辣根过氧化物酶在多壁碳纳米管——壳聚糖膜中的电化学和生物传感性质

采用壳聚糖包裹的多壁碳纳米管膜固定辣根过氧化物酶(HaP)于玻碳电极表面,实现了HRP的直接电化学并以此酶膜制备了NO生物传感器.在磷酸缓冲溶液中固定在电极表面的HRP氧化还原式电位为-0.354 V(us.SCE),直接电子转移速率常数为4.24±1.02 s-1.研究结果表明,固定在电极表面的HRP能保持其对一氧化氮还原的生物电催化活性,该传感器在NO浓度为1.0×10-4~1.4×10-3 mol L-1范围内存在线性响应,响应时间小于11 s,NO的检出限为7×10-4 mol L-1.多壁碳纳米管特殊的电学性质和壳聚糖良好的生物相容性性使得构筑的HRP生物传感器呈现了良好的应用前景,尤其适用于痕量NO的检测.     

La_(0.7)Sr_(0.3)NiO_3/壳聚糖/聚吡咯/牛血红蛋白修饰玻碳电极的制备及构建过氧化氢传感器

在玻碳电极上修饰一层表面均匀的聚吡咯膜,然后利用钙钛矿和壳聚糖的复合膜来固定牛血红蛋白(Hb),制备出性能良好的过氧化氢生物传感器.采用循环伏安(CV)和扫描电镜对修饰电极进行了表征.该传感器对H2O2具有好的催化响应,且响应快.在优化的实验条件下,所制备的传感器对H2O2的线性范围为7.0×10-6～1.5×10-3mol/L,检测限为9.0×10-8mol/L.     

La0.7Sr0.36NiO3/壳聚糖/聚吡咯/牛血红蛋白修饰玻碳电极的制备及构建过氧化氢传感器

在玻碳电极上修饰一层表面均匀的聚吡咯膜,然后利用钙钛矿和壳聚糖的复合膜来固定牛血红蛋白(Hb),制备出性能良好的过氧化氢生物传感器.采用循环伏安(CV)和扫描电镜对修饰电极进行了表征.该传感器对H2O2具有好的催化响应,且响应快.在优化的实验条件下,所制备的传感器对H2O2的线性范围为7.0×10-6～1.5×10-3...     

基于[C_(10)-mim~+]Br~-固定HRP于Au/石墨烯复合材料电极表面的新型H_2O_2酶生物传感器

利用长链离子液体特殊的性质,用其固定HRP于Au/graphene电极表面(Nafion/HRP/[C10-mim+]Br-/Au/Gr/GCE)组装成H2O2传感器。用透射电镜来表征Au/氧化石墨烯的形貌,金纳米颗粒很均匀的分散在石墨烯表面,并不存在团聚现像。电化学技术检测Nafion/HRP/[C10-mim+]Br-/Au/Gr修饰电极对H2O2的响应情况,显示修饰电极对H2O2有很好的响应,在H2O2浓度2.0×10-6~1.2×10-3 mol/L的范围内,还原电流与浓度存在线性关系(R=0.997),检测限为3.0×10-7 mol/L;另外传感器具有很好的稳定性和选择性,为生物分子的检测提供新方法。     

杯芳烃主客体化学传感器

以C-十一烷基间苯二酚杯(6)芳烃作为主体分子修饰玻碳电极表面,制成一种主客体化学传感器.并用其对溶液中的客体分子--对甲酚进行测定.该电极具有良好的选择性,对5.0×10-5～2.0×10-3mol/L的对甲酚具有很好的线性响应,检测下限为3.0×10-5mol/L.同时,对修饰前后玻碳电极的表面状态进行了研究.     

