Interactions Between Amino Acid‐Tagged Naphthalenediimide and Single Walled Carbon Nanotubes for the Design and Construction of New Bioimaging Probes

A new synthetic route to functionalized single walled carbon nanotubes (SWNTs) via supramolecular interactions using a specifically designed naphthalenediimide (NDI) nanoreceptor is demonstrated. The tendency of the NDI to spontaneously form composites with carbon nanomaterials leads to fluorescent amino acid tagged SWNTs, which are dispersible in widely accessible organic solvents (CHCl₃, DMSO) as well as in biocompatible cell medium (EMEM, Eagle's modified essential medium). The X‐ray crystal structure of the first iodine‐tagged and amino acid‐functionalized NDI molecule, designed especially to facilitate the high resolution transmission electron microscopy (HR TEM) imaging whilst retaining its ability to self‐assemble into a nanodimensional receptor in weakly polar solvents, is also described. A new hybrid material, NDI@SWNT, was prepared and characterized as dispersed in organic solvents and aqueous media and in the solid state by HR TEM, tapping mode atomic force microscopy (TM AFM), scanning electron microscopy (SEM), circular dichroism, Raman and fluorescence spectroscopies (steady‐state single and two‐photon techniques). Combined microscopy techniques, density functional theory (DFT) calculations using the Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) program and spectroscopic measurements in solution indicate that amino acid‐functionalized NDI interacts strongly with SWNTs and forms a donor‐acceptor complex. Density functional theory (DFT) calculations predicted the geometry and the binding energies of an NDI molecule loaded onto a SWNT strand and the possibility of charge transfer interactions within the hybrid. The NDI@SWNT composite translocates into cells (e.g. FEK‐4, HeLa, MCF‐7) as an intact object and localizes in the cells' cytoplasm and partially in the nucleus. The NDI coating enhances the biocompatibility of SWNTs and mediates its intracellular localization as shown by confocal fluorescence imaging and fluorescence lifetime imaging (FLIM) techniques. The excited state fluorescence lifetime of the probes in cells versus solution phase indicates that the probes remain unaffected by the change in their chemical environment within the experimental timescale (2 h).     

银表面上直立单壁碳纳米管阵列的制备

本文报道了如何用自组装技术在银表面构筑直立的单壁碳纳米管阵列,将化学气相沉积合成（CVD）的单壁碳纳米管在混酸（浓硫酸／浓硝酸＝3／1）中氧化使其在末端开口处带有羧基,利用羟基在银表面的成盐自组装来制备单壁碳纳米管阵列。结果表明,碳纳米管可有效地固定并直立在银表面,直立在银表面上的碳纳米管长度约在60－200nm。     

Growing and characterizing one-dimensional crystals within single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have been used as growth templates for spatially confined crystal growth. The comparative crystallization and high-resolution transmission electron microscopy imaging properties of simple binary halides formed by the alkali iodides MI (M = Li, K, Na, Rb and Cs) within SWNTs are described. The most common structure type observed within SWNTs was the rocksalt archetype, although CsI was observed to form both body-centred cubic (bcc) and rocksalt structure types. ThCl4 was found to form a chain structure of Th[Cl]8 polyhedra. HgI2 crystallized within nanotubes with ultra-narrow (i.e. 0.8 nm) capillaries was observed to form helical 2 x 1 layer crystals.     

Enzyme‐Mediated Deposition of a TiO2 Coating onto Biofunctionalized WS2 Chalcogenide Nanotubes

A chemically specific and facile method for the biofunctionalization of WS₂ nanotubes (NT‐WS₂) is reported. The covalent modification strategy is based on the affinity of the nitrilotriacetic acid (NTA) side chain, which serves as a ligand for the surface binding to NT‐WS₂ and simultaneously as an anchor group for the binding of His‐tagged proteins to the polymer backbone. The polymer functionalized WS₂ nanotubes can be solubilized either in water or organic solvents; they are stable for at least one week. The probes were characterized by FT‐IR and UV‐vis spectroscopy. The immobilization of silicatein, a hydrolytic protein encountered in marine sponges, was visualized by scanning force microscopy (SFM) and confocal laser scanning microscopy (CLSM). The formation of the biotitania coating mediated by the immobilized silicatein onto the surface was characterized by scanning electron microscopy (SEM), and transmission electron microscopy (TEM).     

