预混合自组装辣根过氧化物酶生物活性膜及其催化活性研究

以阳离子化的辣根过氧化物酶 (HRP)和阴离子聚苯乙烯磺酸钠 (PSS)的预混合溶液 ,与阳离子聚电解质聚二甲基二烯丙基氯化铵 (PDDA)通过逐层组装 ,在阴离子化聚对苯二酸乙二酯 (PET)表面构建了多层生物活性膜 .用紫外 可见光谱仪 (UV Vis)和原子力显微镜 (AFM)研究了交替自组装膜的结构和表面形膜 ,并测定了自组装膜的生物催化活性 .结果表明 ,预混合溶液中的PSS与HRP一起沉积在PDDA膜层上组装成 (PSS+HRP)膜层 ,且每层中PSS和HRP的比例一致 ;(PSS +HRP)膜层呈条状分布 ,膜表面较为平整 ;多层膜中的HRP催化H2 O2 与 4 氨基安替比林的显色反应的表观米氏常数为 9 7× 10 - 5mol·L- 1 (相对于H2 O2 底物 ) ,较溶液中 (1 5 2× 10 - 4mol·L- 1 )的小 .     

Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers

A facile way to prepare free-standing polyelectrolyte multilayer films of poly(sodium 4-styrenesulfonate)(PSS)/poly(diallyldimethylammonium)(PDDA) was developed by applying a new pH-dependent sacrificial system based on cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) microgels. The tertiary amine groups of PDMAEMA microgels can be protonated in acidic environment, and the protonated microgels were deposited by layer-by-layer (LbL) technique with PSS. PSS/PDDA multilayer films were constructed on the top of the PSS/microgels sacrificial layers. The LbL assembly process was investigated by UV–vis spectroscopy. Further study shows that the free-standing PSS/PDDA multilayer films can be obtained within 3 min by treating the as-prepared films in alkali aqueous solution with a pH of 12.0. The pH-triggered exfoliation of PSS/PDDA multilayer films provides a simple and facile way to prepare LbL assembled free-standing multilayer films.     

Alternate assemblies of polyelectrolyte functionalized carbon nanotubes and platinum nanoparticles as tunable electrocatalysts for dioxygen reduction

A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (MPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium–tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet–visible–near-infrared spectroscopy (UV–vis–NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV–vis–NIR. SEM provides the morphology of the multilayer films. The PtNPs containing multilayer films exhibit high electrocatalytic activity for the reduction of dioxygen. Furthermore, the electrocatalytic activity of the films could be further tailored by simply choosing different cycles in the LBL process. This assembling method for polyelectrolyte functionalized carbon nanotubes and nanoparticles introduces new opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent nanostructures.     

Preparation of Polyelectrolyte Nanotubes by a Pressure filter-template Technique Using Microporous Anodic Aluminum Oxide (AAO) as the Template

Polyelectrolyte nanotubes of poly(sodium 4‐styrene‐sulfonate) (PSS) with cationic poly(diallyl dimethyl ammonium chloride) (PDDA) (PSS/PDDA) were fabricated by a pressure‐filter‐template technique using microporous anodic aluminum oxide (AAO) as the template. UV‐Vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and infrared spectroscopy (FT‐IR) were applied to characterize the obtained PSS/PDDA nanotubes. The results have shown that the PSS/PDDA nanotubes exhibit an amorphous structure and have the outer diameter of 200 nm and length of 25 µm respectively, which are in good agreement with the dimensions of the AAO template pores. The wall thickness of the nanotubes may be controlled by the number of the self‐assembled layers. Formation of the nanotubes follows a layer‐by‐layer (LbL) mechanism due to the electrostatic interactions, where the SO^?₃ groups of PSS are first adsorbed on the Lewis acid sites of AAO template pores.     

