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.     

Carbon nanotube dielectrophoresis: Theory and applications

Carbon nanotubes (CNTs) are one of the most extensively studied nanomaterials in the 21st century. Since their discovery in 1991, many studies have been reported advancing our knowledge in terms of their structure, properties, synthesis, and applications. CNTs exhibit unique electrothermal and conductive properties which, combined with their mechanical strength, have led to tremendous attention of CNTs as a nanoscale material in the past two decades. To introduce the various types of CNTs, we first provide basic information on their structure followed by some intriguing properties and a brief overview of synthesis methods. Although impressive advances have been demonstrated with CNTs, critical applications require purification, positioning, and separation to yield desired properties and functional elements. Here, we review a versatile technique to manipulate CNTs based on their dielectric properties, namely dielectrophoresis (DEP). A detailed discussion on the DEP aspects of CNTs including the theory and various technical microfluidic realizations is provided. Various advancements in DEP-based manipulations of single-walled and multiwalled CNTs are also discussed with special emphasis on applications involving separation, purification, sensing, and nanofabrication.     

Use of Mercury Film Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotubes in Electrochemical Analysis of DNA

Mercury film plated on a glassy carbon electrode modified with multiwalled carbon nanotubes (MF/MWNTs/GCE) was used for the analysis of single (ss) and double stranded (ds) DNA, as well as for Jurkat genomic DNAs methylated to different degrees. The results indicated that the DNA molecules adsorbed quite strongly on the MF/MWNTs/GCE surface allowing ex situ adsorption and produce well developed peaks (due to cytosine and adenine) by using adsorptive stripping (Ads, ex situ) square wave voltammetry (SWV). Also, SWV of Jurkat DNA mixtures methylated to different degrees revealed a linear decrease of the peak height with increasing methylation indicating an increase of structural rigidity.     

Sensitive voltammetric determination of paracetamol by poly (4-vinylpyridine)/multiwalled carbon nanotubes modified glassy carbon electrode

A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02–450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.     

纳米材料修饰电极上吸附态葡萄糖氧化酶的酶活性和电活性的比较

采用石英晶体微天平(QCM)技术, 监测了裸金(Au)电极、电沉积纳米金的金电极(Au_ed/Au)、多壁碳纳米管(MWCNTs)修饰的金电极(MWCNTs/Au)以及MWCNTs 修饰后再电沉积纳米金的金电极(Au_ed/MWCNTs/Au)上葡萄糖氧化酶(GOx)的吸附过程, 测算了吸附固定的GOx质量. 通过阳极恒电位检测吸附酶与葡萄糖发生酶反应所产生的过氧化氢, 考察了这些酶电极的安培响应, 并测算了各吸附态GOx的质量比生物活性(MSBAi).也通过循环伏安法研究酶的直接电化学, 测算了各吸附态GOx的电活性百分数(EAP_i). 实验结果表明, 酶吸附量和酶电极的安培响应满足MWCNTs/Au > Au_ed/MWCNTs/Au > Au_ed/Au > Au 的顺序; MSBA_i满足Au > Au_ed/MWCNTs/Au > Au_ed/Au > MWCNTs/Au的顺序; 而EAP_i则满足MWCNTs/Au > Au_ed/MWCNTs/Au > Au_ed /Au > Au的顺序. 根据酶和纳米材料的亲疏水作用以及酶的吸附量对实验结果进行了合理解释, 也定量验证了电极上吸附酶分子的总生物活性与酶电极的安培响应呈正相关关系, 所得数据和结论有助于纳米材料固定酶及其安培酶电极的研究.     

Extraction of methocarbamol from human plasma with a polypyrrole/multiwalled carbon nanotubes composite decorated with magnetic nanoparticles as an adsorbent followed by electrospray ionization ion mobility spectrometry detection†

In this work, a polypyrrole/multiwalled carbon nanotubes composite decorated with Fe₃O₄ nanoparticles was chemically synthesized and applied as a novel adsorbent for the extraction of methocarbamol from human plasma. Electrospray ionization ion mobility spectrometry was used for the determination of the analyte. The properties of the magnetic‐modified adsorbent were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, and X‐ray diffraction. The effects of experimental parameters on the extraction efficiency of the sorbent were investigated. Under the optimized conditions, the linear dynamic range was found to be 2–150 ng/mL with the detection limit of 0.9 ng/mL. The relative standard deviation was 5.3% for three replicate measurements of methocarbamol in plasma sample. The extraction efficiency of the sorbent for the determination of different drugs with various polarities was also compared to that of Fe₃O₄‐polypyrrole and Fe₃O₄‐multiwalled carbon nanotubes sorbents. Finally, the method was used for the determination of methocarbamol in blood samples.     

