Schwarzites and Triply Periodic Minimal Surfaces: From Pure Topology Mathematics to Macroscale Applications.

Schwarzites are porous (spongy-like) carbon allotropes with negative Gaussian curvatures. They are proposed by Mackay and Terrones inspired by the works of the German mathematician Hermann Schwarz on Triply-Periodic Minimal Surfaces (TPMS). This review presents and discusses the history of schwarzites and their place among curved carbon nanomaterials. The main works on schwarzites are summarized and are available in the literature. Their unique structural, electronic, thermal, and mechanical properties are discussed. Although the synthesis of carbon-based schwarzites remains elusive, recent advances in the synthesis of zeolite-templates nanomaterials have brought them closer to reality. Atomic-based models of schwarzites are translated into macroscale ones that are 3D-printed. These 3D-printed models are exploited in many real-world applications, including water remediation and biomedical ones.

Self-Healing E-tongue.

Self-healing materials inspire the next generation of multifunctional wearables and Internet of Things appliances. They expand the realm of thin film fabrication, enabling seamless conformational coverage irrespective of the shape complexity and surface geometry for electronic skins, smart textiles, soft robotics, and energy storage devices. Within this context, the layer-by-layer (LbL) technique is versatile for homogeneously dispersing materials onto various matrices. Moreover, it provides molecular level thickness control and coverage on practically any surface, with poly(ethylenimine) (PEI) and poly(acrylic acid) (PAA) being the most used materials primarily employed in self-healing LbL structures operating at room temperature. However, achieving thin film composites displaying controlled conductivity and healing ability is still challenging under ambient conditions. Here, PEI and PAA are mixed with conductive fillers (gold nanorods, poly(3,4-ethylene dioxythiophene): polystyrenesulfonate (PEDOT:PSS), reduced graphene oxides, and multiwalled carbon nanotubes) in distinct LbL film architectures. Electrical (AC and DC), optical (Raman spectroscopy), and mechanical (nanoindentation) measurements are used for characterizing composite structures and properties. A delicate balance among electrical, mechanical, and structural characteristics must be accomplished for a controlled design of conductive self-healing composites. As a proof-of-concept, four LbL composites were chosen as sensing units in the first reported self-healing e-tongue. The sensor can easily distinguish basic tastes at low molar concentrations and differentiate trace levels of glucose in artificial sweat. The formed nanostructures enable smart coverages that have unique features for solving current technological challenges.

Improving Quantitative EDS Chemical Analysis of Alloy Nanoparticles by PCA Denoising: Part II. Uncertainty Intervals.

Analytical studies of nanoparticles (NPs) are frequently based on huge datasets derived from hyperspectral images acquired using scanning transmission electron microscopy. These large datasets require machine learning computational tools to reduce dimensionality and extract relevant information. Principal component analysis (PCA) is a commonly used procedure to reconstruct information and generate a denoised dataset; however, several open questions remain regarding the accuracy and precision of reconstructions. Here, we use experiments and simulations to test the effect of PCA processing on data obtained from AuAg alloy NPs a few nanometers wide with different compositions. This study aims to address the reliability of chemical quantification after PCA processing. Our results show that the PCA treatment mitigates the contribution of Poisson noise and leads to better quantification, indicating that denoised results may be reliable from the point of view of both uncertainty and accuracy for properly planned experiments. However, the initial data need to be of sufficient quality: these results can only be obtained if the signal-to-noise ratio of input data exceeds a minimal value to avoid the occurrence of random noise bias in the PCA reconstructions.

Influence of the Flow Rate in an Automated Microfluidic Electronic Tongue Tested for Sucralose Differentiation.

Incorporating electronic tongues into microfluidic devices brings benefits as dealing with small amounts of sample/discharge. Nonetheless, such measurements may be time-consuming in some applications once they require several operational steps. Here, we designed four collinear electrodes on a single printed circuit board, further comprised inside a straight microchannel, culminating in a robust e-tongue device for faster data acquisition. An analog multiplexing circuit automated the signal's routing from each of the four sensing units to an impedance analyzer. Both instruments and a syringe pump are controlled by dedicated software. The automated e-tongue was tested with four Brazilian brands of liquid sucralose-based sweeteners under 20 different flow rates, aiming to systematically evaluate the influence of the flow rate in the discrimination among sweet tastes sold as the same food product. All four brands were successfully distinguished using principal component analysis of the raw data, and despite the nearly identical sucralose-based taste in all samples, all brands' significant distinction is attributed to small differences in the ingredients and manufacturing processes to deliver the final food product. The increasing flow rate improves the analyte's discrimination, as the silhouette coefficient reaches a plateau at ~3 mL/h. We used an equivalent circuit model to evaluate the raw data, finding a decrease in the double-layer capacitance proportional to improvements in the samples' discrimination. In other words, the flow rate increase mitigates the formation of the double-layer, resulting in faster stabilization and better repeatability in the sensor response.

