Synthesis of Eu2O3 nanotube arrays through a facile sol-gel template approach

Eu2O3 nanotubes have been successfully fabricated by an improved sol-gel template method within the nanochannels of porous anodic alumina templates. The morphology, structure, and composition of the nanotubes were characterized by means of X-ray diffraction techniques, scanning electron microscope, transmission electron microscopy, and selected-area electron diffraction. The results show that the Eu2O3 nanotubes are polycrystalline with a cubic structure. The outer diameter of nanotubes is 50-80 nm, and the thickness of the tube wall is about 5 nm. The mechanism of nanotube formation was discussed.     

Crystal structure and morphology of poly(16-hexadecalactone) chain-folded lamellar crystals

Solution-grown, chain-folded lamellar crystals of poly(16-hexadecalactone) (PHDL) were crystallized isothermally from 1-hexanol at 70 degrees C. The morphology of lozenge-shaped crystals was studied by TEM and AFM. The lamellae are ca. 10 nm thick and the chains run orthogonal to the lamellar surface with folding along (110) and (110) planes. The crystal structure of PHDL was determined by XRD and election diffraction of single crystals. The chains are in the 2(1) helix conformation close to all-trans and the structure consists of an orthorhombic unit cell with a P2(1)2(1)2(1) space group with the lattice constants a = 0.746 +/- 0.001 nm, b = 0.504 +/- 0.001 nm, and c (chain axis) = 4.116 +/- 0.003 nm. There are two chains per unit cell, which exist in an antiparallel arrangement. Molecular packing structure has been studied in detail, taking into account both diffraction data and energy calculations. The setting angles, with respect to a axis, were +/-40 degrees for the corner and center chains, respectively. By using the electron and XRD data, the best molecular packing model was refined to R-factors of 0.168 and 0.196, respectively. A brief comparison of chain-packing structure is also made with related polymer structures.     

Thin film structure of tetraceno[2,3-b]thiophene characterized by grazing incidence X-ray scattering and near-edge X-ray absorption fine structure analysis

Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on charge carrier mobility are discussed.     

Studies of the thermotropic mesophase behaviour exhibited by a highly asymmetric tetrabenzotriazaporphyrin derivative

The thermotropic mesophase behaviour of an asymmetrically shaped and highly substituted tetrabenzotriazaporphyrin (TBTAP) derivative has been studied by optical microscopy, DSC and X-ray diffraction. The TBTAP macrocycle differs from the more common phthalocyanine ring system by the substitution of a methine for a nitrogen at one meso-position. The TBTAP core was substituted with a single heptadecyl chain at this meso-position and four neopentyl groups were statistically distributed around the peripheral benzene rings. In contrast to an earlier study of this system which described the structure of the mesophase as discotic lamellar, detailed X-ray diffraction study indicates that the TBTAP derivative forms a disordered hexagonal columnar mesophase (Col hd ), with a weak tendency towards antiparallel orientation of neighbouring molecules observed in the form of a weak pseudo-centred rectangular packing.     

Chain packing in the inverted hexagonal phase of phospholipids: a study by X-ray anomalous diffraction on bromine-labeled chains

Although lipid phases are routinely studied by X-ray diffraction, construction of their unit cell structures from the diffraction data is difficult except for the lamellar phases. This is due to the well-known phase problem of X-ray diffraction. Here we successfully applied the multiwavelength anomalous dispersion (MAD) method to solve the phase problem for an inverted hexagonal phase of a phospholipid with brominated chains. Although the principle of the MAD method for all systems is the same, we found that for lipid structures it is necessary to use a procedure of analysis significantly different from that used for protein crystals. The inverted hexagonal phase has been used to study the chain packing in a hydrophobic interstice where three monolayers meet. Hydrophobic interstices are of great interest, because they occur in the intermediate states of membrane fusion. It is generally believed that chain packing in such a region is energy costly. Consequently, it has been speculated that the inverted lipid tube is likely to deviate from a circular shape, and the chain density distribution might be nonuniform. The bromine distribution obtained from the MAD analysis provides the information for the chain packing in the hexagonal unit cell. The intensity of the bromine distribution is undulated around the unit cell. The analysis shows that the lipid chains pack the hexagonal unit cell at constant volume per chain, with no detectable effect from a high-energy interstitial region.     

