This work presents a simple methodology for coating small unilamellar liposomes bearing different degrees of positive charge with polyelectrolyte multilayers using the sequential layer-by-layer ...deposition method. The liposomes were made of mixtures of 1,2-dioleyl-sn-glycero-3-phosphocoline and dimethyl dioctadecyl ammonium bromide (DODAB) and coated by alternated layers of the sodium salt of poly(4-styrenesulfonate) (PSS) and poly(allylamine) (PAH) as polyanions and polycations, respectively. The results show that the zeta potential of the liposomes was not very sensitive to the mole fraction of DODAB in the membrane, X D, in the range 0.3 ≤ X D ≤ 0.8. We were able to coat the liposomes with up to four polymer bilayers. The growth of the capsule size was followed by dynamic light scattering, and in some cases, by cryo-transmission electron microscopy, with good agreement between both techniques. The thickness of the layers, measured from the hydrodynamic radius of the coated liposome, depends on the polyelectrolyte used, so that the PSS layers adopt a much more packaged conformation than the PAH layers. An interesting finding is that the PSS amount needed to reach the isoelectric point of the capsules increases linearly with the charge density of the bare liposomes, whereas the amount of PAH does not depend on it. As expected, the preparation of the multilayers has to be done in such a way that when the system is close to the isoelectric point, the capsules do not aggregate. For this, we dropped the polyelectrolyte solution quickly, stirred it fast, and used dilute liposome suspensions. The method is very flexible and not limited to liposomes or polyelectrolyte multilayers; also, coatings containing charged nanoparticles can be easily made. Once the liposomes have been coated, lipids can be easily eliminated, giving rise to polyelectrolyte nanocapsules (polyelectrosomes) with potential applications as drug delivery platforms.
The optical control of ferroic properties is a subject of fascination for the scientific community, because it involves the establishment of new paradigms for technology1–9. Domains and domain walls ...are known to have a great impact on the properties of ferroic materials1–24. Progress is currently being made in understanding the behaviour of the ferroelectric domain wall, especially regarding its dynamic control10–12,17,19. New research is being conducted to find effective methodologies capable of modulating ferroelectric domain motion for future electronics. However, the practical use of ferroelectric domain wall motion should be both stable and reversible (rewritable) and, in particular, be able to produce a macroscopic response that can be monitored easily12,17. Here, we show that it is possible to achieve a reversible optical change of ferroelectric domains configuration. This effect leads to the tuning of macroscopic polarization and its related properties by means of polarized light, a non-contact external control. Although this is only the first step, it nevertheless constitutes the most crucial one in the long and complex process of developing the next generation of photo-stimulated ferroelectric devices.
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The internal organization of polyelectrolyte layers deposited on colloidal templates plays a very important role for the potential applications of these systems as capsules for drug ...delivery purposes.
The mutual arrangement of oppositely charged polyelectrolyte layers upon their deposition on positively charged liposomes has been studied by combining up three different scattering techniques and Electronic Spin Resonance, which has provided information about the inter-layer interactions and their effect on the final structure of the capsules.
The sequential deposition of oppositely charged polyelectrolytes on the external leaflet of positively charged liposomes allows modulating the organization of the obtained supramolecular structures, impacting the packing and rigidity of the obtained capsules due to the change of the ionic cross-linking of the multi-layered film as a result of the specific charge of the last deposited layer. The possibility to modulate the properties of the LbL capsules by tuning the characteristics of the last deposited layers offers a very interesting route for the design of materials for encapsulation purposes with their properties controlled almost at will by changing the number of deposited layers and their chemistry.
This paper presents a discrete-time output feedback controller to regulate the output voltage of a DC-DC buck converter. The proposal’s main feature is the application of a discrete-time equivalent ...of the robust exact filtering differentiator. First, the document exposes a theoretical analysis of the closed-loop system, where it is considered the problem of implementing a real-time differentiator with a good relationship between exactness and noise filtration performance. Hence, secondly, the controller in a laboratory setup is presented. The first experimental results suggest that the proposed controller exhibits good robustness against noise and maintains the asymptotic accuracy, even with saturated control inputs, as in the case of the DC-DC buck converter. Consequently, aiming to verify the features of the proposed method, the controller is validated through multiple experiments, showing satisfactory voltage tracking accuracy, good suppression of instantaneous load and supply voltage disturbances, and robustness against bounded measurement noise.
