Biodegradable nanocomposites of amyloid fibrils and graphene with shape-memory and enzyme-sensing properties

Graphene–DNA hybrid materials: Assembly, applications, and prospects

Graphene is a two-dimensional, atomic thin, usually impermeable nanomaterial with astonishing electrical, magnetic and mechanical properties and can therefore at its own right be found in applications as sensors, energy storage or reinforcement in composite materials. By introducing nanoscale pores graphene alter and extend its properties beyond permeability. Graphene then resembles a nanoporous sensor, a nanoporous, atomic thin membrane which opens up for such varied applications such as water purification, industrial waste water treatment, mineral recovery, analytical chemistry separation, molecular size exclusion and supramolecular separations. Due to its nanoscopic size it can serve as nanofilters for ion separation even at ultralow nano- or picomolar concentrations. It is an obvious choice for DNA translocation, reading of the sequence of nucleotides in a DNA molecule, and other single molecular analyses as well for biomedical nanoscopic devices since dimensions of conventional membranes does not suffice in those applications. Even though graphene nanopores are known to be unstable against filling by carbon adatoms they can be stabilized by dangling bond bridging via impurity or foreign atoms resulting in a robust nanoporous material. Finally, graphene’s already exceptional electronic properties, its charge carriers exhibit an unusual high mobility and ballistic transport even at 300 K, can be made even more favorable by the presence of nanopores; the semimetallic graphene turns into a semiconductor. In the pores, semiconductor bands with an energy gap of one electron volt coexist with localized states. This may enable applications such as nanoscopic transistors.

Carbon nanotubes: Exceptional mechanical and electronic properties

The microelectronics industry has seen explosive growth during the last thirty years. Extremely large markets for logic and memory devices have driven the development of new materials, and technologies for the fabrication of even more complex devices with features sized now don at the sub micron and nanometer level. Recent interest has arisen in employing these materials, tools and technologies for the fabrication of miniature sensors and actuators and their integration with electronic circuits to produce smart devices and systems. This effort offers the promise of: 1) increasing the performance and manufacturability of both sensors and actuators by exploiting new batch fabrication processes developed including micro stereo lithographic an micro molding techniques; 2) developing novel classes of materials and mechanical structures not possible previously, such as diamond like carbon, silicon carbide and carbon nanotubes, micro-turbines and micro-engines; 3) development of technologies for the system level and wafer level integration of micro components at the nanometer precision, such as self-assembly techniques and robotic manipulation; 4) development of control and communication systems for MEMS devices, such as optical and RF wireless, and power delivery systems, etc. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composite provide a new avenue for future smart systems. The integration of NEMS (NanoElectroMechanical Systems), MEMS, IDTs (Interdigital Transducers) and required microelectronics and conformal antenna in the multifunctional smart materials and composites results in a smart system suitable for sensing and control of a variety functions in automobile, aerospace, marine and civil structures and food and medical industries. This unique combination of technologies also results in novel conformal sensors that can be remotely sensed by an antenna system with the advantage of no power requirements at the sensor site. This paper provides a brief review of MEMS and NEMS based smart systems for various applications mentioned above. Carbon Nano Tubes (CNT) with their unique structure, have already proven to be valuable in their application as tips for scanning probe microscopy, field emission devices, nanoelectronics, H<SUB>2</SUB>-storage, electromagnetic absorbers, ESD, EMI films and coatings and structural composites. For many of these applications, highly purified and functionalized CNT which are compatible with many host polymers are needed. A novel microwave CVD processing technique to meet these requirements has been developed at Penn State Center for the engineering of Electronic and Acoustic Materials and Devices (CEEAMD). This method enables the production of highly purified carbon nano tubes with variable size (from 5-40 nm) at low cost (per gram) and high yield. Whereas, carbon nano tubes synthesized using the laser ablation or arc discharge evaporation method always include impurity due to catalyst or catalyst support. The Penn State research is based on the use of zeolites over other metal/metal oxides in the microwave field for a high production and uniformity of the product. An extended conventional purification method has been employed to purify our products in order to remove left over impurity. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross- linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composites will be presented.

