Dry Powder Precursors of Cubic Liquid Crystalline Nanoparticles (cubosomes)

Cubosomes are dispersed nanostructured particles of cubic phase liquid crystal that have stimulated significant research interest because of their potential for application in controlled-release and drug delivery. Despite the interest, cubosomes can be difficult to fabricate and stabilize with current methods. Most of the current work is limited to liquid phase processes involving high shear dispersion of bulk cubic liquid crystalline material into sub-micron particles, limiting application flexibility. In this work, two types of dry powder cubosome precursors are produced by spray-drying: (1) starch-encapsulated monoolein is produced by spray-drying a dispersion of cubic liquid crystalline particles in an aqueous starch solution and (2) dextran-encapsulated monoolein is produced by spray-drying an emulsion formed by the ethanol–dextran–monoolein–water system. The encapsulants are used to decrease powder cohesion during drying and to act as a soluble colloidal stabilizer upon hydration of the powders. Both powders are shown to form (on average) 0.6m colloidally-stable cubosomes upon addition to water. However, the starch powders have a broader particle size distribution than the dextran powders because of the relative ease of spraying emulsions versus dispersions. The developed processes enable the production of nanostructured cubosomes by end-users rather than just specialized researchers and allow tailoring of the surface state of the cubosomes for broader application.     

Dynamics of structural transformations between lamellar and inverse bicontinuous cubic lyotropic phases

The liquid crystalline lamellar (L(alpha)) to double-diamond inverse bicontinuous cubic (Q(D)(pi)) phase transition for the amphiphile monoelaidin in excess water exhibits a remarkable sequence of structural transformations for pressure or temperature jumps. Our data imply that the transition dynamics depends on a coupling between changes in molecular shape and the geometrical and topological constraints of domain size. We propose a qualitative model for this coupling based on theories of membrane fusion via stalks and existing knowledge of the structure and energetics of bicontinuous cubic phases.     

A bicontinuous structure in some systems with cubic mesophases

A cubic structure of polymer colloid complexes is studied. The technique of the research includes i) an analysis of well-known literature SAXS data; on this basis, ii) constructing a simple model to estimate geometric structure parameters and to obtain a simulated scattering curve; and iii) comparing the model with the real structure obtained from the SAXS data, using the reconstruction of electron density distribution. A bicontinuous structure in cubic mesophases is formed. Dedicated to the memory of Alexander T. Dembo     

Particle Size Characterization of an Extra Fine Milled Product

The present research aims to characterize the particle size distribution of sub micron particles suspended in a liquid. The particles milled are an organic poorly water soluble crystalline product. To characterize the size of these particles, different techniques have been tested: imaging techniques (SEM, CryoTEM), static light scattering techniques, dynamic light scattering techniques, centrifugation and flow field flow fractionation. The results indicate that the studied milled particles have a primary particle size close to 180nm and there is strong evidence of larger particles which are very likely aggregates. This is clearly seen from the Cryo TEM results. All the above mentioned techniques should in principle be able to measure samples of dispersion containing particles of ca 180 nm but several are disturbed by the presence of large aggregates. It is difficult to estimate the amount of aggregate present, but most of the time one is interested in what the primary particle size distribution is. It is clear that no single piece of equipment is capable of exactly determining the particle size distribution of our samples, but the static light scattering with low shear on mixing does give a good representation of what is seen with the image analysis by cryo TEM.     

Pressure-induced phase changes of cubic monoolein - Cytochrome C mesophases

Incorporation of the protein cytochrome c (cyt c) into the hydrated bicontinuous Ia3d cubic mesophase of monoolein (MO) was investigated within a wide range of pressures by small-angle X-ray scattering (SAXS). We found that incorporation of cyt c into the cubic phase of MO has a drastic effect on the structure and pressure stability of the system: At high pressures, the lipid systems with less than 0.2 wt.% embedded protein undergo a transition to a fluid lamellar phase with smaller partial molar lipid volume. Incorporation of cyt c at levels above 0.2 wt.% promotes the formation of a new cubic phase, probably a cubic micellar phase of space group P4₃32 (Q²¹²) whose pressure stability rises with increasing protein content.     

DETERMINATION OF CRYSTALLINE LAMELLAR THICKNESS IN POLY(ETHYLENE TEREPHTHALATE) USING SMALL-ANGLE X-RAY SCATTERING AND TRANSMISSION ELECTRON MICROSCOPY*

The crystalline lamellar thickness of semicrystalline poly(ethylene terephthalate) (PET) was evaluated using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) techniques. Both SAXS onedimensional (1D) correlation function and interface distribution function analyses were utilized to determine the crystalline lamellar thickness. The two-dimensional fast Fourier transformation (2D-FFT) of the TEM image and the Gaussian-like lamellar thickness distribution determined from the TEM image were also performed. Results indicate that the larger value of the two correlation lengths calculated from the SAXS analysis should be assigned to the crystalline lamellar thickness in PET. Discussions and comparison among different methods for characterizing the lamellar thickness of semicrystalline polymers are made.

