Mid-Infrared Mapping of Four-Layer Graphene Polytypes Using Near-Field Microscopy.

The mid-infrared (MIR) spectral region attracts attention for accurate chemical analysis using photonic devices. Few-layer graphene (FLG) polytypes are promising platforms, due to their broad absorption in this range and gate-tunable optical properties. Among these polytypes, the noncentrosymmetric ABCB/ACAB structure is particularly interesting, due to its intrinsic bandgap (8.8 meV) and internal polarization. In this study, we utilize scattering-scanning near-field microscopy to measure the optical response of all three tetralayer graphene polytypes in the 8.5-11.5 µm range. We employ a finite dipole model to compare these results to the calculated optical conductivity for each polytype obtained from a tight-binding model. Our findings reveal a significant discrepancy in the MIR optical conductivity response of graphene between the different polytypes than what the tight-binding model suggests. This observation implies an increased potential for utilizing the distinct tetralayer polytypes in photonic devices operating within the MIR range for chemical sensing and infrared imaging.

One-pot green bio-assisted synthesis of highly active catalytic palladium nanoparticles in porcine gastric mucin for environmental applications.

In this work, palladium nanoparticles were synthesized using one-pot synthesis utilizing porcine gastric mucin glycoproteins as reducing and capping agents. It is shown that the particles exhibited noticeable catalytic activity through both nitrophenol reduction and Suzuki-Miyaura coupling reactions. The catalytic performance was demonstrated with exceptionally high product yield, a fast reaction rate, and low catalyst use. The palladium-mucin composites obtained could be used in particle solution and as hydrogel catalysts to increase their reusability for at least ten reaction cycles with minimum loss in their catalytic effectiveness.

Unidirectional rotation of micromotors on water powered by pH-controlled disassembly of chiral molecular crystals.

Biological and synthetic molecular motors, fueled by various physical and chemical means, can perform asymmetric linear and rotary motions that are inherently related to their asymmetric shapes. Here, we describe silver-organic micro-complexes of random shapes that exhibit macroscopic unidirectional rotation on water surface through the asymmetric release of cinchonine or cinchonidine chiral molecules from their crystallites asymmetrically adsorbed on the complex surfaces. Computational modeling indicates that the motor rotation is driven by a pH-controlled asymmetric jet-like Coulombic ejection of chiral molecules upon their protonation in water. The motor is capable of towing very large cargo, and its rotation can be accelerated by adding reducing agents to the water.

From nanoparticles to crystals: one-pot programmable biosynthesis of photothermal gold structures and their use for biomedical applications.

Inspired by nature, green chemistry uses various biomolecules, such as proteins, as reducing agents to synthesize metallic nanostructures. This methodology provides an alternative route to conventional harsh synthetic processes, which include polluting chemicals. Tuning the resulting nanostructure properties, such as their size and shape, is challenging as the exact mechanism involved in their formation is still not well understood. This work reports a well-controlled method to program gold nanostructures' shape, size, and aggregation state using only one protein type, mucin, as a reduction and capping material in a one-pot bio-assisted reaction. Using mucin as a gold reduction template while varying its tertiary structure via the pH of the synthesis, we demonstrate that spherical, coral-shaped, and hexagonal gold crystals can be obtained and that the size can be tuned over three orders of magnitude. This is achieved by leveraging the protein's intrinsic reducing properties and pH-induced conformational changes. The systematic study of the reaction kinetics and growth steps developed here provides an understanding of the mechanism behind this phenomenon. We further show that the prepared gold nanostructures exhibit tunable photothermal properties that can be optimized for various hyperthermia-induced antibacterial applications.

Slow release of copper from jellyfish-based hydrogels for soil enrichment.

Nanotechnology has shown great potential to increase global food production and enhance food security. However, large-scale application of nano-enabled plant agriculture necessitates careful adjustments in design to overcome barriers associated with targeted nanomaterial delivery and their safety concerns. The research herein proposes the delivery of copper (Cu) from immobilized and non-immobilized copper oxide nanoparticles (Cu2O), an active nanomaterial with antifungal and micro-nutrient properties. A benign and biodegradable jellyfish-based hydrogel was used as a platform during Cu2O delivery to soils. The delivery kinetics and Cu dissolution from the nanocomposite were compared to those obtained with crosslinked ionic Cu in hydrogel, which was found to be a less controlled composite. In addition, changing environmental conditions from DI to soil extracts resulted in a decrease in the Cu dissolution rate (from 0.025 to 0.015 h-1) and an increase in the overall normalized Cu release (0.27 to 0.76 mg g-1). Use of hydrogels from natural sources allowed biodegradability over several months, adding nutrients (in the form of elements such as sulfur, nitrogen, and carbon) back to the environment, which ultimately minimizes nanomaterial required for a given desired nanomaterial yield and enhances the overall performance. Altogether, this work demonstrates the potential of Cu2O embedded hydrogels as a benign composite for Cu slow-release and therefore bolsters the field of nano-enabled plant agriculture and supports its safe deployment at large scales.

