Targeted single-wall carbon nanotube-mediated Pt(IV) prodrug delivery using folate as a homing device

Most low-molecular-weight platinum anticancer drugs have short blood circulation times that are reflected in their reduced tumor uptake and intracellular DNA binding. A platinum(IV) complex of the formula c, c, t-[Pt(NH 3) 2Cl 2(O 2CCH 2CH 2CO 2H)(O 2CCH 2CH 2CONH-PEG-FA)] ( 1), containing a folate derivative (FA) at an axial position, was prepared and characterized. Folic acid offers a means of targeting human cells that highly overexpress the folate receptor (FR). Compound 1 was attached to the surface of an amine-functionalized single-walled carbon nanotube (SWNT-PL-PEG-NH 2) through multiple amide linkages to use the SWNTs as a "longboat delivery system" for the platinum warhead, carrying it to the tumor cell and releasing cisplatin upon intracellular reduction of Pt(IV) to Pt(II). The ability of SWNT tethered 1 to destroy selectively FR(+) vs FR(-) cells demonstrated its ability to target tumor cells that overexpress the FR on their surface. That the SWNTs deliver the folate-bearing Pt(IV) cargos into FR(+) cancer cells by endocytosis was demonstrated by the localization of fluorophore-labeled SWNTs using fluorescence microscopy. Once inside the cell, cisplatin, formed upon reductive release from the longboat oars, enters the nucleus and reacts with its target nuclear DNA, as determined by platinum atomic absorption spectroscopy of cell extracts. Formation of the major cisplatin 1,2-intrastrand d(GpG) cross-links on the nuclear DNA was demonstrated by use of a monoclonal antibody specific for this adduct. The SWNT-tethered compound 1 is the first construct in which both the targeting and delivery moieties have been incorporated into the same molecule; it is also the first demonstration that intracellular reduction of a Pt(IV) prodrug leads to the cis-{Pt((NH 3) 2} 1,2-intrastrand d(GpG) cross-link in nuclear DNA.     

Amperometric Detection of Hydrogen Peroxide Using Glassy Carbon Electrodes Modified with Chromium Hexacyanoferrate/Single‐Walled Carbon Nanotube Nanocomposites

Chemical functionalization of single‐walled carbon nanotubes (SWNTs) has constructed plenty of new structures with useful properties. But the modification was often confined to organic molecules, either by covalence or noncovalence. In this report, SWNTs were successfully functionalized with one kind of electroactive inorganic compounds: chromium hexacyanoferrate (Cr hcf). The resulting Cr hcf/SWNTs nanocomposites were confirmed by Field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. Cr hcf crystallites are observed to be finely attached to the SWNTs. The electrochemical properties of Cr hcf/SWNTs nanocomposites were also investigated. The nanocomposites modified glassy carbon (GC) electrode shows high electrocatalytic activity towards the reduction of H₂O₂ and the amperometric responses show a linear dependence on the concentration of H₂O₂ in a range of 0.5 μM to 10 mM (R=0.9989). In addition, the sensor has good stability and reproducibility.     

碳纳米管/超支化重氮盐自组装膜的制备及性能研究

利用静电吸附自组装技术将酸化处理后的单壁碳纳米管(SWNTs)与超支化重氮盐(DAS)组装成多层膜.利用紫外光谱、椭偏仪、原子力显微镜、扫描电镜、拉曼光谱等对自组装膜的生长过程、膜厚增长、自组装膜表面形貌以及纳米管在膜中的存在状态等进行了检测,并利用纳米压痕仪测试了自组装膜的硬度和弹性模量.研究结果表明,SWNTs与DAS不仅发生了静电吸附,而且还发生了化学交联.同时碳纳米管均匀分散在自组装膜中.这两种因素的共同作用使得自组装膜表现出良好的纳米力学性能,硬度达到2.0GPa左右,弹性模量达到10.0GPa左右,而且可以从基底上剥离下来成为独立支撑膜.     

A New Amperometric Hydrazine Sensor Based on Prussian Blue/Single‐walled Carbon Nanotube Nanocomposites

A slow reaction process has been successfully used to synthesize Prussian blue/single‐walled carbon nanotubes (PB/SWNTs) nanocomposites. Electrochemical and surface characterization by cyclic voltammetry (CV), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) confirmed the presence of PB nanocrystallites on SWNTs. PB/SWNTs modified glassy carbon electrode (GCE) exhibits efficient electron transfer ability and high electrochemical response towards hydrazine. The fabricated hydrazine sensor showed a wide linear range of 2.0×10^?6–6.0×10^?3 M with a response time less than 4 s and a detection limit of 0.5 μM. PB/SWNTs modified electrochemical sensors are promising candidates for cost‐effective in the hydrazine assays.     