Effects of In, Al and Sn dopants on the structural and optical properties of ZnO thin films

Effect of In, Al and Sn dopants on the optical and structural properties of ZnO thin films have been investigated by X-ray diffraction technique and optical characterization method. X-ray diffraction patterns confirm that the films have polycrystalline nature. The thin films have (002) as the preferred orientation. This (002) preferred orientation is due to the minimal surface energy which the hexagonal structure, c-plane to the ZnO crystallites, corresponds to the densest packed plane. The grain size values of the films are found to be 29.0, 35.2 and 39.5 nm for In, Al and Sn doped ZnO thin films, respectively. The optical band gaps of the films were calculated. The absorption edge shifts to the lower wavelengths with In, Al and Sn dopants. The inclusion of dopant into films expands also width of localized states as E(UIn)>E(UAl)>E(USn). The refractive index dispersion curves obey the single oscillator model. The dispersion parameters and optical constants of the films were determined. These parameters changed with In, Al and Sn dopants.     

Metal-ion induced transition from multi- to single-bilayer tubes in histidine bearing lipids and formation of monodisperse Au nanoparticles

We report that a histidine based cationic lipid forms multi-bilayer nanotubes and the addition of metal ions such as Cu(2+) and Au(3+) induces transformation into single-bilayer nanotubes owing to coordination of the metal ions on the nanotube surface. The morphological transition was detected with X-ray scattering and electron microscopy. IR showed that the metal coordination is presumably the major driving force. The reduction of Au(3+) ions on the tube surface produced gold nanoparticles attached on the nanotube surface. The nanoparticle was almost monodisperse with the average diameter of 1.7 nm and the standard deviation σ of 0.29, which is remarkably narrower than that of previously reported lipid systems. The obtained particles were stable and no further aggregation and growth was observed after one week, providing a powerful and facile tool for producing nanoparticles in a wide range of applications.     

二氧化钛纳米管/镍复合材料的可控制备及其微波电磁性能

二氧化钛纳米管可作为载体,经过磁性金属修饰,制备陶瓷基金属纳米复合材料.本文利用二氧化钛纳米管为载体,经过硅烷化改性,钯催化沉积金属镍,制备一种陶瓷基/镍纳米复合材料,并利用TEM,XRD,FTIR和XPS等方法表征该复合材料的结构特征.结果表明二氧化钛纳米管表面镍沉积均匀,镍晶粒度尺寸为9.7nm,具有衍射宽化特征.沉积镍后,纳米管端部呈开口特征,仍具有空腔结构.在外加电磁场作用下(8～12GHz),复合材料具有较高的磁导率和磁损耗,但具有很低的介电损耗.该复合材料具有长径比高、比重小、重量轻、镍含量少等特点.人们还可在二氧化钛纳米管外部沉积其他金属或合金(如铁、钴),调控复合材料的电磁性能,用于开发薄而轻的电磁活性复合材料.     

Epitaxygens: mesomorphic properties of triptycene derivatives

The structure of mesophases derived from a triptycene subunit substituted with five paraffinic chains has been determined by X-ray diffraction at small angles. They all show a smectic ordering. This is the first example of a smectogen whose rigid core belongs to the D_3h symmetry. A hexagonal order has been observed in the X-ray diffraction patterns; it has been associated with a p31m packing of the rigid cores within the layers. The intralamellar cell parameter is in agreement with the molecular dimensions determined from CPK models. The calculated molecular length is in accordance with the experimental interlamellar distance. The difference in mesomorphic behaviour between the five and six chain derivatives is discussed.     

Fabrication and characterization of pseudo-ceramide-based liposomal membranes

We present a facile and straightforward method to fabricate liposomal membranes with a significantly stable lamellar structure consisting of pseudo-ceramide, fatty acid, and cholesterol. Characterizing their membrane properties, in which we have used differential scanning calorimetry, X-ray diffraction, and FT-IR spectra, enables us to demonstrate that pseudo-ceramide with appropriate amounts of stearic acid and cholesterol can assemble to form a stable lamellar α-phase. Moreover, we show that cholesterol is indeed important and plays a role in controlling the melting entropy of lipid membranes, which is attributed to a disordered molecular packing, thus creating more flexible liposomal membranes. This approach to use pseudo-ceramide offers a useful means to fabricate a variety of biocompatible liposomes with controllable membrane properties, which enlarges their applicability in the field of drug delivery, dermatology, and cosmetics.     

