Cheng-bin Gong

An organically modified silicate molecularly imprinted solid-phase microextraction device for the determination of polybrominated diphenyl ethers.

An organically modified silicate (ORMOSIL) SPME stationary phase molecularly imprinted with BDE-209 has been successfully fabricated by conventional sol-gel technique from phenyltrimethoxysilane and tetraethoxysilane. The thickness of the ORMOSIL-SPME stationary phase, on fused-silica optical fibres, was measured to be ca. 9.5 microm with a volume of ca. 0.12 microL. Rebinding assays and Scatchard analysis revealed that the imprinted ORMOSIL-SPME stationary phase possessed a binding affinity, K(B), of 7.3+/-1.7 x 10(10)M(-1) for BDE-209, with a receptor site density, B(max), of 1.2 x 10(-3)pmol per SPME device. Besides its molecular template, the ORMOSIL-SPME stationary phase also showed good affinity (logK(B)>/=9.5) for smaller BDE congeners commonly found in the natural environment. The density of receptor sites within the imprinted matrix for those smaller BDE congeners was even higher than that for BDE-209. This may be attributable to the binding site heterogeneity of the imprinting process that creates deformed binding sites that are suitable for the accommodation of the smaller BDE congeners. Compared to the commercially available polyacrylate and polydimethylsiloxane SPME stationary phases, the imprinted ORMOSIL-SPME devices showed much higher pre-concentration ability towards polybrominated diphenyl ethers (PBDEs), even in direct immersion sampling at room temperature. Coupled with GC-NCI-MS and GC-muECD, the imprinted ORMOSIL-SPME device was able to achieve detection sensitivity of 0.2-3.6 pgmL(-1) and 1-8.8 pgmL(-1), respectively, for commonly occurring BDE congeners, including medium to high molecular weight PBDEs. The imprinted ORMOSIL-SPME device has been successfully applied to monitor PBDE contents in municipal wastewaters.

Photo-responsive molecularly imprinted hydrogels for the detection of melamine in aqueous media

In this paper, by combination of the specificity of a molecularly imprinted technique, the water solubility of hydrogels and the photoisomerization property of azobenzene chromophores, we report a new and quick detection method for trace melamine in aqueous media based on photo-responsive molecularly imprinted hydrogels (MIHs). The MIHs were fabricated using a water-soluble azobenzene-containing 4-[(4-methacryloyloxy)phenylazo]benzenesulfonic acid (MAPASA) as the functional monomer, 1,3,5-benzenetriol as a mimic template, and tetramethacryloyl triethylene tetramine (TTT) as the cross-linker. The MIHs show specific affinity to melamine with a binding constant of 3.20 × 104 M−1 in aqueous Tris–HCl buffer at pH 7.0. The density of the melamine-specific receptor sites in the MIHs material is 2.69 μmol g−1 MIHs. Upon alternate irradiation at 365 and 440 nm, the MIHs can quantitatively uptake and release melamine. The photoisomerization rate of MIHs is related to the concentration of melamine in the detecting solution, and therefore, a quick detection method for trace melamine is established. Analytical application of the MIHs to detect the melamine concentration in both milk and milk powder has been accomplished successfully with a simple pre-treatment of the samples.

Ultrasensitive detection of bisphenol A in aqueous media using photoresponsive surface molecular imprinting polymer microspheres

Photoresponsive surface molecular imprinting polymer (SMIP) microspheres were synthesized on silica microspheres by surface polymerization using a water-soluble azobenzene-containing 4-[(4-methacryloyloxy)phenylazo]benzenesulfonic acid as the functional monomer. The SMIP microspheres displayed good photoresponsive properties and specific affinity towards bisphenol A (BPA) with high recognition ability (maximal adsorption capacity: 6.96 μmol g−1) and fast binding kinetics (binding constant: 2.47 × 104 M−1) in aqueous media. Upon alternate irradiation at 365 and 440 nm, the SMIP microspheres could quantitatively bind and release BPA. Analytical application of the SMIP microspheres for the detection of trace BPA concentration in mineral water and tap water has been carried out successfully, and therefore a simple and quick detection method for trace BPA in the environment was established.

Photocontrolled solid-phase extraction of guanine from complex samples using a novel photoresponsive molecularly imprinted polymer

A novel photoresponsive molecularly imprinted polymer (MIP) was developed for the selective extraction of guanine from complex samples. The photoresponsive MIP was fabricated using guanine as the template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as the functional monomer, and water-soluble triethanolamine trimethacrylate as the cross-linker. The MIP displayed good selectivity toward guanine with a dissociation constant of (2.70 ± 0.16) × 10(-5) mol L(-1) in aqueous media. The density of the guanine-specific receptor sites in the MIP material was (4.49 ± 0.22)μmol g(-1). Quantitatively release and uptake of guanine by the MIP occurred with irradiation at 365 and 440 nm, respectively. The MIP could efficiently extract guanine from beer and then release it into aqueous media under photocontrol. This method could be used for selective separation and subsequent determination of a specific analytes from complex samples.

Synthesis and characterization of photo- and pH-responsive nanoparticles containing amino-substituted azobenzene

A novel dual responsive nanomaterial sensitive to both photo- and pH stimuli has been successfully developed. The polymer-based nanoparticles were fabricated from a specially designed photo- and pH-responsive amino-substituted azobenzene monomer, 4-amino-4′-methacrylatylazobenzene (AMAAB), via free radical polymerization with trimethylolpropane trimethacrylate (TRIM) cross-linkers. The trans-cis photoisomerization properties of AMAAB were retained after incorporation into the rigid three-dimensional cross-linked polymer matrix. The TRIM/AMAAB molar ratio significantly influenced the kinetics of the trans-cis photoisomerization. The nanoparticles also possessed good pH-responsive properties. The change in absorbance with media pH was monitored at 402 nm, and a “titration type” curve was obtained with a pKa value of 0.61 ± 0.06. At this transition point, the color of the nanoparticle suspension changed colour from yellow to pink. Thermogravimetric analysis (TGA) indicated that the nanoparticles were thermally stable.