Pyridine-functionalized single-walled carbon nanotubes as gelators for poly(acrylic acid) hydrogels

Pyridine-functionalized single-walled carbon nanotubes (SWNTs) are prepared from the addition of a pyridine diazonium salt to nanotubes. The location and distribution of the functional groups is determined by atomic force microscopy using electrostatic interactions with gold nanoparticles. The pyridine-functionalized SWNTs are able to act as cross-linkers and hydrogen bond to poly(acrylic acid) to form SWNT hydrogels. The pyridine-functionalized SWNTs are further characterized using Raman, FTIR, UV/vis-NIR, and X-ray photoelectron spectroscopy and thermogravimetric analysis-mass spectrometry.     

Functionalization of Single‐Walled Carbon Nanotubes with Cubic Prussian Blue and Its Application for Amperometric Sensing

In this work, we synthesized electroactive cubic Prussian blue (PB) modified single‐walled carbon nanotubes (SWNTs) nanocomposites using the mixture solution of ferric‐(III) chloride and potassium ferricyanide under ambient conditions. The successful fabrication of the PB‐SWNTs nanocomposites was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and cyclic voltammetry (CV). PB nanocrystallites are observed to be finely attached on the SWNTs sidewalls in which the SWNTs not only act as a carrier of PB nanocrystallites but also as Fe(III)‐reducer. The electrochemical properties of PB‐SWNTs nanocomposites were also investigated. Using the electrodeposition technique, a thin film of PB‐SWNTs/chitosan nanocomposites was prepared onto glassy carbon electrode (GCE) for the construction of a H₂O₂ sensor. PB‐SWNTs/chitosan nanocomposites film shows enhanced electrocatalytic activity towards the reduction of H₂O₂ and the amperometric responses show a linear dependence on the concentration of H₂O₂ in a range of 0.5–27.5 mM and a low detection limit of 10 nM at the signal‐to‐noise ratio of 3. The time required to reach the 95% steady state response was less than 2 s. CV studies demonstrate that the modified electrode has outstanding stability. In addition, a glucose biosensor is further developed through the simple one‐step electrodeposition method. The observed wide concentration range, high stability and high reproducibility of the PB‐SWNTs/chitosan nanocomposites film make them promising for the reliable and durable detection of H₂O₂ and glucose.     

Single‐Walled Carbon Nanotubes in Highly Viscous Media: A Comparison between the Dispersive Agents [BMIM][BF4], L121, and Triton X‐100

Dispersions of single‐walled carbon nanotubes (SWNTs) have been prepared by using the room‐temperature ionic liquid [BMIM][BF₄] (1‐butyl‐3‐methylimidazolium tetrafluoroborate), the triblock copolymer Pluronic L121 [poly(ethylene oxide)₅‐poly(propylene oxide)₆₈‐poly(ethylene oxide)₅] and the non‐ionic surfactant Triton X‐100 (TX100) in the pure state. The size of the SWNTs aggregates and the dispersion degree in the three viscous systems depend on the sonication time, as highlighted by UV/Vis/NIR spectroscopy and optical microscopy analysis. A nonlinear increase in conductivity can be observed as a function of the SWNTs loading, as suggested by electrochemical impedance spectroscopy. The generation of a three‐dimensional network of SWNTs showing a viscoelastic gel‐like behavior above a critical percolation concentration has been found at 25 °C in all the investigated systems by oscillatory rheology measurements.     

Spectroscopic Analysis of Two Distinct Equilibrium States for the Exchange Reaction of Sodium Cholate and Oligo‐DNA on Single‐Walled Carbon Nanotubes

Understanding the quantitative analysis of the transition adsorption structures of molecules on single‐walled carbon nanotubes (SWNTs) is of importance from the point of view of both fundamental science and applications of nanotubes. Absorption spectroscopy reveals that two different equilibrium states are existent for the exchange reaction of sodium cholate (SC) and oligo‐DNA (single‐stranded 20‐mer cytosine) on SWNTs. This is derived from the transitions of the adsorption structures of different chirality‐types of SWNTs and SC/DNA at certain SC concentrations below the critical micelle concentration of SC.     

