In Situ Generation of Quinolinium Ylides from Diazo Compounds: Copper-Catalyzed Synthesis of Indolizine.

The Cu-catalyzed three-component reaction between quinolines, diazo compounds, and alkenes has been established for direct construction of indolizine derivatives via quinolinium ylides. This methodology is distinguished by the use of a commercially inexpensive catalyst and readily available starting materials, wide substrate scope, and operational simplicity.

In situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement: copper-catalyzed synthesis of unsymmetrical diacylglycine esters.

A novel in situ generation of nitrilium from a nitrile ylide and the subsequent Mumm rearrangement of carboxylic acid, nitrile, and diazo compounds gave various unsymmetrical diacylglycine esters in moderate to high yields. This copper-catalyzed cascade reaction enables one-pot generation of two C-N bonds, one C[double bond, length as m-dash]O bond, and one C-H bond, with nitrogen as the only byproduct. The reaction has a broad functional-group tolerance, is rapid, easily scales up to the 100 mmol scale, and is insensitive to air and moisture.

[3 + 2] cycloaddition and subsequent oxidative dehydrogenation between alkenes and diazo compounds: a simple and direct approach to pyrazoles using TBAI/TBHP.

A novel Bu4NI-catalyzed pyrazole formation reaction is well described via sequential [3 + 2] cycloaddition and oxidative dehydrogenation reactions using TBHP as the primary oxidant. In comparison with previous cases toward pyrazoles from alkenes and diazo compounds, alkenes without a pre-organized leaving group were applied in this transformation. In addition, this methodology was distinguished by its broad substrate scope, commercially available inexpensive starting materials, high atom economy and operational simplicity.

A Cu-catalyzed four-component cascade reaction to construct ß-ester-γ-amino ketones.

Herein, a novel Cu-catalyzed four-component cascade reaction, which encompasses styrenes, diazo compounds, amines, and tert-butyl hydroperoxide (TBHP), was developed for the synthesis of ß-ester-γ-amino ketones. Mechanistically, this transformation was initiated by the interception of an electrophilic Cu-based carbene with nucleophilic α-aminoalkyl radicals, followed by a radical cascade process and an ionic Kornblum-DeLaMare reaction. The methodology was also distinguished by its wide substrate scope, easily available starting materials, and operational simplicity.

Preparation of 17ß-estradiol-imprinted material by surface-initiated atom transfer radical polymerization and its application.

A novel 17ß-estradiol molecularly imprinted polymer was grafted onto the surface of initiator-immobilized silica by surface-initiated atom transfer radical polymerization. The resulting molecularly imprinted polymer was characterized by elemental analysis and thermogravimetric analysis. The binding property of molecularly imprinted polymer for 17ß-estradiol was also studied with both static and dynamic methods. The results showed that the molecularly imprinted polymer possessed excellent recognition capacity for 17ß-estradiol (180.65 mg/g at 298 K), and also exhibited outstanding selectivity for 17ß-estradiol over the other competitive compounds (such as testosterone and progesterone). Then, the determination of trace 17ß-estradiol in beef samples was successfully developed by using molecularly imprinted polymer solid-phase extraction coupled with high-performance liquid chromatography. The limit of detection was 0.25 ng/mL, and the amount of 17ß-estradiol in beef samples was detected at 2.83 ng/g. This work proposed a sensitive, rapid, reliable, and convenient approach for the determination of trace 17ß-estradiol in complicated beef samples.

Preparation of Imazethapyr Surface Molecularly Imprinted Polymers for Its Selective Recognition of Imazethapyr in Soil Samples.

A novel strategy based on imazethapyr (IM) molecular-imprinting polymers (MIPs) grafted onto the surface of chloromethylation polystyrene resin via surface-initiated atom transfer radical polymerization (SI-ATRP) for specific recognition and sensitive determination of trace imazethapyr in soil samples was developed. The SI-ATRP was performed by using methanol-water (4 : 1, v/v) as the solvent, acrylamide as the functional monomer, trimethylolpropane trimethacrylate (TRIM) as the cross-linker, imazethapyr as the template, and CuBr/2,2'-bipyridine as the catalyst. The resulting MIPs were characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Then, the binding selectivity, adsorption capacity, and reusability of the MIPs were evaluated. The results indicated that the prepared MIPs exhibited specific recognition and high selectivity for imazethapyr. The MIPs were further used as solid-phase extraction (SPE) materials coupled with high-performance liquid chromatography (HPLC) for selective extraction and detection of trace imazethapyr from soil samples. The results showed that good linearity was observed in the range of 0.10-5.00 µg/mL, with a correlation coefficient of 0.9995. The limit of detection (LOD) of this method was 15 ng/g, and the extraction recoveries of imazethapyr from real samples were in the range of 91.1-97.5%, which proved applicable for analysis of trace imazethapyr in soils. This work proposed a sensitive, rapid, and convenient approach for determination of trace imazethapyr in soil samples.

