Self-assembly of gold nanoparticles to carbon nanotubes using a thiol-terminated pyrene as interlinker

Gold nanoparticles were self-assembled onto the surface of solubilized carbon nanotubes through an interlinker of bi-functionalized molecule (PHT) terminated with pyrenyl unit at one end and thiol group at the other end. While the fluorescence of PHT is quenched moderately by the carbon nanotubes, the fluorescence is almost totally quenched by the further binding of gold nanoparticles. The enhancement of the Raman responses of nanotubes by the gold nanoparticles is also observed. These results imply there are charge transfer interactions between nanotubes and gold nanoparticles.     

Simple Dip-Coating Process for the Synthesis of Small Diameter Single-Walled Carbon Nanotubes-Effect of Catalyst Composition and Catalyst Particle Size on Chirality and Diameter

We report on a dip-coating method to prepare catalyst particles (mixture of iron and cobalt) with a controlled diameter distribution on silicon wafer substrates by changing the solution's concentration and withdrawal velocity. The size and distribution of the prepared catalyst particles were analyzed by atomic force microscopy. Carbon nanotubes were grown by chemical vapor deposition on the substrates with the prepared catalyst particles. By decreasing the catalyst particle size to below 10 nm, the growth of carbon nanotubes can be tuned from few-walled carbon nanotubes, with homogeneous diameter, to highly pure single-walled carbon nanotubes. Analysis of the Raman radial breathing modes, using three different Raman excitation wavelengths (488, 633, and 785 nm), showed a relatively broad diameter distribution (0.8-1.4 nm) of single-walled carbon nanotubes with different chiralities. However, by changing the composition of the catalyst particles while maintaining the growth parameters, the chiralities of single-walled carbon nanotubes were reduced to mainly four different types, (12, 1), (12, 0), (8, 5), and (7, 5), accounting for about 70% of all nanotubes.     

Conductive polymer nanocomposites containing <Emphasis Type="Italic">in situ</Emphasis> ultra-fine metal particles

A conductive polymeric composite containing in situ ultra-fine metal particles is prepared by melt blending. Incorporation of elastomeric nano-particles and carbon nanotubes hinders the coalescing of metal particles and causes a shift to the breakup direction in the breakup/coalescence equilibrium of metal particles. The prime metal particles (about 26 μm) are in situ converted into the ultra-fine metal particles (UFMP, about 932 nm). The network of carbon nanotubes has been improved due to in situ ultra-fine metal particles and the percolation threshold of the composite with 1.96 vol% UFMP is only 0.25 vol% carbon nanotubes.     

Constrained iron catalysts for single-walled carbon nanotube growth

The diameter of single walled carbon nanotubes (SWNTs) determines the electronic properties of the nanotube. The diameter of carbon nanotubes is dictated by the diameter of the catalyst particle. Here we describe the use of iron nanoparticles synthesized within the Dps protein cage as catalysts for the growth of single-walled carbon nanotubes. The discrete iron particles synthesized within the Dps protein cages when used as catalyst particles gives rise to single-walled carbon nanotubes with a limited diameter distribution.     

Near-infrared fluorescence microscopy of single-walled carbon nanotubes in phagocytic cells

The uptake of pristine single-walled carbon nanotubes into macrophage-like cells has been studied using the nanotubes' intrinsic near-infrared fluorescence. Macrophage samples that have been incubated in growth media containing suspended single-walled nanotubes show characteristic nanotube fluorescence spectra. The fluorescence intensities increase smoothly with incubation time and external nanotube concentration. Near-infrared fluorescence microscopy at wavelengths above 1100 nm provides high contrast images indicating localization of nanotubes in numerous intracellular vesicles. Nanotube uptake appears to occur through phagocytosis. Population growth of macrophage cultures is unaffected by exposure to single-walled nanotube concentrations of ca. 4 mug/mL for up to 96 h.     

Nanotubes from isomeric dibenzoylmethane molecules

Organic nanotubes of various diameters were fabricated from the isomeric molecule dibenzoylmethane (DBM) by using an immersing technique with ordered porous alumina membrane as the template. The ratio of the enol isomers of DBM increased as the diameters of the nanotubes decreased. In addition, although almost no fluorescence could be detected for the DBM monomer, a striking enhancement in the fluorescence emission intensity of the nanotubes was observed as the diameters decreased. This is due to the increased ratio of the enol isomers.     

