Noncovalent Assembly of Picket‐Fence Porphyrins on Nitrogen‐Doped Carbon Nanotubes for Highly Efficient Catalysis and Biosensing

A water‐insoluble picket‐fence porphyrin was first assembled on nitrogen‐doped multiwalled carbon nanotubes (CN_x MWNTs) through Fe? N coordination for highly efficient catalysis and biosensing. Scanning electron micrographs, Raman spectra, X‐ray photoelectron spectra, UV/Vis absorption spectra, and electrochemical impedance spectra were employed to characterize this novel nanocomposite. By using electrochemical methods on the porphyrin at low potential in neutral aqueous solution, the presence of CN_x MWNTs led to the direct formation of a high‐valent iron(IV)–porphyrin unit, which produced excellent catalytic activity toward the oxidation of sulfite ions. By using sulfite ions, a widely used versatile additive and preservative in the food and beverage industries, as a model, a highly sensitive amperometric biosensor was proposed. The biosensor showed a linear range of four orders of magnitude from 8.0×10^?7 to 4.9×10^?3 mol L^?1 and a detection limit of 3.5×10^?7 mol L^?1 due to the highly efficient catalysis of the nanocomposite. The designed platform and method had good analytical performance and could be successfully applied in the determination of sulfite ions in beverages. The direct noncovalent assembly of porphyrin on CN_x MWNTs provided a facile way to design novel biofunctional materials for biosensing and photovoltaic devices.     

Polyelectrolyte‐Assisted Noncovalent Functionalization of Carbon Nanotubes with Ordered Self‐Assemblies of a Water‐Soluble Porphyrin

The self‐assembly and induced supramolecular chirality of meso‐tetrakis(4‐sulfonatophenyl)porphyrin (TSPP) on both single‐wall (SWCNT) and multiwall carbon nanotubes (MWCNT) are investigated. Under mild pH conditions (pH 3), TSPP forms aggregates when CNTs are dispersed in an aqueous solution containing positively charged polyelectrolytes such as poly‐L ‐lysine (PLL) or poly(allylamine hydrochloride) (PAH). Evidence for the geometry of the porphyrin aggregates is obtained from absorption spectra, whereby the fingerprints of J‐ and H‐aggregates are clearly seen only in the presence of smaller‐diameter nanotubes. J‐aggregates are better stabilized with PLL, whereas in the presence of PAH mainly H‐aggregates prevail. Excited‐state interactions within these nanohybrids are studied by steady‐state and time‐resolved fluorescence. The porphyrin emission intensity in the nanohybrid solution is significantly quenched compared to that of TSPP alone, and this implies strong electronic interaction between CNTs and porphyrin molecules. Fluorescence lifetime imaging microscopy (FLIM) further supports that porphyrin arrays are associated with the MWCNT sidewalls wrapped in PLL. In the case of the SWCNT hybrid, spherical structures associated with longer fluorescence lifetime appeared after one week, indicative of H‐aggregates of TSPP. The latter are the result of π–π stacking of porphyrin units on neighboring nanotubes facilitated by the strong tendency of these nanotubes to interact with each other. These results highlight the importance of optimum dimensions and surface‐area architectures of CNTs in the control/stability of the porphyrin aggregates with promising properties for light harvesting.     

Functionalization of Carbon Nanotubes by an Ionic‐Liquid Polymer: Dispersion of Pt and PtRu Nanoparticles on Carbon Nanotubes and Their Electrocatalytic Oxidation of Methanol

Small beginnings : Metal nanoparticle/CNT nanohybrids are synthesized from carbon nanotubes (CNTs) functionalized with an ionic‐liquid polymer. The Pt and PtRu nanoparticles with narrow size distribution (average diameter: (1.3±0.4) nm for PtRu, (1.9±0.5) nm for Pt) are dispersed uniformly on the CNTs (see images) and show good performance in methanol electrooxidation.