激光功率对连续CO2激光制备单壁碳纳米管的影响

在室温下用大功率连续CO2激光制备单壁碳纳米管，测量了500～850W激光功率下产生的碳纳米管样品的透射电镜和拉曼(Raman)光谱，对单壁碳纳米管的生长条件和直径分布与激光功率的关系进行了研究，实验证明在长波长激光制备单壁碳纳米管中，激光功率对单壁碳纳米管的形成和管径的大小起着关键的作用。激光功率越高，单壁碳纳米管的产率越大。对不同管径的单壁碳纳米管，激光功率较高所制备得到的平均管径较大。     

Reactive Spinning of Cyanate Ester Fibers Reinforced with Aligned Amino‐Functionalized Single Wall Carbon Nanotubes

We report a new approach of reactive spinning to fabricate thermosetting cyanate ester micro‐scale diameter fibers with aligned single walled carbon nanotubes (SWNTs). The composite fibers were produced by first dispersing the SWNTs (1 wt %) in cyanate ester (CE) via solvent blending, followed by pre‐polymerization, spinning and then multiple‐stage curing. The pre‐polymerization, spinning and post‐spinning cure temperatures were carefully controlled to achieve good spun crosslinked fibers. Both pristine and amino‐functionalized SWNTs were used for the reinforced fiber spinning. Amino‐functionalized SWNTs (f‐SWNTs) were prepared by reacting acid‐treated SWNTs with toluene 2,4‐diisocyanate and then ethylenediamine (EDA). FTIR, optical microscopy and scanning electron microscopy (SEM) showed that the amino‐functionalized SWNTs were covalently and uniformly dispersed into the cyanate ester matrix and aligned along the fiber axis. The alignment was further confirmed using polarized Raman spectroscopy. The composite fibers with aligned amino‐functionalized SWNTs possess improved tensile properties with respect to neat CE fibers, showing 85, 140, and 420% increase in tensile strength, elongation and stress‐strain curve area (i.e., toughness), respectively. NH₂‐functionalization of SWNTs improves their dispersibility, alignment and interfacial strength and hence tensile properties of composite spun fibers. Fiber spinning to align SWNTs using thermosetting resin is novel. Others have reported fiber spinning to align SWNTs in thermoplastics. However, thermosetting CE resins offer the advantages of low and controllable viscosity during spinning and reactivity with amino functional groups to enable f‐SWNT/CE covalent bonding.     

竹节形碳纳米管的制备

采用乙醇催化燃烧法制备竹节形碳纳米管,利用乙醇作为碳源和燃料提供材料生长所需的能量,以Cu薄片作为基底,FeCl3与Fe(NO3)3作为催化剂先体。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、喇曼光谱对黑色絮状的沉积产物进行表征。实验结果表明,产物中的碳纳米管具有较好的竹节形结构,竹节形碳纳米管的形貌和微结构与独特的制备条件有关。并对竹节形碳纳米管的生成机理进行了初步探讨。     

Structural and optical properties of functionalized multi-walled carbon nanotubes

