A whisker-like carbon composite for the immobilization of laccase and its bioelectrochemistry

A novel mesoporous carbon/whisker-like carbon (MCWC) composite was used for the immobilization of laccase (Lac) and its bioelectrochemical behaviors were studied. It was confirmed by XPS that Lac was strongly adsorbed on the surface of the MCWC composite. The cyclic voltammetric results showed that the immobilized Lac underwent a direct quasi-reversible electrochemical reaction. The value of the electron transfer rate constant k _s was estimated to be 0.770 s^?1, indicating a reasonably fast electron transfer between the immobilized Lac and the underlying electrode. The surface concentration (Γ) of Lac was estimated to be 2.730 × 10^?12 mol/cm². Further experimental results showed that the immobilized Lac displayed an appreciable electrocatalytic activity to the electrochemical reduction of O₂. These properties could be attributed to the particular structure of loosely packed nanometer-scale carbon whiskers and the existence of a large amount of oxygen-containing groups. The immobilization method and the novel carrier (MCWC) may find new applications in fabricating the biocatalysts for biofuel cells.     

Encapsulation hemoglobin in ordered mesoporous silicas: Influence factors for immobilization and bioelectrochemistry

The encapsulation of hemoglobin (Hb) on the mesoporous silicas SBA-15 and Au-doped SBA-15 (Au-SBA-15) has been studied as a model protein adsorption system. The influences of solution pH, structure of mesoporous silicas and gold nanoparticles incorporation on Hb immobilization are investigated in detail. The spectral characteristics of Hb/SBA-15 and Hb/Au-SBA-15 nanoconjugate show an absorption curve quite similar to that of native Hb, indicating that Hb retains its higher-order structure in the mesopores of SBA-15. Direct electrochemistry of Hb is obtained when Hb is adsorpted by mesoporous silicas SBA-15 or Au-SBA-15. Moreover, Hb/Au-SBA-15 exerts enhancing electron transfer ability because of the Au incorporation. Additionally, the Hb/Au-SBA-15 displays good electrocatalytic reduction of hydrogen peroxide with a detection limit of 1.0 μM, about 3 times as low as that for the Hb/SBA-15. The Hb/Au-SBA-15 exhibits higher peroxidase-like activity with the apparent Michaelis–Menton constant (K_m) of 2.87 mM, significantly lower than the 7.78 mM value for the Hb/SBA-15.     

ZnO-MWCNTs/Nafion Inorganic-organic composite film： Preparation and application in bioelectrochemistry of hemoglobin

Multi-walled carbon nanotubes(MWCNTs) were coated with ZnO by a hydrothermal method.The resulting nanocomposites were mixed with the Nafion solution to form a composite matrix for the fabrication of hemoglobin(Hb) biosensor.To prevent the leak of Hb molecules of the biosensor,silica sol-gel film was coated on the surface of the Hb/ZnO-MWCNTs/Nafion electrode.The silica sol-gel/Hb/ZnO-MWCNTs/Nafion film exhibited a pair of well-defined,quasi-reversible redox peaks.This biosensor showed excellent electroca...     

Facile method to synthesize graphene-ZnS nanocomposites: preparation and application in bioelectrochemistry of hemoglobin

A novel electrochemical platform based on ZnS-doped graphene (GR-ZnS) nanocomposites was developed to achieve the direct electron transfer between hemoglobin (Hb) and the modified electrode. GR-ZnS nanocomposites were synthesized via noncovalent functionalization of pristine graphene (GR) by 1-aminopyrene and subsequent in situ synthesis of ZnS nanoparticles on the GR surface. During this process, the intrinsic electronic properties of GR could be efficiently protected. The as-prepared GR-ZnS nanocomposites were characterized and identified by means of transmission electron microscopy and energy dispersive X-ray spectrometer analysis, indicating the uniform formation of ZnS nanoparticles on the surface of GR. Fourier transform infrared spectra spectroscopic results confirmed that Hb remained its native structure in the nanocomposite material. The GR-ZnS nanocomposites could efficiently promote the direct electron transfer between Hb and electrode with the electron transfer rate constant (k _s) of 3.42 s^?1. The modified electrode was then used for the determination of H₂O₂ based on the electrocatalytic activity of Hb towards H₂O₂, which exhibited a linear range from 10 to 250 μM with a detection limit of 1.12 μM. The proposed method to fabricate GR-based hybrid nanomaterials would have a great potential for applications in various fields such as electrochemical sensing, catalytic reaction, and super capacitors.     