     

Generation and characterization of NiO nanoparticles by continuous wave fiber laser ablation in liquid

Pulsed laser ablation in liquid (PLAL) has been widely applied for the generation of nanoparticles (NPs). We report on the generation of NiO NPs using a high-power, high-brightness continuous wave (CW) fiber laser source at a wavelength of 1,070 nm. Characterization of such NPs in terms of size distribution, shape, chemical composition, and phase structure was carried out by transmission electron microscopy (TEM), high-resolution TEM equipped with energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). The results revealed the formation of NiO NPs in water with an average size of 12.6 nm. The addition of anionic surfactant sodium dodecyl sulfate (SDS) reduced the size of NiO NPs down to 10.4 nm. The shape of the NPs was also affected by the SDS, showing the change of shapes from spherical domination in water to tetragonal with increased SDS concentrations. Furthermore, the NiO NPs generated in water and SDS solutions were dual phase containing both cubic and rhombohedral structures. It was also found that the NiO NPs were single crystalline in nature irrespective of the size and shape.     

Electron microscopy of nanoemulsions: an essential tool for characterisation and stability assessment

The characterisation of pharmaceutical formulations by microscopic techniques is essential to obtain reliable data about the actual morphology of the system. Since the size range of colloidal drug delivery systems has long ago reached the lower end of the nanometer scale, classical light microscopy has been replaced by electron microscopy techniques which provide sufficient resolution for the visualisation of nano-sized structures. Indeed, the superior resolution and methodological versatility of electron microscopy has rendered this technique an indispensable tool for the analysis of nanoemulsions. Microscopic analysis of these lipid-based drug delivery systems with particle sizes in the lower submicron range provides critical information about the size, shape and internal structure of the emulsion droplets. Moreover, surfactant aggregates such as liposomes or multilamellar structures which remain unnoticed during particle size measurements can be detected in this fashion. This review provides a brief overview about both transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques which have been employed to characterise nanoemulsions. Of special interest are sophisticated cryo techniques of sample preparation for both TEM and SEM which deliver high-quality images of nanoemulsions in their natural state. An overview about the instrumentation and sample preparation for all presented methods is given. Important practical aspects, sources of error and common artefacts as well as recent methodological advances are discussed. Selected examples of electron microscopic studies of nanoemulsions are presented to illustrate the potential of this technique to reveal detailed and specific information.     

Physico-chemical properties of titania nanotubes synthesized via hydrothermal and annealing treatment

Titania nanotubes are synthesized via hydrothermal treatment of TiO₂ powders in NaOH solution at 110 °C for 90 h, followed by annealing at 400 °C. The morphology of nanotubes is characterized by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Microscopic observations on the transformation process indicate that the nanotubes retain their shapes after the annealing process. The crystalline structure and composition are examined by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX). The results confirm the absence of impurity peaks and the crystal structure change from nanotubes to anatase phase after annealing treatment. The average specific surface area of the particles is probed using gas adsorption-desorption measurements. The prepared tubular samples exhibit greater specific surface areas and higher pore volumes than the precursor. Moreover, it is apparent that the hydrothermal treatment modifies the optical properties of the titania samples and red-shifts the UV absorption to a band gap energy of 3.04 eV after annealing treatment.     

Structural and spectroscopic studies of thin film of silver nanoparticles

We report the deposition of thin film of silver (Ag) nanoparticles by wet chemical method. The as-synthesized Ag nanoparticles have been characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray energy dispersive spectroscopy (EDS), field emission transmission electron microscopy (FETEM) and high-resolution TEM (HRTEM), UV-vis spectroscopy and thermogravimetric-differential thermal analysis (TG-DTA) respectively. FESEM image indicates that the silver film prepared on the quartz substrate is smooth and dense. XRD pattern reveals the face-centered cubic (fcc) structure of silver nanoparticles. EDS spectrum indicates that samples are nearly stoichiometric. From TEM analysis, it is found that the size of high purity Ag nanoparticles is ranging from 10 to 20 nm with slight agglomeration. Absorption in UV-vis region by these nanoparticles is characterized by the features reported in the literature, namely, a possible Plasmon peak at ∼403 nm. Optical absorbance spectra analysis reveals that the Ag film has an indirect band structure with bandgap energy 3.88 eV. TGA/DTA studies revealed that a considerable weight loss occurs between 175 and 275 °C; and the reaction is exothermic.     

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper–niobium system

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu–Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200?°C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300?°C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.     

MISTRAL: a transmission soft X‐ray microscopy beamline for cryo nano‐tomography of biological samples and magnetic domains imaging

The performance of MISTRAL is reported, the soft X‐ray transmission microscopy beamline at the ALBA light source (Barcelona, Spain) which is primarily dedicated to cryo soft X‐ray tomography (cryo‐SXT) for three‐dimensional visualization of whole unstained cells at spatial resolutions down to 30 nm (half pitch). Short acquisition times allowing for high‐throughput and correlative microscopy studies have promoted cryo‐SXT as an emerging cellular imaging tool for structural cell biologists bridging the gap between optical and electron microscopy. In addition, the beamline offers the possibility of imaging magnetic domains in thin magnetic films that are illustrated here with an example.     

