Functional Organic Nanomaterials

π-Conjugated polymers have a wide range of applications such as photovoltaics, light-emitting diodes, and sensors. To gain a better understanding of these systems, monodisperse oligomers can be used as a more simplistic model to generate predictive structural and physical properties of corresponding polymers. A divergent/convergent synthetic approach to synthesis of monodisperse π-conjugated oligomers has been developed. These well-defined, thiophene-containing molecular building blocks have been successfully coupled to a ferrocene hinge, which has been found to be highly efficient in the transport of gold atoms using a gold scanning tunneling microscopy tip. Carbon nanotubes (CNTs) represent a rare class of materials, which exhibit a number of outstanding properties in a single material system, such as high aspect ratio, small diameter, light weight, high mechanical strength, high electrical and thermal conductivities, and near-IR optical and optoelectronic properties. Aerogels are highly porous, low-density materials comprised of a solid, three-dimensional (3D) nanoscale network fully accessible to ions and molecules. By combining the extraordinary properties of CNTs with those of aerogels, a new class of materials becomes accessible with unique multifunctional material properties. CNT aerogels that are mechanically stable and stiff, highly porous, and exhibit excellent electrical conductivity and large specific surface area have been developed. CNTs are recognized as the ultimate carbon fibers for high-performance, multifunctional materials, where an addition of only a small amount of CNTs, if engineered appropriately, could lead to simultaneously enhanced mechanical strength and electrical conductivity. For the first time, using core-shell multi-walled CNTs as a filler to increase the dielectric constant and reduce the dielectric loss of nanotube-polymer composites has been demonstrated. While most efforts in the field of CNT-polymer composites have been focused on passive material properties such as mechanical, electrical, and thermal, there is growing interest in harnessing active material functions such as actuation, sensing, and power generation in designed CNT-polymer materials. The synergy between CNTs and the polymer matrix has been judiciously exploited to create highly desirable active material functions in smart material systems. By incorporating CNTs in a Nafion matrix, multi-shape memory healable composites capable of reversible remote, local, and chemical programming have been developed

Layered microporous polymers by solvent knitting method

Two-dimensional (2D) nanomaterials, especially 2D organic nanomaterials with unprecedentedly diverse and controlled structure, have attracted decent scientific interest. Among the preparation strategies, the top-down approach is one of the considered low-cost and scalable strategies to obtain 2D organic nanomaterials. However, some factors of their layered counterparts limited the development and potential applications of 2D organic nanomaterials, such as type, stability, and strict synthetic conditions of layered counterparts. We report a class of layered solvent knitting hyper-cross-linked microporous polymers (SHCPs) prepared by improving Friedel-Crafts reaction and using dichloroalkane as an economical solvent, stable electrophilic reagent, and external cross-linker at low temperature, which could be used as layered counterparts to obtain previously unknown 2D SHCP nanosheets by method of ultrasonic-assisted solvent exfoliation. This efficient and low-cost strategy can produce previously unreported microporous organic polymers with layered structure and high surface area and gas storage capacity. The pore structure and surface area of these polymers can be controlled by tuning the chain length of the solvent, the molar ratio of AlCl(3), and the size of monomers. Furthermore, we successfully obtain an unprecedentedly high–surface area HCP material (3002 m(2) g(−1)), which shows decent gas storage capacity (4.82 mmol g(−1) at 273 K and 1.00 bar for CO(2); 12.40 mmol g(−1) at 77.3 K and 1.13 bar for H(2)). This finding provides an opportunity for breaking the constraint of former knitting methods and opening up avenues for the design and synthesis of previously unknown layered HCP materials

Impact of the Intermolecular Interactions on the Electronic and Charge-Transport Properties of Organic Materials: A Joint Experimental and Theoretical Approach

The use of organic materials to design electronic devices has actually presented a broad interest because they constitute an ecological and suitable resource for our current "electronic world". These materials provide several advantages (low cost, light weight, good flexibility and solubility to be easily printed) that cannot be afforded with silicon.[1] They can also potentially interact with biological systems, something impossible with inorganic devices. The performance of the organic-based electronic devices critically depends not only to the intrinsic properties of the conjugated cores but also to the supramolecular arrangement.[2] In this contribution, we present some of our more recent investigations on this field dealing with the better understanding of the complex structure-properties relationships of organic nanomaterials.[3] For this purpose, we use a joint experimental and theoretical approach that includes spectroscopic measurements and molecular modeling.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Nanomaterials for Healthcare Biosensing Applications