     

Direct Electrochemistry of Hemoglobin on Single‐Walled Carbon Nanotubes Modified Carbon Ionic Liquid Electrode and Its Electrocatalysis

In this article we report on the fabrication of a carbon ionic liquid electrode (CILE) by using a room temperature ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) as binder. It was further modified by single‐walled carbon nanotubes (SWCNTs) to get a SWCNTs modified CILE denoted as SWCNTs/CILE. The redox protein of hemoglobin (Hb) was further immobilized on the surface of SWCNTs/CILE with the help of Nafion film. UV‐vis and FT‐IR spectra indicated that the immobilized Hb retained its native conformation in the composite film. The direct electrochemistry of Hb on the SWCNTs/CILE was carefully studied in pH 7.0 phosphate buffer solution (PBS). Cyclic voltammetric results indicated that a pair of well‐defined and quasireversible voltammetric peaks of Hb heme Fe(III)/Fe(II) was obtained with the formal potential (E°') at ?0.306 V (vs. SCE). The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n) and the apparent heterogeneous electron transfer rate constant (k_s) were calculated as 0.34, 0.989 and 0.538 s^?1, respectively. The fabricated Hb modified electrode showed good electrocatalytic ability to the reduction of trichloroacetic acid (TCA) in the concentration range from 20.0 to 150.0 mmol/L with the detection limit of 10.0 mmol/L (3σ).     

Direct Electrochemistry of Hemoglobin on Vertically Aligned Carbon Hybrid TiO2 Nanotubes and Its Highly Sensitive Biosensor Performance

The present work is focused on developing a novel biomaterial platform to achieve enhanced direct electron transfer (DET) of hemoprotein and higher biosensor performance on vertically aligned carbon hybrid TiO₂ nanotubes (C‐TiO₂ NTs). Using a simple surfactant‐assisted method, controllable hybridization of TiO₂ NTs with conductive amorphous carbon species is realized. The obtained C‐TiO₂ NTs is ingeniously chosen to serve as an ideal "vessel" for protein immobilization and biosensor applications. Results show that the appropriate hybridization of C into TiO₂ NTs leads to a much better conductivity of TiO₂ NTs without destroying their preponderant tubular structures or damaging their excellent biocompatibility and hydrophilicity. When used in loading proteins, the C‐TiO₂ NTs can be used as a super vessel for rapid and substantive immobilization of hemoglobin (Hb), with a large surface electroactive Hb coverage ( Γ ??) of 3.3×10^?9 mol·cm^?2. Enhanced DET of Hb is commendably observed on the constructed Hb/C‐TiO₂ NTs biosensor with a couple of well‐defined redox peaks in a fast electron transfer process. The biosensor further exhibits fast response, high sensitivity and stability for the amperometric biosensing of H₂O₂ with the detection limit as low as 3.1×10^?8 mol/L.     

Direct Electrochemistry and Electrocatalytic Properties of Hemoglobin Immobilized on Carbon Nanotubes Ionic Liquid Electrode

Hemoglobin (Hb) was directly immobilized on a multiwalled carbon nanotubes ionic liquid electrode by immersing this electrode in a solution consisting of Hb and 1‐octyl‐pyridinium chloride as an ionic liquid. The immobilized Hb displayed a pair of well‐defined cyclic voltammetric peaks with a formal potential of ?0.187 V in acetate buffer solution, pH 5.0. This modified electrode exhibits fast response, a long linearity range, a low detection limit, high stability and excellent sensitivity through hydrogen peroxide detection with a detection limit (3σ) of 3.18 µM. The electrode was also used for electrocatalysis and voltammetric determination of oxygen and trichloroacetic acid.     

Microwave‐Assisted Functionalization of Carbon Nanostructures in Ionic Liquids

The effect of microwave (MW) irradiation and ionic liquids (IL) on the cycloaddition of azomethine ylides to [60]fullerene has been investigated by screening the reaction protocol with regard to the IL medium composition, the applied MW power, and the simultaneous cooling of the system. [60]Fullerene conversion up to 98 % is achieved in 2–10 min, by using a 1:3 mixture of the IL 1‐methyl‐3‐n‐octyl imidazolium tetrafluoroborate ([omim]BF₄) and o‐dichlorobenzene, and an applied power as low as 12 W. The mono‐ versus poly‐addition selectivity to [60]fullerene can be tuned as a function of fullerene concentration. The reaction scope includes aliphatic, aromatic, and fluorous‐tagged (FT) derivatives. MW irradiation of IL‐structured bucky gels is instrumental for the functionalization of single‐walled carbon nanotubes (SWNTs), yielding group coverages of up to one functional group per 60 carbon atoms of the SWNT network. An improved performance is obtained in low viscosity bucky gels, in the order [bmim]BF₄> [omim]BF₄> [hvim]TF₂N (bmim=1‐methyl‐3‐n‐butyl imidazolium; hvim=1‐vinyl‐3‐n‐hexadecyl imidazolium). With this protocol, the introduction of fluorous‐tagged pyrrolidine moieties onto the SWNT surface (1/108 functional coverage) yields novel FT‐CNS (carbon nanostructures) with high affinity for fluorinated phases.     

