact time, adsorbent dosage, sample volume, concentration and volume of desorbing solution, and co-existing ions on solid-phase extraction (SPE) of Pb²⁺ were studied by batch equilibrium technique. The experimental adsorption data were well fitted to the Langmuir isotherm model. The Langmuir adsorption capacity and equilibrium time were found to be 100 mg g^?1 and 20 min, respectively. The adsorption data were also fitted to kinetic pseudo-first-order and pseudo-second-order models. Kinetic studies showed that the adsorption followed pseudo-second-order model. Under the optimal SPE conditions, the enrichment factor, detection limit and relative standard deviation for determination of Pb²⁺ were found to be 211, 1 μg L^?1, and 3.7 % for 50 μg L^?1, respectively. The proposed method was successfully applied to the determination of lead in a real sample with satisfactory results.     

Synthesis and characterization of ammonium molybdophosphate–silica nano-composite (AMP–SiO2) as a prospective sorbent for the separation of 137Cs from nuclear waste

The ammonium molybdophosphate–silica (AMP–SiO₂) nano-composites were prepared by sol–gel method. The material synthesized was nanocrystalline, with average crystallite size of primary particles in the range of 10–25 nm. Small angle X-ray scattering showed presence of mass fractal aggregates made of small particles with rough pore boundaries. To realize the scope of using AMP–SiO₂ nano-composites sorbent for removal of ¹³⁷Cs from nuclear waste solutions, its adsorption characteristics for cesium were evaluated. It was found that the AMP–SiO₂ nanocomposites were amenable for column operation, have high affinity for Cs, and possess very high adsorption capacity for Cs. From the perspective of separation of ¹³⁷Cs from acidic radioactive waste solution, AMP–SiO₂ nanocomposite holds significant promise.     

Theoretical studies on the electronic structures and spectroscopic properties for a series of Osmium(II)-2,2′,6′,2′′-terpyridine complexes

A series of Osmium(II) complexes [Os (trpy-R)₂]²⁺(trpy=2,2′,6′,2′′-terpyridine and R=H (1), OH (2), and C₆H₅(3)) have been investigated by the density functional (DF) and ab initio calculations. The structures of 1–3 in the ground and excited states were fully optimized at the B3LYP and CIS level, respectively, and their absorption and emission spectra in the acetonitrile solution were obtained using the TD-DFT (B3LYP) method associated with the PCM model. The calculations indicated that, for 1–3, the variation of the substituents on the terpyridine ligand only slightly changes their geometrical structures in the ground and excited states but leads to a sizable difference in the electronic structures. The results show that the low-lying MLCT/ILCT transitions (at 446 (1), 465 (2), and 499 nm (3)) are red-shifted according to the electron-donating ability of substituents on the terpyridine ligand, but blue-shift trend of the high-lying ILCT transitions (at 301 (1), 297 (2), and 272 nm (3)). It also reveals that the lowest energy emissions of 1–3 at 649 nm, 656 nm, and 676 nm have the character of mixing ³[π*(trpy) → d(Os)] and ³ ππ* (³MLCT/³ILCT) transitions localized on the terpyridine ligand, which are identical to the transition properties of the lowest-energy absorptions.     

Preparation and chiral recognitio of a novel chiral stationary phase for HPLC,based on mono(6~A-N-1-(2-hydroxyl)-phenylethylimino-6~A-deoxy)-β-cyclodextrin and covalently bonded silica gel

A novel chiral stationary phase (CSP)was prepared by immobilizing mono(6~A-N-1-(2-hydroxyl)-phenylethylimino-6~A- deoxy)-β-cyclodextrin onto the surface of silica gel via a longer spacer.This chiral stationary phase exhibited good enantios- electivity for a variety of chiral compounds under reversed-phase conditions.     

2-[2′-(6′-Methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid as a new reagent for rapid spectrophotometric determination of copper

2-[2-(6-methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid (MBTAMB) has been synthesized and employed as a new reagent for the spectrophotometric determination of copper(II). A blue complex is formed from MBTAMB and Cu(II) in the range of pH 2.0–5.0 in aqueous ethanol. The composition of the complex is Cu(II) MBTAMB=1 1. The maximum absorption of the complex is at 660 nm, its apparent molar absorptivity is 7.0 × 10⁴ 1· mole^–1 · cm^–1. Beer's law is obeyed for copper in the range of 0–0.72 g/ml. The method has been used for the determination of micro amounts of copper in aluminium alloy. The proposed method is simple, rapid and accurate.     