基于二氧化硅球腔阵列的葡萄糖传感器研究

在二氧化硅球腔阵列电极上,通过电沉积普鲁士蓝和直接吸附葡萄糖氧化酶,制备了一种新型葡萄糖生物传感器。该传感器对酶催化反应产物过氧化氢的选择性催化还原特性可实现对葡萄糖的检测,实验结果表明,传感器的最佳工作电位是－0．3V,测试溶液的最佳pH值为6．0。在选定的工作条件下,传感器的线性范围为2．49×10-5－2．42×10-3mol／L,检测极限值为7．2×10-6mol／L（S／N=3）,米氏常数为1．136mmol／L。该方法制备的生物传感器能有效降低干扰,具有潜在的应用价值。     

基于石墨烯/金纳米棒的甲硝唑电化学行为及其检测

碱性条件下制备水中分散性良好的石墨烯,并通过一步还原法得到石墨烯/AuNRs复合材料。利用滴涂法制备石墨烯/AuNRs修饰电极,并研究了甲硝唑在该修饰电极上的电化学行为。结果表明,在pH=7.4时,甲硝唑在修饰电极上出现明显的氧化还原峰。甲硝唑在该修饰电极的还原峰峰电流与浓度在3.0×10-7～5.0×10-5 mol/L(S/N=3)范围内呈良好的线性关系,检出限为9.2×10-8 mol/L。该检测方法具有良好的灵敏度、选择性和稳定性,可用于甲硝唑药物的分析。同时也展现了这种新型的复合纳米材料在药物的检测中的应用潜力。     

聚邻苯二胺负载纳米铜氧化物修饰玻碳电极的制备及表征

在磷酸盐缓冲溶液中于玻碳电极表面聚合邻苯二胺,再负载纳米铜氧化物,成功制备了邻苯二胺负载纳米铜氧化物修饰玻碳电极(CuO/P-oPD/GC).探讨了聚合和负载机理,用电化学交流阻抗谱表征了修饰电极界面的阻抗变化,用扫描电镜表征了聚邻苯二胺膜和负载铜氧化物后的表面形态,发现CuO/P-oPD/GC电极对H2O2有显著的电催化氧化、还原双重活性,并呈现"协同增敏"效应.考察了制备条件对CuO/P-oPD/GC电极电催化活性的影响,最佳CoO负载扫描次数为20,Cu2+的质量浓度为1.67mmol/L.对H2O2电催化氧化的线性方程为△ip8(μA)=0.08+5.64c(mmol/L)(R=0.9982),线性范围为2.4×10-2～48mmol/L,检测限为2.8×10-3mmol/L(3S/k);电催化还原的线性方程为△ipc(μA)=0.11-2.45c(mmol/L)(R=0.9820),线性范围为2.4×10-3～38.4mmol/L,检测限为2.0×10-4mmol/L(3S/k).该复合材料修饰电极的灵敏度高、稳定性好,用于实际水样中H2O2测定结果满意.     

基于layer-by-layer技术构建胆碱检测生物传感器酶电极的研究

基于层层累积自组装法将PDDA高分子材料和胆碱氧化酶逐层固定在高分子聚合膜PVS/PDDA修饰的电极表面,制备了电流型胆碱检测生物传感器.利用石英晶体微天平(QCM)分别分析了PDDA和胆碱氧化酶的固定过程,结果表明酶的固定量可以得到有效控制.探讨了自组装膜层数、pH值、温度对传感器电流响应的影响.制备的生物传感器在胆碱浓度为5×10-7～1×10-4 mol/L的范围内对胆碱有良好的线性响应,响应时间为10 s,检出限为5×10-7 mol/L.传感器的稳定性好,30天时的响应值仍保持90%.     