Metal-enhanced fluorescence of carbon nanotubes

The photoluminescence (PL) quantum yield of single-walled carbon nanotubes (SWNTs) is relatively low, with various quenching effects by metallic species reported in the literature. Here, we report the first case of metal enhanced fluorescence (MEF) of surfactant-coated carbon nanotubes on nanostructured gold substrates. The photoluminescence quantum yield of SWNTs is observed to be enhanced more than 10-fold. The dependence of fluorescence enhancement on metal-nanotube distance and on the surface plasmon resonance (SPR) of the gold substrate for various SWNT chiralities is measured to reveal the mechanism of enhancement. Surfactant-coated SWNTs in direct contact with metal exhibit strong MEF without quenching, suggesting a small quenching distance for SWNTs on the order of the van der Waals distance, beyond which the intrinsically fast nonradiative decay rate in nanotubes is little enhanced by metal. The metal enhanced fluorescence of SWNTs is attributed to radiative lifetime shortening through resonance coupling of SWNT emission to the reradiating dipolar plasmonic modes in the metal.     

Iron silicide root formation in carbon nanotubes grown by microwave PECVD

Aligned carbon nanotubes have been grown using microwave plasma enhanced chemical vapor deposition (PECVD). The carbon nanotubes are nucleated from iron catalyst particles which, during growth, remain adherent to the silicon substrates. By analysis with high-resolution electron microscopy, we observe iron silicide roots penetrating into the silicon substrate at the interface of the catalyst particles and the substrate, thus providing strong adhesion of the carbon nanotubes onto the substrate. The iron silicide roots assist in the attachment of the catalyst particles to the substrate and play a role in the evolution of the catalyst particle morphology and resulting base growth mode. Carbon nanotubes grown by microwave PECVD could exhibit superior electrical and thermal transport properties over other PECVD processes, so an understanding of the growth mechanism is important for utilization in device applications.     

Lipid bilayers covalently anchored to carbon nanotubes

The unique physical and electrical properties of carbon nanotubes make them an exciting material for applications in various fields such as bioelectronics and biosensing. Due to the poor water solubility of carbon nanotubes, functionalization for such applications has been a challenge. Of particular need are functionalization methods for integrating carbon nanotubes with biomolecules and constructing novel hybrid nanostructures for bionanoelectronic applications. We present a novel method for the fabrication of dispersible, biocompatible carbon nanotube-based materials. Multiwalled carbon nanotubes (MWCNTs) are covalently modified with primary amine-bearing phospholipids in a carbodiimide-activated reaction. These modified carbon nanotubes have good dispersibility in nonpolar solvents. Fourier transform infrared (FTIR) spectroscopy shows peaks attributable to the formation of amide bonds between lipids and the nanotube surface. Simple sonication of lipid-modified nanotubes with other lipid molecules leads to the formation of a uniform lipid bilayer coating the nanotubes. These bilayer-coated nanotubes are highly dispersible and stable in aqueous solution. Confocal fluorescence microscopy shows labeled lipids on the surface of bilayer-modified nanotubes. Transmission electron microscopy (TEM) shows the morphology of dispersed bilayer-coated MWCNTs. Fluorescence quenching of lipid-coated MWCNTs confirms the bilayer configuration of the lipids on the nanotube surface, and fluorescence anisotropy measurements show that the bilayer is fluid above the gel-to-liquid transition temperature. The membrane protein α-hemolysin spontaneously inserts into the MWCNT-supported bilayer, confirming the biomimetic membrane structure. These biomimetic nanostructures are a promising platform for the integration of carbon nanotube-based materials with biomolecules.     

Electrolytic Formation of Crystalline Silicon/Germanium Alloy Nanotubes and Hollow Particles with Enhanced Lithium‐Storage Properties

Crystalline silicon(Si)/germanium(Ge) alloy nanotubes and hollow particles are synthesized for the first time through a one‐pot electrolytic process. The morphology of these alloy structures can be easily tailored from nanotubes to hollow particles by varying the overpotential during the electro‐reduction reaction. The continuous solid diffusion governed by the nanoscale Kirkendall effect results in the formation of inner void in the alloy particles. Benefitting from the compositional and structural advantages, these SiGe alloy nanotubes exhibit much enhanced lithium‐storage performance compared with the individual solid Si and Ge nanowires as the anode material for lithium‐ion batteries.     