The microelectronics industry has seen explosive growth during the last thirty years. Extremely large markets for logic and memory devices have driven the development of new materials, and technologies for the fabrication of even more complex devices with features sizes now down at the sub micron and nanometer level. Recent interest has arisen in employing these materials, tools and technologies for the fabrication of miniature sensors and actuators and their integration with electronic circuits to produce smart devices and systems. This effort offers the promise of: (1) increasing the performance and manufacturability of both sensors and actuators by exploiting new batch fabrication processes developed including micro stereo lithographic and micro molding techniques; (2) developing novel classes of materials and mechanical structures not possible previously, such as diamond like carbon, silicon carbide and carbon nanotubes, micro-turbines and micro-engines; (3) development of technologies for the system level and wafer level integration of micro components at the nanometer precision, such as self-assembly techniques and robotic manipulation; (4) development of control and communication systems for MEMS devices, such as optical and RF wireless, and power delivery systems, etc. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composite provide a new avenue for future smart systems. The integration of NEMS (NanoElectroMechanical Systems), MEMS, IDTs (Interdigital Transducers) and required microelectronics and conformal antenna in the multifunctional smart materials and composites results in a smart system suitable for sending and control of a variety functions in automobile, aerospace, marine and civil strutures and food and medical industries. This unique combination of technologies also results in novel conformal sensors that can be remotely sensed by an antenna system with the advantage of no power requirements at the sensor site. This paper provides a brief review of MEMS and NEMS based smart systems for various applications mentioned above. Carbon Nano Tubes (CNT) with their unique structure, have already proven to be valuable in their application as tips for scanning probe microscopy, field emission devices, nanoelectronics, H2-storage, electromagnetic absorbers, ESD, EMI films and coatings and structural composites. For many of these applications, highly purified and functionalized CNT which are compatible with many host polymers are needed. A novel microwave CVD processing technique to meet these requirements has been developed at Penn State Center for the Engineering of Electronic and Acoustic Materials and Devices (CEEAMD). This method enables the production of highly purified carbon nano tubes with variable size (from 5 - 40 nm) at low cost (per gram) and high yield. Whereas, carbon nano tubes synthesized using the laser ablation or arc discharge evaporation method always include impurity due to catalyst or catalyst support. The Penn State research is based on the use of zeolites over other metal/metal oxides in the microwave field for a high production and uniformity of the product. An extended coventional purification method has been employed to purify our products in order to remove left over impurity. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composites will be presented.

