Magneto-Mechanical Surfaces Design.

Magneto-mechanically active surfaces (MMAS) represent a new family of nano/micro-structured surfaces in which motion is induced by an external magnetic field. Under the name of "artificial cilia", "biomimetic cilia", "magnetic actuated patterns", "nanopillars", etc., published works in this area continue their quick growth in number. Notwithstanding their potential application in microfluidic, chemical sensors, catalytic processes and microelectronics to increase device perfomances, there is still a lot to do in the development of these materials. Improvement and optimization of the performance of these structures are essential tasks in order to fulfil their complete development. Along this article, a critical review involving the main aspects in the design of the patterned nanocomposites will be presented.

Multiphoton reactive surfaces using ruthenium(II) photocleavable cages.

Photoreactive surfaces derived from a new photocleavable surface modification agent and with photosensitivity in the Vis and IR region are described. A ruthenium(II) caged aminosilane, [Ru(bpy)(2)(PMe(3))(APTS)](PF(6))(2), was synthesized and attached to silica surfaces. Light irradiation removed the cage and generated surface patterns with reactive amine groups. The photosensitivity of this compound under single (460 nm) and two-photon (900) excitation is demonstrated. Functional patterns with site-selective attachment of other molecular species are described.

Recent Advances in MXene/Epoxy Composites: Trends and Prospects.

Epoxy resins are thermosets with interesting physicochemical properties for numerous engineering applications, and considerable efforts have been made to improve their performance by adding nanofillers to their formulations. MXenes are one of the most promising functional materials to use as nanofillers. They have attracted great interest due to their high electrical and thermal conductivity, hydrophilicity, high specific surface area and aspect ratio, and chemically active surface, compatible with a wide range of polymers. The use of MXenes as nanofillers in epoxy resins is incipient; nevertheless, the literature indicates a growing interest due to their good chemical compatibility and outstanding properties as composites, which widen the potential applications of epoxy resins. In this review, we report an overview of the recent progress in the development of MXene/epoxy nanocomposites and the contribution of nanofillers to the enhancement of properties. Particularly, their application for protective coatings (i.e., anticorrosive and friction and wear), electromagnetic-interference shielding, and composites is discussed. Finally, a discussion of the challenges in this topic is presented.

Polyacrylonitrile-b-Polystyrene Block Copolymer-Derived Hierarchical Porous Carbon Materials for Supercapacitor.

The use of block copolymers as a sacrificial template has been demonstrated to be a powerful method for obtaining porous carbons as electrode materials in energy storage devices. In this work, a block copolymer of polystyrene and polyacrylonitrile (PS-b-PAN) has been used as a precursor to produce fibers by electrospinning and powdered carbons, showing high carbon yield (~50%) due to a low sacrificial block content (fPS ≈ 0.16). Both materials have been compared structurally (in addition to comparing their electrochemical behavior). The porous carbon fibers showed superior pore formation capability and exhibited a hierarchical porous structure, with small and large mesopores and a relatively high surface area (~492 m2/g) with a considerable quantity of O/N surface content, which translates into outstanding electrochemical performance with excellent cycle stability (close to 100% capacitance retention after 10,000 cycles) and high capacitance value (254 F/g measured at 1 A/g).

Wavelength-selective caged surfaces: how many functional levels are possible?

The possibility of wavelength-selective cleavage of seven photolabile caging groups from different families has been studied. Amine-, thiol-, and carboxylic-terminated organosilanes were caged with o-nitrobenzyl (NVOC, NPPOC), benzoin (BNZ), (coumarin-4-yl)methyl (DEACM), 7-nitroindoline (DNI, BNI), and p-hydroxyphenacyl (pHP) derivatives. Caged surfaces modified with the different chromophores were prepared, and their photosensitivity at selected wavelengths was quantified. Different pairs, trios, and quartets of chromophore combinations with wavelength-selective photoresponse were identified. Our results show, for the first time, the possibility of generating surfaces with up to four different and independently addressable functional levels. In addition, this manuscript presents the first systematic comparison of the photolytic properties of different photolabile groups under different irradiation conditions.

Photoactivatable caged cyclic RGD peptide for triggering integrin binding and cell adhesion to surfaces.

We report the synthesis and properties of a photoactivatable caged RGD peptide and its application for phototriggering integrin- and cell-binding to surfaces. We analysed in detail 1) the differences in the integrin-binding affinity of the caged and uncaged forms by quartz crystal microbalance (QCM) studies, 2) the efficiency and yield of the photolytic uncaging reaction, 3) the biocompatibility of the photolysis by-products and irradiation conditions, 4) the possibility of site, temporal and density control of integrin-binding and therefore human cell attachment, and 5) the possibility of in situ generation of cell patterns and cell gradients by controlling the UV exposure. These studies provide a clear picture of the potential and limitations of caged RGD for integrin-mediated cell adhesion and demonstrate the application of this approach to the control and study of cell interactions and responses.