Bio-assisted synthesis of bimetallic nanoparticles featuring antibacterial and photothermal properties for the removal of biofilms.

Biofilms are responsible for about considerable amounts of cases of bacterial infections in humans. They are considered a major threat to transplant and chronic wounds patients due to their highly resistant nature against antibacterial materials and due to the limited types of techniques that can be applied to remove them. Here we demonstrate a successful in-situ bio-assisted synthesis of dual functionality nanoparticles composed of Silver and Gold. This is done using a jellyfish-based scaffold, an antibacterial material as the templating host in the synthesis. We further explore the scaffold's antibacterial and photothermal properties against various gram-negative and positive model bacteria with and without photo-induced heating at the Near-IR regime. We show that when the scaffold is loaded with these bimetallic nanoparticles, it exhibits dual functionality: Its photothermal capabilities help to disrupt and remove bacterial colonies and mature biofilms, and its antibacterial properties prevent the regrowth of new biofilms.

Realization of Molecular-Based Transistors.

Molecular-based devices are widely considered as significant candidates to play a role in the next generation of "post-complementary metal-oxide-semiconductor" devices. In this context, molecular-based transistors: molecular junctions that can be electrically gated-are of particular interest as they allow new modes of operation. The properties of molecular transistors composed of a single- or multimolecule assemblies, focusing on their practicality as real-world devices, concerning industry demands and its roadmap are compared. Also, the capability of the gate electrode to modulate the molecular transistor characteristics efficiently is addressed, showing that electrical gating can be easily facilitated in single molecular transistors and that gating of transistor composed of molecular assemblies is possible if the device is formed vertically. It is concluded that while the single-molecular transistor exhibits better performance on the lab-scale, its realization faces signifacant challenges when compared to those faced by transistors composed of a multimolecule assembly.

Orientation and Incorporation of Photosystem I in Bioelectronics Devices Enabled by Phage Display.

Interfacing proteins with electrode surfaces is important for the field of bioelectronics. Here, a general concept based on phage display is presented to evolve small peptide binders for immobilizing and orienting large protein complexes on semiconducting substrates. Employing this method, photosystem I is incorporated into solid-state biophotovoltaic cells.

Investigation of the pH-dependence of dye-doped protein-protein interactions.

Proteins can dramatically change their conformation under environmental conditions such as temperature and pH. In this context, Glycoprotein's conformational determination is challenging. This is due to the variety of domains which contain rich chemical characters existing within this complex. Here we demonstrate a new, straightforward and efficient technique that uses the pH-dependent properties of dyes-doped Pig Gastric Mucin (PGM) for predicting and controlling protein-protein interaction and conformation. We utilize the PGM as natural host matrix which is capable of dynamically changing its conformational shape and adsorbing hydrophobic and hydrophilic dyes under different pH conditions and investigate and control the fluorescent properties of these composites in solution. It is shown at various pH conditions, a large variety of light emission from these complexes such as red, green and white is obtained. This phenomenon is explained by pH-dependent protein folding and protein-protein interactions that induce different emission spectra which are mediated and controlled by means of dye-dye interactions and surrounding environment. This process is used to form the technologically challenging white light-emitting liquid or solid coating for LED devices.

Light-Induced Conductivity in a Solution-Processed Film of Polydiacetylene and Perylene Diimide.

We prepared a solution-processed film comprising a drop-casted mixture of melamine-diacetylene and perylene bis(dicarboximide) (PDI). We show that the diacetylene monomers adopt distinct crystalline organization in the presence of the PDI residues. Importantly, the drop-casted diacetylene/PDI film exhibits ultraviolet light-induced conductivity, ascribed to effective transport of charge carriers in the conjugated polymerized network.

Filling the Green Gap of a Megadalton Photosystem I Complex by Conjugation of Organic Dyes.

Photosynthesis is Nature's major process for converting solar into chemical energy. One of the key players in this process is the multiprotein complex photosystem I (PSI) that through absorption of incident photons enables electron transfer, which makes this protein attractive for applications in bioinspired photoactive hybrid materials. However, the efficiency of PSI is still limited by its poor absorption in the green part of the solar spectrum. Inspired by the existence of natural phycobilisome light-harvesting antennae, we have widened the absorption spectrum of PSI by covalent attachment of synthetic dyes to the protein backbone. Steady-state and time-resolved photoluminescence reveal that energy transfer occurs from these dyes to PSI. It is shown by oxygen-consumption measurements that subsequent charge generation is substantially enhanced under broad and narrow band excitation. Ultimately, surface photovoltage (SPV) experiments prove the enhanced activity of dye-modified PSI even in the solid state.

Rapid Particle Patterning in Surface Deposited Micro-Droplets of Low Ionic Content via Low-Voltage Electrochemistry and Electrokinetics.