CONSPECTUS: Nanostructures based on molybdenum disulfide (MoS2) are by far the most common and well-studied systems among two-dimensional (2D) semiconducting materials. Although still being characterized as a "promising material", catalytic activity of MoS2 nanostructures has been found, and applications in lubrication processes are pursued. Because exfoliation techniques have improved over the past years, monolayer MoS2 is easily at hand; thus, experimental studies on its electronic properties and applicability are in scientific focus, and some MoS2-based electronic devices have been reported already. Additionally, the improvement of atomic force microscopy led to nanoindentation experiments, in which the exceptional mechanical properties of MoS2 could be confirmed. In this Account, we review recent results from density-functional based calculations on several MoS2-based nanostructures; we have chosen to follow several experimental routes focusing on different nanostructures and their specific properties. MoS2-based triangular nanoflakes are systems that are experimentally well described and studied with a special focus on their optical absorption. The interpretation of our calculations fits well to the experimental picture: the absorption peaks in the visible light range show a quantum-confinement effect; they originate from excitations into the edge states. Additionally, delocalized metallic-like states are present close to the Fermi level, which do not contribute to photoabsorption in the visible range. Additionally, nanoindentation experiments have been simulated to obtain mechanical properties of the MoS2 material and to study the influence of deformation on the system's electronics. In these molecular-dynamics simulations, a tip penetrates a MoS2 monolayer, and the obtained Young's modulus and breaking stress agree very well with experimentally obtained values. Whereas the structural properties, such as bond lengths and layer contraction, vary locally differently upon indentation, the electronic structure in terms of the density of states, the gap between occupied and unoccupied states, or the quantum transport change only slightly. The robustness of the material with respect to electronic and mechanical properties makes monolayer MoS2 special. However, it is important to note that this robustness refers to a local disturbance through deformation and still seems to be dependent on the defect concentration. Finally, we present a comparison of the thermodynamic stabilities of different MoS2-based nanostructures with a focus on nanoflakes, fullerene-like nanooctahedra, and smaller Chevrel-type and non-Chevrel-type clusters (nanowires). All studied systems are stable in comparison to MoS2, Mo bulk, and the S8 crown, but only the studied nanoflakes and nanowires show specific stoichiometries, either sulfur-rich or sulfur-poor, whereas the nanooctahedra may adopt both. From the thermodynamic stabilities, it should be possible to deliberately choose specific nanostructures by thoughtful choices of the synthesis conditions. In conclusion, we present in this Account exceptional properties of MoS2-based nanostructures studied by means of density-functional theory. The focus lies on optical absorption in the visible range observed in triangular nanoflakes, which originate in the system's edge states, the robustness of monolayer MoS2 with respect to punctual loads regarding both mechanical and electronic properties, and the thermodynamic stability of most studied MoS2-based nanosystems revealing a correlation between composition and preferred morphology, particularly for 2D systems.

Graphynes, a class of two-dimensional carbon allotropes, exhibit exceptional electronic properties, similar to graphene, but with intrinsic band gaps, making them promising for semiconducting applications. The incorporation of acetylene linkages allows for systematic modulation of their properties. However, the theoretical characterization of graphynes remains computationally demanding, particularly for electron-phonon coupling (EPC) analyses. Here, we employ the density functional tight binding method within the DFTBEPHY framework, providing an efficient and accurate approach for computing EPC and transport properties. We investigate the structural, mechanical, electronic, and transport properties of graphynes, comparing transport calculations using the constant relaxation-time approximation and the self-energy relaxation-time approximation (SERTA) alongside analytical models based on parabolic- and Kane-band approximations. For graphyne, the SERTA relaxation time is 0.63 (1.69) ps for holes (electrons). In graphdiyne, the relaxation time is 0.04 (0.14) ps for holes (electrons). While the hole mobilities in graphyne are on the order of 103 cm2 V-1 s-1, the electron mobilities reach up to 104 cm2 V-1 s-1. In graphdiyne, the mobility values for both types of charge carriers are on the order of 102 cm2 V-1 s-1. The phonon-limited mobilities at room temperature in graphyne fall between those of graphene and MoS2, while in graphdiyne, they are comparable to those of MoS2.

Amyloids are associated with severe degenerative diseases and show exceptional mechanical properties, in particular great stiffhess. Amyloid fibrils, forming protein nanotube structures, are elongated fibers with a diameter of ≈8 nm with a characteristic dense hydrogen-bond (H-bond)patterning in the form of beta-sheets (β-sheets). Here we report a series of molecular dynamics simulations to study mechanical failure properties of a twofold symmetric Aβ(l–40) amyloid fibril, a pathogen associated with Alzheimer’s disease. We carry out computational experiments to study the response of the amyloid fibril to compressive loading. Our investigations reveal atomistic details of the failure process, and confirm that the breakdown of H-bonds plays a critical role during the failure process of amyloid fibrils. We obtain a Young’s modulus of ≈12.43 GPa, in dose agreement with earlier experimental results. Our simulations show that failure by buck-ling and subsequent shearing in one of the layers initiates at ≈1% compressive strain, suggesting that amyloid fibrils can be rather brittle mechanical elements.

