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ABSTRACT: A novel chiral electrochemical sensor based on multi-walled carbon nanotubes (MWCNTs)/ionic liquids (ILs) nanocomposite was developed and applied to the enantiomeric recognition of propranolol (PRO). Mechanisms for chiral sensing were discussed in terms of the formation of an efficient chiral nanospace originating from the weak interactions between quasi-chiral MWCNTs and versatile ILs. This work provided new evidence that the electro-oxidation of PRO should result from its hydroxyl group. Herein the ratio of oxidation peak currents, instead of the commonest shift of peak potential, was used to sense the enantiomeric fraction (EF) of (R)-PRO with a linear correlation coefficient of 0.9936. This simple and reliable sensor was successfully applied in an accurate determination of the enantiomeric purity of reagent, as well as the evaluation of waste water treatment efficiency.
Talanta 02/2013; 105C:250-254. · 3.79 Impact Factor
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ABSTRACT: A fast, simple and quantitative approach was established for monitoring autophagy in HeLa cells by directly detecting the conversion of green fluorescent protein (GFP) labelled autophagy markers, GFP-LC3-I to GFP-LC3-II, in crude cellular extract using capillary electrophoresis (CE) with laser-induced fluorescence (LIF). Compared with the traditional methods, this proposed method is simpler and more reliable. Moreover, high sensitivity, with a limit of detection (LOD) of 0.48 ppt (bovine serum albumin as standard protein), was obtained by an in-capillary derivatization method coupled with a field-enhanced sample injection (FESI) technique, this may allow the success of this technique in the detection of endogenous markers of autophagy in cells.
The Analyst 10/2012; · 4.23 Impact Factor
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ABSTRACT: Successful simultaneous enantioseparation and sensitive determination of three β-blockers (PIN, OX and PRO), have been achieved by capillary electrophoresis using an achiral ionic liquid, [GTMA]Cl, as a modifier to cooperate with dual CDs containing DM-β-CD and TM-β-CD. The influence of aIL was investigated in details, including various aILs, the concentration of aIL and molar ratio of aIL to CD. The ratio of DM-β-CD to TM-β-CD in dual CDs was also discussed. DM-β-CD and TM-β-CD favor the enantioseparations of PIN/OX and PRO, respectively. Meanwhile, the presence of [GTMA]Cl was found to play a key role in enantioseparations, and it widened the scope of application of DM-β-CD and TM-β-CD. Furthermore, FESI as an effective on-line sample enrichment technique was developed to improve the detection sensitivity. Under the optimum conditions, the detection limits of the three pairs of enantiomers range from 0.10 to 0.65 nM, which are much lower than those in the conventional methods. Eventually, the proposed method was successfully applied to the analysis of spiked urine sample with good recoveries.
Talanta 01/2012; 89:149-54. · 3.79 Impact Factor
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ABSTRACT: Gold nanoparticles (GNPs) embedded in a Bucky gel consisting of carbon nanotubes (CNTs) and ionic liquid (IL) show an excellent electrocatalytic activity to glucose oxidation owing to some synergistic effects among GNPs, CNTs and IL. Each component in such a composite has its specific function while there are complicate interactions among them. Based on this strategy, the use of composite as the modified coating allows the fabrication of a novel nonenzymatic glucose electrochemical sensor, which shows a substantial enhancement in detection sensitivity. This paper centers on the influence of several ILs with various anions and cations as well as alkyl branch lengths on the function of sensor. Based on our results, the performance of the sensor is strongly influenced by ILs. A few conclusions can be drawn. Firstly, an imidazolium cation facilitates both the stability of sensor and the efficiencies of GNPs and CNTs, while the alkyl branch lengths have few effects on the performance of sensor. Secondly, a hydrophilic anion is beneficial to the formation of environment where the direct oxidation of glucose takes place. Thirdly, other anions such as BF(4)(-) and PF(6)(-) do not matter for imidazolium-based IL. Fourthly, non-imidazolium-based IL militates against the dispersion of CNTs and GNPs in Bucky gel, reducing the detection sensitivity to glucose. Of the ILs studied, the best performance for glucose determination is obtained with an IL mainly benefitted by the combination of imidazole and sulfonate.