Voltammetric Determination of Uric Acid with a Glassy Carbon Electrode Coated by Paste of Multiwalled Carbon Nanotubes and Ionic Liquid

The voltammetric behavior of uric acid (UA) has been studied at a multiwalled carbon nanotube‐ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF₆) paste coated glassy carbon electrode (MWNTs‐BMIMPF₆/GC). It is found that UA can effectively accumulate at this electrode and cause a sensitive anodic peak at about 0.49 V (vs. SCE) in pH 4.0 phosphate buffer solutions. Experimental parameters influencing the response of the electrode, such as solution pH and accumulation time, are optimized for uric acid determination. Under the optimum conditions, the anodic peak current is linear to UA concentration in the range of 1.0×10^?8 M to 1.0×10^?6 M and 2.0×10^?6 M to 2.0×10^?5 M. The detection limit is 5.0×10^?9 M for 180 s accumulation on open circuit. The electrode can be regenerated by successively cycling in a blank solution for about 3 min and exhibits good reproducibility. A 1.0×10^?6 M UA solution is measured for eight times using the same electrode regenerated after every determination, and the relative standard deviation (RSD) of the peak current is 3.2%. As for different electrodes fabricated by the same way the RSD (i.e., the electrode to electrode deviation) is 4.2%(n=9). This method has been applied to the determination of UA in human urine samples, and the recoveries are 99%–100.6%. In addition, comparison is made between MWNTs‐BMIMPF₆/GC and MWNTs/GC. Results show that the MWNTs‐BMIMPF₆/GC exhibits higher sensitivity, selectivity and ratio of peak current to background current.     

Direct Electrochemistry of Hemoglobin in Layer‐by‐Layer Films Assembled with DNA and Room Temperature Ionic Liquid

Based on electrostatic interaction and electrodeposition, poly‐anionic deoxyribonucleic acid (DNA), room temperature ionic liquid 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate (BMIMBF₄), hemoglobin (Hb) and Poly(diallyldimethylammonium chloride) (PDDA) were successfully assembled into Hb/IL/DNA/PDDA layer‐by‐layer complex films on the surface of ITO electrode. FTIR spectroscopy, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to characterize the composite film. The obtained results demonstrated that the Hb molecule in the film kept its native structure and showed its good electrochemical behavior. A pair of well‐defined redox peaks of Hb with the formal potentials (E°′) of ?0.180 V (vs. SCE) was appeared in phosphate buffer solution (PBS, pH 7.0). The Hb/IL/DNA/PDDA/ITO modified electrode also showed an excellent electrocatalytic behavior to the reduction of hydrogen peroxide (H₂O₂). Therefore, the IL/DNA/PDDA complex film as a novel matrix open up a possibility for further study on the direct electrochemistry of other proteins and the fabrication of the third‐generation electrochemical biosensors.     

Optical and Bioelectrochemical Characterization of Water‐Miscible Ionic Liquids Based Composites of Multiwalled Carbon Nanotubes

Acidic treated multiwalled carbon nanotubes (AMWNTs) were ground with water‐miscible room temperature ionic liquids, 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄), and resulted in AMWNTs‐[bmim]BF₄ composite. Its electrical‐ionic conductivity and optical properties were compared with the other two types of carbon materials‐[bmim]BF₄ composites: pyrolytic graphite powder (PGP), pristine multiwalled carbon nanotubes (PMWNTs), through the ac impedance technology and Raman spectroscopy. The impedance data show that AMWNTs‐[bmim]BF₄ composite exhibits the highest conductivity. Raman spectra study exhibits that the [bmim]BF₄ can form gel with PMWNTs and AMWNTs but only form a viscous liquid with PGP. AMWNTs‐[bmim]BF₄ gel modified GC electrode was applied in direct electrochemistry of heme proteins (Hb and HRP) and it catalysis to the reduction of H₂O₂ was investigated.     