Graphene distinctive electronic and optical properties have sparked intense interest throughout the scientific community bringing innovation and progress to many sectors of academia and industry. Graphene manufacturing has rapidly evolved since its discovery in 2004. The diverse growth methods of graphene have many comparative advantages in terms of size, shape, quality and cost. Specifically, epitaxial graphene is thermally grown on a silicon carbide (SiC) substrate. This type of graphene is unique due to its coexistence with the SiC underneath which makes the process of transferring graphene layers for devices manufacturing simple and robust. Raman analysis is a sensitive technique extensively used to explore nanocarbon material properties. Indeed, this method has been widely used in graphene studies in fundamental research and application fields. We review the principal Raman scattering processes in SiC substrate and demonstrate epitaxial graphene growth. We have identified the Raman bands signature of graphene for different layers number. The method could be readily adopted to characterize structural and exceptional electrical properties for various epitaxial graphene systems. Particularly, the variation of the charge carrier concentration in epitaxial graphene of different shapes and layers number have been precisely imaged. By comparing the intensity ratio of 2D line and G line—“I2D/IG”—the density of charge across the graphene layers could be monitored. The obtained results were compared to previous electrical measurements. The substrate longitudinal optical phonon coupling “LOOPC” modes have also been examined for several epitaxial graphene layers. The LOOPC of the SiC substrate shows a precise map of the density of charge in epitaxial graphene systems for different graphene layers number. Correlations between the density of charge and particular graphene layer shape such as bubbles have been determined. All experimental probes show a high degree of consistency and efficiency. Our combined studies have revealed novel capacitor effect in diverse epitaxial graphene system. The SiC substrate self-compensates the graphene layer charge without any external doping. We have observed a new density of charge at the graphene—substrate interface. The located capacitor effects at epitaxial graphene-substrate interfaces give rise to an unexpected mini gap in graphene band structure.

Atomically thin sheets of materials, the so-called two-dimensional (2D) materials arrived on the scene in early 2000s with the successful isolation of graphene as freestanding monolayer films. Graphene, a single atom thick sheet of sp2-hybridized carbon bonded in a honeycomb lattice, has exceptional electronic, optical, mechanical and thermal properties that outperform those of most of the existing materials. The research on graphene further fuelled emergence of related 2D materials such as black phosphorous, silicene, germanene and transition metal dichalcogenides (TMDs) such as MoS2. Due to their exotic properties, these materials offer virtually endless opportunities for fundamental research as well as cutting edge applications. Most of these 2D materials however exist as single layers only when supported by another solid surface or when stabilized by physisorbed or chemisorbed organic molecules. Given their layered nature, most 2D materials are extremely difficult to disperse in typical solvents. Chemisorption of organic molecules onto their basal plane allows dispersion of these materials in (organic) solvents thereby improving their solution processability. Such dispersions can be used in composite materials and as functional inks. Moreover, covalent functionalization allows modification of the intrinsic electrical, electronic and optical properties of these 2D materials. In this talk, I will discuss covalent modification graphene, graphite and MoS2 using diazonium chemistry. Two different routes for reductive decomposition of diazonium salts namely, chemical and electrochemical, will be discussed in detail. Special focus is on sub-nanometer characterization of modified materials using scanning tunneling and atomic force microscopy (STM and AFM). Initial results towards patterned covalent functionalization using physisorbed self-assembled templates will also be presented besides the discussion on the use of such surfaces as seed layers for atomic layer deposition (ALD).

Carbon nanotubes, which possess an atomic arrangement that closely resembles graphene, form a class of nanomaterials with an exceptional application portfolio including electronics, batteries, sensors, etc. Both carbon nanotubes and graphene have exceptional mechanical and electronic properties. These exceptional properties of graphene are attributed to the combined effect of σ and π bonds which form upon sp2 hybridization, resulting in what is known as resonant bonding. Here, we use atom probe tomography (APT, a technique based on controlled desorption of atoms under high electric field) to observe its bond-rupture characteristics. Results show that the bond rupture of carbon nanotubes, which are resonantly bonded, is similar to that observed for covalently bonded systems. However, a significant difference is observed when compared with those solids which are metavalently bonded. This clearly justifies that resonant bonding, a sub-branch of covalent bonding, is very different from "metavalent" bonding.