Enhanced mobility and controlled transparency in multilayered reduced graphene oxide quantum dots: a charge transport study.

Reduced graphene oxide (rGO) layers are known to be significantly conductive along the basal plane throughout delocalized sp2 domains. Defects present in rGO implies in disordered systems with numerous localized sites, resulting in a charge transport governed mainly by a 2D variable range hopping (VRH) mechanism. These characteristics are observed even in multilayered rGO since the through-plane conduction is expected to be insubstantial. Here, we report on the multilayer assembly of functionalized rGO quantum dots (GQDs) presenting 3D VRH transport that endows elevated charge carrier mobility, ca âˆ¼ 236 cm2 V-1 s-1. Polyelectrolyte-wrapped GQDs were assembled by layer-by-layer technique (LbL), ensuring molecular level thickness control for the formed nanostructures, along with the adjustment of the film transparency (up to 92% in the visible region). The small size and the random distribution of GQDs in the LbL structure are believed to overcome the translational disorder in multilayered films, contributing to a 3D interlayer conduction that enhances the electronic properties. Such high-mobility, transparency-tunable films assembled by a cost-effective method possess interesting features and wide applicability in optoelectronics.

Poole-Frenkel emission on functionalized, multilayered-packed reduced graphene oxide nanoplatelets.

The unique electronic, mechanical and optical properties of graphene make it a remarkable 2D material, widely explored in a plethora of applications. However, graphene zero-bandgap and the production of defect-free pristine graphene in large areas still limit some applications. To circumvent these issues, graphene-derived 2D materials have arisen as attractive candidates for low-dimensional systems, which requires a better comprehension of their properties. Here, we report a detailed investigation of the conduction mechanisms of two functionalized reduced graphene oxides (rGOs) nanoplatelets, named GPAH and GPSS. The functionalized rGO nanoplatelets were bottom-up assembled via the layer-by-layer technique, enabling molecular-level thickness control of nanostructures with well-defined composition and structure. For the reported multilayered GPAH/GPSS films the charge carriers followed Mott's law, presenting a typical conduction behavior of 2D systems described by the Poole-Frenkel model. The multilayered GPAH/GPSS nanostructure presented a conductivity of 10-4 S cm-1, optical bandgap of ∼3.3 eV and a relative dielectric permittivity (ε r) of 6.4. Temperature-dependent I-V measurements indicated a strong variation of ε r below the critical temperature (T C = 237 K), associated with a high dipole reorientation in the formed GPAH/GPSS nanostructure. All these characteristics make the GPAH/GPSS nanocomposite attractive for graphene-oriented applications, such as electronic devices.

3D Printed e-Tongue.

Nowadays, one of the biggest issues addressed to electronic sensor fabrication is the build-up of efficient electrodes as an alternative way to the expensive, complex and multistage processes required by traditional techniques. Printed electronics arises as an interesting alternative to fulfill this task due to the simplicity and speed to stamp electrodes on various surfaces. Within this context, the Fused Deposition Modeling 3D printing is an emerging, cost-effective and alternative technology to fabricate complex structures that potentiates several fields with more creative ideas and new materials for a rapid prototyping of devices. We show here the fabrication of interdigitated electrodes using a standard home-made CoreXY 3D printer using transparent and graphene-based PLA filaments. Macro 3D printed electrodes were easily assembled within 6 min with outstanding reproducibility. The electrodes were also functionalized with different nanostructured thin films via dip-coating Layer-by-Layer technique to develop a 3D printed e-tongue setup. As a proof of concept, the printed e-tongue was applied to soil analysis. A control soil sample was enriched with several macro-nutrients to the plants (N, P, K, S, Mg, and Ca) and the discrimination was done by electrical impedance spectroscopy of water solution of the soil samples. The data was analyzed by Principal Component Analysis and the 3D printed sensor distinguished clearly all enriched samples despite the complexity of the soil chemical composition. The 3D printed e-tongue successfully used in soil analysis encourages further investments in developing new sensory tools for precision agriculture and other fields exploiting the simplicity and flexibility offered by the 3D printing techniques.

Multiscale Geometric Design Principles Applied to 3D Printed Schwarzites.