Amperometric choline biosensor fabricated through electrostatic assembly of bienzyme/polyelectrolyte hybrid layers on carbon nanotubes

We report a flow injection amperometric choline biosensor based on the electrostatic assembly of the choline oxidase (ChO) enzyme and a bienzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternately assembling a cationic poly(diallydimethylammonium chloride) (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, a bioactive nanocomposite film of PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and PDDA/ChO/PDDA/CNT (ChO/CNT) was fabricated on the GC surface. Owing to the electrocatalytic effect of carbon nanotubes, the measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. The ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g., applied potential, flow rate, etc., were optimized and potential interference was examined. The response time for this choline biosensor is fast (few seconds). The linear range of detection for the choline biosensor is from 5.0 x 10(-5) to 5.0 x 10(-3) M and the detection limit is about 1.0 x 10(-5) M.     

Photoresponsive water‐dispersible polyaniline nanoparticles through template synthesis with copolymer micelle containing coumarin groups

A novel kind of photosensitive water‐dispersible polyaniline (PANI) nanoparticles was designed and prepared by template synthesis using a photo‐responsive vinyl‐coumarin (VM)/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) copolymer micelle containing coumarin moieties. The resulting PANI nanoparticles exhibited reversible photo‐crosslinking and photo‐decrosslinking behavior similar to coumarin moiety upon irradiation with different UV light as verified by UV–vis absorption. In addition, photoinduced size change of the PANI nanoparticles after 365 nm UV light irradiation was successfully monitored by dynamic light scattering and transmission electron microscopy measurements, further confirming the photosensitivity of the obtained PANI nanoparticles by the incorporation of VM/AMPS copolymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Layered Zirconium(IV) Aminoethylphosphonate Intercalated with Horseradish Peroxidase for an Amperometric Biosensor

Layered zirconium(IV) aminoethylphosphonate (ZrAEP) have been used as matrices for immobilization of horseradish peroxidase (HRP) to fabricate enzyme electrode for an amperometric biosensor. The biocompatible HRP–ZrAEP films were fabricated on gold electrode surface by electro‐co‐deposition method. The morphology of the HRP–ZrAEP composite was characterized by scanning electron microscopy (SEM). UV–vis spectroscopy indicated that the intercalated HRP retained its native structure after incorporation in the ZrAEP. The immobilized HRP at the HRP–ZrAEP films exhibited good electro catalytic responses to the reduction of hydrogen peroxide. The response time of the biosensor was less than 3 s, and the linear range is from 2.5 × 10^?6 to 3.22 × 10^?3 M, with a detection limit of 7.0 × 10^?7 M (S/N = 3). The Michaelis–Menten constant (K^app_M) value is estimated to be 2.21 mM. In addition, the obtained biosensor possesses high sensitivity, good stability and reproducibility.     

Comparative study on the enzymatic polymerization of N‐substituted aniline derivatives

A series of water‐soluble N‐substituted poly(alkylanilines) (PNAAs) have been enzymatically synthesized with a variety of groups, from methyl to n‐butyl, such as poly(N‐methylaniline), poly(N‐ethylaniline), poly(N‐butylaniline) and poly(N‐phenylethanolamine). The syntheses were made in the presence of poly(4‐sodium styrene sulfonate) (SPS) as a template and horseradish peroxidase (HRP) as a catalyst. The size and type of the groups have a great effect on the properties of the final polymers. UV‐vis spectroscopy and cyclic voltammetry measurements confirmed that for enzymatically synthesized PNAAs/SPS complexes, the electroactivity increased with the bulkiness of the substituents. These polymers have been studied in the doped and undoped states by FT‐IR and UV‐vis spectroscopy. Also these polymers show multiple and reversible optical transitions that can be ascribed to the formation of polaron and bipolaron states. Copyright © 2005 John Wiley & Sons, Ltd.     

四磺基铁(II)酞菁生物模拟合成导电聚苯胺

利用四磺基铁(II)酞菁（FeTSPc）在木质素磺酸钠模板体系中模拟过氧化物酶催化合成导电聚苯胺/木质素磺酸复合物(PANI/LGS)。讨论了溶液pH 值、苯胺浓度、LGS浓度、H2O2浓度及反应时间对FeTSPc催化聚合反应产物的影响。结果表明该反应具有明显的pH值依赖性,pH（1.0～4.0）是合成导电聚苯胺所必须需的,其最适pH值为1.5。用元素分析法、紫外-可见分光光度法、FTIR、循环伏安法、电导率测试、热重分析法等对PANI/LGS复合物表征, 结果表明该复合物具有较好的热稳定性和可逆的电化学活性。     

