Biosensors for phenol derivatives using biochemical signal amplification

Two different approaches, both exploiting two enzymes cooperative functioning, to enhance the sensitivity of tyrosinase (PPO) based biosensor for amperometric detection of phenols have been compared. For this purpose, one monoenzyme electrode (PPO) and two bienzyme electrodes (PPO and d-glucose dehydrogenase, GDH; PPO and horseradish peroxidase, HRP) were constructed using agar-agar gel as enzyme immobilization matrix. The biosensors responses for l-tyrosine detection were recorded at −50 mV versus saturated calomel electrode (SCE). The highest sensitivity (74 mA M⁻¹) was observed for the PPO-GDH couple, while that recorded for PPO-HRP couple system was only 32 times higher than that measured for monoenzyme electrode (0.01 mA M⁻¹). The ability of the PPO-, PPO-GDH-, PPO-HRP-based biosensors to assay phenols was demonstrated by quantitative determination of phenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2-amino-3 (4-hydroxyphenyl) propanoic acid, 2-hydroxytoluene, 3-hydroxytoluene, 4-hydroxytoluene, 4-clorophenol, 3-clorophenol, 2-clorophenol, 4-hydroxybenzoic acid.     

Phenolic compounds,essential oil composition,and antioxidant activity of Angelica purpurascens (Avé-Lall.) Gill

In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•⁺), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•⁺, DPPH•, and FRAP activities (IC₅₀: 0.05 ± 0.0001 mg/mL, IC₅₀: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC₅₀: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source.     

Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Phenols monitoring and Hill coefficient evaluation using tyrosinase-based amperometric biosensors

Sensitive amperometric biosensors for phenols compounds, based on tyrosinase (polyphenoloxidase, PPO) immobilized on a Pt electrode in an electropolymerized poly-amphiphilic pyrrole matrix or cross-linked with glutaraldehyde, were constructed and compared. Steady-state amperometric measurements, performed at -50 mV vs. SCE in aqueous phosphate buffer containing LiClO(4) 0.1 M (pH 7) as well as in a chloroform solution containing 0.1 M C(6)H(5)CH(2)N(CH(3))(3)Cl, were used in order to compare the electroanalytical and kinetic parameters of the investigated amperometric biosensors in aqueous and nonaqueous media. It was established that the polypyrrole matrix has a higher efficiency for enzyme retention resulting in higher bioelectrode sensitivity, both in aqueous buffer (690 microA M(-1)) and in chloroform (149 microA M(-1)).     

Uptake of Well‐Defined,Highly Glycosylated,Pentafluorostyrene‐Based Polymers and Nanoparticles by Human Hepatocellular Carcinoma Cells

Chain length, size, composition, surface charge, and other properties of polymeric materials affect their recognition and uptake by cells and must be optimized to deliver polymers selectively to their target. However, it is often not possible to precisely modify selected properties without changing other parameters. To overcome these difficulties, well‐defined poly(pentafluorostyrene)‐based polymers are prepared that can be grafted via thiol/para‐fluorine “click” reaction with 1‐thio‐β‐D ‐glucose and 1‐thio‐β‐D ‐galactose. Fluorescence microscopy and flow cytometry show that nanoparticles are taken up by HepG2 cells to a higher degree than the respective water‐soluble polymers, and that internalization of both galactosylated homo‐ and nanoprecipitated block copolymers is enhanced.

     

A C‐linked Glycomimetic in the Gas Phase and in Solution: Synthesis and Conformation of the Disaccharide Manα(1,6)‐C‐ManαOPh

The effect of carbon is subtle but sweet : The flexible C‐linkage in the newly synthesised C‐glycosyl mimetic, Manα(1,6)‐C‐ManαOPh allows OH? π bonding, both in the gas phase and in aqueous solution. This interaction is absent in the O‐linked disaccharide (see figure).

     

Photochromic and fluorescence properties of coumarin fulgimides

Four new fulgimides possessing a fluorescent coumarin unit were synthesized from the corresponding fulgides, and their photochromic as well as fluorescence properties were investigated. The open-ring forms of coumarin fulgimides were found to exhibit fluorescence in the visible region. Upon exposure to UV light, the fulgimides were transformed into the nonfluorescent closed-ring forms, which can be reverted to the initial fluorescent open-ring forms on exposure to visible light. The efficiency of quenching of fluorescence was as high as 95% at the photostationary state of UV irradiation.     

Theoretical investigation of the ultrafast NeNePo spectroscopy of Au 4 and Ag 4 Clusters

Ultrafast ground state nuclear dynamics of Au₄ and Ag₄ is theoretically explored in the framework of negative ion - to neutral - to positive ion (NeNePo) pump-probe spectroscopy based on the ab initio Wigner distribution approach. This involves the preparation of a nonequilibrium neutral ensemble by pump induced photodetachment of a thermal anionic ground state distribution, gradient corrected DFT classical trajectory simulations “on the fly” on the neutral ground state, and detection of the relaxation process of the ensemble in the cationic ground state by a time-delayed probe pulse. In Au₄, the initially prepared linear structure is close to a local minimum of the neutral state giving rise to characteristic vibrations in the signals for probe wavelength near the initial Franck-Condon transition. A timescale of ∼1 ps for the structural relaxation towards the stable rhombic D_2h neutral isomer was determined by the increase of the signal for probe wavelength in vicinity of the vertical ionization energy of the rhombic structure. In contrast, the relaxation dynamics in Ag₄ is characterized by normal mode vibrations since both the initially prepared anionic ground state and the neutral ground state have rhombic minimum geometries. Thus, time-resolved oscillations of pump-probe signals are fingerprints of structural behaviour which can be used experimentally for the identification of particular isomers in the framework of NeNePo spectroscopy. Received 22 December 2000     

掺杂Eu2O3的SrTiO3及SnO2光致发光

用具有大能隙的本征半导体(SrTiO₃及SnO₂)粉末作本体,分别掺杂1%(原子百分数)的Eu₂O₃;所得物质表现出Eu³⁺离子的线发射光谱特性,但相对发光强度及光谱形状有相当大的变化。X射线衍射结构分析显示Eu³⁺在SrTiO₃晶格里是处在间隙位置,而它在SnO₂晶格里则形成新物相Eu₂Sn₂O₇。