杯[8]芳烃及其C60络合物有序阵列的构筑

文章介绍了最近作者对杯芳烃及其C60络合物有序阵列的研究结果，以多孔的杯[8]芳烃阵列为模板，通过主客体相互作用，在Au(111)表面上成功构筑了高度有序的C60阵列，这一结果为富勒烯等功能分子有序阵列的制备、表面可控组装以及纳米信息存储器件的构筑等提供了又一可能性。     

ESR study of calix[4]arene by spin-trapping method

Electron spin resonance (ESR) measurements are introduced to investigate the interaction between 5,11,17,23-tetrabromo-25,26,27,28-tetramethoxycalix[4]arene (II ₄) and 2-methyl-2-nitrosopropane (MNP) or nitrosodurene (ND) which are used as spin-trapping reagents under ultraviolet irradiation. In most cases, the complicated ESR spectra were observed because of the overlap of ESR signals attributed to several spin adducts in different conformations or in an inclusion state. However, after the optimum amount of ND was added into theII ₄ solution, the ESR spectrum showed that each nitrogen hyperfine line was further split to 1:2:1 triplet lines, and this is a typical spectrum ascribed to the spin adduct of ND at one para position ofII ₄.     

Studies on the adsorption of arsenic on calix[6]arene

p‐tert‐butyl calix[6]arene (PTC6) was synthesized and characterized by solid‐ and liquid‐state NMR and LC‐MS techniques. The adsorption of arsenite and arsenate on calix[6]arene under different pH conditions and adsorbate doses was studied. The maximum adsorption of arsenic species on calix[6]arene was observed around neutral pH and the adsorption density of As (III) was higher than that of As (V). The adsorption of neutral H₃AsO₃ and negatively charged H₂AsO molecules on calix[6]arene was attributed to the condensation reaction between hydroxyl groups of PTC6 and arsenic species. The complexation of arsenite with phenolic oxygen was confirmed by solid‐state ¹³C NMR CP‐MAS. Exo attack mechanism was proposed to describe the interaction of arsenous and arsenic acid molecules with PTC6. The specific interaction between calix[6]arene and arsenic species was further substantiated by zeta‐potential (ζ‐potential) measurements and free energy of adsorption. The free energy of adsorption ( ) estimated from Stern–Grahame equation was found to be 25 kJ/mole for As (III) and 19 kJ/mole for As (V). Copyright © 2010 John Wiley & Sons, Ltd.     

Aspects of proton transport in calix[6]arene sulfonic acid

The features of proton transport and proton hydration shell structure of calix[6]arene sulfonic acid were studied. XRD and NMR data indicate the existence of crystalline and amorphous phases and various conformations in the acid structure. The hydration process occurs in three stages by thermal analysis and IR spectroscopy. The change in the composition of the hydrate affected the conductivity only at low humidity; an inverse relationship between the water uptake and the activation energy of conductivity is observed in the entire investigated range of humidity.     

Spectrophotometric Studies on the Complexes of 25,26,27,28-Tetraepoxypropoxy-p-tert-butylcalix[4]arene and 25,26,27,28-Tetrahydroxypropilaminoxy-p-tert-butylcalix[4]arene with Iodine

Two p-tert-butylcalix[4]arene derivatives were synthesized from the reaction of calixarene with epichlorohydrine and then its reaction of ammonia. These donor macromolecular compounds were interacted with iodine in chloroform and interaction was investigated by using a UV-visible spectrophotometer. The chargetransfer spectra of n-[sgrave] type interactions were observed at 362 nm and 369 nm. The stability constants and some thermodynamic parameters were found.     