Synthesis and physico-chemical properties of a novel series of aromatic electron acceptors based on N-heterocycles

The synthesis of a novel series of N-based heterocyclic salts using a simple and efficient N-alkylation of 1,2-bis(4-pyridyl)ethane with reactive halides is reported. These compounds can be transformed into the corresponding pyridinium methylides by addition of a base. The former exhibit an unstable absorption bands at 395–410 nm. The structures of the salts were fully characterized by UV–vis, IR, NMR and MS spectroscopy and elemental analysis. The pK values of selected compounds were also determined and the acid–basic equilibrium was investigated by UV–vis spectrophotometry. The thermal stability of all species was determined by thermogravimetric analysis.     

Photoelectronic properties of horseradish peroxidase-functionalized CdSe/silica mesoporous composite and its sensing towards hydrogen peroxide

CdSe nanocrystals were prepared within a template of mesoporous silica (MS) spheres via chemical reaction, and then the as-synthesized CdSe/MS composites were dip coated on an optically transparent electrode. The photoelectric properties of CdSe/MS composite film were examined under ultraviolet (UV) illumination at the excitation wavelength of 365 nm. The CdSe/MS composite can facilitate charge rectification and minimize charge recombination as shown by its higher photocurrent. Most importantly, horseradish peroxidase (HRP)-functionalized CdSe/MS-modified electrode (HRP/CdSe/MS) had a stronger response toward hydrogen peroxide (H₂O₂) under UV illumination than in the dark. The result demonstrates the potential application of HRP/CdSe/MS composite film as a novel biosensor for monitoring H₂O₂ under UV illumination.     

A facile preparation method for synthesis of silica sulfuric acid/poly(o‐methoxyaniline) core–shell nanocomposite

A new nanocomposite of poly(o‐methoxyaniline) (POMA) is introduced by overlayer formation of POMA on silica. The key appealing feature of the synthesis is the role of silica sulfuric acid (SSA) both as solid acid dopant and template in overlayer self‐assembly of POMA on silica surface. Hereon siloxide group (Si―O^?) of silica surface is replaced with dopant anion of SSA (≡Si―O―SO₃^?), which leads to formation of a overlayer of POMA on the silica surface. The composite particles are spherical in the nanoscale range of 50 nm without application of any external template (no‐template synthesis). Nanocomposite was fully characterized by various instrumentation methods: Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–vis), thermogravimetric analysis (TGA), diffrential thermal analysis (DTA), elemental analysis (CHNS), energy dispersive X‐ray (EDX), X‐ray photoelectron spectroscopy (XPS) and X‐ray difraction (XRD). Based on XPS and CHNS results, it is demonstrated that the doping level of POMA is as high as 50% and for the first time the ratio of 4:2:2 is obtained for ―NH― (amine): ―HN^.+― (polarons): ?HN⁺― (bipolarons), respectively. In fact, bipolarons may also coexist with polarons with a 1:1 ratio of them. Moreover, the synthesis benefits from the perspective of green chemistry which is preparation under solid‐state (solvent‐free) condition. Copyright © 2015 John Wiley & Sons, Ltd.     

In situ synthesis and preconcentration of cetylpyridinium complexed hexaiodo platinum nanoparticles from spent automobile catalytic converter leachate using cloud point extraction

