Laboratório Nacional de Nanotecnologia

Abstract Recent advances in experimental and computational methods are increasing the quantity and complexity of generated data. This massive amount of raw data needs to be stored and interpreted in order to advance the materials science field. Identifying correlations and patterns from large amounts of complex data is being performed by machine learning algorithms for decades. Recently, the materials science community started to invest in these methodologies to extract knowledge and insights from the accumulated data. This review follows a logical sequence starting from density functional theory as the representative instance of electronic structure methods, to the subsequent high-throughput approach, used to generate large amounts of data. Ultimately, data-driven strategies which include data mining, screening, and machine learning techniques, employ the data generated. We show how these approaches to modern computational materials science are being used to uncover complexities and design novel materials with enhanced properties. Finally, we point to the present research problems, challenges, and potential future perspectives of this new exciting field.

Abstract A solution blow spinning technique was developed using elements of both electrospinning and melt blowing technologies as an alternative method for making non‐woven webs of micro‐ and nanofibers with diameters comparable with those made by the electrospinning process with the advantage of having a fiber production rate (measured by the polymer injection rate) several times higher. The diameters of fibers produced ranged from 40 nm for poly(lactic acid) to several micrometers for poly(methyl methacrylate). This solution blow spinning method uses a syringe pump to deliver a polymer solution to an apparatus consisting of concentric nozzles whereby the polymer solution is pumped through the inner nozzle while a constant, high velocity gas flow is sustained through the outer nozzle. Analysis of the process showed that pressure difference and shearing at the gas/solution interface jettisoned multiple strands of polymer solution towards a collector. During flight, the solvent component of the strands rapidly evaporates forming a web of micro and nanofibers. The effect of injection rate, gas flow pressure, polymer concentration, working distance, and protrusion distance of the inner nozzle was investigated. Polymer type and concentration had a greater effect on fiber diameter than the other parameters tested. Injection rate, gas flow pressure, and working distance affected fiber production rate and/or fiber morphology. Fibers were easily formed into yarns of micro‐ and nanofibers or non‐woven films that could be applied directly onto biological tissue or collected in sheets on a rotating drum. Indeed, virtually any type of target could be used for fiber collection. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

The use of slow release fertilizer has become a new trend to save fertilizer consumption and to minimize environmental pollution. Due to its polymeric cationic, biodegradable, bioabsorbable, and bactericidal characteristics, chitosan (CS) nanoparticle is an interesting material for use in controlled release systems. However, there are no attempts to explore the potential of chitosan nanoparticles as controlled release for NPK fertilizers. In this work chitosan nanoparticles were obtained by polymerizing methacrylic acid for the incorporation of NPK fertilizers. The interaction and stability of chitosan nanoparticle suspensions containing nitrogen (N), phosphorus (P) and potassium (K) were evaluated by FTIR spectroscopy, particle size analysis and zeta-potential. The FTIR results indicated the existence of electrostatic interactions between chitosan nanoparticles and the elements N, P and K. The stability of the CS-PMAA colloidal suspension was higher with the addition of nitrogen and potassium than with the addition of phosphorus, due to the higher anion charge from the calcium phosphate than the anion charges from the potassium chloride and urea. The mean diameter increase of the CS-PMAA nanoparticles in suspension with the addition of different compounds indicated that the elements are being aggregated on the surface of the chitosan nanoparticles.

We describe nanoscale tools in the form of autonomous and remotely guided catalytically self-propelled InGaAs/GaAs/(Cr)Pt tubes. These rolled-up tubes with diameters in the range of 280-600 nm move in hydrogen peroxide solutions with speeds as high as 180 μm s(-1). The effective transfer of chemical energy to translational motion has allowed these tubes to perform useful tasks such as transport of cargo. Furthermore, we observed that, while cylindrically rolled-up tubes move in a straight line, asymmetrically rolled-up tubes move in a corkscrew-like trajectory, allowing these tubes to drill and embed themselves into biomaterials. Our observations suggest that shape and asymmetry can be utilized to direct the motion of catalytic nanotubes and enable mechanized functions at the nanoscale.

The fabrication of fungicides in cost-effective and eco-friendly ways is particularly important for agriculture.