Layer-by-layer fabrication and characterization of DNA-wrapped single-walled carbon nanotube particles

Carbon nanotubes have been proposed as support materials for numerous applications, including the development of DNA sensors. One of the challenges is the immobilization of DNA or other biological molecules on the sidewall of carbon nanotubes. This paper introduces a new fabrication of DNA-carbon nanotubes particles using the layer-by-layer (LBL) technique on single-walled carbon nanotubes (SWCNTs). Poly(diallyldimethylammonium) (PDDA), a positively charged polyelectrolyte, and DNA as a negatively charged counterpart macromolecule are alternatively deposited on the water-soluble oxidized SWCNTs. Pure DNA/PDDA/SWCNTs particles can be prepared and separated by simple unltracentrifugation. The characterization of DNA/PDDA/SWCNTs particles was carried out by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy, Raman spectroscopy, and thermogravimetric analysis (TGA). An electrode modified by the DNA/PDDA/SWCNTs particles shows a dramatic change of the electrochemical signal in solutions of tris(2,2'-bipyridyl)ruthenium(II) ((Ru(bpy)(3)2+) as a reporting redox probe. A preliminary application of the DNA-modified carbon nanotubes in the development of DNA sensors used in the investigation of DNA damage by nitric oxide is presented.     

微波等离子体化学气相沉积法低温合成纳米碳管

纳米碳管的低温合成是纳米碳管合成的一个重要研究方向。在众多的合成方法 中,化学气相沉积法,特别是等离子体化学气相沉积法在纳米碳管的低温合成方面 意义重大。本研究利用溶胶-凝胶法结合等离子体还原,获得了负载在SiO_2上的纳 米金属钻颗粒。以甲烷为碳源、氢气为载气,在纳米金属钴颗粒的催化作用下,利 用微波等离子体化学气相沉积法在低于500 ℃ 的温度条件下合成了纯度较高的纳 米碳管。     

Fluorescent probe for Fe(III) based on pyrene grafted multiwalled carbon nanotubes by click reaction

The attempt to decorate carbon nanotubes with organic molecules to form new functional materials has attracted broad attention in the scientific community. Here, we report the covalent functionalization of multiwalled carbon nanotubes (MWCNTs) with pyrene via Cu(I)-catalysed azide/alkyne click (CuAAC) reactions under mild conditions to afford the nanocomposites of pyrene-MWCNTs. Fourier transform infrared spectroscopy (FT-IR), ultraviolet and visible spectroscopy (UV-Vis), and fluorescence spectroscopy were used to characterize the nanocomposites of pyrene clicked MWCNTs. Experimental results indicate that the CuAAC reaction occurs in an efficient manner and the spacer linking MWCNTs and the photoactive molecule is well defined. In contrast to the noncovalent functionalization of π-π stacking, the nanocomposites of pyrene clicked MWCNTs show relatively strong fluorescence and have potential applicability in photoluminescent devices as a highly sensitive and selective fluorescence "turn-off" sensor for Fe(3+).     

The mechanism of unification of carbon nanotubes with small numbers of walls into bundles. Calculation of the domains of existence of different types of nanotubes at different temperatures and catalytic particle sizes

A model of nucleation of carbon nanotubes (CNTs) from catalytic particles oversaturated with carbon has been constructed. The temperature dependences of the number and size of nanotubes on the parameters of the model were derived. The nanotubes begin to grow as individual nanotubes. Then the axis of the nanotube starts to vibrate relative to the normal to the particle surface. In a certain range of conditions, the nanotubes are united into bundles. The diagram of the domains of existence of individual nanotubes and bundles was plotted as the particle size versus temperature.     

Single carbon nanotube optical spectroscopy.

This Minireview discusses novel insights into the electronic structure of carbon nanotubes obtained using single-molecule fluorescence spectroscopy. Fluorescence spectra from single nanotubes are well described by a single, Lorentzian lineshape. Nanotubes with identical structures fluoresce with different energies due to local electronic perturbations. Carbon nanotube fluorescence unexpectedly does not-show any intensity or spectral fluctuations at 300 K The lack of intensity blinking or bleaching demonstrates that carbon nanotubes have the potential to provide a stable, single-molecule infrared photon source, allowing for the exciting possibility of applications in quantum optics and biophotonics.     

Temperature effects on femtosecond transient absorption kinetics of semiconducting single-walled carbon nanotubes

We report femtosecond transient absorption kinetics measured for selected semiconducting single-walled carbon nanotubes at different temperatures between 77 and 290 K. The nanotubes are embedded in a thin polymethylmethacrylate film, and the dominance of individual species enabled to probe selectively the kinetics associated with two desired tube types, the (6,5) and (7,5) tubes. A strikingly similar temperature dependence is found between the maximum change in the amplitude of transient absorption kinetics, the overall decay time and steady-state fluorescence emission intensity. The simplest explanation for our data is that the temperature dependence of the fluorescence intensity and the exciton decay kinetics are dominated by nonradiative decay and that the radiative decay rate is weakly temperature dependent.     