Herein, we report the functionalization of multiwalled carbon nanotubes (MWCNTs) using meta-Chloroperoxybenzoic acid (mCPBA) as an oxidizing agent. Epoxy groups are incorporated into the sidewall of MWCNTs and the prepared functionalized multiwalled carbon nanotubes (F-MWCNTs) were characterized using FT-IR spectroscopy, X-ray diffraction, Raman spectroscopy and UV–visible spectroscopy. Morphology of MWCNTs and F-MWCNTs was determined using Scanning electron microscopy (SEM) and transmission electron microscopy (TEM). TEM results clearly indicated that the diameter of F-MWCNTs is increased by 120% as compared to neat MWCNTs. From UV–visible spectroscopy data, band gap of F-MWCNTs was calculated using Tauc equation and it was found to be 3.9 eV. Photo emission property of F-MWCNTs was analyzed using photoluminescence spectroscopy. F-MWCNTs showed nice emission in the visible region and it depended upon the excited wavelength. These functionalized carbon nanotubes could find use as tunable optoelectronic devices in future nanotechnology.     

Improvement in Performance of Carbon Nanotube Field-Effect Transistors on Patterned SiO<Subscript>2</Subscript>/Si Substrates

Horizontally aligned single-walled carbon nanotubes (SWNTs) were fabricated on patterned SiO₂/Si substrates with groove-and-terrace structures, which were obtained using electron-beam lithography and reactive ion etching. Scanning electron microscopy observation revealed that SWNTs were aligned in the direction parallel to the groove-and-terrace structures and were preferentially grown along the edges of terraces. Using aligned SWNTs as multichannels, carbon nanotube field-effect transistors (CNTFETs) were fabricated on the patterned SiO₂/Si substrates. This method will be promising to control the direction of SWNTs on SiO₂/Si substrates for fabrication of high-performance CNTFETs with high current outputs.     

RF-PECVD法研究碳纳米管的生长特性

采用射频等离子体增强化学气相沉积(RF-PECVD),以Fe作为催化剂,在Si基片上生长了碳纳米管(CNT),采用扫描电子显微镜(SEM),高分辨透射电子显微镜(HR TEM)以及显微Raman光谱等对制备的CNT的形貌及结构进行了表征.结果表明:700℃和800℃温度下生长的CNT均取向无序、弯曲缠结,由整齐排列的圆...     

Synthesis optimization and characterization of multiwalled carbon nanotubes

The unique properties of carbon nanotubes (CNTs) have suggested applications in a variety of fields. Multiwalled nanotubes were synthesized using chemical vapor deposition (CVD) procedures and subsequently characterized. Reaction parameters such as catalyst type and carrier gas flow rate were optimized to produce well-aligned multiwalled nanotubes with lengths between a few microns to several millimeters. Characterization was performed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), energy dispersive x-ray spectroscopy (EDS), thermo-gravimetric analysis, and Raman spectroscopy, focusing on composition and purity. Results show the synthesis of high-purity nanotubes of several millimeters in length from iron, nickel, cobalt, and titanium carbide catalysts with thermal stability to above 550°C.     

A Facile Strategy for Preparation of Fluorescent SWNT Complexes with High Quantum Yields Based on Ion Exchange

The fluorescent imidazolium salt (1,3‐bis(9‐anthracenylmethyl)imidazolium chloride, [bamim]Cl) has been grafted onto the surfaces of single‐walled carbon nanotubes (SWNTs) using an ion exchange strategy based on metathesis of the K⁺ ion in CO₂K derivatized SWNTs with [bamim]⁺. The resulting SWNT‐[bamim] complex has been characterized with high‐resolution transmission electron microscopy (HR‐TEM), X‐ray photoelectron spectroscopy (XPS), elemental mapping, and elemental linear profiles analysis. A blue light emission can be observed at 392, 414 and 438 nm for SWNT‐[bamim] upon being excited at 254 nm. The quantum yield (QY) of the SWNT‐[bamim] complex (0.40) is much higher than that of SWNT/[bamim]Cl (0.02), used as a control, and prepared using a π‐π stacking method, indicating that ion exchange is a far more effective strategy for retaining a high QY. Additionally, UV‐Vis‐NIR and Raman spectroscopy show that the SWNT‐[bamim] complex can maintain the one‐dimensional electronic states of SWNTs. Other imidazolium salts have also been successfully grafted onto SWNTs via the same strategy, indicating that the ion exchange process can serve as a universal strategy for the functionalization of SWNTs.     