Crystal structure, thermal behavior and enzymatic degradation of poly(tetramethylene adipate) solution-grown chain-folded lamellar crystals

Solution-grown chain-folded lamellar single crystals of poly(tetramethylene adipate) (PTMA) were prepared from a dilute solution of 2-methyl-1-propanol by isothermal crystallization. PTMA crystals were hexagonal-shaped and polyethylene decoration of the crystals resulted in a "six cross-sector" surface morphology and showed that the average direction of chain folding is parallel to the crystal growth planes of [110] and [010]. Chain-folded lamellar crystals gave well-resolved electron diffraction diagrams corresponding to all the equatorial reflections of the X-ray fiber diagram obtained from stretched PTMA melt-quenched film (beta structure). The unit cell parameters of the beta structure of PTMA were determined as a = 0.503 nm, b = 0.732 nm and c (fiber axis) = 1.442 nm with an orthorhombic crystal system. The fiber repeat distance is appropriate for an all-trans backbone conformation for the straight stems. The setting angle, with respect to the a axis, is +/-46 degrees for the corner and center chains. Thermal behavior of lamellar crystals has been investigated by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The lamellar thickness at the edges of the crystal increased after thermal treatment with taking the molecular chains into recrystallization parts; the holes then opened up at the thickening front of the crystal. The morphological changes of lamellar crystals after enzymatic degradation by Lipase type XIII from Pseudomonas sp. and water-soluble products were characterized by TEM, AFM, gel permeation chromatography, high performance liquid chromatography and fast atom bombardment mass spectrometry. The degradation progressed mainly from the edges of the lamellar crystals without decreasing the molecular weights and the lamellar thicknesses. The central portion of single crystals was often degraded by enzymatic attacks. This result combined with thermal behavior indicates that the loosely chain-packing region exists inside the single crystal, and that molecular chains in this region have higher mobility against thermal and enzymatic treatments.     

Photoemission and absorption spectroscopy of carbon nanotube interfacial interaction

Element-specific techniques including near edge X-ray absorption fine structure, extended X-ray absorption fine structure and X-ray photoemission spectroscopy for the characterization of the carbon nanotube interfacial interactions are reviewed. These techniques involve soft and hard X-rays from the laboratory-based and synchrotron radiation facilities. The results provided information of how the nano-particles of catalysts are involved in the initial stage of nanotube growth, the nanotube chemical properties after purification, functionalization, doping and composite formation.     

Nanosilica-supported polyethoxyamines as low-cost, reversible carbon dioxide sorbents

Nanoparticles capped with amine ligands with different steric properties, dodecylamine and oleylamine, respectively, are investigated in the solid state as well as in solution. A combined X-ray diffraction, small angle X-ray scattering and electron microscopy investigation showed that the nanoparticles exhibit the sphalerite modification of ZnS as crystal phase with a diameter of 3-5 nm. A close packing of the monocrystalline nanoparticles in the solid state is observed. However, in the dodecylamine sample, besides spherical particles, a fraction of the nanoparticles is elongated. The nanoparticles are readily resoluble in apolar solvents like hexane. Dynamic light scattering (DLS) and SAXS investigations of the solutions reveal that the nanoparticles are dissolved as singular particles. In the case of oleylamine-capped ZnS, a defined core-shell structure with a ZnS core with a diameter of 4 nm and an organic shell with a thickness of approximately 2 nm have been found. Dodecylamine-capped nanoparticles slightly tend to form agglomerates with a diameter of approximately 40 nm.     

碳纳米管负载金属Pt催化剂的制备和机理研究

本文报道了高温裂解法沉积铂纳米颗粒于碳纳米管壁的新方法。利用红外光谱技术考察了碳纳米管壁的官能团衍生化以及这些官能团与铂颗粒沉积间的关系。利用透射电镜(TEM)、X-射线粉末衍射(XRD)以及光电子能谱技术(XPS)对碳纳米管壁上负载的铂纳米颗粒进行了表征。结果表明，大小约为5 nm的铂纳米颗粒以金属Pt(0)的形式均匀分散在纳米管表面，主要晶面定向为(111)面。同时，考察了甲醇在碳纳米管负载铂纳米颗粒复合材料电极上的电催化氧化。     

Molecular structure of glucopyranosylamide lipid and nanotube morphology

A series of glucopyranosylamide lipids, N-(X-octadecenoyl)-beta-D-glucopyranosylamine [X = 13-cis (1), 11-cis (2), 9-cis (3), 6-cis (4), and 9-cis,12-cis (5)] and their saturated homologue N-octadecanoyl-beta-d-glucopyranosylamine (6), which differ in the position of a cis double bond in the C18 hydrocarbon chains, have been synthesized. The effect of the cis double bond position on the chiral self-assembly of each glycolipid has been examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV, and circular dichroism (CD). The 11-cis derivative 2 was observed to self-assemble in water to form a uniform hollow cylinder structure with about 200-nm outer diameters in >98% yields. The obtained nanotubes from 2 showed the narrowest distribution of outer diameters and also gave a negative CD band around 234-236 nm, showing the largest CD intensity among the glycolipids investigated. Thus, we found that the position of a cis double bond significantly influences the homogeneity of the outer diameters as well as growth behavior of the self-assembled nanotube structures. Chiral molecular packing driven by a possible bending structure of the unsaturated glycolipids is playing a critical role in determining tubular morphology through molecular self-assembly.     