Photoresponsive surface molecularly imprinted polymer on ZnO nanorods for uric acid detection in physiological fluids

A photoresponsive surface molecularly imprinted polymer for uric acid in physiological fluids was fabricated through a facile and effective method using bio-safe and biocompatible ZnO nanorods as a support. The strategy was carried out by introducing double bonds on the surface of the ZnO nanorods with 3-methacryloxypropyltrimethoxysilane. The surface molecularly imprinted polymer on ZnO nanorods was then prepared by surface polymerization using uric acid as template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as functional monomer, and triethanolamine trimethacryl ester as cross-linker. The surface molecularly imprinted polymer on ZnO nanorods showed good photoresponsive properties, high recognition ability, and fast binding kinetics toward uric acid, with a dissociation constant of 3.22×10(-5)M in aqueous NaH2PO4 buffer at pH=7.0 and a maximal adsorption capacity of 1.45μmolg(-1). Upon alternate irradiation at 365 and 440nm, the surface molecularly imprinted polymer on ZnO nanorods can quantitatively uptake and release uric acid.

Synthesis and characterization of novel electrochromic and photoresponsive materials based on azobenzene-4,4′-dicarboxylic acid dialkyl ester

Novel electrochromic and photoresponsive materials based on azobenzene-4,4′-dicarboxylic acid dialkyl ester derivatives (ADDEDs) were successfully prepared and characterized through nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and high-performance liquid chromatography-mass spectrometry. The electrochromic behavior, electrochromic mechanism, electro-optical properties, and photoresponsive properties of ADDEDs were investigated through cyclic voltammetry and ultraviolet-visible absorption spectra. ADDEDs displayed not only outstanding electrochromic behavior but also good and reversible photoisomerization properties even under electrochromic conditions. Electrochromic devices (ECDs) based on ADDEDs were fabricated, and their electrochromic performance was analyzed. The ECDs presented a color change from colorless to magenta between 0.0 V (bleached state) and ±3.0 V (colored state). In addition, the ECDs exhibited fast switching times, reasonable contrast, satisfactory optical memories, and redox stability. The novel redox-active azobenzene derivatives are promising candidates for full-color EC display devices, electronic paper, smart windows, optical memory devices, dual-stimuli-responsive systems, as well as other potential new applications.

Colorimetric test paper for cyanide ion determination in real-time

A colorimetric cyanide ion (CN−) sensor 4-[(1E)-2-(2-hydroxyphenyl)ethenyl]-1-allylpyridinium bromide (2-HPEAPB) was synthesized via condensation and N-alkylation reactions using 4-methylpyridine and salicylaldehyde as the starting materials. 2-HPEAPB displayed good selectivity, fast response, and high sensitivity toward CN− over other competing anions in acetonitrile–water (95:5, v/v) with a limit of detection of 8.0 × 10−6 mol L−1 by the naked eye. The sensing mechanism and the influence of pH and temperature on sensing properties were investigated. Colorimetric test paper for CN− was prepared by absorption of 2-HPEAPB to a chromatography paper, which could be used to detect CN− directly and quickly. Analytical application of measuring CN− concentration in an electroplating wastewater in real-time was conducted successfully.

A New Simple Route To N-Substituted 2-Aminoethylphosphonic Acids

Abstract 2-Aminoethylphosphonic acid (AEPA) and its N-substituted compounds were prepared by one step reaction using 2-chloroethylphosphonic acid with ammonia and amines (H2NMe, HNMeMe, HNEtEt, H2NPr-n, H2NCH2ph, H2NCH2CH2NH2 and H2N(C=NH)NH2 in a dilute alkaline solution below 20 °C with simple work-up and easy purification. The reaction was accelerated by catalytic amount of potassium iodide. The yield for the reaction products were 35.6 to 48.6% for the KI absence and 78.2 to 88.0% for the KI presence.

Photoresponsive molecularly imprinted hydrogel casting membrane for the determination of trace tetracycline in milk

This study aimed to develop a photoresponsive molecularly imprinted hydrogel (MIH) casting membrane for the determination of trace tetracycline (TC) in milk. This MIH casting membrane combined the specificity of MIHs, the photoresponsive properties of azobenzene, and the portable properties of a membrane. Photoresponsive TC‐imprinted MIHs were initially fabricated and then cast on sodium dodecyl sulfonate polyacrylamide gel. After TC removal, a photoresponsive MIH casting membrane was obtained. The photoresponsive properties of the MIH casting membrane were robust, and no obvious photodegradation was observed after 20 cycles. The MIH casting membrane displayed specific affinity to TC upon alternate irradiation at 365 and 440 nm; it could quantitatively uptake and release TC. The TC concentration (0.0–2.0 × 10−4 mol l−1) in aqueous solution displayed a linear relationship with the photoisomerization rate constant of azobenzene within the MIH casting membrane. As such, a quick detection method for trace TC in aqueous foodstuff samples was established. The recovery of this method for TC in milk was investigated with a simple pretreatment of milk, and a high recovery of 100.54–106.35% was obtained. Therefore, the fabricated membrane can be used as a portable molecular sensor that can be easily recycled. Copyright