The emergence of synthetic ceramics as a prominent class of materials with a unique combination of properties has been an important part of the materials-science scene over the past 20 years. These 'high-technology' ceramics have varied applications in areas utilizing their exceptional mechanical, thermal, optical, magnetic or electronic properties. A notable development of the 1970s was that of 'Si-based' ceramics (Si3N4' SiC and 'Sialons') as high-temperature engineering solids. More recently the zirconia-based ceramics have evolved as a class of material with significant improvements in fracture-toughness. In the 1980s we are on the threshold of development of ceramic-matrix composites with the promise of over coming major limitations in engineering design with 'brittle' ceramics and the development of novel properties unattainable with monolithic micro structures. Throughout this period there have been significant but less well-publicized developments in the field of glass-ceramics and glasses. It is the purpose of this publication to review selected topics within this important area of materials science. A key element in understanding the relation between properties and microstructure is a knowledge of atomic arrangement in ceramic phases. Recent developments in NMR and X-ray absorption spectroscopies have had considerable impact on studies of atomic co-ordination in glasses and crystalline ceramic materials and are reviewed in Chapters 1 and 2. Glass-ceramics are derived from the parent glasses by controlled crystal lization and have properties dictated, in part, by the efficiency of crystal nucleation within the glass volume.

This work focuses on developing a novel thermal‐responsive shape memory Poly(ε‐caprolactone) (PCL)/maleic‐anhydride grafted poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS‐g‐MAH) blends, with enhanced shape memory and mechanical properties, which is tailored for 3D printing applications. The thermal, mechanical, and rheological properties of the blends were rigorously assessed by DSC, TGA, mechanical testing, and dynamic rheological analysis. The results show that the elongation at the break of the blends exceeds 1000%, which can be attributed to the formation of the co‐continuous structure. Thermal‐responsive shape memory properties characterized by the water bath circulation method showed that the PCL4/MAH6 exhibited the optimal overall performance (shape fixation rate of 97.22%, shape recovery rate of 96.67%) and remained stable after 10 cycles of testing. Moreover, the effect of printing parameters on shape memory properties was investigated, revealing that blends perform the most promising memory behavior at a layer thickness of 0.1 mm, hot‐bed temperature of 40°C, and printing speed of 40 mm/s. In addition, the relationship between the composition of the blends and their properties was investigated at the molecular level by molecular dynamics simulations, which were in agreement with the experimental observations. In conclusion, this study provides new perspectives on the development of advanced materials suitable for 4D printing applications. Highlights The co‐continuous structure effectively enhances blends' mechanical properties. The storage modulus exerts a dominant influence on the shape memory properties. Molecular dynamics simulations are employed to validate experimental observations.

Development of sustainable bioplastic films for food packaging using zein protein-derived amyloid fibrils: characterization and functional properties.

Carbon nanotubes (CNTs) have gained considerable attention in drug delivery applications due to their high surface area and exceptional electronic and mechanical properties. Doping CNTs with metals like aluminum (Al) and gallium (Ga) can modify their electronic, chemical, and stability characteristics, enhancing their suitability for drug delivery. This study investigates the interaction of the drug molecule 5-fluorouracil (5-FU) with pristine and doped (8,8) CNTs using density functional theory (DFT) calculations with the B3LYP functional and the 6-31 G basis set. The results reveal significant changes in the electronic properties after doping. Aluminum doping increases the energy gap, reducing system reactivity, while gallium doping decreases the energy gap, promoting stronger interactions with the drug. Aluminum doping improves the structural stability of CNTs with 5-FU, whereas gallium enhances the chemical potential and hardness, favoring interactions with the drug molecule. In conclusion, aluminum- and gallium-doped CNTs exhibit different behaviors in drug interactions, allowing for optimization of targeted drug delivery systems. Based on energy gap, chemical potential, and chemical hardness values, both doping types can enhance drug delivery properties, with the specific doping choice dependent on the therapeutic application.