Self-assembly of ionogenic surfactants during their interaction with poly(propylenimine) dendrimers

The structure of complexes formed by poly(propylenimine) dendrimers of five generations and anionic micelle-forming surfactants is studied by X-ray diffraction. It is shown that, in complexes of lower generation dendrimers, the lamellar packing of surfactants is dominant. In complexes formed by dendrimers of the fourth and fifth generations, packing typical of compact dendrimer molecules prevails. This packing can be attributed to the distorted dense packing of ball-like complex species. Structural models of complexes that allow for penetration of surfactants into the dendrimer molecule and the size ratio of the aliphatic radical of a surfactant and a dendrimer are advanced.     

Fabrication of self-organized TiO2 nanotubes from columnar titanium thin films sputtered on semiconductor surfaces

Self-organized nanotube arrays of TiO₂ have been grown from titanium (Ti) thin films deposited on p-type Si(1 0 0) substrates. Structural and morphological characterizations carried out by X-ray diffraction and scanning electron microcopy indicate that the sputtered crystalline Ti thin films used for subsequent anodization are hexagonally closed packed (hcp-Ti) and show a columnar morphology. Electrochemical anodization of the Ti films was carried out by potentiostatic experiments in 1 M H₃PO₄ + 1 M NaOH + 0.5 wt% HF electrolyte at room temperature. The TiO₂ nanotubes on a semiconductor substrate have an average tube length of approximately 560 nm, diameter in the order of 80 nm and wall thickness approximately 20 nm.     

Supramolecular self-assembly of nanotubes and supercoils from long-chain derivatives of pyrimindinetrione and triazine

The self-assembly of two complementary components, 5-(4-N-methyl-N-dodecylaminobenzylidene)-2,4,6-(1H,3H)-pyrimidi-netrione (1) and 4-amino-2,6-didodecylamino-1,3,5-triazine (2) was found to result in the formation of a hollow supramolecular nanotube with about 6 nm in diameter and hundreds of nanometers in length as observed directly by transmission electron microscope (TEM). X-ray diffraction patterns indicate that a periodical layered structure with a d spacing of 0.49 nm in the nanotube exists. If staining treatment were employed in TEM observations, the self-assembly was found to show a supercoil structure about 300 nm in diameter.     

Aqueous dispersions of cubic lipid–water phases

Inverse lipid–water phases such as cubic phases can form kinetically stable dispersions by fragmentation in water. Cubic lipid phases can be dispersed by polar lipids favoring lamellar phases or by block copolymers, which can close the bilayer at the surface so that the hydrocarbon chain core is not exposed to water. Monodisperse particles based on glycerol monooleate, with their bilayer curved as the P-, D- or G-minimal surface, have been prepared in this way. Their inner bilayer conformation and outer shape have been examined, mainly by X-ray diffraction and cryo transmission electron microscopy. There is also a different type of cubic lipid bilayer particles with a periodicity in the micrometer range, which have been identified in phospholipid–water dispersions and in cell membrane assemblies. The mechanism behind formation in vivo of such cubic membranes, which also follow the P-, D- and G-surfaces, is discussed. Other lipid–water dispersions with lower symmetry are finally considered; dispersions formed by the inverse hexagonal phase and the dispersed state of a tetragonal bilayer structure formed by lung surfactants.     

Surface-interface investigations of an ultrathin pulsed laser deposited NiO/ZnO bilayer structure

We hereby report detailed structural and morphological studies for an ultrathin NiO/ZnO bilayer structure grown on sapphire (001) substrate using pulsed laser deposition technique. The combined X-ray reflectivity (XRR) and grazing incidence X-ray fluorescence (GIXRF) studies revealed formation of a low-density defective ZnO interfacial layer of thickness ~32 Å at the ZnO/sapphire interface prior to growth of main ZnO layer. Our results further indicate that the variation of electron density across the NiO/ZnO bilayer structure is smooth and we do not observe presence of any interface layer between them. X-ray diffraction measurements show that deposited ZnO layer is epitaxial in nature whereas NiO is highly oriented along (100) direction. The angle dependent X-ray absorption near edge fine structure (XANES) measurements at Ni–K edge has been utilized to determine depth-resolved oxidation state of Ni and the results have been correlated with the depth-resolved electron density of NiO layer. The method described here offers nondestructive determination of the microstructural parameters as well as depth-resolved mapping of oxidation state of a thin film-based heterojunction device. It extends several advantages over destructive methods which are abundantly reported in literature.