高温煅烧Mo改性的Fe／MgO催化剂用于制备管径分布均一的单壁碳纳米管

研究了在以甲烷化学气相沉积法制备单壁碳纳米管的过程中高温煅烧预处理(900℃煅烧10h)对Mo改性Fe/MgO催化剂的作用.发现这种预处理有利于Fe在催化剂中的稳定和分散,从而制备出管径均一的单壁碳纳米管.采用能谱元素分析、高分辨透射电镜、X射线衍射、比表面积测量、拉曼光谱和热重分析对样品进行了表征.结果表明,在碳纳米管生长的过程中,铁元素在催化剂表面富集,单壁碳纳米管生长于富集铁的纳米颗粒上,并存在碳管直径与铁颗粒尺寸的依赖关系.Mo存在时可煅烧形成FeMoO4复合氧化物,后者比MgFe2O4相更加稳定.Mo/Fe比例对提高单壁碳纳米管的生长密度、纯度与管径均一性等均有明显影响.上述研究对进一步精确控制制备单壁碳纳米管有重要意义.     

Synthesis and characterization of conducting polythiophene/carbon nanotubes composites

Conducting polythiophene (PTh)/single‐wall carbon nanotubes (SWNTs) composites were synthesized by the in situ chemical oxidative polymerization method. The resulting cablelike morphology of the composite (SWNT–PTh) structures was characterized with elemental analysis, X‐ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared, ultraviolet–visible spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, and transmission electron microscopy. The standard four‐point‐probe method was used to measure the conductivity of the samples. Field emission scanning electron microscopy and transmission electron microscopy analysis revealed that the SWNT–PTh composites were core (SWNTs) and shell (PTh) hybrid structures. Spectroscopic analysis data for the composites were almost identical to those for PTh, supporting the idea that SWNTs served as templates in the formation of a coaxial nanostructure for the composites. The physical properties of the composites were measured and also showed that the SWNTs were modified by conducting PTh with an enhancement of various properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5283–5290, 2006     

Aligned single‐wall carbon nanotube polymer composites using an electric field

While high shear alignment has been shown to improve the mechanical properties of single‐wall carbon nanotube (SWNT)‐polymer composites, this method does not allow for control over the electrical and dielectric properties of the composite and often results in degradation of these properties. Here, we report a novel method to actively align SWNTs in a polymer matrix, which permits control over the degree of alignment of the SWNTs without the side effects of shear alignment. In this process, SWNTs were aligned via AC field‐induced dipolar interactions among the nanotubes in a liquid matrix followed by immobilization by photopolymerization under continued application of the electric field. Alignment of SWNTs was controlled as a function of magnitude, frequency, and application time of the applied electric field. The degree of SWNT alignment was assessed using optical microscopy and polarized Raman spectroscopy, and the morphology of the aligned nanocomposites was investigated by high‐resolution scanning electron microscopy. The structure of the field induced aligned SWNTs was intrinsically different from that of shear aligned SWNTs. In the present work, SWNTs are not only aligned along the field, but also migrate laterally to form thick, aligned SWNT percolative columns between the electrodes. The actively aligned SWNTs amplify the electrical and dielectric properties of the composite. All of these properties of the aligned nanocomposites exhibited anisotropic characteristics, which were controllable by tuning the applied field parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1751–1762, 2006     

Effect of electron-donating and electron-withdrawing groups on peptide/single-walled carbon nanotube interactions

Nano-1, a designed peptide, has been demonstrated to efficiently disperse individual single-walled carbon nanotubes (SWNTs) by folding into an amphiphilic alpha-helix wherein the phenylalanine (Phe) residues on the hydrophobic face of the helix interact via pi-stacking with the aromatic surface of the SWNT. In this study, the ability of electron-donating (hydroxyl) and electron-withdrawing (nitro) groups on the phenyl ring of Phe to affect the interactions between the peptide and SWNTs is examined by substituting the Phe residues in the nano-1 sequence with tyrosine and p-nitro-phenylalanine, respectively. Atomic force microscopy measurements and optical absorption spectroscopy revealed that the ability to disperse individual SWNTs increases with increasing electron density of the aromatic residue on the hydrophobic face of the amphiphilic helical peptides. Scanning tunneling spectroscopy (STS) and Raman analyses were used to examine the effect of noncovalent protein functionalization on the electronic properties of SWNTs. Small shifts in the Raman G band peak for the peptide/SWNT composites, as well as weak features that appear near the Fermi energy (Ef) in the STS dI/dV spectra of the peptide-coated SWNTs, are suggestive of a weak charge-transfer interaction between the peptides and the SWNTs.     