Schwartzites are 3D porous solids with periodic minimal surfaces having negative Gaussian curvatures and can possess unusual mechanical and electronic properties. The mechanical behavior of primitive and gyroid schwartzite structures across different length scales is investigated after these geometries are 3D printed at centimeter length scales based on molecular models. Molecular dynamics and finite elements simulations are used to gain further understanding on responses of these complex solids under compressive loads and kinetic impact experiments. The results show that these structures hold great promise as high load bearing and impact-resistant materials due to a unique layered deformation mechanism that emerges in these architectures during loading. Easily scalable techniques such as 3D printing can be used for exploring mechanical behavior of various predicted complex geometrical shapes to build innovative engineered materials with tunable properties.

Charge carrier transport in defective reduced graphene oxide as quantum dots and nanoplatelets in multilayer films.

Graphene is a breakthrough 2D material due to its unique mechanical, electrical, and thermal properties, with considerable responsiveness in real applications. However, the coverage of large areas with pristine graphene is a challenge and graphene derivatives have been alternatively exploited to produce hybrid and composite materials that allow for new developments, considering also the handling of large areas using distinct methodologies. For electronic applications there is significant interest in the investigation of the electrical properties of graphene derivatives and related composites to determine whether the characteristic 2D charge transport of pristine graphene is preserved. Here, we report a systematic study of the charge transport mechanisms of reduced graphene oxide chemically functionalized with sodium polystyrene sulfonate (PSS), named as GPSS. GPSS was produced either as quantum dots (QDs) or nanoplatelets (NPLs), being further nanostructured with poly(diallyldimethylammonium chloride) through the layer-by-layer (LbL) assembly to produce graphene nanocomposites with molecular level control. Current-voltage (I-V) measurements indicated a meticulous growth of the LbL nanostructures onto gold interdigitated electrodes (IDEs), with a space-charge-limited current dominated by a Mott-variable range hopping mechanism. A 2D intra-planar conduction within the GPSS nanostructure was observed, which resulted in effective charge carrier mobility (µ) of 4.7 cm2 V-1 s-1 for the QDs and 34.7 cm2 V-1 s-1 for the NPLs. The LbL assemblies together with the dimension of the materials (QDs or NPLs) were favorably used for the fine tuning and control of the charge carrier mobility inside the LbL nanostructures. Such 2D charge conduction mechanism and high µ values inside an interlocked multilayered assembly containing graphene-based nanocomposites are of great interest for organic devices and functionalization of interfaces.

Low-cost nanomanipulator for in situ experiments in a SEM.

Here, we describe the development of an inexpensive and versatile manipulation system for in situ experiments in a field emission scanning electron microscope based on a parallel-guiding plate-spring mechanism and low cost materials. The system has been tested for a wide range of applications, such as collecting, moving, and positioning particles, fabricating atomic force microscopy tips based on carbon nanotubes, and characterizing individual nanobjects. The nanomanipulation results demonstrate that there are many opportunities for the use of physical manipulation in the bottom-up approach to fabrication of nanodevices.

Contaminants in suspended gold chains: an ab initio molecular dynamics study.

Recently, we have proposed that the origin of anomalously long interatomic distances in suspended gold chains could be the result of carbon contamination during sample manipulation [Phys. Rev. Lett. 88, 076105 (2002)]]. More recently, however, other works have proposed that hydrogen instead of carbon should be the most probable contaminant. We report ab initio molecular dynamics results for different temperatures considering different possible contaminants. Our results show that at nonzero temperatures (more realistic to simulate the experimental conditions) hydrogen may be ruled out and carbon atoms remain the best candidate for contamination.

Evidence for spontaneous spin-polarized transport in magnetic nanowires.

The exploitation of the spin in charge-based systems is opening revolutionary opportunities for device architecture. Surprisingly, room temperature electrical transport through magnetic nanowires is still an unresolved issue. Here, we show that ferromagnetic (Co) suspended atom chains spontaneously display an electron transport of half a conductance quantum, as expected for a fully polarized conduction channel. Similar behavior has been observed for Pd (a quasimagnetic 4d metal) and Pt (a nonmagnetic 5d metal). These results suggest that the nanowire low dimensionality reinforces or induces magnetic behavior, lifting off spin degeneracy even at room temperature and zero external magnetic field.

Origin of anomalously long interatomic distances in suspended gold chains.

The discovery of long bonds in gold atom chains has represented a challenge for physical interpretation. In fact, interatomic distances frequently attain 3.0-3.6 A values, and distances as large as 5.0 A may be occasionally observed. Here we studied gold chains by transmission electron microscopy and performed theoretical calculations using cluster ab initio density functional formalism. We show that the insertion of two carbon atoms is required to account for the longest bonds, while distances above 3 A may be due to a mixture of clean and one C atom contaminated bonds.