Talanta 09/2011; 85(3):1592-7. · 3.79 Impact Factor
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ABSTRACT: Two kinds of online preconcentration techniques including large-volume sample stacking-sweeping and selective-exhaustive injection-sweeping (SEI-S) were employed in CE to develop a rapid, simple and sensitive method for determination of melamine (MM) and its derivatives such as ammeline (AMN), ammelide (AMD) and cyanuric acid (CA) in liquid milk products. Though the sensitivity of large-volume sample stacking-sweeping is not particularly high, it can be used to detect all the four compounds simultaneously. However, it is very difficult to improve the sensitivity of these four compounds by using single SEI-S method directly, owing to their completely different extents of protonation or deprotonation. Grouping can solve this problem perfectly. After the four compounds are divided into two groups (MM/AMN and AMD/CA), cation-SEI-S or anion-SEI-S can be applied for their online stacking. In cation-SEI-S, the detection limits for MM and AMN were both 0.01 ng/mL based on the signal-to-noise ratio of 3. In anion-SEI-S, the detection limits were 0.05 and 0.02 ng/mL for CA and AMD, respectively. Results of this study show a great potential for the SEI-S method to be a useful tool for the rapid and sensitive determination of MM and its derivatives in liquid milk products.
Electrophoresis 12/2010; 31(23-24):3913-20. · 3.30 Impact Factor
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ABSTRACT: The electrochemical behaviors of graphene sheets attached to a self-assembled monolayer (SAM) on a gold electrode have been investigated. A gold electrode is sequentially modified by the SAM of n-octadecyl mercaptan (C18H37SH), followed by controllable adsorption of graphene sheets to obtain a graphene/SAM modified Au electrode. The graphene/SAM modified Au electrode is characterized electrochemically by using ruthenium hexaammine (Ru(NH3)63+) as a redox probe, and by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The experimental results indicate that the heterogeneous electron transfer (ET) blocked by the SAM can be restored by graphene sheets and that the graphene/SAM modified Au electrode has a smaller interfacial capacitance, as compared with that of a bare Au electrode. The apparent ET rate constant of Ru(NH3)63+, kapp, on the graphene/SAM modified Au electrode has been also evaluated quantitatively by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM), and is equal to 4.2 × 10−2 and 6.8 × 10−2 cm s−1, respectively. In addition, the electrochemical responses of free bases of DNA (guanine (G), adenine (A), thymine (T), and cytosine (C)) on the graphene/SAM modified Au electrode show that the graphene/SAM modified Au electrode possesses electrochemical properties similar to those of a graphene modified electrode rather than an Au electrode.
08/2010;
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ABSTRACT: A reliable and highly sensitive electrochemical sensor was first developed for analysis of non-electroactive melamine (Mel) based on its conversion to an electroactive complex by coordination of copper salt to Mel. This provides a simple and easy approach to the detection of Mel in milk products.
Chemical Communications 04/2010; 46(13):2259-61. · 6.17 Impact Factor
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ABSTRACT: We demonstrate a novel electrochemical sensor for highly sensitive detection of natural double-stranded deoxyribonucleic acid (dsDNA) based on thionin (Th) attached to Mo(6)S(9-X)I(X) nanowires (MoSI NWs) self-assembled on a gold electrode. The sensing detection is based on a decrease of the voltammetric response of the immobilized Th due to the binding of Th with dsDNA through intercalation. MoSI NWs act as molecular connectors to provide an amplification and conductive sensing platform for the electrochemical detection of dsDNA, because many sulfur atoms at the ends and sides of MoSI NWs permit covalent bonds to be formed with gold as well as MoSI NWs with negative charges allow electrostatic binding with Th. A determination limit of 0.62 ng/mL for dsDNA with this novel sensor is achieved, which is three orders of magnitude lower than that in the absence of MoSI NWs. The operation is simple and label-free.
Biosensors & bioelectronics 02/2010; 26(5):1866-70. · 5.43 Impact Factor
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ABSTRACT: In this paper, a novel nonenzymatic glucose voltammetric sensor based on a kind of nanocomposite of gold nanoparticles (GNPs) embedded in multi-walled carbon nanotubes (MWCNTs)/ionic liquid (IL) gel was reported. The surface morphology of this nanocomposite was characterized using X-ray photoelectron spectrometer (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. It can be found that most of GNPs lie close to the ektexine of MWCNTs and the others have obviously inserted the inner of MWCNTs through the defects or ends of MWCNTs, due to the attraction between GNPs and MWCNTs as well as the repulsion between GNPs and IL. Voltammetry was used to evaluate the electrocatalytic activities of the nanocomposite biosensor toward nonenzymatic glucose oxidation in alkaline media. The GNPs embedded in MWCNTs/IL gel have strong and sensitive voltammetric responses to glucose, owing to a possible synergistic effect among GNPs, MWCNTs and IL. Under the optimal condition, the linear range for the detection of the glucose is 5.0-120 microM with the correlation coefficient of 0.998, based on the oxidation peak observed during cathodic direction of the potential sweep. The kinetics and mechanism of glucose electro-oxidation were intensively investigated in this system. This kind of nanocomposite biosensor is also highly resistant toward poisoning by chloride ions and capable of sensing glucose oxidation in the presence of 20 microM uric acid and 70 microM ascorbic acid. This work provides a simple and easy approach to the detection of glucose in body fluid with high sensitivity and excellent selectivity.
