Self-assembly: a minimalist route to the fabrication of nanomaterials

Self-assembly of molecular or nonmolecular components by non-covalent interactions offers an invaluable tool for the preparation of discrete nanostructures and extended 2D and 3D materials, which are often not accessible by any other fabrication process. In this article we summarize the most recent advances in the generation of nanomaterials such as self-assembled monolayers (SAMs) and structures formed from amphiphilic molecules, colloids, peptides, and polymers by nontemplated self-assembly either at the solid state or in solution. The current status of templated self-assembly and the use of self-assembled structures as template and for patterning other materials is also covered. A special emphasis is placed on strategies presenting either original and somehow exploratory approaches, eventually combining bottom-up and top-down methods, or that concern methods for the production of materials with potential application, e.g., in photonics, as sensors, for drug delivery and electric and magnetic devices. In all the sections, we outline self-organization and applications enabled with self-separated block copolymers.     

Synthesis and characterization of large specific surface area nanostructured amorphous silica materials

Large specific surface area materials attract wide attention because of their applications in adsorption, catalysis, and nanotechnology. In the present study, we describe the synthesis and characterization of nanostructured amorphous silica materials. These materials were obtained by means of a modification of the Stobe-Fink-Bohn (SFB) method. The morphology and essential features of the synthesized materials have been studied using an automated surface area and pore size analyzer and scanning electron microscopy. The existence of a micro/mesoporous structure in the obtained materials has been established. It was also found that the obtained particle packing materials show large specific surface area up to 1,600 m2/g. (To our best knowledge, there is no any reported amorphous silica material with such a higher specific surface area.) The obtained materials could be useful in the manufacture of adsorbents, catalyst supports, and other nanotechnological applications.     

Effect of Ionomeric Compatibilizer on Clay Dispersion in Polyethylene/Clay Nanocomposites

Summary: Linear low‐density polyethylene (LLDPE)/clay nanocomposites are obtained and studied by using a zinc‐neutralized carboxylate ionomer as a compatibilizer. LLDPE‐g‐MA is used as a reference compatibilizer. Two different clays, natural montmorillonite (Closite Na⁺) and a chemically modified clay Closite 20A have been used. Nanocomposites are prepared by melt blending in a twin‐screw extruder using two mixing methods: two‐step mixing and one‐step mixing. The relative influence of each compatibilizer is determined by wide‐angle X‐ray diffraction structural analysis and mechanical properties. The results are analyzed in terms of the effect of the compatibilizing agent and incorporation method in the clay dispersion, and the mechanical properties of the nanocomposites. Experimental results confirm that the film samples with ionomer show a good mechanical performance only slightly below that of the samples with maleic anhydride (MA). The two‐step mixing conditions result in better dispersion and intercalation for the nanofillers than one‐step mixing. The exfoliation of clay platelets leads to an improved thermal stability of the composite. The oxygen permeability of the clay nanocomposites, using ionomer as a compatibilizer, is decreased by the addition of the clay.

TEM image of a PE/4 wt.‐% Closite 20A nanocomposite formed using ionomer.     

Determination of the bound conformation of a competitive nanomolar inhibitor of mycobacterium tuberculosis type II dehydroquinase by NMR spectroscopy

The synergy between tuberculosis and the AIDS epidemic, along with the surge of multidrug-resistant isolates of M. tuberculosis, has reaffirmed tuberculosis as a primary public health threat. It is therefore necessary to discover new, safe, and more efficient antibiotics against this disease. On the other hand, mapping the dynamic interactions of inhibitors of a target protein can provide information for the development of more potent inhibitors and consequently, more potent potential drugs. In this context, the conformational binding of our previously reported nanomolar inhibitor of M. tuberculosis type II dehydroquinase, the 3-nitrophenyl derivative 1, was studied using saturation transfer difference (STD) and transferred NOESY experiments. These studies have shown that in the bound state, one conformation of those present in solution of the competitive nanomolar inhibitor 3-nitrophenyl derivative 1 is selected. In the bound conformation, the aromatic ring is slightly shifted from coplanarity, with the double bond and the nitro group of 1 oriented towards the double bond side.     

In-vial dual extraction for direct LC-MS analysis of plasma for comprehensive and highly reproducible metabolic fingerprinting

Metabolic fingerprinting of biological tissues has become an important area of research, particularly in the biomarker discovery field. Methods have inherent analytical variation, and new approaches are necessary to ensure that the vast numbers of intact metabolites present in biofluids are detected. Here, we describe an in-vial dual extraction (IVDE) method and a direct injection method that shows the total number of features recovered to be over 4500 from a single 20 μL plasma aliquot. By applying a one-step extraction consisting of a lipophilic and hydrophilic layer within a single vial insert, we showed that analytical variation was decreased. This was achieved by reducing sample preparation stages including procedures of drying and transfers. The two phases in the vial, upper and lower, underwent HPLC-QTOF analysis on individually customized LC gradients in both positive and negative ionization modes. A 60 min lipid profiling HPLC-QTOF method for the lipophilic phase was specifically developed, enabling the separation and putative identification of fatty acids, glycerolipids, glycerophospholipids, sphingolipids, and sterols. The aqueous phase of the extract underwent direct injection onto a 45 min gradient, enabling the detection of both polarities. The IVDE method was compared to two traditional extraction methods. The first method was a two-step ether evaporation and IPA resuspension, and the second method was a methanol precipitation typically used in fingerprinting studies. The IVDE provided a 378% increase in reproducible features when compared to evaporation and a 269% increase when compared to the precipitate and inject method. As a proof of concept, the method was applied to an animal model of diabetes. A 2-fold increase in discriminant metabolites was found when comparing diabetic and control rats with IVDE. These discriminant metabolites accounted for around 600 entities, out of which 388 were identified in available databases.     