Optical and structural properties of calix[4]arene thin films elaborated by pulsed laser deposition

p-tert-butylcalix[4]arene thin films were elaborated by pulsed laser deposition (PLD) using a KrF excimer laser with fluences from 0.13 to 1 J/cm². The conservation of the molecule composition and conformation, as verified by FTIR, is obtained for fluences lower than about 0.45 J/cm². The refractive indices and thicknesses were measured by m-lines spectroscopy. The refractive indices have a step profile and are higher than for films elaborated by thermal evaporation. At higher fluences, the molecule conformation is changed and the step index profile is no longer valid. The effect of annealing on surface morphology and crystallization was studied by AFM and XRD. PACS 81.15.Fg; 81.05.Lg; 33.20.Ea; 78.20 Ci     

不同参数多壁碳纳米管太赫兹谱特性

探索不同管径和长度的多壁碳纳米管（MWCNT）的太赫兹（THz）谱特性,采用透射型太赫兹时域光谱系统研究了5个不同管径和长度的MWCNT样品的太赫兹吸收谱和折射率谱,并对比和分析了它们的差异。结果表明：在0.2～2.0 THz内,多壁碳纳米管太赫兹吸收没有特征吸收峰,吸收强度随着频率的增加而增加,并可以拟合为不同斜率的直线,且MWCNT在THz波段的吸收强度与管径和长度成正比。折射率随着频率的增加呈指数衰减,同时,管径是影响其折射率的一个重要因素,而长度对其影响不大。     

不同参数多壁碳纳米管太赫兹谱特性

探索不同管径和长度的多壁碳纳米管(MWCNT)的太赫兹(THz)谱特性,采用透射型太赫兹时域光谱系统研究了5个不同管径和长度的MWCNT样品的太赫兹吸收谱和折射率谱,并对比和分析了它们的差异。结果表明:在0.2~2.0THz内,多壁碳纳米管太赫兹吸收没有特征吸收峰,吸收强度随着频率的增加而增加,并可以拟合为不同斜率的直线,且MWCNT在THz波段的吸收强度与管径和长度成正比。折射率随着频率的增加呈指数衰减,同时,管径是影响其折射率的一个重要因素,而长度对其影响不大。     

Tubular composite of doped polyaniline with multi-walled carbon nanotubes

We report on the synthesis of tubular composite of doped polyaniline (PANI) with carboxylic groups contained multi-walled carbon nanotube (MWNTs) by in situ polymerization. Based on the interaction between aniline monomers and c-MWNTs , aniline molecules were adsorbed and polymerized on the surface of c-MWNTs . The structural characterization showed that tubular composites are core (c-MWNTs )-shell (doped-PANI) structures with diameters of several tens of nanometers, and lengths of up to several hundreds of nanometers. The conductivities of these tubular composites are several times higher than that of PANI without MWNT, which will offer new application possibilities. PACS 81.05.Qk; 81.05.Tp     

Thermal transport enhancement of multi-walled carbon nanotubes/ high-density polyethylene composites

Multi-walled carbon nanotubes (MWCNTs) enhanced high-density polyethylene (HDPE) composites were prepared and their thermophysical properties were measured. The thermal diffusivity of the composites increases with the increase in the amount of MWCNTs. A thermal diffusivity of more than three times that of pure HDPE was obtained for 38 vol. % MWCNTs/HDPE composites. An equation based on an effective medium approach model was used to discuss the thermal diffusivity enhancement of MWCNTs/HDPE composites as a function of the volume fraction of MWCNTs. The results from this analysis can be a predictive guideline for further improvements in the thermal transport properties of MWCNTs/HDPE composites. Moreover, the intrinsic longitudinal thermal conductivity k_z of an individual MWCNT was deduced from the measured results on the MWCNTs/HDPE composites. PACS 67.55.Hc; 61.46.Fg; 66.30.Xj     