CuZnAl mixed-metal oxides prepared by a novel sol–gel route and the application for synthesis of 2- methylpyrazine

Metal (Cu, Zn, Al) nitrates and chlorides were used for preparing CuZnAl xerogels by a sol–gel route with propylene oxide as gelation initiator. The CuZnAl mixed-metal oxides were further obtained by thermal treatment the xerogels at 500 °C for 5 h in air. Thermal decomposition behavior of the CuZnAl xerogels, the microstructures and the reducibility of the calcined xerogels were investigated by thermogravimetry (TG), scanning electron microscope (SEM), powder X-ray diffraction (XRD), N₂ adsorption/desorption (BET, BJH) and temperature-programmed reduction (TPR) techniques. The catalytic activity in dehydrocyclization of ethylenediamine (ED) with 1, 2-propyleneglycol (PG) to 2-methylpyrazine (2-MP) was carried out at 380 °C. The results displayed that the CuZnAl mixed-metal oxides prepared using nitrates as the metal precursors had a higher metallic Cu dispersion and a superior low-temperature reducibility than those prepared by chlorides, which results in a higher catalytic activity for the synthesis of 2-methylpyrazine. Especially when the molar ratio of Cu/Zn/Al = 2:1:2, the catalyst using nitrates as the metal precursors improved the selectivity of 2-MP to 87.5%.     

X-ray photoelectron spectroscopy as a tool for studies of the surface layer of microspheres. The case of polystyrene and poly(styrene–acrolein) microspheres with attached human serum albumin

The application of X-ray photoelectron spectroscopy (XPS) for studies of surface layers of objects with spherical shape was investigated using as examples polystyrene and poly(styrene–acrolein) microspheres with attached human serum albumin (HSA). The amounts of immobilized protein were determined by the standard biochemical Lowry method and by XPS, using the intensity of the N1s signals of HSA as a basis for evaluation. The XPS data were treated by taking into account the spherical shape of the particles analyzed (variable take-off angle of ejected electrons). The best agreement between the results of the biochemical and XPS determinations was found assuming that for the average particle the takeoff angle varies from 0° to 72.7°. This reflects the fact that in the multilayer arrangement of particles, placed onto the support of the XPS apparatus, the particles from the upper layer partially screen the edges of the particles in the layer below. Received: 23 November 1999 Accepted: 16 March 2000     

The physical properties and electrochemical performance of Ca-doped Sr2MgMoO6-δ as perspective anode for solid oxide fuel cells

Journal of Solid State Electrochemistry - The double perovskites Sr2-xCaxMgMoO6–δ with x = 0, 0.25, and 0.5 were obtained by combustion of organometallic precursors and were...     

Reaction of β-lactam carbenes with 2-pyridyl isonitriles: a one-pot synthesis of 2-carbonyl-3-(pyridylamino)imidazo[1,2-a]pyridines useful as fluorescent probes for mercury ion

The one-pot reaction of β-lactam carbenes with 2-pyridyl isonitriles followed by an acidic hydrolysis was reported, which produced 2-carbonyl-3-(pyridylamino)imidazo[1,2-a]pyridines in moderate to good yields. Among the resulting novel imidazo[1,2-a]pyridine derivatives, 1-(6-chloro-3-(5-chloropyridin-2-ylamino)imidazo[1,2-a]pyridin-2-yl)-2-ethylbutan-1-one was demonstrated to be an efficient fluorescent probe for mercury ion both in acetonitrile and in buffered aqueous solution.     

Copper-catalyzed intramolecular hydroalkoxylation of α-(1-hydroxy-1-alkyl- and -aryl)methylallenoates by a 5-endo mode for preparation of 2-alkyl- and 2-aryl-2,5-dihydrofurans

Ethyl α-(1-hydroxy-1-alkyl)methylallenoates and α-(1-hydroxy-1-aryl)methylallenoates containing not only electron-donating groups but also an electron-withdrawing group on the aryl group at the α-position have been shown to undergo an efficient and selective copper-catalyzed intramolecular hydroalkoxylation to give functionalized 3-ethoxycarbonyl-2-alkyl- and -aryl-2,5-dihydrofurans in good to excellent yields through a 5-endo mode.     

Determining binding constants for 1:1 and 1:2 inclusion complexes of ester betulin derivatives with (2-hydroxypropyl)-β-cyclodextrin by affinity capillary electrophoresis

The complexation of ester betulin derivatives with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was studied by mobility shift affinity CE. Electrophoretic mobility for triangular peaks was calculated using the parameter a₁ of the Haarhoff–Van der Linde function instead of the peak top time. Dependences of the viscosity corrected electrophoretic mobility on HP-β-CD concentration were not described on the basis of only complexes with 1:1 stoichiometry due to the fact that these binding curves did not reach a plateau. However, the dependences were well described taking into account both 1:1 and 1:2 complexes. The presence of higher order equilibria was also revealed by x-reciprocal plots. The values of apparent binding constant logarithm, obtained for the first time, for 1:1 and 1:2 HP-β-CD complexes of betulin 3,28-diphthalate and betulin 3,28-disuccinate with 95% confidence interval limits in brackets are the same within error and are equal to 4.85 (4.73–4.95), 8.56 (7.75–8.82), 4.92 (4.86–4.97), and 8.54 (8.23–8.72) at 25°C, respectively. These values for 1:1 and 1:2 HP-β-CD complexes of betulin 3,28-disulfate at 25°C are 4.61 (4.57–4.64) and 7.11 (6.57–7.34), respectively. The binding constants for betulin 3,28-disulfate agree with the previously obtained results from the separation in the thermostatted capillary segment.