Self-assembly of C60, SWNTs and few-layer graphene and their binary composites at the organic-aqueous interface

Self-assembly of C(60), single-walled carbon nanotubes (SWNTs) and few-layer graphene at the toluene-water interface has been investigated, starting with different concentrations of the nanocarbons in the organic phase and carrying out the assembly to different extents. Morphologies and structures of the films formed at the interface have been investigated by electron microscopy and other techniques. In the case of C(60), the films exhibit hcp and fcc structures depending on the starting concentration in the organic phase, the films being single crystalline under certain conditions. Self-assembly of the composites formed by pairs of nanocarbons (C(60)-SWNT, C(60)-few-layer graphene and SWNT-few-layer graphene) at the interface has been studied by electron microscopy. Raman spectroscopy and electronic absorption spectroscopy of the films formed at the interface have revealed the occurrence of charge-transfer interaction between SWNTs and C(60) as well as between few-layer graphene and C(60).     

Pt nanoparticles/graphene paste electrode for sodium borohydride electrooxidation

The graphene paste electrode (GPE), modified with platinum nanoparticles (NPt), is fabricated and characterized by electrochemical impedance spectroscopy and cyclic voltammetry. Borohydride electrooxidation and hydrogen evolution reaction (HER) are investigated by cyclic voltammetry at surface of the fabricated electrode. Linear sweep voltammetry of NPt/GPE and NPt/carbon paste electrode in different concentrations of borohydride was studied. Results demonstrate good conductivity and electrocatalytic activity of NPt/GPE toward borohydride electrooxidation and HER. The morphology of platinum nanoparticles is studied by atomic force microscopy.     

In situ Raman studies on lithiated single-wall carbon nanotubes in liquid ammonia

The charge transfer induced lithiation of single-wall carbon nanotubes (SWNTs) was investigated by in situ monitoring by Raman spectroscopy as lithium was added incrementally to a dispersion of SWNTs in liquid ammonia. Charge transfer from liquid ammonia solvated lithium to the SWNTs led to intercalation of lithium into the SWNT ropes, as well as to the semi-covalent lithiation of the SWNTs. Raman spectra of the SWNTs recorded as lithium was added showed a 30 wavenumber downshift of the G band (1594 cm⁻¹) with the concomitant appearance of a new peak at 1350 cm⁻¹ that was assigned as the signature of the lithiated SWNTs. Addition of 1-iodododecane to the lithiated SWNTs resulted in the covalent attachment of dodecyl groups. The intercalation of lithium throughout the SWNT ropes led to complete dodecylation of all individual SWNTs.     

Synthesis of nearly uniform single-walled carbon nanotubes using identical metal-containing molecular nanoclusters as catalysts

Uniform and small-diameter single-walled carbon nanotubes (SWNTs) have been produced using identical molecular nanoclusters containing Fe and Mo atoms with a defined molecular formula and a specific structure as catalysts in a chemical vapor deposition method. The average diameter of the SWNTs produced in these experiments is 1.0 nm with a standard deviation for the diameter distribution of 17%. The diameters of SWNTs were obtained by atomic force microscopy and Raman spectroscopy.     

Air‐tolerant Fabrication and Enhanced Thermoelectric Performance of n‐Type Single‐walled Carbon Nanotubes Encapsulating 1,1′‐Bis(diphenylphosphino)ferrocene

The thermally‐triggered n‐type doping of single‐walled carbon nanotubes is demonstrated using 1,1′‐bis(diphenylphosphino)ferrocene, a novel n‐type dopant. Through a simple thermal vacuum process, the phosphine compounds are moderately encapsulated inside single‐walled carbon nanotubes. The encapsulation into SWNTs is carefully characterized using Raman/X‐ray spectroscopy and transmission electron microscopy. This easy‐to‐handle doping with air‐stable precursors for n‐type SWNTs enables the large‐scale fabrication of thermoelectric materials showing an excellent power factor exceeding approximately 240 μW mK^?2.     

Importance of aromatic content for peptide/single-walled carbon nanotube interactions

We have previously demonstrated that a designed amphiphilic peptide helix, denoted nano-1, coats and debundles single-walled carbon nanotubes (SWNTs) and promotes the assembly of these coated SWNTs into novel hierarchical structures via peptide-peptide interactions. The purpose of this study is to better understand how aromatic content impacts interactions between peptides and SWNTs. We have designed a series of peptides, based on the nano-1 sequence, in which the aromatic content is systematically varied. Atomic force microscopy measurements and optical absorption spectroscopy reveal that the ability to disperse individual SWNTs increases with increasing aromatic residues in the peptide. Altogether, the results indicate that pi-stacking interactions play an important role in peptide dispersion of SWNTs.     