In recent years, an increasing number of nanomaterials have been explored for their applications in biomedical diagnostics, making their applications in healthcare biosensing a rapidly evolving field. Nanomaterials introduce versatility to the sensing platforms and may even allow mobility between different detection mechanisms. The prospect of a combination of different nanomaterials allows an exploitation of their synergistic additive and novel properties for sensor development. This paper covers more than 290 research works since 2015, elaborating the diverse roles played by various nanomaterials in the biosensing field. Hence, we provide a comprehensive review of the healthcare sensing applications of nanomaterials, covering carbon allotrope-based, inorganic, and organic nanomaterials. These sensing systems are able to detect a wide variety of clinically relevant molecules, like nucleic acids, viruses, bacteria, cancer antigens, pharmaceuticals and narcotic drugs, toxins, contaminants, as well as entire cells in various sensing media, ranging from buffers to more complex environments such as urine, blood or sputum. Thus, the latest advancements reviewed in this paper hold tremendous potential for the application of nanomaterials in the early screening of diseases and point-of-care testing

1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers

yes2D materials such as graphene, LAPONITE® clays or molybdenum disulfide nanosheets are of extremely high interest to the materials community as a result of their high surface area and controllable surface properties. While several methods to access 2D inorganic materials are known, the investigation of 2D organic nanomaterials is less well developed on account of the lack of ready synthetic accessibility. Crystallization-driven self-assembly (CDSA) has become a powerful method to access a wide range of complex but precisely-defined nanostructures. The preparation of 2D structures, however, particularly those aimed towards biomedical applications, is limited, with few offering biocompatible and biodegradable characteristics as well as control over self-assembly in two dimensions. Herein, in contrast to conventional self-assembly rules, we show that the solubility of polylactide (PLLA)-based amphiphiles in alcohols results in unprecedented shape selectivity based on unimer solubility. We use log Poct analysis to drive solvent selection for the formation of large uniform 2D diamond-shaped platelets, up to several microns in size, using long, soluble coronal blocks. By contrast, less soluble PLLA-containing block copolymers yield cylindrical micelles and mixed morphologies. The methods developed in this work provide a simple and consistently reproducible protocol for the preparation of well-defined 2D organic nanomaterials, whose size and morphology are expected to facilitate potential applications in drug delivery, tissue engineering and in nanocomposites.University of Warwick, Materials GRP, EPSRC, The Royal Society, ER

DFT based study on structural stability and transport properties of Sr3AsN: A potential thermoelectric material

Antiperovskite materials are well known for their high thermoelectric performance and gained huge research interest. Here, we report the structural stability and transport properties of Sr$_3$AsN from a precise first-principles study. The calculated equilibrium lattice parameters are in a good agreement with the available data. We find that Sr$_3$AsN is a mechanically, energetically and dynamically stable at ambient condition. Our calculated electronic structure indicates that it is a direct bandgap semiconductor, with a value ~1.2 eV. Sr-4d and N-2p orbitals mainly formulate the direct bandgap. This antiperovskite possesses a high Seebeck coefficient. Although its lattice thermal conductivity is comparatively low, electronic thermal conductivity is very high. The calculated maximum TE figure of merit is 0.75 at 700 K, indicating that it is a potential material for thermoelectric applications.Comment: 22 pages, 11 figure

A glassy phase in quenched disordered graphene and crystalline membranes

We investigate the flat phase of $D$-dimensional crystalline membranes embedded in a $d$-dimensional space and submitted to both metric and curvature quenched disorders using a nonperturbative renormalization group approach. We identify a second order phase transition controlled by a finite-temperature, finite-disorder fixed point unreachable within the leading order of $\epsilon=4-D$ and $1/d$ expansions. This critical point divides the flow diagram into two basins of attraction: that associated to the finite-temperature fixed point controlling the long distance behaviour of disorder-free membranes and that associated to the zero-temperature, finite-disorder fixed point. Our work thus strongly suggests the existence of a whole low-temperature glassy phase for quenched disordered graphene, graphene-like compounds and, more generally, crystalline membranes.Comment: 6 pages, 1 figur

Reversible, Opto-Mechanically Induced Spin-Switching in a Nanoribbon-Spiropyran Hybrid Material

It has recently been shown that electronic transport in zigzag graphene nanoribbons becomes spin-polarized upon application of an electric field across the nanoribbon width. However, the electric fields required to experimentally induce this magnetic state are typically large and difficult to apply in practice. Here, using both first-principles density functional theory (DFT) and time-dependent DFT, we show that a new spiropyran-based, mechanochromic polymer noncovalently deposited on a nanoribbon can collectively function as a dual opto-mechanical switch for modulating its own spin-polarization. These calculations demonstrate that upon mechanical stress or photoabsorption, the spiropyran chromophore isomerizes from a closed-configuration ground-state to a zwitterionic excited-state, resulting in a large change in dipole moment that alters the electrostatic environment of the nanoribbon. We show that the electronic spin-distribution in the nanoribbon-spiropyran hybrid material can be reversibly modulated via noninvasive optical and mechanical stimuli without the need for large external electric fields. Our results suggest that the reversible spintronic properties inherent to the nanoribbon-spiropyran material allow the possibility of using this hybrid structure as a resettable, molecular-logic quantum sensor where opto-mechanical stimuli are used as inputs and the spin-polarized current induced in the nanoribbon substrate is the measured output.Comment: Accepted by Nanoscal