In the present study, a green chemistry based cloud point extraction (CPE) method has been developed for the in situ synthesis and preconcentration of cetylpyridinium complexed hexaiodo platinum nanoparticles (Pt-I NP) from the leachate of spent automobile catalytic converter using potassium iodide (KI) and assisted by a combination of cationic and non-ionic surfactants; cetylpyridinium bromide (CPB) and Triton X-114, respectively. The process parameters such as concentrations of hydrochloric acid, platinum, KI, sodium chloride, CPB, Triton X-114; incubation temperature and complexation time on CPE were optimized. The synthesized nanoparticles were characterized by UV–visible spectroscopy (UV–vis), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and zeta potential techniques. The formation of Pt-I NP was followed with UV–vis. The XRD pattern established the tetragonal crystal structure of the produced nanoparticles. The nanoparticles were spherical in shape and the particle size obtained with TEM was about 5.6 nm. Further, the preconcentrated nanoparticles were quantified by continuum source electro-thermal atomic absorption spectrometry (ET-AAS) and a preconcentration factor of 25 was obtained for a reaction volume of 25 mL. The accuracy of the developed method was confirmed by analyzing the certified reference materials such as CCRMP PTM-1a (copper-nickel sulphide matte) and CCRMP PTC-1a (copper-nickel sulphide concentrate). The current CPE protocol demonstrates advantages such as simultaneous synthesis and preconcentration; synthesis at micromolar concentration from metal scrap, higher nanoparticle recovery; biodegradability and biocompatibility of the employed surfactants and dual solubility of the synthesized Pt-I NP. Thus, the developed method can be applied for the separation, large scale synthesis and preconcentration of Pt-I NP from various environmental and industrial wastes, in a single pot.     

Effects of AC‐Electrolysis on the Enzymatic Activity of Glucose Oxidase

The change in the activity of glucose oxidase subjected to an asymmetrical alternating current (AC) electric field is investigated via horseradish peroxidase (HRP)‐coupled bioassay. The effect of the amplitude, frequency and enzyme concentration have been shown to affect the enzyme activity towards glucose oxidation. The decrease in the enzyme activity is directly related to the change in pH and temperature of the GOx solution during AC electrolysis. The enzyme activity reduces with increasing amplitude, enzyme concentration and decreasing frequency. Results from UV‐vis, FT‐IR and UV CD spectroscopy showed that the AC treated GOx samples undergo structural modifications.     

A MgO Nanoparticles Composite Matrix‐Based Electrochemical Biosensor for Hydrogen Peroxide with High Sensitivity

A novel horseradish peroxidase (HRP) electrochemical biosensor based on a MgO nanoparticles (nano‐MgO)‐chitosan (chit) composite matrix was developed. The morphology of nano‐MgO‐chit nanocomposite was examined by scanning electron microscopy (SEM). The interaction between nano‐MgO‐chit nanocomposite matrix and enzyme was characterized with UV‐vis spectra. This proposed composite material combined the advantages of inorganic nanoparticles and organic polymer chit. The HRP immobilized in the nanocomposite matrix displayed excellent electrocatalytic activity to the reduction of H₂O₂ in the presence of hydroquinone as a mediator. The effects of the experimental variables such as solution pH and the working potential were investigated using steady‐state amperometry. The present biosensor (HRP‐modified electrode) had a fast response towards H₂O₂ (less than 10 s), and excellent linear relationships were obtained in the concentration range of 0.1–1300 μM, with a detection limit of 0.05 μM (S/N=3). Moreover, the stability and reproducibility of this biosensor were evaluated with satisfactory results.     

Upconversion Nanoparticle-Assisted Photopolymerization

Near-infrared (NIR) laser has deeper penetration and lower thermal effect compared with ultraviolet–visible (UV/vis) laser. NIR laser can stimulate upconversion nanoparticles (UCNPs) to emit UV/vis light efficiently. Therefore, the UCNPs become an important kind of materials to produce upconversion luminescence through NIR laser. Compared with photopolymerization induced with UV/vis laser, the UV/vis light from UCNP-assisted photopolymerization presents some unique characters. This review focuses on the research progress of UCNP-assisted photopolymerization and its potential applications. We will discuss the influencing factors of UCNP-assisted polymerization, illustrate the relation between the gel size and monomer concentration and propose the development prospects of UCNP-assisted polymerization in the biological field.     