Acerate ZnO whiskers and sodium alginate films: preparation and application in bioelectrochemistry of hemoglobin

A novel biocompatible acerate ZnO whiskers (AZW) has been prepared. We explored AZW and sodium alginate for the construction of electrochemical biosensors. The composition, morphology, and size were studied by scanning electron microscopy. UV–vis spectra revealed that hemoglobin (Hb) adsorbed in the acerate ZnO whiskers and sodium alginate retained its native structure. The amperometric response was measured as a function of H₂O₂ concentration at a fixed potential of −0.25 V in phosphate-buffered saline (pH 7.0). The electrochemical parameters of Hb in acerate ZnO whiskers and sodium alginate were calculated with the results of the electron transfer coefficient (α) and the apparent heterogeneous electron transfer rate constant (k _s) as 0.5 and 2.5 s⁻¹, respectively, indicating good facilitation of the electron transfer between Hb and the modified electrode, which may result from the unique nanostructures and larger surface area of acerate ZnO whiskers. The hydrogen peroxide biosensor showed a fast response of <5 s of linear range 2.1 μM–4.8 mM, with a detection of 0.7 μM (S/N = 3). The apparent Michaelis–Menten constant K_m^app K_m^{{app}} is 0.8 mM. The biosensor possesses high sensitivity, good reproducibility, and long-term stability.     

Control of carbon capping for regrowth of aligned carbon nanotubes

The regrowth of carbon nanotubes (CNTs) in a second growth stage after a first growth stage has been completely stopped has been found to be strongly related to the carbon capping present on their catalyst particles. It is shown that the undesirable carbon capping can be prevented from forming or removed and the nanotube growth can be rejuvenated by either control of plasma processing conditions during chemical vapor deposition or by inserting a room-temperature sputter etching process. The ability to cause sequential growth stages to take place in different directions makes it possible for us to clearly compare the occurrence and extent of CNT regrowth. Such a CNT regrowth process and understanding of controlling parameters can enable the creation of new nanowire configurations that could potentially be used for applications such as sharply bending nanointerconnections, nanosprings, bent AFM nanoprobes, or nanobarcodes.     

Soluble carbon nanotubes

Carbon nanotubes have attracted great interdisciplinary interest because of their unique structure and properties. However, carbon-nanotube research is challenged by several problems, such as: i) mass production of material, ii) control of length, diameter, and chirality, and iii) manipulation for use in diverse technological fields. Issues regarding the synthesis and purification as well as the functionalization and solubilization of carbon nanotubes are relevant topics in this rapidly growing field. In this paper, covalent and noncovalent approaches to functionalized and solubilized nanotubes are examined in detail, with particular emphasis on the change of properties that accompany the chemical modification.     

Polymer-masking for controlled functionalization of carbon nanotubes

An effective and versatile method for tube-length-specific functionalization of carbon nanotubes through a controllable embedment of vertically-aligned carbon nanotubes into polymer matrices is reported, which allows not only asymmetric functionalization of nanotube sidewalls, but also facile introduction of new properties (e.g. magnetic) onto the region-selectively functionalized carbon nanotubes.     

Removal of amorphous carbon for the efficient sidewall functionalisation of single-walled carbon nanotubes

The sidewall functionalisation of carbon nanotubes using the standard nitric acid treatment can be greatly enhanced by first removing the amorphous carbon present in the sample.     