Improved vapor selectivity and stability of localized surface plasmon resonance with a surfactant-coated Au nanoparticles film

Here, we report the use of tetraoctylammonium bromide (TOABr)-coated Au nanoparticles (NPs) for the optical sensing of volatile organic compounds (VOCs). We find that the film responded selectively to the presence of polar and nonpolar vapors by changes in the maximum wavelength (λ(max)) toward higher and lower wavelengths, respectively, as determined by UV-visible spectroscopy. We also observed that the organic coating reorganizes when vapors partition into the film indicated by FT-IR and the film contracts in the presence of water indicated by scanning electron microscopy (SEM). In the present sensor, the metallic Au core serves as the plasmonic signal while the organic coating acts as the receptor material providing vapor selectivity and sensor stability. Correlating changes in (λ(max)) with changes in the refractive index (RI) and nanoparticle-to-nanoparticle separation in the film is important both fundamentally and for improving selectivity in localized surface plasmon resonance (LSPR) sensors.     

Comparative system analysis of direct steam generation and synthetic oil parabolic trough power plants with integrated thermal storage

Parabolic trough power plants are currently the most commercially applied systems for CSP power generation. To improve their cost-effectiveness, one focus of industry and research is the development of processes with other heat transfer fluids than the currently used synthetic oil. One option is the utilization of water/steam in the solar field, the so-called direct steam generation (DSG).Several previous studies promoted the economic potential of DSG technology (Eck et al., 2008b, Price et al., 2002, Zarza, 2002). Analyses’ results showed that live steam parameters of up to 500 °C and 120 bars are most promising and could lead to a reduction of the levelized electricity cost (LEC) of about 11% (Feldhoff et al., 2010). However, all of these studies only considered plants without thermal energy storage (TES).Therefore, a system analysis including integrated TES was performed by Flagsol GmbH and DLR together with Solar Millennium AG, Schott CSP GmbH and Senior Berghöfer GmbH, all Germany. Two types of plants are analyzed and compared in detail: a power plant with synthetic oil and a DSG power plant. The design of the synthetic oil plant is very similar to the Spanish Andasol plants (Solar Millennium, 2009) and includes a molten salt two-tank storage system. The DSG plant has main steam parameters of 500 °C and 112 bars and uses phase change material (PCM) for the latent and molten salt for the sensible part of the TES system. To enable comparability, both plants share the same gross electric turbine capacity of 100 MWel, the same TES capacity of 9 h of full load equivalent and the same solar multiple of the collector field of about two.This paper describes and compares both plants’ design, performance and investment. Based on these results, the LEC are calculated and the DSG plant’s potential is evaluated. One key finding is that with currently proposed DSG storage costs, the LEC of a DSG plant could be higher than those of a synthetic oil plant. When considering a plant without TES on the other hand, the DSG system could reduce the LEC. This underlines the large influence of TES and the still needed effort in the development of a commercial storage system for DSG.     

Extended rotation-free shell triangles with transverse shear deformation effects

The paper extends recent work of the authors to include transverse shear effects on rotation-free triangular element for plates (O?ate and Zárate in Int J Numer Methods Eng 83(2):196–227, 2010). Two new shell triangular elements are presented, the EBST+ and the EBST+1. Transverse shear deformation effects are important for thick shells, as well when the shell is laminated or formed by composite material. The ingredients for the element formulation are: a Hu-Washizu type mixed functional and linear interpolation for the displacement field. In both elements presented a finite volume approach is used for computing the bending moments and the curvatures over a patch of elements. The nodal translational degrees of freedom of the original enhanced basic shell triangle (EBST) are extended with the two shear deformation angles via two different approaches. The first one uses a linear interpolation of the rotation angles inside the element (EBST+) and the second one assumes a constant field for the rotation angles (EBST+1). For the thin shell case the shear angles vanish and the new elements reproduce the good behaviour of the original thin EBST element. As a consequence the elements can reproduce the solutions for thick to thin shells situations without exhibiting shear locking. The numerical solution for the thick shell case can be found iteratively starting from the deflection values for the Kirchhoff theory using the original thin EBST element. Examples of the good performance of the new rotation-free shell triangles are given.     

Mechanochemical synthesis and characterization of nanocrystalline BiSe, Bi2Se3 semiconductors

Mechanochemical synthesis of bismuth selenides (BiSe, Bi₂Se₃) was performed by high-energy milling of bismuth and selenium powders in a planetary ball mill. The particle size distribution and the specific surface area of Bi/Se and 2Bi/3Se powder mixtures were analysed at increasing milling time. The products were characterized by X-ray diffraction, differential scanning calorimetry and transmission electron microscopy. The presence of bismuth selenide phases was observed after only 1?min of milling and full conversion into hexagonal BiSe phase (nevskite) and rhombohedral Bi₂Se₃ phase (paraguanajuatite) was reached after 10?min of milling. The nanocrystalline nature of both mechanochemically synthesised bismuth selenides was confirmed and their optical band gap energies were obtained on the basis of the recorded absorption spectra in UV–Vis spectral region.