Quenching of Pyrene Fluorescence by Calix[4]arene and Calix[4]resorcinarenes

Interactions involving calixarene and its derivatives are of major importance due to their widespread applications as unique hosts. Fluorescence from a common probe pyrene is used to study interactions involving calix[4]resorcinarene [1a] and its tetra-morpholine derivative [1b] in 1 M aqueous NaOH. These compounds efficiently quench the pyrene fluorescence. A comparison with the fluorescence quenching behavior of N-methylmorpholine clearly indicates the presence of long-range interactions involving 1a and 1b; the interactions are specific to the calixarene molecular framework. This is not the case for a tetra-nitro-substituted calix[4]arene [2b], an electron/charge acceptor quencher, as p-nitrophenol also shows similar interactions with pyrene. Effectiveness of cesium as the quencher of pyrene fluorescence is reduced in the presence of electron/charge donating 1b; fluorescence enhancement is observed upon addition of cesium as the concentration of 1b is increased in the solution. The role of calixarene framework in interactions involving such compounds is established.     

Enhanced interlaminar fracture toughness of unidirectional carbon fiber/epoxy composites modified with sprayed multi-walled carbon nanotubes

A recently reported solvent spraying technique was used herein for incorporation of multi-walled carbon nanotubes (MWCNTs) on unidirectional carbon fiber/epoxy prepregs. The role of the agglomerates reduction of oxidized MWCNTs on Mode-I interlaminar fracture toughness (G_IC) of laminated composites was investigated using double cantilever beam tests. Multiscale laminate composites were fabricated using MWCNTs without and with an acid oxidation, agglomerates reduction (AR) and a sequential treatment based on oxidation and AR. For comparison, specimens without MWCNTs were also prepared and tested. Fourier transform infrared analysis shows evidence of an important amount of oxygenated functional groups on the surface of as-received and oxidized MWCNTs. The results also show Mode-I fracture toughness improvements for all the laminated composites compared to reference samples. A substantial 52% increase in the average G_IC initiation was achieved for laminated composites reinforced with oxidized AR-MWCNTs prepared with only 0.05 wt.% MWCNTs.     

A Fluorescent and Phosphorescent Nanoporous Solid: Crystalline Calix[4]arene

Calix[4]arene forms elongated nanoporous microcrystals. The pores are linear nano-channels (1.7 nm diameter) arranged in a honeycomb network. The crystals luminesce at room temperature according to a variety of processes that include monomer fluorescence (lifetime of ca. 1.1 ns), dimer fluorescence (lifetime of ca. 5.4 ns), and monomer phosphorescence (lifetime of ca. 2 s). The dimers result from pi-orbital overlap of adjacent phenol groups from neighboring nano-channels, with C-C distances of ca. 4 A.     

A new one-step synthesis method for coating multi-walled carbon nanotubes with iron oxide nanorods

A facile solution-chemical method has been developed to be capable of covering a multiwalled carbon nanotube (MWNTs) with iron oxide nanorods without using any bridging species. MWNTs in this composite were decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 15–30 nm. The formation route to anchor α-Fe₂O₃ nanorods onto MWNTs was proposed as the intercalation and adsorption of iron ions onto the wall of MWNTs, followed by the nucleation and growth of α-Fe₂O₃ nanorods. α-Fe₂O₃/MWNTs nanocomposites show specific high Brunauer–Emmett–Teller surface areas. The photocatalytic activity experiment indicated that the prepared α-Fe₂O₃/MWNTs nanocomposites exhibited a higher photocatalytic activity for the photocatalytic decolorization of rhodamine B aqueous solution under the visible-light illumination than the single phase α-Fe₂O₃ samples. This methodology made the synthesis of MWNTs-nanorods composites possible and may be further extended to prepare more complicated nanocomposites based on MWNTs for technological applications.     