The use of fiber-reinforced composites in marine applications such as components of tidal turbines and wave energy converters is becoming attractive because of their reduced weight and improved ...corrosion resistance. However, when these polymer matrix composite structures are exposed to seawater environment, degradation of material properties is produced affecting reliability. A deep understating of seawater ageing effect on composite structures is essential to ensure long-term performance and durability. A systematic investigation was conducted in this work to evaluate the effect of seawater ageing on mechanical properties of five different composites manufactured with two types of fiber fabrics (unidirectional glass and carbon) and three types of resin systems (epoxy, vinylester and polyester). The behavior of samples with and without accelerated seawater ageing and subjected to tensile, compressive, flexural and shear loading was evaluated. A significant strength reduction due to seawater ageing was observed on composites with epoxy and polyester matrices. Low strength and stiffness values of composites with vinylester matrix are in general observed; however, seawater ageing makes these properties increase slightly. Fracture surface examination by scanning electron microscopy revealed delamination, fiber debonding and resin crumbling due to seawater effect.
Finding a feasible principle for a future generation of nano-optomechanical systems is a matter of intensive research, because it may provide new device prospects for optoelectronics and ...nanomanipulation techniques. Here we show that the strain of a ferroelectric crystal can be manipulated to achieve macroscopic, stable, and reproducible dimensional changes using illumination with photon energy below the material bandgap. The photoresponse can be activated without direct light incidence on the actuation area, because the cooperative nature of the phenomenon extends the photoinduced strain to the whole material. These results may be useful for developing the next generation of high-efficiency photocontrolled ferroelectric devices.
The monohydrates of thenyl alcohol and thenyl mercaptan have been probed in a supersonic jet expansion using chirped-pulse and Fabry-Perot Fourier-transform microwave spectroscopy. The rotational ...spectra revealed a single isomer for each of the dimers. The thenyl alcohol hydrate is stabilized by an O-H O
w
hydrogen bond between the alcohol and water, with water acting as a proton acceptor and additionally engaging in an O
w
-H π interaction with the thenyl ring. Conversely, water behaves as a proton donor in the thenyl mercaptan hydrate, linking to the thiol group though an O
w
-H S hydrogen bond and secondary O
w
-H π interactions with the ring. In both dimers water retains internal mobility, as tunneling doublings in the spectrum confirm an internal rotation motion of water inside the cluster. The experimental results have been complemented with density-functional-theory molecular orbital calculations, binding energy decomposition and a topological analysis of the electronic density, providing a comparative description of the effects of hydrogen bonding of water to the alcohol and thiol groups in the dimers, relevant to understand hydrogen bonding to sulfur centers.
Water forms weak H-bonds with thenyl compounds, simultaneously retaining internal mobility in the dimer.
A novel DFT-based Reaction Kinetics (DFT-RK) simulation approach, employed in combination with real-time data from reaction monitoring instrumentation (like UV–vis, FTIR, Raman, and 2D NMR benchtop ...spectrometers), is shown to provide a detailed methodology for the analysis and design of complex synthetic chemistry schemes. As an example, it is applied to the opening of epoxides by titanocene in THF, a catalytic system with abundant experimental data available. Through a DFT-RK analysis of real-time IR data, we have developed a comprehensive mechanistic model that opens new perspectives to understand previous experiments. Although derived specifically from the opening of epoxides, the prediction capabilities of the model, built on elementary reactions, together with its practical side (reaction kinetics simulations of real experimental conditions) make it a useful simulation tool for the design of new experiments, as well as for the conception and development of improved versions of the reagents. From the perspective of the methodology employed, because both the computational (DFT-RK) and the experimental (spectroscopic data) components can follow the time evolution of several species simultaneously, it is expected to provide a helpful tool for the study of complex systems in synthetic chemistry.
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