新型CMCS/WMCNTs修饰电极对槲皮素的电化学检测及应用

研究了一种黄酮类物质槲皮素在新颖的多壁碳纳米管(WMCNTs)/羧甲基壳聚糖(CMCS)复合物修饰电极上的循环伏安行为。实验采用直接滴涂方法制备CMCS/WMCNTs修饰电极,在不同的pH、扫描速度、底液浓度、修饰材料等条件下通过循环伏安法来研究槲皮素在修饰电极上电化学行为。修饰电极与裸电极相比,峰电流有明显提升,表明修饰材料对槲皮素的电化学氧化还原行为有一定的催化增敏作用。槲皮素在pH=5.0的醋酸-醋酸钠(NaAc-HAc)缓冲溶液中有一对明显的氧化还原峰,电极过程为等量质子和电子参与的吸附控制过程,且还原峰电流与槲皮素浓度在(1.0×10~(-4)~1.0×10~(-3))mol/L范围内呈良好的线性关系。     

Length Distribution of Single‐Walled Carbon Nanotubes in Aqueous Suspension Measured by Electrospray Differential Mobility Analysis

The first characterization of the length distribution of single‐walled carbon nanotubes (SWCNT) dispersed in a liquid by electrospray differential mobility analysis (ES‐DMA) is presented. Although an understanding of geometric properties of SWCNTs, including length, diameter, aspect ratio, and chirality, is essential for commercial applications, rapid characterization of nanotube length distributions remains challenging. Here the use of ES‐DMA to obtain length distributions of DNA‐wrapped SWCNTs dispersed in aqueous solutions is demonstrated. Lengths measured by ES‐DMA compare favorably with those obtained from multiangle light scattering, dynamic light scattering, field flow fractionation with UV/vis detection, and atomic force microscopy, validating ES‐DMA as a technique to measure SWCNTs of <250 nm in length. The nanotubes are previously purified and dispersed by wrapping with oligomeric DNA in aqueous solution and centrifuging to remove bundles and amorphous carbon. These dispersions are particularly attractive due to their amenability to bulk processing, ease of storage, high concentration, compatibility with biological and high‐throughput manufacturing environments, and for their potential applications ranging from electronics and hydrogen‐storage vessels to anticancer agents.     

Influence of Single-Walled Carbon Nanotubes on Thermal Expansion of Water

This article reports the results of an investigation of the influence of single-walled carbon nanotubes (SWCNTs) functionalized with carboxyl groups on PVT data of water. Specifically, the impact of an aqueous suspension of SWCNTs (maximum concentration of 3.0 mg $\cdot $ mL $^{-1}$ ) on the isobaric thermal expansion of water in the temperature and pressure ranges of 293 K to 342 K and 0.1 MPa to 152.3 MPa, respectively, was investigated. The obtained results are discussed in terms of different structures of water confined inside and outside SWCNTs.     

Ultra-high oxidation resistance of suspended single-wall carbon nanotube bundles grown by an "all-laser" process

Single-wall carbon nanotubes (SWCNTs) were laterally grown on SiO2/Si substrates by means of an "all-laser" growth process. Our "all-laser" process stands out by its exclusive use of the same pulsed UV laser, first, to deposit the CoNi nanocatalyst and, second, to grow SWCNTs through the laser ablation of a pure graphite target. The "all-laser" grown SWCNTs generally self-assemble into bundles (5-15 nm-diam.) sprouting from the CoNi nanocatalyst and laterally bridging the 2 microm gap separating adjacent catalysed electrodes (in either "suspended" or "on-substrate" geometries). A comparative study of the oxidation resistance of both suspended and on-substrate SWCNTs was achieved. The "all-laser" grown SWCNTs were subjected to annealing under flowing oxygen at temperatures ranging from 200 to 1100 degrees C. Systematic scanning electron microscopy observations combined with micro-Raman analyses revealed that more than 20% of suspended nanotubes were still stable at temperatures as high as 900 degrees C under flowing O2 while the on-substrate counterpart were completely burnt out at this temperature. Accordingly, the activation energy, as deduced from the Arrhenius plot, of the suspended SWCNTs is found to be as high as approximately 180 kJ mol(-1) (approximately 9 times higher than that of the on-substrate ones). The high quality (almost defect-free) of the nanotubes synthesized by the "all-laser" approach, their protected tips into the embedded CoNi catalyst nanolayer together with their suspended geometry are thought to be responsible for their unprecedented ultra-high oxidation resistance. This opens up new prospects for the use of these suspended nanotubes into nanodevices that have to operate under highly oxidizing environments.     