Importance of capillary forces in the assembly of carbon nanotubes in a polymer colloid lattice

We highlight the significance of capillary pressure in the directed assembly of nanorods in ordered arrays of colloidal particles. Specifically, we discuss mechanisms for the assembly of carbon nanotubes at the interstitial sites between latex polymer particles during composite film formation. Our study points to general design rules to be considered to optimize the ordering of nanostructures within such polymer matrices. In particular, gaining an understanding of the role of capillary forces is critical. Using a combination of electron microscopy and atomic force microscopy, we show that the capillary forces acting on the latex particles during the drying process are sufficient to bend carbon nanotubes. The extent of bending depends on the flexural rigidity of the carbon nanotubes and whether or not they are present as bundled ensembles. We also show that in order to achieve long-range ordering of the nanotubes templated by the polymer matrix, it is necessary for the polymer to be sufficiently mobile to ensure that the nanotubes are frozen into the ordered network when the film is formed and the capillary forces are no longer dominant. In our system, the polymer is plasticized by the addition of surfactant, so that it is sufficiently mobile at room temperature. Interestingly, the carbon nanotubes effectively act as localized pressure sensors, and as such, the study agrees well with previous theoretical predictions calculating the magnitude of capillary forces during latex film formation.     

Skin Constituents as Cosmetic Ingredients. Part III: A Molecular Modeling Study of Bio‐Mimetic Monoglycerides Behavior at the Squalene‐Water Interface

Tetrakis(4-hydroxylphenyl)porphyrin (THPP) modified multi-walled carbon nanotubes were synthesized. Meanwhile, THPP or tetrakis(4-hydroxylphenyl)porphyrin cobalt(II) (CoTHPP) was introduced on the surface of carboxyl-functionalized multi-walled carbon nanotubes (MWNTs-COOH) and amino-functionalized multi-walled carbon nanotubes (MWNTs-NH₂) to form a series of complexes, respectively. TEM images indicated that the assemblies were made of the short chipping carbon nanotubes and the long assembled carbon nanotubes. The UV-vis spectra and fluorescence spectra were used to investigate the properties of the porphyrins assembled on the carbon nanotubes.     

Optical sensing quantum dot-labeled polyacrolein particles prepared by layer-by-layer deposition technique

Optical sensing polymer particles with tailored semiconductor nanocrystal (QD) loading are prepared by layer-by-layer deposition technique (LbL). Polyacrolein particles of 1.2 μm diameter are used as solid support for deposition of hydrophilic CdSe/ZnS nanocrystal/polyelectrolyte multilayers formed by electrostatic interactions. The pH-dependent fluorescence of QDs and pH-dependent conformations of polyelectrolytes, which likely passivate the surface state of nanocrystals, allow a creation of both mono- and multiplex coded polymer particles with pH-dependent fluorescence intensity. Bovine serum albumin (BSA) as outermost layer makes it possible to design the optical sensing polymer particles with reversibly responded fluorescence at pH variations. The fluorescence of such polymer particles with BSA outer layer is sensitive to copper(II) ion while the fluorescence of these particles is practically insensitive to the other divalent cations (Zn(2+), Ca(2+), Ba(2+), Co(2+), Mg(2+)). The detection limit of Cu(2+) is about 15 nM. Adaptation of LbL method to prepare QD-labeled polymer particles with enhanced complexity (e.g. several types of QDs, multiple biofunctionality) is expected to open new opportunities in biotechnological applications.     

多壁碳纳米管的制备及改性处理

用自制的镍 硅二元气凝胶作催化剂,合成了多壁碳纳米管.甲烷在680℃催化裂解120min,再升温至800℃继续裂解20min,得到多壁碳纳米管.TEM、HRTEM和Raman光谱分析表明,所得多壁碳纳米管与高定向石墨具有相似的层状结构,其管径分布均匀,约15～30nm左右,长径比大,管端封闭,并含有金属催化剂粒子;采用不同方法改性处理,发现经过稀硝酸浸泡和空气氧化处理后,能去除碳管中金属催化剂,同时碳纳米管管长变短,端帽开口,能有效利用内表面,比表面积增大.