Optical and photocatalytic properties of indium phosphide nanoneedles and nanotubes

Large scale indium phosphide (InP) nanoneedles and nanotubes were synthesized through a facile solvothermal reaction. The morphology and microstructure of the samples were analyzed by employing scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and Ultraviolet-visible (UV–vis) spectroscopy. The room temperature photoluminescence (PL) measurements showed that the InP nanoneedles and nanotubes possessed a pronounced blue shift in contrast to the bulk counterpart, which was ascribed to the crystalline defects effect. Moreover, the InP nanotubes exhibited an enhanced photocatalytic performance as compared to the InP nanoneedles and nanoparticles.     

Growth of High-Density Self-Aligned Carbon Nanotubes and Nanofibers Using Palladium Catalyst

In this paper we demonstrate vertical self-aligned growth of carbon nanotubes (CNT) and carbon nanofibers (CNF) using 1 nm of Pd as the catalyst material. Results were compared with those obtained using traditional catalysts (Co, Fe, and Ni). Pd is of interest as it has been demonstrated to be an excellent material for electrical contact to nanotubes. CNT were grown using plasma-enhanced chemical vapor deposition (PECVD) at 450°C to 500°C and using atmospheric-pressure chemical vapor deposition (APCVD) between 450°C and 640°C. The results were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. High-density (10¹¹ cm⁻² to 10¹² cm⁻²) self-aligned CNT growth was obtained using APCVD and Pd as the catalyst, while Co and Fe resulted in random growth. TEM revealed that the CNT grown by Pd with PECVD form large bundles of tubes, while Ni forms large-diameter CNF. It was found that the CNT grown using Pd or Ni are of low quality compared with those grown by Co and Fe.     

用FeCl_3作催化剂先体制备碳纳米结构

以不同浓度的FeCl3溶液作为催化剂先体,利用乙醇催化燃烧法,在铜片上生长出了碳纳米管和碳纳米纤维。讨论了不同浓度的FeCl3催化剂先体对生长碳纳米材料产物和形貌的影响。利用扫描电镜,透射电镜和喇曼光谱对样品的形貌和结构进行了表征。实验结果表明,随着催化剂先体浓度增大,碳纳米材料产量增大,直径呈现增大趋势,其直径范围也逐渐变大。当催化剂先体浓度为0.01mol/L时,可以制备出直径较小的碳纳米管;当催化剂先体浓度为0.1mol/L时,可以制备出直径分布均匀的碳纳米管与碳纳米纤维的混合物;当催化剂先体浓度为1mol/L时,可以制备出直径分布不均匀的碳纳米纤维。     

Effect of SWNT Defects on the Electron Transfer Properties in P3HT/SWNT Hybrid Materials

Poly(3‐hexylthiophene) (P3HT) hybrids with single‐walled carbon nanotubes (SWNTs) were prepared using a series of SWNTs with various defect contents on their surfaces. The hybrids were synthesized by exploiting the π–π interaction between P3HT and the SWNTs, resulting in efficient dispersion of the carbon nanotubes in the P3HT solution. UV‐visible and photoluminescence (PL) spectra showed that the carbon nanotubes quench the PL of P3HT in the hybrids, indicating that electron transfer occurs from photo‐excited P3HT to the SWNTs. This electron transfer from P3HT to carbon nanotubes was disrupted by the presence of defects on the SWNT surfaces. However, the PL lifetime of P3HT in the hybrids was found to be the same as that of pure P3HT in solution, indicating the formation of a ground‐state non‐fluorescent complex of P3HT/SWNTs.     