Direct Electrochemistry of Cytochrome c Based on Poly(diallyldimethylammonium Chloride)‐ Graphene Nanosheets/Gold Nanoparticles Hybrid Nanocomposites and Its Biosensing

A novel biosensor was developed by entrapping cytochrome c (Cyt c) in thin films of the room temperature ionic liquid (RTIL) containing nanocomposites of poly(diallyldimethylammonium chloride)‐graphene nanosheets‐gold nanoparticles (PDDA‐Gp‐AuNPs) at a 11‐mercaptoundecanoic acid‐6‐mercapto‐1‐hexanol modified gold electrode. The synthesized PDDA‐Gp‐AuNPs hybrid nanocomposites were characterized by UV‐vis spectroscopy, Raman spectroscopy, scanning electron microscopy and atomic force microscopy. The PDDA‐Gp‐AuNPs nanocomposites could increase the effective surface of the electrode, enhance the fixed amount of Cyt c on the electrode surface, promote the electron transfer and facilitate the catalytic activity of Cyt c. The RTIL could provide a biocompatible microenvironment to keep Cyt c biological activities, act as an effective mediator to immobilize a large number of Cyt c on the electrode and have good conductivity to improve electron transfer. Therefore, the resultant electrode exhibited good electrochemical performance and electrocatalytic activity. It could be used for electrochemical detection of H₂O₂ with rapid response, high sensitivity, wide linear range and low detection limit, as well as good stability, repeatability and selectivity. The sensor might be promising for practical application.     

Sucrose ester micellar-mediated synthesis of Ag nanoparticles and the antibacterial properties

Ag nanoparticles with diameter in the range of 10–25 nm had been synthesized using a simple sucrose ester micellar-mediated method. Ag nanoparticles were formed by adding AgNO₃ solution into the sucrose ester micellar solution containing sodium hydroxide at atmospheric condition after 24 h of aging time. Trace amount of dimethyl formamide (DMF) in the sucrose ester solution served as a reducing agent while NaOH acted as a catalyst. The produced Ag nanoparticles were highly stable in the sucrose ester micellar system as there was no precipitation after 6 months of storage. The as-synthesized Ag nanoparticles were characterized using transmission electron microscope (TEM), X-ray diffractometer (XRD), dynamic light scattering (DLS) and UV–vis spectroscopy (UV–vis). Formation mechanism of Ag nanoparticles in the micellar-mediated synthesis is postulated. The antibacterial properties of the Ag nanoparticles were tested against Methicillin-resistant Staphylococcus aureus (MRSA) (Gram-positive) and Aeromonas hydrophila (Gram-negative) bacteria. This work provides a simple and “green” method for the synthesis of highly stable Ag nanoparticles in aqueous solution with promising antibacterial property.     

Preparation and photocatalytic activity under visible light irradiation of mesostructured titania particles modified with phthalocyanine in the pores

Mesostructured titania particles modified with phthalocyanine (Pc) were prepared by using molecular self-assemblies of cetyltrimethylammonium bromide (CTAB) with solubilized Pc as a template. Low-angle X-ray diffraction pattern and transmission electron microscopy (TEM) image clearly show the formation of Pc/titania particles with hexagonal mesopore structures. Diffuse reflectance UV–vis spectrum and fluorescence spectrum of Pc/titania indicate that Pc molecules in the pores are in a monomeric state. In addition, Pc/titania particles have photocatalytic activity under visible light irradiation (>610 nm) due to the reduction reaction by the electrons transferred from Pc to titania.     

Synthesis of silver nanoparticles via green method using ultrasound irradiation in seaweed <Emphasis Type="Italic">Kappaphycus alvarezii</Emphasis> media

Green methods are a safer alternative to natural chemical and physical methods for the synthesis of silver nanoparticles (Ag-NPs), due to their being environmentally friendly and cost effective. This study offers a new green approach using ultrasound irradiation as the reducing agent and seaweed Kappaphycus alvarezii (K. alvarezii) as the natural bio-media. The seaweed K. alvarezii/Ag-NPs was characterised by ultraviolet–visible (UV–vis), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope with energy dispersive X-ray (FESEM-EDX), zeta potential, and Fourier transform infrared (FTIR) studies. UV–vis shows that surface plasmon resonance (SPR) arises from this solution due to the combined oscillations from the nanoparticles. The XRD study indicates the crystalline nature of the Ag-NPs. From the TEM images, the Ag-NPs are almost spherical with an average diameter of 11.78 nm. The FTIR spectrum provides adequate evidence of phytochemicals stabilising the nanoparticles. Synthesised Ag-NPs were successfully obtained using this green method.