Electrokinetic phenomena are a powerful tool used in various scientific and technological applications for the manipulation of aqueous solutions and the chemical entities within them. However, the use of DC-induced electrokinetics in miniaturized devices is highly limited. This is mainly due to unavoidable electrochemical reactions at the electrodes, which hinder successful manipulation. Here we present experimental evidence that on-chip DC manipulation of particles between closely positioned electrodes inside micro-droplets can be successfully achieved, and at low voltages. We show that such manipulation, which is considered practically impossible, can be used to rapidly concentrate and pattern particles in 2D shapes in inter-electrode locations. We show that this is made possible in low ion content dispersions, which enable low-voltage electrokinetics and an anomalous bubble-free water electrolysis. This phenomenon can serve as a powerful tool in both microflow devices and digital microfluidics for rapid pre-concentration and particle patterning.

Spatial modulation of light transmission through a single microcavity by coupling of photosynthetic complex excitations to surface plasmons.

Molecule-plasmon interactions have been shown to have a definite role in light propagation through optical microcavities due to strong coupling between molecular excitations and surface plasmons. This coupling can lead to macroscopic extended coherent states exhibiting increment in temporal and spatial coherency and a large Rabi splitting. Here, we demonstrate spatial modulation of light transmission through a single microcavity patterned on a free-standing Au film, strongly coupled to one of the most efficient energy transfer photosynthetic proteins in nature, photosystem I. Here we observe a clear correlation between the appearance of spatial modulation of light and molecular photon absorption, accompanied by a 13-fold enhancement in light transmission and the emergence of a distinct electromagnetic standing wave pattern in the cavity. This study provides the path for engineering various types of bio-photonic devices based on the vast diversity of biological molecules in nature.

Solid-state biophotovoltaic cells containing photosystem I.

The large multiprotein complex, photosystem I (PSI), which is at the heart of light-dependent reactions in photosynthesis, is integrated as the active component in a solid-state organic photovoltaic cell. These experiments demonstrate that photoactive megadalton protein complexes are compatible with solution processing of organic-semiconductor materials and operate in a dry non-natural environment that is very different from the biological membrane.

Efficient separation of conjugated polymers using a water soluble glycoprotein matrix: from fluorescence materials to light emitting devices.

Optically active bio-composite blends of conjugated polymers or oligomers are fabricated by complexing them with bovine submaxilliary mucin (BSM) protein. The BSM matrix is exploited to host hydrophobic extended conjugated π-systems and to prevent undesirable aggregation and render such materials water soluble. This method allows tuning the emission color of solutions and films from the basic colors to the technologically challenging white emission. Furthermore, electrically driven light emitting biological devices are prepared and operated.

Surface-induced conformational changes in doped bovine serum albumin self-assembled monolayers.

Evidence for considerable stabilization of doped bovine serum albumin (BSA) molecules upon adsorption on gold surfaces is provided. This is compared to the surface-induced conformational changes of the bare BSA and its corresponding monolayer. The BSA unfolding phenomenon is correlated with dehydration, which in turn enables improved monolayer coverage. The stabilization mechanism is found to be partially controllable via nanodoping of the BSA molecules, upon which the dehydration process is suppressed and molecular rigidity can be varied. Our experimental data and calculations further point to the intermixing of structural characteristics and inherent molecular properties in studies of biological monolayers.

"Beating speckles" via electrically-induced vibrations of Au nanorods embedded in sol-gel.

Generation of macroscopic phenomena through manipulating nano-scale properties of materials is among the most fundamental goals of nanotechnology research. We demonstrate cooperative "speckle beats" induced through electric-field modulation of gold (Au) nanorods embedded in a transparent sol-gel host. Specifically, we show that placing the Au nanorod/sol-gel matrix in an alternating current (AC) field gives rise to dramatic modulation of incident light scattered from the material. The speckle light patterns take form of "beats", for which the amplitude and frequency are directly correlated with the voltage and frequency, respectively, of the applied AC field. The data indicate that the speckle beats arise from localized vibrations of the gel-embedded Au nanorods, induced through the interactions between the AC field and the electrostatically-charged nanorods. This phenomenon opens the way for new means of investigating nanoparticles in constrained environments. Applications in electro-optical devices, such as optical modulators, movable lenses, and others are also envisaged.

Controlled electroluminescence from films composed of mixed bio-composites and nanotubes.

Good things come in threes: A new type of light emitting bio-composites allowing for the nanometric separation of the active components is demonstrated. A protein with large host-guest capacities is used for the encapsulation of a water-soluble composite dye in a nano-sized shell, which efficiently reduces Förster resonance energy transfer and related mechanisms. Blending of this bio-composite with multi-walled nanotubes increases the charge injection efficiency, in the electro-luminescent device.

DNA-nanoparticle assemblies go organic: macroscopic polymeric materials with nanosized features.

BACKGROUND: One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. METHOD: Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. RESULTS AND CONCLUSIONS: One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network.

Tuning the critical temperature of cuprate superconductor films with self-assembled organic layers.

Control over the T(c) value of high-T(c) superconductors by self-assembled monolayers is demonstrated (T(c) = critical temperature). Molecular control was achieved by adsorption of polar molecules on the superconductor surface (see scheme) that change its carrier concentration through charge transport or light-induced polarization.