Anodic formation of aligned and bamboo-type TiO2 nanotubes at constant low voltages

Bamboo-type TiO2 nanotubes with a highly ordered structure on titanium surface were synthesized by a self-assembly electrochemical anodization in viscous glycerol solution at constant low voltages. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology of the bamboo-type TiO2 nanotubes. The experimental results show that the morphologies of the nanotubes are markedly influenced by the viscosity (the water content) of the electrolytes solution, the anodization voltage and the anodization time. Besides, a possible formation mechanism for the bamboo-type TiO2 nanotubes was proposed.     

Structural and electrical investigation of BLT films deposited at different times using electron beam evaporation technique

Thin films Bi4Ti3O12 (BLT) were deposited using electron beam evaporation on silicon substrate at several times, also on AlN/Si and SiO2/Si substrates. Thin films morphology and thickness were measured via scanning electron microscopy (SEM). The crystallography was studied using X-ray diffraction (XRD) technique for films which have a (0010) preferred orientation in all substrate types. The capacitance values were contingent on frequency value in C-V measurement. The ferroelectric characterization was investigated for BLT film deposited on isolator layer (SiO2 or AlN) for Al/Bi4Ti3O12/SiO2/Si devices. Memory effect value varied from 1 V to 3 V depending on the thin films isolator on substrate.     

Poly(ϵ‐caprolactone)‐Functionalized Carbon Nanotubes and Their Biodegradation Properties

Biodegradable poly(?‐caprolactone) (PCL) has been covalently grafted onto the surfaces of multiwalled carbon nanotubes (MWNTs) by the “grafting from” approach based on in‐situ ring‐opening polymerization of ?‐caprolactone. The grafted PCL content can be controlled easily by adjusting the feed ratio of monomer to MWNT‐supported macroinitiators (MWNT‐OH). The resulting products have been characterized with Fourier‐transform IR (FTIR), NMR, and Raman spectroscopies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). After PCL was coated onto MWNT surfaces, core/shell structures with nanotubes as the “hard” core and the hairy polymer layer as the “soft” shell are formed, especially for MWNTs coated with a high density of polymer chains. Such a polymer shell promises good solubility/dispersibility of the MWNT–PCL nanohybrids in low‐boiling‐point organic solvents such as chloroform and tetrahydrofuran. Biodegradation experiments have shown that the PCL grafted onto MWNTs can be completely enzymatically degraded within 4 days in a phosphate buffer solution in the presence of pseudomonas (PS) lipase, and the carbon nanotubes retain their tubelike morphologies, as observed by SEM and TEM. The results present possible applications for these biocompatible PCL‐functionalized CNTs in bionanomaterials, biomedicine, and artificial bones.     

Protamine Functionalized Single‐Walled Carbon Nanotubes for Stem Cell Labeling and In Vivo Raman/Magnetic Resonance/Photoacoustic Triple‐Modal Imaging

Stem cells have shown great potential in regenerative medicine and attracted tremendous interests in recent years. Sensitive and reliable methods for stem cell labeling and in vivo tracking are thus urgently needed. Here, a novel approach to label human mesenchymal stem cells (hMSCs) with single‐walled carbon nanotubes (SWNTs) for in vivo tracking by triple‐modal imaging is presented. It is shown that polyethylene glycol (PEG) functionalized SWNTs conjugated with protamine (SWNT‐PEG‐PRO) exhibit extremely efficient cell entry into hMSCs, without affecting their proliferation and differentiation. The strong inherent resonance Raman scattering of SWNTs is used for in vitro and in vivo Raman imaging of SWNT‐PEG‐PRO‐labeled hMSCs, enabling ultrasensitive in vivo detection of as few as 500 stem cells administrated into mice. On the other hand, the metallic catalyst nanoparticles attached on nanotubes can be utilized as the T2‐contrast agent in magnetic resonance (MR) imaging of SWNT‐labeled hMSCs. Moreover, in vivo photoacoustic imaging of hMSCs in mice is also demonstrated. The work reveals that SWNTs with appropriate surface functionalization have the potential to serve as multifunctional nanoprobes for stem cell labeling and multi‐modal in vivo tracking.