In‐vitro toxicity of carbon nanotube/polylysine colloids to colon cancer cells

Single‐walled carbon nanotubes (SWCNTs) are thoroughly purified and dispersed in an aqueous solution of high molecular weight poly‐L‐lysine (pLlys). Human intestinal epithelial Caco‐2/TC7 cells are incubated with the SWCNT dispersions in pLlys, and their effects on cell viability are studied by image flow cytometry. No significant changes are observed in the cell culture wells up to pLlys concentrations of 10 μg ml⁻¹. However, high mortality is detected at pLlys concentrations of 100 μg ml⁻¹. The presence of oxygen‐free SWCNTs does not modify the effects of pLlys on cell cultures at any of the tested concentrations (≤1 μg ml⁻¹). In addition, SWCNTs having an 8 wt.% of surface oxygen are tested with identical results. Thus, purified SWCNTs, even bearing oxygen functional groups, act as inert particles in the cell culture medium. This result supports the applicability of SWCNTs as carriers in pharmacological formulations against digestive tract diseases.Inspec keywords: single‐wall carbon nanotubes, cellular biophysics, molecular weight, filled polymers, biochemistry, cancer, colloidsOther keywords: surface oxygen, mortality, cell culture wells, image flow cytometry, human intestinal epithelial Caco‐2/TC7 cells, molecular weight, aqueous solution, single walled carbon nanotubes, colon cancer cells, carbon nanotube‐polylysine colloids, toxicity     

Optical pH response of DNA wrapped HiPco carbon nanotubes

Solubilization of single-walled carbon nanotubes in aqueous solution by surface functionalization is of great interest for biosensor applications and separation of individual nanotubes. Here we have observed that HiPco nanotubes can be stably dispersed into double-stranded DNA aqueous solutions. Interestingly, the first optical interband transitions of the DNA wrapped semiconducting HiPco nanotubes possess a unique pH dependence, a phenomenon observed in SDS-encased and carboxylic group functionalized single-walled carbon nanotubes. The unique optical pH dependence of surface modified semiconducting nanotubes may have promising applications in optical biosensors.     

Highly conductive interwoven carbon nanotube and silver nanowire transparent electrodes

Abstract

Electrodes fabricated using commercially available silver nanowires (AgNWs) and single walled carbon nanotubes (SWCNTs) produced sheet resistances in the range 4–24 Ω □^?1 with specular transparencies up to 82 %. Increasing the aqueous dispersibility of SWCNTs decreased the bundle size present in the film resulting in improved SWCNT surface dispersion in the films without compromising transparency or sheet resistance. In addition to providing conduction pathways between the AgNW network, the SWCNTs also provide structural support, creating stable self-supporting films. Entanglement of the AgNWs and SWCNTs was demonstrated to occur in solution prior to deposition by monitoring the transverse plasmon resonance mode of the AgNWs during processing. The interwoven AgNW/SWCNT structures show potential for use in optoelectronic applications as transparent electrodes and as an ITO replacement.     