Investigations on the liquid crystalline phases of cation-induced condensed DNA

Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physicochemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li-DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.     

Pressure-induced electronic and structural transformations in bulk GeSe2 glass

The pressure dependence of the electrical resistivity of bulk GeSe₂ glass shows a semiconductor-to-metal transition at 7 GPa pressure. The high pressure phase is examined using the x-ray diffractometer and is found to be crystalline, with a face-centred cubic structure havinga = 4·06 A. The electrical conductivity has also been studied as a function of temperature at various pressures.     

低压等离子体增强化学汽相沉积法制备立方氮化碳薄膜

用低压等离子体增强化学汽相沉积法和氮化硅中间过渡层的方法，在硅片和玻璃上，制备了立方氮化碳薄膜.用光电子能谱测试了其成分和结合能，薄膜含氮量为42.96%.C1s和N1s的结合能分别为285.01和398.60eV.透射电子显微镜研究表明，制备的氮化碳属于体心立方结构，根据衍射花样，计算的晶格常量a为0.536nm，这与理论预言的结果a为0.53973nm很接近.随着沉积的时间增长，还观测到了氮化碳薄膜的菊池花样.在玻璃上沉积的氮化碳薄膜在可见光和近红外区域是透明的，在400nm处有光吸收. 关键词：     

Nanocrystals of CdSe Formed by the Pressure Cycle Method

CdSe nanocrystals were prepared by the pressure cycle method using the Paris-Edinburgh cell up to 7 GPa. The recovered samples are nanocrystals in the cubic phase (zinc-blende structure) and were characterized using transmission electron microscopy (TEM), electron diffraction and Raman scattering. Transmission electron micrographs shows that these nanocrystals are nearly spherical with diameters ranging from 20 to 50 nm. The Raman scattering measurement confirm the existence of CdSe nanocrystals in the cubic phase (ZB).     

Large-scale fabrication and characterization of Cd-doped ZnO nanocantilever arrays

We demonstrate bulk synthesis of highly crystalline Cd-doped ZnO nanocantilever arrays (CZNAs) using Cd and Zn powders at 600 degrees C, which is characterized via scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy, selected area electron diffraction, and high resolution TEM. The results show that the as-prepared CZNAs have diameters of about 15-50 nm, and lengths up to 400 nm and the corresponding process of growth is suggested for conventional vapor solid mechanism.     

Structural phase modification in Cu incorporated nanostructured zinc sulfide thin films

Cu incorporated zinc sulfide (ZnS) films are prepared by a RF magnetron sputtering technique and the influence of Cu doping concentration on the structural, morphological and optical properties is systematically analyzed using techniques like grazing incidence X-Ray diffraction (GIXRD), micro-Raman spectroscopy, atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and UV–vis spectroscopy. XRD examination of the as-prepared films revealed the presence of polycrystalline structure with co-existence of cubic and hexagonal phases in the pure and lower Cu incorporated films. Increase in Cu doping concentration causes a gradual phase transformation from mixed phase to cubic phase. Micro-Raman spectra further confirms the structural phase modifications with the addition of Cu in ZnS. Morphological analysis shows compact distribution of elongated grain geometry with good connectivity and detectable grain boundary in the pure and Cu incorporated films. Increase in Cu incorporation results in the systematic reduction of RMS surface roughness. EDS analysis confirms the incorporation of Cu and surface vacancy defects in the doped films. All the films are transparent in the visible region and band gap calculation by Tauc plot shows that increase in Cu incorporation results in band gap renormalization.     

Tin-doped indium oxide nanobelts grown by carbothermal reduction method

This communication discusses the formation of doped nanobelts produced by a simple route. Tin-doped indium oxide (ITO) nanobelts were obtained by a carbothermal reduction method. The nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) and wavelength-dispersive X-ray spectroscopy (WDX). The results show that the nanobelts have a cubic structure, are single crystalline and doped with tin and grow in the [400] direction. PACS 81.07.-b; 61.46.+w; 68.37.Hk; 68.37.Lp     

Simultaneous synthesis of TiO2 microrods in situ decorated with Ag nanoparticles and their bactericidal efficiency

In this study, we report a simple and cost-effective method for in situ decoration of Ag NPs onto nanoporous TiO₂ microrods by one medium (ethylene glycol) that can produce two different morphologies. In order to investigate the morphology, phase composition, crystalline structure, and chemical state (valency) of samples before and after annealing in air at different temperatures, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were performed. The present results show that the size, morphology and crystallinity of both Ag NPs and TiO₂ microrod substrate depend on the post-annealing treatment temperatures. The annealed Ag–TiO₂ NP/microrod composites show large inhibition zones against E. coli bacteria. The obtained Ag–TiO₂ composites have the potential for use as a novel antibacterial material and in water treatment applications.