Aromaticity of carbon nanotubes

Carbon nanotubes are composed of cylindrical graphite sheets. Both nanotubes and graphite sheets are benzenoid derivatives composed of sp2 carbon atoms arranged in a hexagonal pattern. Therefore both systems are aromatic. The extent of the aromatic character of a molecule G (here benzenoids) can be explained in terms of the number of possible Kekulé structures in G. In this work the Kekulé structures in carbon nanotubes and the corresponding, rectangular, graphite-sheets the tubes might originate from, were enumerated. It was shown that (2,2), (3,3), and (4,4) carbon nanotubes are more aromatic than the corresponding, rectangular, planar structures. This explains why it might be more difficult to saturate nanotubes by addition reactions than the respective, "narrow", graphite sheets.     

Self-networking of carbon nanotubes

Carbon nanotube self-assembly into honeycomb-networks via controlling the ratio of the catalyst over hydrocarbon in the vapor phase using a tunable chemical vapor deposition process.     

Cytotoxicity of carbon nanotubes

With large-scale production and application at large scale, carbon nanotubes (CNTs) may cause ad-verse response to the environment and human health. Thus, study on bio-effects and safety of CNTs has attracted great attention from scientists and governments worldwide. This report briefly summa-rizes the main results from the in vitro toxicity study of CNTs. The emphasis is placed on the descrip-tion of a variety of factors affecting CNTs cytotoxicity, including species of CNTs, impurities contained, lengths of CNTs, aspect ratios, chemical modification, and assaying methods of cytotoxicity. However, experimental information obtained thus far on CNTs' cytotoxicity is lacking in comparability, and some-times there is controversy about it. In order to assess more accurately the potential risks of CNTs to human health, we suggest that care should be taken for issues such as chemical modification and quantitative characterization of CNTs in cytotoxicity assessment. More importantly, studies on physical and chemical mechanisms of CNTs' cytotoxicity should be strengthened; assaying methods and evaluating criteria characterized by nanotoxicology should be gradually established.     

The conversion of polyaniline nanotubes to nitrogen-containing carbon nanotubes and their comparison with multi-walled carbon nanotubes

Polyaniline (PANI) nanotubes were prepared by the oxidation of aniline in solutions of acetic or succinic acid, and subsequently carbonized in a nitrogen atmosphere during thermogravimetric analysis running up to 830 °C. The nanotubular morphology of PANI was preserved after carbonization. The molecular structure of the original PANI and of the carbonized products has been analyzed by FTIR and Raman spectroscopies. Carbonized PANI nanotubes contained about 8 wt.% of nitrogen. The molecular structure, thermal stability, and morphology of carbonized PANI nanotubes were compared with the properties of commercial multi-walled carbon nanotubes.     

Amine-functionalized low-cost industrial grade multi-walled carbon nanotubes for the capture of carbon dioxide

Industrial grade multi-walled carbon nanotubes (IG-MWCNTs) are a low-cost substitute for commercially purified multi-walled carbon nanotubes (P-MWCNTs). In this work, IG-MWCNTs were functionalized with tetraethylenepentamine (TEPA) for CO₂ capture. The TEPA impregnated IG-MWCNTs were characterized with various experimental methods including N₂ adsorption/desorption isotherms, elemental analysis, X-ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis. Both the adsorption isotherms of IG-MWCNTs-n and the isosteric heats of different adsorption capacities were obtained from experiments. TEPA impregnated IG-MWCNTs were also shown to have high CO₂ adsorption capacity comparable to that of TEPA impregnated P-MWCNTs. The adsorption capacity of IG-MWCNTs based adsorbents was in the range of 2.145 to 3.088 mmol/g, depending on adsorption temperatures. Having the advantages of low-cost and high adsorption capacity, TEPA impregnated IG-MWCNTs seem to be a promising adsorbent for CO₂ capture from flue gas.     

Metallic single-walled carbon nanotubes for conductive nanocomposites

This article reports an unambiguous demonstration that bulk-separated metallic single-walled carbon nanotubes offer superior performance (consistently and substantially better than the as-produced nanotube sample) in conductive composites with poly(3-hexylthiophene) and also in transparent conductive coatings based on PEDOT:PSS. The results serve as a validation on the widely held view that the carbon nanotubes are competitive in various technologies currently dominated by conductive inorganic materials (such as indium tin oxide).     