Molecular-dynamic studies of carbon-water-carbon composite nanotubes

We recently reported the discovery via molecular-dynamic simulations that single-walled carbon nanotubes (SWCNTs) with different diameters, lengths, and chiralities can coaxially self-assemble into multi-walled carbon nanotubes (MWCNTs) in water via the spontaneous insertion of smaller tubes into larger ones. Here, we extend that study to investigate the various water structures formed between two selected SWCNTs after such coaxial assembly. Depending on the tube geometry, typical water structures, besides the bulk phase, include a one-dimensional (1D) ordered water chain inside the smaller tube, a uniform or nonuniform water shell between the two tubes, and a "boundary layer" of water near the exterior wall of the larger tube. It was found that a concentric water shell consisting of up to three layers of water molecules can form between the two SWCNTs, which leads to a class of carbon-water-carbon composite nanotubes. Analysis of the potential energy of the SWCNT-water system indicated that the composite nanotubes are stabilized by both the tube-tube and tube-water van der Waals interactions. Geometrically confined between the two SWCNTs, water mono- and bilayers are found to be stable, highly condensed, and ordered, although the average number of hydrogen bonds per water molecule is reduced. In contrast, a water trilayer between the two CNTs can be easily disrupted by thermal fluctuations.     

Raman Spectroscopy and SEM Study of SWNTs in Aqueous Solution and Films with Surfactant or Polymer Surroundings

Raman spectra of single-walled carbon nanotubes (SWNTs) in aqueous solutions with sodium dodecylsulfate (SDS) or fragmented single-stranded DNA (ss-DNA) and films obtained from these solutions have been studied. Scanning electron microscope (SEM) film study shows that micelles formed by SDS molecules around SWNT in solution do not keep individual nanotubes from sticking together in bundles during drying out the film. DNA wrapped around SWNT precludes the full nanotubes sticking in the film that facilitates the following splitting of these bundles.     

Fibrinogen binding-dependent cytotoxicity and degradation of single-walled carbon nanotubes

Carbon nanotubes are widely used in the area of biomedicine, and the binding of protein to carbon nanotubes are believed to play an important role in the potential cytotoxicity of nanomaterials. In this work, we investigated the effects of human fibrinogen-surface coatings on the biodegradation and cytotoxicity of carboxylated single-walled carbon nanotubes (SWCNTs). It was found that the electrostatic and π-π stacking interactions might be the crucial factors in stabilizing the binding of fibrinogen with SWCNTs by both theoretical and experimental approaches. Although naked SWCNTs could induce significant toxicity to macrophages, coating these nanomaterials with fibrinogen could greatly attenuate their toxicity. On the other hand, although SWCNTs and fibrinogen-preincubated SWCNTs were resistant to biodegradation in resting macrophages, both naked and fibrinogen-coated SWCNTs could be effectively and similarly degraded through myeloperoxidase (MPO) and peroxynitrite (ONOO^?)-dependent pathways in activated macrophages, where NADPH oxidase played a determinant role in the biodegradation process. Importantly, degraded SWCNTs by ONOO^? pathway in vitro induced less cytotoxicity than non-degraded nanotubes. These findings demonstrated that the binding of fibrinogen to SWCNTs could reduce cytotoxicity without affecting the biodegradation of nanotubes in activated inflammatory cells, providing a new route to design the safer nanotubes for future biomedical applications.     

Water-processable polyaniline with covalently bonded single-walled carbon nanotubes: enhanced electrochromic properties and impedance analysis

Hybrid electrochromic materials were readily synthesized via copolymerization of aniline with p-phenylenediamine-functionalized single-walled carbon nanotubes (SWCNTs) in the presence of poly(styrene sulfonate) (PSS) dopant in an aqueous medium. Polyaniline (PANI)-grafted SWCNTs are formed, and they are uniformly dispersed in the PANI/PSS matrix. Impedance analysis shows that the charge-transfer resistances of the hybrids at all states are reduced drastically with increasing SWCNT loading. With 0.8 wt % SWCNTs, the charge-transfer resistances of the hybrid at +1.5 and -1.5 V are only about 20% and 12% of those of PANI/PSS, respectively, which is due to the greatly increased redox reactivity given by the enhanced electron transport in the hybrid and further doping function of the SWCNTs. The remarkable increase in redox reactivity leads to much enhanced electrochromic contrast from 0.34 for PANI to 0.47 for PANI-SWCNT-0.8%.