Connection of silicon nanocrystals (Si-nc) with multi-walled carbon nanotubes

During the last decade silicon nanocrystals (Si-nc) have received widespread interest because of their high quantum efficiency for light emission at room temperature. However, the challenge still ahead is to study and apply these to single Si-ncoptoelectronics, i.e., solving problems linked with connection and manipulation. In this letter we report on connecting (wiring) single Si-nc with conducting multi-walled carbon nanotubes (MWNTs). We have been able to establish a strong mechanical connection by direct growth of MWNTs on Si-nc used as support of iron nanoparticles, by catalytic chemical vapor deposition (CCVD). To monitor the initial stage of the MWNTs growth process, we used a tapered element oscillating microbalance (TEOM). We compared the growth process on Si-nc coated by iron (Fe/Si-nc) to the standard process of growing MWNTs on alumina as support for iron (Fe/Al). The results showed that in the case of Fe/Si-nc catalyst, we obtained three times larger diameter of multi-walled CNTs compared to Fe/Al. This was mainly due to the Si-nc size. The diameter of the CNTs only depended on the size of the Si-nc particles that rested stuck on the tip of the MWNTs. The connected Si-nc kept their photoluminescence properties at room temperature. The present findings open new opportunities in the development of nanodevices for the optoelectronic application field. PACS 81.07.Bc; 81.07.Lk; 81.07.De     

Analytical Evaluation of Cu<Superscript>2+</Superscript> Selective Behavior of calix[4]arene Derivative

The present article describes the solvatochromic effect including solvent system selection, time study and a detailed complexation study along with exploration of extraction properties of 5,11,17,23-tetrakis[(diethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4) that bears nitrogen atom as a donor group available for chelating metal ions. Complexation properties of 4 toward selected transition metal ions have been investigated by UV-visible and fluorescence spectroscopies. The% efficiency of 4 toward selected transition metal ions was found in order Cu²⁺> Ni²⁺> Hg²⁺> Zn²⁺> Co²⁺> Cd²⁺> Pb²⁺. It has been noticed that 4 is not only proved to be an efficient Cu²⁺ selective chromoionophore but also possesses an effective extraction property for transferring Cu²⁺ ions from an aqueous to dichloromethane layer. The FT-IR spectroscopic method has also been applied for further confirmation of the complexation phenomenon of 4 with Cu²⁺ ion and found adequate.     

多壁碳纳米管阵列场发射研究

研究了Ar离子束轰击及温度对多壁碳纳米管阵列场发射性能的影响.经Ar离子轰击35min后，发现阵列顶端的Fe催化剂颗粒明显减少，弯曲的顶部被轰击掉，使碳纳米管的场发射电流明显减小而场发射像无明显改变.温度的增加引起碳纳米管的场发射电流也随之增加.还研 究了在透明阳极技术中涂在阳极的荧光粉对场发射电流的影响.对同一碳纳米管阵列样品，发现涂有荧光粉的透明阳极使测量到的场发射电流大幅度减小，只是未涂荧光粉阳极电流的 1/30左右.直接用二氧化锡导电膜作阳极时，测得样品的开启场强为1.0V/μm.沉积了荧光粉的二 关键词： 多壁碳纳米管 场发射     

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (>50 wt. %). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications. PACS 61.46.Fg; 81.15.Gh; 82.45.Jn     

Surface modification of multi-walled carbon nanotubes by O2 plasma

The surface modification of multi-walled carbon nanotubes (MWCNTs) by O₂ plasma was carried out in this study. In order to achieve a relatively homogeneous treatment of MWCNTs powder, a rotating barrel fixed between the two discharge electrodes was used. The effect of plasma treatment parameters, such as power, time, and positions of samples (inside and outside the barrel), on the morphology and structure of MWCNTs surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results showed that the direct discharge (outside the barrel) could result in not only a quick grafting of polar functional groups but also an easy damage of MWCNTs after longer time, particularly under intensive power. It was found that the surface of MWCNTs powder might be changed in three steps—expansion (loosed structure formed), peel off and oxidization with increasing of treatment time during the irradiation. In this way, a complete purification of MWCNTs powder could be finished within 30 min via plasma treatment. Our work suggested that plasma treatment could be a simple and nonpolluting method for a large scale purification of MWCNTs.     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.