Nitrogen-doped carbon nanotubes for heat transfer applications

In this research, it is aimed to enhance the heat transfer properties of the carbon nanotubes through nitrogen doping. To this end, nitrogen-doped multiwall carbon nanotubes (N-CNTs) were synthesized via chemical vapor deposition method. For supplying carbon and nitrogen during the synthesis of N-CNTs, camphor and urea were used, respectively, at 1000 °C over Co–Mo/MgO nanocatalyst in a hydrogen atmosphere. N-CNTs with three different nitrogen loadings of 0.56, 0.98, and 1.38 mass% were synthesized, after which, water/N-CNT nanofluids of these three samples with concentrations of 0.1, 0.2, and 0.5 mass% were prepared. To obtain a stable nanofluid, N-CNTs were functionalized by nitric acid followed by stabilizing in water by employing the ultrasonic bath. Investigation on the stability of the samples showed a high stability level for the prepared water/N-CNT nanofluids in which the zeta potential of ??43.5 mV was obtained for the best sample. Also for studying the heat transfer properties, the thermal conductivity in the range of 0.1–0.5 mass% and convection heat transfer coefficients of nanofluids in the range of 0.1–0.5 mass%, and Reynolds number in the range of 4000–9000 were evaluated. The results showed 32.7% enhancement of the convection heat transfer coefficients at Reynolds number of 8676 and 27% increase in the thermal conductivity at 0.5 mass% and 30 °C.

     

Supramolecular catalysts for the gas-phase synthesis of single-walled carbon nanotubes

Reversed micelles containing metallic ions have been used as precursors of novel catalysts for the gas-phase synthesis of single-walled carbon nanotubes (SWNTs). This technique possesses the following advantages: (i) excellent solubility in organic solvents, which are used as reactants and (ii) facile preparation of multicomponent catalysts enabling systematic screening of catalyst compositions for the synthesis of SWNTs. In this study, we report the results of the screening study on the catalytic behavior of Fe-Mo binary catalysts during the synthesis of SWNTs. The results suggested that the catalytic ability was closely related to the strain of the crystal structure of Fe-Mo catalysts formed in the reaction and/or the phase transition caused by dissolution of the Mo atoms. The addition of lithium to the Fe-Mo binary catalysts has revealed an increase in the yield of SWNTs.     

Assessment of chemically separated carbon nanotubes for nanoelectronics

It remains an elusive goal to obtain high performance single-walled carbon-nanotube (SWNT) electronics such as field effect transistors (FETs) composed of single- or few-chirality SWNTs, due to broad distributions in as-grown materials. Much progress has been made by various separation approaches to obtain materials enriched in metal or semiconducting nanotubes or even in single chiralties. However, research in validating SWNT separations by electrical transport measurements and building functional electronic devices has been scarce. Here, we performed length, diameter, and chirality separation of DNA functionalized HiPco SWNTs by chromatography methods, and we characterized the chiralities by photoluminescence excitation spectroscopy, optical absorption spectroscopy, and electrical transport measurements. The use of these combined methods provided deeper insight to the degree of separation than either technique alone. Separation of SWNTs by chirality and diameter occurred at varying degrees that decreased with increasing tube diameter. This calls for new separation methods capable of metallicity or chirality separation of large diameter SWNTs (in the approximately 1.5 nm range) needed for high performance nanoelectronics. With most of the separated fractions enriched in semiconducting SWNTs, nanotubes placed in parallel in short-channel (approximately 200 nm) electrical devices fail to produce FETs with high on/off switching, indicating incomplete elimination of metallic species. In rare cases with a certain separated SWNT fraction, we were able to fabricate FET devices composed of small-diameter, chemically separated SWNTs in parallel, with high on-/off-current (I(on)/I(off)) ratios up to 105 owing to semiconducting SWNTs with only a few (n,m) chiralities in the fraction. This was the first time that chemically separated SWNTs were used for short channel, all-semiconducting SWNT electronics dominant by just a few (n,m)'s. Nevertheless, the results suggest that much improved chemical separation methods are needed to produce nanotube electronics at a large scale.