Concentration Effect over Thermoresponse Derived from Organometallic Compounds of Functionalized Poly(N-isopropylacrylamide-co-dopamine Methacrylamide).

The functionalization of smart polymers is opening a new perspective in catalysis, drug carriers and biosensors, due to the fact that they can modulate the response regarding conventional devices. This smart response could be affected by the presence of organometallic complexes in terms of interactions which could affect the physical chemical properties. In this sense, the thermoresponsive behavior of copolymers based on N-isopropylacrylamide (NIPAM) could be affected due to the presence of hydrophobic groups and concentration effect. In this work, the functionalization of a copolymer based on NIPAM and dopamine methacrylamide with different amounts of bis(cyclopentadienyl)titanium (IV) dichloride was carried out. The resulting materials were characterized, showing a clear idea about the mechanism of functionalization through FTIR spectroscopy. The thermoresponsive behavior was also studied for various polymeric solutions in water by UV-vis spectroscopy and calorimetry. The hydrophobic interactions promoted by the organometallic complex could affect the transition associated with the lower critical solution temperature (LCST), specifically, the segments composed by pure NIPAM. That fact would explain the reduction of the width of the LCST-transition, contrary to what could be expected. In addition, the hydrophobicity was tested by the contact angle and also DNA interactions.

Polyelectrolyte multilayers containing triblock copolymers of different charge ratio.

Multilayers formed by the sodium salt of poly(4-styrenesulfonate), PSS, and triblock copolymers of the form PDMAEMA-PCL-PDMAEMA (PDMAEMA corresponding to poly[2-(N,N-dimethylamino)ethyl methacrylate), and PCL to poly(epsilon-caprolactone) have been built by layer-by-layer self-assembly from the aqueous polyelectrolyte solutions. Two types of block copolymers have been used which differ on the type of the amino groups, either hydrochloride or quaternized. This leads to changes in the charge density of the chains for the same content of amino groups. The growth of the multilayers has been followed using dissipative quartz crystal microbalance and ellipsometry techniques. The results show that, independently of the conditions used in the assembling, the film thickness grows linearly with the number of layers. The comparison of the thickness values obtained from D-QCM and ellipsometry has allowed us to calculate the water content of the polymer film. The analysis of the D-QCM data also provides the shear modulus, whose values are typical of a rubber-like polymer system. The analysis of the mass adsorbed calculated by the ellipsometric measurements indicated that the nature of the charge compensation mechanism is extrinsic for all the studied systems, although the degree of extrinsic compensation is strongly dependent on the copolymer used and the concentration in solution. Finally, it was found that the adsorption kinetic of the layers is bimodal for all the films built. Even though the characteristic adsorption times depend on the specific copolymer used, no dependence on the number of layers has been found for a given multilayer.

Fabrication and Characterization of PEEK/PEI Multilayer Composites.

Polyetheretherketone (PEEK)/polyetherimide (PEI) blends (50/50, v/v) keeping the crystal phase of PEEK have been manufactured by alternate PEEK/PEI layer stacking. This strategy avoided the complete miscibility of both polymers, keeping layers of PEEK and PEI unmixed along the sample thickness, as well as promoting the formation of a smooth interfacial layer where PEEK and PEI were mixed. The properties of this interface after processing at molten state and different times was studied by DSC, DMA, and X-Ray synchrotron. These techniques allowed monitoring the evolution of glass transition, where isolated Tg's for both pristine polymers were observed even after long processing time. PEEK crystallinity slightly decreased during manufacturing, whereas PEEK crystal parameters did not vary. These observations show that, although the interface-the zone where both polymers are mixed-grew, layers with pristine polymers remained even after prolonged processing time. The preservation of the PEEK crystallinity was also observed in the mechanical properties of the multilayer PEEK/PEI films, which were compared with pristine PEEK and PEI films. Multilayer samples processed for shorter times rendered higher young modulus, tensile strength, and strain at break.

Fluorescently tagged polymer bioconjugates from protein derived macroinitiators.

BSA and lysozyme have been transformed into macroinitiators for living radical polymerisation and used to produce well-defined bioconjugates which can be fluorescently labelled providing a versatile strategy for the preparation of bioconjugates which is complementary to traditional PEGylation.