Talanta 11/2009; 79(5):1446-53. · 3.79 Impact Factor
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ABSTRACT: A new oxyfluorinated titanium phosphate Na3[Ti2P2O10F]·xH2O (TiP)-modified electrode was prepared by casting the dispersion of TiP on a glassy carbon electrode. The electrochemical behavior of the modified electrode was investigated by cyclic voltammetry, and a couple of reduction/reoxidation peaks corresponding to the reduction of Ti (IV) were found at −1.29 V versus SCE in the 0.1 M NaCl solution, which was supported by UV−vis and FTIR characterization. The modified electrode showed electrocatalysis toward the reduction of H2O2. Furthermore, the addition of phosphate in the supporting electrolyte resulted in an easier reduction of Ti(IV) and direct electron transfer of cytochrome c at the modified electrode due to changes in the surface structure of the TiP films. The results indicate that TiP can act as not only a good electron-transfer mediator but also an electron-transfer promoter.
03/2009;
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ABSTRACT: C121 and C121/didodecyldimethylammonium bromide (DDAB) film modified electrodes have been constructed and their electrochemistry has been studied. In the acetonitrile solution containing 0.1M tetrabutylammonium perchlorate, the C121 films show three couples of relatively stable redox peaks corresponding to three two-electron transfer processes involving reduction of two fullerene units in the dimers. In an aqueous solution containing 0.1M tetrabutylammonium bromide, the C121 films display an irreversible reduction peak, whereas the C121/DDAB films display two couples of quasi-reversible redox peaks with the splitting first peak, and the C121/DDAB films have good reversibility and stability in the aqueous solution due to existence of DDAB. All of these experimental results indicate that voltammetric behaviors of the C121 films are different from those of C60 films due to different structures though C121 is carbon-bridged C60 dimer, and the common characteristics are that their electrochemical behaviors are dependent on the nature of solvent and cation of supporting electrolyte. Furthermore, electrocatalysis of H2O2 at the C121/DDAB films was explored in the aqueous solution, which indicates that C121 is a good electron-transfer mediator.
Journal of Electroanalytical Chemistry - J ELECTROANAL CHEM. 01/2009; 629(1):152-157.
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ABSTRACT: The heterogeneous electron transfer (ET) reactions between dimethylferrocenium (DiMFc+) or ferrocenium (Fc+) produced in situ in o-nitrophenyl octyl ether (NPOE) and hexacyanoferrite [Fe(CN)64−] in aqueous phase have been investigated by scanning electrochemical microscopy (SECM). The potential difference across the water/NPOE (W/NPOE) interface was controlled externally to maintain a certain driving force for the ET reactions. The standard kinetic rate constants (k120) for the above bimolecular ET reactions were measured to be 0.075 and 0.050 cm s−1 M−1 when DiMFc and Fc were employed as the respective organic reactants. The transfer coefficients (α) were calculated to be 1.09 and 1.62, respectively. Those abnormal values of α were analyzed and ascribed to the Frumkin effect (or diffuse layer effect) at both sides of the interfaces. Some of the previous reports are summarized and also analyzed based on the Frumkin effect. The possible effect of ion transfer on the ET process is discussed in detail.