Multiwalled Carbon Nanotubes Modified with Silylated-salicylaldimine Co(II) and Pd(II) Complexes as Precatalysts in Ethylene Oligomerization

MWCNTs-Co(II) and Pd(II) were prepared through grafting silylated-salicylaldimine Pd(II) and Co(II) on multiwalled carbon nanotubes(MWCNTs) for ethylene oligomerization. The structures of the two MWCNTs-supported catalysts were characterized by means of scanning electron microscopy(SEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, thermogravimetric analyses(TGA) and nitrogen adsorption and desorption. And the influence of the supported pattern on the catalytic properties for ethylene oligomerization was investigated. The results revealed that the silylated-salicylaldimine complexes were grafted on the inner and outer surfaces of the carbon nanotubes and the pore size and BET surface area of MWCNTs decreased. Compared with the homogeneous catalysts, the two MWCNTs-supported catalysts had higher selectivity for hexene and 1-hexene in the presence of diethylaluminum chloride(DEAC) with a small molecule size due to confinement effect. MWCNTs-Pd exhi-bited higher activity and higher selectivity for C₈⁺ olefin compared to MWCNTs-Co due to electronic factors. The catalytic activities of MWCNTs-Pd and MWCNTs-Co decreased from 24.18×10⁵g·(mol Pd·h)^–1 and 20.57×10⁵g·(mol Co·h)^–1 to 19.79×10⁵g·(mol Pd·h)^–1 and 13.14×10⁵g·(mol Co·h)^–1 after the third recycle reaction, respectively.     

EMI shielding and dynamic mechanical analysis of graphene oxide-carbon nanotube-acrylonitrile butadiene styrene hybrid composites

Carbon nanomaterials such as carbon nanotubes (CNTs), graphene and their hybrid have been studied extensively. Despite having excellent properties of CNTs and graphene have not yet been fully realized in the polymer composites. During fabrication agglomeration of CNTs and restacking of graphene is a serious concern that results in the degradation of properties of nanomaterials into the final composites. To improve the dispersion of CNTs and restacking graphene, in the present research work, we focused on the hybridization of graphene oxide and CNTs. Multiwalled carbon nanotubes (MWCNTs), functionalized carbon nanotubes (FCNTs), and graphene oxide-carbon nanotubes (GCNTs) reinforced acrylonitrile butadiene styrene (ABS) composites were prepared separately by vacuum filtration followed by hot compression molding. Further, dynamic mechanical analysis (DMA), and electromagnetic interference (EMI) shielding properties of ABS composites reinforced carbon nanofillers were investigated. The dynamic mechanical properties of polymers strongly depend on the adhesion of fillers and polymer, entanglement density of polymer chains in the presence of carbon fillers. The dynamic mechanical characteristics such as storage, loss modulus, and damping factor of prepared composites were significantly affected by the incorporation of MWCNTs, FCNTs, and GCNTs. Maximum EMI shielding effectiveness of −49.6 dB was achieved for GCNT-ABS composites which were highest compared to MWCNTs-ABS composites (−38.6 dB) and FCNTs-ABS composites (−36.7 dB) in the Ku band (12.4–18 GHz). These results depict the great potential of GCNTs-ABS composites to be used in various applications of efficient heat dissipative EMI shielding materials for electronic devices.     

维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定

研究了维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定。实验结果表明,在0.2 mol/L PBS(pH6.0)缓冲溶液中,修饰电极对抗坏血酸的氧化具有明显的催化和增敏效应,其氧化峰电位由 0.5 V负移至 0.1 V(vs.AgCl/Ag)。对修饰剂碳纳米管的用量、支持电解质、富集电位和富集时间等进行了优化。采用半微分伏安法进行定量测定,其线性范围为4.0×10-6~2.0×10-3mol/L,r=-0.998 3,检出限为1.0μmol/L。对抗坏血酸在修饰电极上的电化学行为进行了探讨,其电极反应为具有吸附特性和不可逆的电极过程,测得参加反应的质子数为2,电极反应的电子转移系数为0.59。测定了维生素C药片中抗坏血酸的含量,回收率在93%~105%。     

多壁碳纳米管-Nafion复合膜修饰玻碳电极测定硝苯地平的研究

研制了以Nafion分散羧基化多壁碳纳米管的化学修饰电极(Nafion-MWCNTs/GC),研究了硝苯地平(NIF)在修饰电极上的电化学行为和测定方法。实验结果表明,在0.1mol/LNH3-NH4Cl(pH9.6)溶液中,Nafion-MWCNTs/GC,对NIF具有明显的催化和增敏作用,还原峰电位由-0.85V(裸电极)正移到-0.75V(vs.AgCl/Ag)(修饰电极),灵敏度增加约7倍。对各种实验条件进行了优化。定量测定的线性范围为2.5×10-7~4.5×10-5mol/L,r为0.9974;检出限为8.0×10-8mol/L。探讨了NIF在Nafion-MWCNTs/GC上的电极过程和反应机理,测得在本体系中参与反应的质子数和电子转移数均为4,电子转移系数α为0.41。对NIF药片进行了测定,回收率为94.5%~101.0%。