Improving the effectiveness of interfacial trapping in removing single-walled carbon nanotube bundles

Single-walled carbon nanotube (SWNT) bundles are selectively removed from an aqueous dispersion containing individually suspended carbon nanotubes coated with gum Arabic via interfacial trapping. The suspensions are characterized with absorbance, fluorescence, and Raman spectroscopy as well as atomic force microscopy (AFM) and rheology. The resulting aqueous suspensions have better dispersion quality after interfacial trapping and can be further improved by altering the processing conditions. A two-step extraction process offers a simple and fast approach to preparing high-quality dispersions of individual SWNTs comparable to ultracentrifugation. Partitioning of SWNTs to the liquid-liquid interface is described by free energy changes. SWNT bundles prefer to reside at the interface over individually suspended SWNTs because of greater free energy changes.     

Zn改性的Pt/SAPO-11催化剂及其提高二甲基烷烃选择性

随着环保法规的日益苛刻,世界各国对发动机燃料指标的要求也越来越严格,汽油组分中的烯烃含量逐渐被限制.作为提高汽油辛烷值的有效手段,正构烷烃的临氢异构化越来越引起人们的重视.烷烃碳数相同时,具有多支链的异构体往往具有更高的辛烷值.因此,在正构烷烃临氢异构化过程中,提高多支链异构体的选择性具有重要意义.Pt/SAPO-11作为双功能催化剂具有适宜的孔结构、温和的酸性和适度的加氢脱氢活性,在烷烃临氢异构化反应中表现出色,得到了广泛研究.已有文献报道中,通过添加第二金属改性可以调节双功能催化剂的物理化学性质,进而影响其催化活性和产物选择性.为了提高异构产物选择性,特别是多支链异构产物的选择性,本文研究了Zn改性的Pt/SAPO-11催化剂在正辛烷临氢异构化中的反应性能,与未改性的Pt/SAPO-11催化剂相比,Zn改性的Pt/SAPO-11催化剂表现出更高的二甲基烷烃选择性.通过动态合成方法合成SAPO-11分子筛,进而制备Zn改性的Pt/SAPO-11催化剂.XRD表征表明,Pt和Zn的引入基本没有引起SAPO-11特征峰改变,并且未发现Pt和Zn氧化物的特征峰,说明金属组分得到很好的分散.氮气吸附-脱附实验表明,随着Zn添加量的增加,载体的比表面积和孔体积略有减少.NH3-TPD和吡啶红外光谱用于表征Zn的加入对催化剂酸性的影响,结果表明,少量Zn的添加可以增加酸量,这是由于Zn的引入可以产生L酸性位;而随着Zn的增加,总酸量减少,这是由于过多的Zn覆盖了载体的酸性位.H2-TPR和H2-TPD表征发现,Zn的引入使得Pt在高温处的还原峰减小,说明Zn改变了Pt在载体上的位置,使其主要负载在分子筛外表面.由于Zn2+是阳离子并具有较小的离子半径,它可以作为竞争吸附剂,首先进入分子筛孔道从而抑制了Pt进入分子筛孔道.H2-TPD表明,Zn的引入使得H2的脱附温度逐渐降低,这与Zn增加了Pt的分散度有关;但是当Zn的添加量达到0.7%时,H2的脱附温度升高,同时溢流氢增加.以正辛烷为模型化合物,在固定床高压微型反应装置中对一系列催化剂进行了评价,考察了Zn改性的Pt/SAPO-11催化剂和未改性的Pt/SAPO-11催化剂的催化性能.与未改性催化剂相比,Zn改性的催化剂在相同转化率条件下,异辛烷的选择性基本相同,但是二甲基己烷的选择性明显提高.当Zn的添加量为0.5%时,二甲基己烷选择性达到最大值,继续提高Zn的添加量,其选择性下降.值得注意的是,在相同反应条件下,未改性的催化剂具有更高的正辛烷转化率.我们分析认为,由于Zn的添加促进了二甲基己烷的产生,而其具有较大的分子尺寸,在反应中存在扩散问题,影响了改性催化剂的异构化活性.本文工作表明,适宜的Zn添加量有利于提高二甲基烷烃的选择性,对于提高汽油辛烷值具有重要意义.