10/2008;
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Li Shen,
Zhong Chen,
Yihan Li,
Shali He,
Shubao Xie,
Xiaodong Xu,
Zhongwei Liang,
Xin Meng,
Qing Li, Zhiwei Zhu,
Meixian Li,
X Chris Le,
Yuanhua Shao
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ABSTRACT: An electrochemical DNAzyme sensor for sensitive and selective detection of lead ion (Pb(2+)) has been developed, taking advantage of catalytic reactions of a DNAzyme upon its binding to Pb(2+) and the use of DNA-Au bio-bar codes to achieve signal enhancement. A specific DNAzyme for Pb(2+) is immobilized onto an Au electrode surface via a thiol-Au interaction. The DNAzyme hybridizes to a specially designed complementary substrate strand that has an overhang, which in turn hybridizes to the DNA-Au bio-bar code (short oligonucleotides attached to 13 nm gold nanoparticles). A redox mediator, Ru(NH3)6(3+), which can bind to the anionic phosphate of DNA through electrostatic interactions, serves as the electrochemical signal transducer. Upon binding of Pb(2+) to the DNAzyme, the DNAzyme catalyzes the hydrolytic cleavage of the substrate, resulting in the removal of the substrate strand along with the DNA bio-bar code and the bound Ru(NH3)6(3+) from the Au electrode surface. The release of Ru(NH3)6(3+) results in lower electrochemical signal of Ru(NH3)6(3+) confined on the electrode surface. Differential pulse voltammetry (DPV) signals of Ru(NH3)6(3+) provides quantitative measures of the concentrations of Pb(2+), with a linear calibration ranging from 5 nM to 0.1 microM. Because each nanoparticle carries a large number of DNA strands that bind to the signal transducer molecule Ru(NH3)6(3+), the use of DNA-Au bio-bar codes enhances the detection sensitivity by five times, enabling the detection of Pb(2+) at a very low level (1 nM). The DPV signal response of the DNAzyme sensor is negligible for other divalent metal ions, indicating that the sensor is highly selective for Pb(2+). Although this DNAzyme sensor is demonstrated for the detection of Pb(2+), it has the potential to serve as a general platform for design sensors for other small molecules and heavy metal ions.
Analytical Chemistry 08/2008; 80(16):6323-8. · 5.86 Impact Factor
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ABSTRACT: The chiral resolution of three beta-blockers including propranolol, pindolol and oxprenolol, was studied by affinity electrokinetic chromatography. The effect of various chiral selectors and some key parameters including buffer pH, buffer concentration, capillary temperature and applied voltage were carefully studied, respectively. At optimum condition, based on the signal-to-noise ratio of 3, the detection limits for the simple resolution and chiral resolution were found to be 1.0x10(-5) and 4.0 x 10(-5)M, respectively. In addition, the interactions of these beta-blockers with bovine serum albumin (BSA) were studied and the binding constant (K(a)) between BSA and each of beta-blockers were calculated. Based on linear correlation coefficient, it can be concluded that the binding ratio of pindolol (oxprenolol) combining with BSA is 1:1, and that the binding number of propranolol interacting with BSA deviates one.
Talanta 04/2008; 75(1):222-6. · 3.79 Impact Factor
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ABSTRACT: Submicro- and nanometer-sized glass double-barrel pipets have been fabricated by a laser puller with new pulling programs and have been used to support submicro- and nanometer dual liquid/liquid interfaces. The smallest pipet that can be made by this approach is approximately 20 nm in radius. These pipets have been characterized by cyclic voltammetry and scanning electron microscopy. Generation/collection mode of charge-transfer reaction is demonstrated at the submicro- and nanometer dual-liquid/liquid interfaces. The dependence of collection efficiency upon geometric parameters of the pipets has been discussed. Among the micro-, submicro-, and nanopipets, we have found that the submicro-double-barrel pipets have higher collection efficiencies than that of others and are also very close to the values predicted by the theory. Therefore, in terms of G/C mode applications, the optimal size of double-barrel pipets should be in submicrometer scale. As one of the examples of special application, we have also demonstrated that in the case of no supporting electrolyte, only the nanometer double-barrel pipets can provide reasonably good G/C results.
Analytical Chemistry 11/2006; 78(19):7034-9. · 5.86 Impact Factor
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ABSTRACT: Electrochemical properties of a new nanomaterial ferrocene (Fc) peapod, Fc-filled single-walled carbon nanotubes (Fc@SWNTs), have been investigated in an aqueous solution in detail by preparing different kinds of Fc@SWNTs-modified glassy carbon electrodes (Fc@SWNTs/GCE and Fc@SWNTs-gel/GCE). One pair of surface-confined redox waves corresponding to the couple of Fc/Fc+ is obtained, which indicates that Fc encapsulated inside SWNTs retains electrochemical activity. The Fc@SWNTs-gel/GCE shows better electrochemical reversibility due to the existence of room temperature ionic liquid (RTIL). Furthermore, it shows excellent mediation of H2O2 based on Fc/Fc+ used as electron-transfer mediators for oxidation of H2O2 to O2 and reduction to H2O, suggesting specific properties of Fc@SWNTs due to a combination of Fc and SWNTs. The interaction between Fc and SWNTs is also characterized by UV-vis-NIR spectrometry and Raman spectrometry. A Fc@SWNTs-based sensor for H2O2 with a determination limit of 5 microM is fabricated, and it shows good stability and reproducibility. This work not only demonstrates that the Fc peapod is a new kind of functional nanomaterial but also appears promising in constructing novel chemical and biosensors and fuel cells.