Hybrid Platforms of Silicon Nanowires and Carbon Nanotubes in an Ionic Liquid Bucky Gel

Silicon nanowires (NWs) are appealing building blocks for low-cost novel concept devices with improved performances. In this research paper, we realized a hybrid platform combining an array of vertically oriented Si NWs with different types of bucky gels, obtained from carbon nanotubes (CNT) dispersed into an ionic liquid (IL) matrix. Three types of CNT bucky gels were obtained from imidazolium-based ionic liquids (BMIM-I, BIMI-BF₄, and BMIM-Tf₂N) and semiconductive CNTs, whose structural and optical responses to the hybrid platforms were analyzed and compared. We investigated the electrical response of the IL-CNT/NW hybrid junctions in dark and under illumination for each platform and its correlation to the ionic liquid characteristics and charge mobility. The reported results confirm the attractiveness of such IL-CNT/NW hybrid platforms as novel light-responsive materials for photovoltaic applications. In particular, our best performing cell reported a short-circuit current density of 5.6 mA/cm² and an open-circuit voltage of 0.53 V.     

新型多壁碳纳米管/壳聚糖/离子液体修饰电极直接测量对苯二酚的研究

本文构建了一种新型多壁碳纳米管/壳聚糖/离子液体修饰电极.研究了支持电解质、酸度和扫描速度等因素对对苯二酚伏安响应的影响,获得了较优的实验条件.在0.1 mol/L pH=6.8磷酸盐缓冲溶液中测定对苯二酚,其氧化峰电流与对苯二酚浓度在8.0×10~(-7)～1.0×10~(-4) mol/L范围内呈良好的线性关系,检出限为7.9×10~(-8) mol/L.该电极对对苯二酚有较高的选择性,可直接测量对苯二酚,结果满意.     

Carbon Nanotubes/Heteroatom‐Doped Carbon Core–Sheath Nanostructures as Highly Active,Metal‐Free Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells

A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom‐doped carbon (CNT/HDC) core–sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom‐containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom‐containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom‐doped nanocarbon catalysts in terms of half‐wave potential and kinetic current density. The four‐electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long‐term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites.     

百草枯在碳纳米管与离子液体复合修饰电极上的电化学行为及测定

制备了碳纳米管(MWCNTs)和疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合修饰电极(MWCNTs-BMIMPF6/GCE),并采用红外光谱(IR)分别对MWCNTs、BMIMPF6及MWCNTs-BMIMPF6进行了表征。运用循环伏安法研究了百草枯(PQ)在该修饰电极上的电化学行为。结果表明,在pH7.0的PBS缓冲溶液中,PQ在MWCNTs-BMIMPF6/GCE上出现2对明显的氧化还原峰,在20~200 mV/s扫描速率范围内,其氧化还原峰电流均与扫描速率平方根(v1/2)呈线性关系,表明该电极过程受扩散控制。计算了电极过程的部分动力学参数:电极有效面积A=0.156 4 cm2,百草枯在pH7.0的PBS缓冲液中的扩散系数D=7.0×10-5cm2/s。优化了方波溶出伏安法(SWSV)的实验参数,发现峰电流Ipa1与PQ浓度在7.729×10-7~9.660×10-5mol/L范围内呈线性关系,检出限为1.576×10-7mol/L。采用该方法对实际水样进行检测,增敏回收率为93%~104%。     

Direct Electrochemistry of Hemoglobin and Its Electrocatalysis Based on Hyaluronic Acid and Room Temperature Ionic Liquid

A biocomposite material of hyaluronic acid (HA) and room temperature ionic liquid, 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate (BMIMBF₄) was fabricated and characterized by voltammetry and electrochemical impedance spectroscopy. Hemoglobin (Hb), as a model protein, was immobilized in this biocomposite on glassy carbon electrode to investigate its direct electrochemistry. A pair of well‐defined, quasireversible cyclic voltammetric peaks appeared with the formal potentials (E°′) at ?0.360 V (vs. SCE). The Hb modified electrode exhibited an excellent electrocatalytic activity to the reduction of H₂O₂ with a wide linear range, good selectivity, sensitivity and reproducibility, which had potential application to fabrication the third‐generation biosensor.     