Interception of Radicals by Molecular Oxygen and Diazo Compounds: Direct Synthesis of Oxalate Esters Using Visible-Light Catalysis.

The synthesis of oxalate esters through a radical process, rather than the traditional ionic reaction, has been well developed in which the radicals induced by visible light are trapped by molecular oxygen and diazo compounds under room temperature. This reaction is operationally simple, mild, and shows broad substrate scopes in α-bromo ketones and diazo compounds.

Radical-carbene coupling reaction: Mn-catalyzed synthesis of indoles from aromatic amines and diazo compounds.

An unprecedented coupling reaction between aromatic amines and diazo compounds was well developed, which afforded a bridge connecting between radical chemistry and metal carbene chemistry. This Mn-catalyzed tandem reaction also provided a fundamentally different and practical approach to the indole skeleton under mild conditions.

[Spectroscopic studies on the binding of prulifloxacin and ct-DNA].

The interaction mechanism of prulifloxacin (PL) and calf thymus DNA (ct-DNA) was studied by UV spectra, fluorescence spectra, and hydrodynamic measurements. The binding of ct-DNA and different concentrations of PL was discussed with UV, FL, phosphate effect and ion strength. The denaturation temperature and viscosity were measured. It is obvious that there is a hypochromic effect on the UV spectra with the fluorescence intensity decreasing regularly after addition of DNA and a red shift of the maximum emission peak with a static quenching constant of 3.1 x 10(4) L x mol(-1). The above results show that a binary complex forms between PL and DNA. It is indicated that there is no static-electro interaction between them by phosphate effect. The outer groove binding is suggested by denaturation temperature of DNA increasing (no more than 7 degrees C) and viscosity slightly decreasing.

Bu4NI-Catalyzed Cross-Coupling between Sulfonyl Hydrazides and Diazo Compounds To Construct ß-Carbonyl Sulfones Using Molecular Oxygen.

A new cross-coupling reaction between sulfonyl hydrazides and diazo compounds has been established, leading to a variety of ß-carbonyl sulfones in good yields. This methodology was distinguished by simple manipulation, easily available starting materials, and wide substrate scope. A plausible mechanism involving a radical process was proposed based upon the experimental observations and literature.

[Preparation and applications of 4-methyl imidazole magnetic surface molecularly imprinted polymers].

The magnetic surface molecularly imprinted polymers (MIPs) with specific recognition of 4-methyl imidazole (4-MI) were prepared by using 4-MI as template molecule, methacrylic acid (MAA) as functional monomer and Fe3O4 as magnetic fluid. The polymers were characterized by of Fourier transform infrared spectrometer (FT-IR) analysis, X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The results demonstrated that an imprinted polymer layer was successfully coated onto the surface of modified Fe3O4 nanomaterials, resulting in a narrow diameter distribution and good magnetic responsibility. The ultraviolet (UV) spectrophotometry was used to demonstrate the interaction between 4-MI and MAA. It was found that one 4-MI molecule was entrapped by one MAA molecule, which was the main existing form of subject and object. By UV spectrophotometric method to study the adsorption performance of magnetic molecularly imprinted polymers, the specific adsorption equilibrium and selectivity were evaluated by batch rebinding studies. The Scatchard analysis showed that there were two kinds of binding sites in the Fe3O4 @ (4-MI-MIP). The corresponding maximum adsorption capacities of 4-MI onto Fe3O4 @ (4-MI-MIP) were 40.31 mg/g and 23.07 mg/g, and the dissociation constants were 64.85 mg/L and 30.41 mg/L, respectively. The kinetic experimental data were correlated with second-order kinetic model. The magnetic molecularly imprinted polymers were used for the adsorption of 4-methyl imidazole in environmental water samples, and good results were obtained.