Analytical Chemistry 10/2006; 78(17):6050-7. · 5.86 Impact Factor
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ABSTRACT: The separation and determination of four parabens (methyl, ethyl, propyl, and butyl p-hydroxybenzoate) which are commonly used as preservatives in cosmetic products, by micellar electrokinetic capillary chromatography (MEKC) with and without large-volume sample stacking (LVSS) technique were compared. As an effective on-line concentration technique, LVSS was successfully combined with MEKC to determine neutral parabens in an acidic media. The effects of some typical parameters such as sample volume, buffer pH, temperature, and concentration of surfactant were examined. The detection limits for this LVSS-MEKC method were found to be 3.0 x 10(-7)M for each of the parabens based on the signal-to-noise ratio of 3, which were around 300 times lower than normal MEKC technique. The curves of peak response versus concentration were linear from 1.0 x 10(-6) to 5.0 x 10(-5)M with regression coefficients of 0.9987, 0.9960, 0.9925 and 0.9864, respectively. A simple and easy-manipulative sample preparation method was developed and validated by analyzing commercially available cosmetic samples. It was found that with current sample preparation process and instrumentation system, 0.5 g of sample is enough for the analysis of parabens preservatives in cosmetic product with satisfactory results.
Talanta 04/2006; 69(1):166-71. · 3.79 Impact Factor
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ABSTRACT: A novel electrochemical biosensor for the detection of uric acid and adenine was prepared based on a gel containing multi-walled carbon nanotubes and room-temperature ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate. The electrochemistry of uric acid and adenine was studied in this gel modified electrode. There was a significant two-way electrocatalytic activity upon both oxidation and reduction of uric acid. Similar to a bare glassy carbon electrode, uric acid undergoes a 2e,2H+ oxidation in phosphate buffer in the modified electrode. A diimine, the oxidation product of uric acid, was found to be an unstable intermediate, which was converted by a follow-up hydration reaction to an imine alcohol, with the reaction rate constant of 8.5 +/- 0.3 M(-1).s(-1) according to Nicholson's theory. Under optimum conditions, linear calibration graphs were obtained over the concentration range of 1.0 x 10(-7) M approximately 1.0 x 10(-5) M (uric acid) and 1.0 x 10(-5) M approximately 6.0 x 10(-4) M (adenine). Based on the signal-to-noise ratio of 3, the detection limits of the current technique was found to be as low as 9.0 x 10(-8) M (uric acid) and 2.0 x 10(-6) M (adenine), respectively. This novel biosensor was successfully applied for the assay of uric acid in human urine. Because of its good stability and long-term durability, such a gel modified electrode can provide a simple and easy approach for sensitive detection of uric acid and adenine.
Frontiers in Bioscience 02/2006; 11:2976-82. · 3.52 Impact Factor
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ABSTRACT: The electrochemistry of dopamine (DA) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and room-temperature ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate (OMIMPF(6)). The thickness of gel on the surface of the electrode has to be controlled carefully because the charging currents increase with the modified layer being thicker. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated since the peak potential of AA is shifted to more negative values, while that of UA is shifted to more positive values due to the modified electrode. At pH 7.08 the three peaks are separated ca. 0.20 and 0.15V, respectively; hence DA can be determined in the presence of UA and more than 100 times excess of AA. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 1.0x10(-6) to 1.0x10(-4)M. The detection limit of the current technique was found to be 1.0x10(-7)M based on the signal-to-noise ratio of 3. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid.
Talanta 04/2005; 66(1):51-7. · 3.79 Impact Factor
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ABSTRACT: A novel glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) is reported. The gel is formed by grinding of MWNTs and BMIPF6. Such gel is then coated on the surface of a glassy carbon electrode. We have employed scanning electron microscopy, Fourier transform infrared spectrometry (FTIR) and cyclic voltammetry to characterize the modified electrode. The direct electron transfers of hemoglobin and catalase on the modified electrode have been observed and studied in detail electrochemically. Hemoglobin is verified to be adsorbed on the modified electrode with the retention of conformation, which has been proved by microscopic FTIR. The electrochemical response of the adsorbed hemoglobin on the modified electrode is very stable, and shows repeated changes in the different pH solutions. It also has shown electrocatalysis to the reduction of oxygen and trichloroacetic acid. Catalase adsorbed on the gel modified electrode still keep activity to hydrogen peroxide. This work provides a simple and easy approach to construct biosensors based on the carbon nanotubes and ionic liquids.
Frontiers in Bioscience 02/2005; 10:326-34. · 3.52 Impact Factor