Gold Nanoparticles Grown on Ionic Liquid‐Functionalized Single‐Walled Carbon Nanotubes: New Materials for Photothermal Therapy

Gold nanoparticles were grown on single‐walled carbon nanotubes (SWNTs) coated with a thiol‐functionalized ionic liquid resulting in the formation of core‐shell structures referred to as SWNT‐IL‐Au nanohybrid materials. The nanohybrid materials were characterized by high‐resolution transmission electron microscopy (HR‐TEM), Raman‐, and UV/Vis absorption spectroscopy. The nanohybrid materials were found to enter lysosomes in HeLa cells and show negligible cytotoxicity. Interestingly, they have an enhanced NIR absorption that is effectively transferred into heat to cause localized hyperthermia, resulting in rapid cell death; overall, the material appears to have excellent properties for photothermal therapeutic applications.     

High Performance Fe Porphyrin/Ionic Liquid Co‐catalyst for Electrochemical CO2 Reduction

The efficient and selective catalytic reduction of CO₂ is a highly promising process for both of the storage of renewable energy as well as the production of valuable chemical feedstocks. In this work, we show that the addition of an ionic liquid, 1‐butyl‐3‐methylimidazolium tetrafluoroborate, in an aprotic electrolyte containing a proton source and FeTPP, promotes the in situ formation of the [Fe⁰TPP]^2? homogeneous catalyst at a less negative potential, resulting in lower overpotentials for the CO₂ reduction (670 mV) and increased kinetics of electron transfer. This co‐catalysis exhibits high Faradaic efficiency for CO production (93 %) and turnover number (2 740 000 after 4 hour electrolysis), with a four‐fold increase in turnover frequency (TOF) when compared with the standard system without the ionic liquid.     

Direct Electrochemistry and Electrocatalysis of Hemoglobin Based on Nafion‐Room Temperature Ionic Liquids‐Multiwalled Carbon Nanotubes Composite Film

A robust and effective composite film combined the benefits of Nafion, room temperature ionic liquid (RTIL) and multi‐wall carbon nanotubes (MWNTs) was prepared. Hemoglobin (Hb) was successfully immobilized on glassy carbon electrode surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Hb were investigated in detail. A pair of well‐defined and quasi‐reversible redox peaks of Hb was obtained in 0.10 mol·L^?1 pH 7.0 phosphate buffer solution (PBS), indicating that the Nafion‐RTIL‐MWNTs film showed an obvious promotion for the direct electron transfer between Hb and the underlying electrode. The immobilized Hb exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis current was linear to H₂O₂ concentration in the range of 2.0×10^?6 to 2.5×10^?4 mol·L^?1, with a detection limit of 8.0×10^?7 mol·L^?1 (S/N=3). The apparent Michaelis‐Menten constant (K_m^app) was calculated to be 0.34 mmol·L^?1. Moreover, the modified electrode displayed a good stability and reproducibility. Based on the composite film, a third‐generation reagentless biosensor could be constructed for the determination of H₂O₂.     

Helical Carbon Nanotubes: Intrinsic Peroxidase Catalytic Activity and Its Application for Biocatalysis and Biosensing

A combined hydrothermal/hydrogen reduction method has been developed for the mass production of helical carbon nanotubes (HCNTs) by the pyrolysis of acetylene at 475 °C in the presence of Fe₃O₄ nanoparticles. The synthesized HCNTs have been characterized by high‐resolution transmission electron microscopy, scanning electron microscopy, X‐ray diffraction analysis, vibrating sample magnetometry, and contact‐angle measurements. The as‐prepared helical‐structured carbon nanotubes have a large specific surface area and high peroxidase‐like activity. Catalysis was found to follow Michaelis–Menten kinetics and the HCNTs showed strong affinity for both H₂O₂ and 3,3′,5,5′,‐tetramethylbenzidine (TMB). Based on the high activity, the HCNTs were firstly used to develop a biocatalyst and amperometric sensor. At pH 7.0, the constructed amperometric sensor showed a linear range for the detection of H₂O₂ from 0.5 to 115 μM with a correlation coefficient of 0.999 without the need for an electron‐transfer mediator. Because of their low cost and high stability, these novel metallic HCNTs represent a promising candidate as mimetic enzymes and may find a wide range of new applications, such as in biocatalysis, immunoassay, and environmental monitoring.