In this work, we synthesized a novel series of hydrogels composed of polyacrylamide (PAAm), methylcellulose (MC), and calcic montmorillonite (MMt) appropriate for the controlled release of fertilizers, where the components presented a synergistic effect, giving very high fertilizer loading in their structure. The synthesized hydrogel was characterized in relation to morphological, hydrophilic, spectroscopic, structural, thermal, and kinetic properties. After those characterizations, the application potential was verified through sorption and desorption studies of a nitrogenated fertilizer, urea (CO(NH2)2). The swelling degree results showed that the clay loading considerably reduces the water absorption capability; however, the hydrolysis process favored the urea adsorption in the hydrogel nanocomposites, increasing the load content according to the increase of the clay mass. The FTIR spectra indicated that there was incorporation of the clay with the polymeric matrix of the hydrogel and that incorporation increased the water absorption speed (indicated by the kinetic constant k). By an X-ray diffraction technique, good nanodispersion (intercalation) and exfoliation of the clay platelets in the hydrogel matrix were observed. Furthermore, the presence of the montmorillonite in the hydrogel caused the system to liberate the nutrient in a more controlled manner than that with the neat hydrogel in different pH ranges. In conclusion, excellent results were obtained for the controlled desorption of urea, highlighting the hydrolyzed hydrogels containing 50% calcic montmorillonite. This system presented the best desorption results, releasing larger amounts of nutrient and almost 200 times slower than pure urea, i.e., without hydrogel. The total values of nutrients present in the system show that this material is potentially viable for application in agriculture as a nutrient carrier vehicle.

This review discusses recent advances in the synthesis, characterization and toxicity of metal oxide nanoparticles obtained mainly through biogenic (green) processes. The in vitro and in vivo toxicities of these oxides are discussed including a consideration of the factors important for safe use of these nanomaterials. The toxicities of different metal oxide nanoparticles are compared. The importance of biogenic synthesized metal oxide nanoparticles has been increasing in recent years; however, more studies aimed at better characterizing the potent toxicity of these nanoparticles are still necessary for nanosafely considerations and environmental perspectives. In this context, this review aims to inspire new research in the design of green approaches to obtain metal oxide nanoparticles for biomedical and technological applications and to highlight the critical need to fully investigate the nanotoxicity of these particles.

Nonwoven mats of poly(lactic acid) (PLA), poly(ethylene oxide) (PEO), and poly( ε -caprolactone) (PCL) were prepared at a nano- and submicron scale by solution blow spinning (SBS) and electrospinning in order to compare crystalline structure and morphology developed by both processes during fiber formation. Polymer solutions were characterized by rheometry and tensiometry. Spun fibers were characterized by several analytical steps. SEM analyses showed that both solution blow spun and electrospun fibers had similar morphology. Absence of residual solvents and characteristic infrared bands in the solution blow spun fibers for PLA, PCL, and PEO was confirmed by FTIR studies. XRD diffraction patterns for solution blow spun and electrospun mats revealed some differences related to distinct mechanisms of fiber formation developed by each process. Significant differences in thermal behavior by DSC were observed between cast films of PLA, PCL, and PEO and their corresponding spun nanofibers. Furthermore, the average contact angles for spun PLA and PCL were higher than for electrospun mats, whereas it was slightly lower for PEO. When comparing electrospun and solution blow spun fibers, it was possible to verify that fiber morphology and physical properties depended both on the spinning technique and type of polymer.

Abstract In recent years, the notion of ‘Quantum Materials’ has emerged as a powerful unifying concept across diverse fields of science and engineering, from condensed-matter and coldatom physics to materials science and quantum computing. Beyond traditional quantum materials such as unconventional superconductors, heavy fermions, and multiferroics, the field has significantly expanded to encompass topological quantum matter, two-dimensional materials and their van der Waals heterostructures, Moiré materials, Floquet time crystals, as well as materials and devices for quantum computation with Majorana fermions. In this Roadmap collection we aim to capture a snapshot of the most recent developments in the field, and to identify outstanding challenges and emerging opportunities. The format of the Roadmap, whereby experts in each discipline share their viewpoint and articulate their vision for quantum materials, reflects the dynamic and multifaceted nature of this research area, and is meant to encourage exchanges and discussions across traditional disciplinary boundaries. It is our hope that this collective vision will contribute to sparking new fascinating questions and activities at the intersection of materials science, condensed matter physics, device engineering, and quantum information, and to shaping a clearer landscape of quantum materials science as a new frontier of interdisciplinary scientific inquiry. We stress that this article is not meant to be a fully comprehensive review but rather an up-to-date snapshot of different areas of research on quantum materials with a minimal number of references focusing on the latest developments.

Abstract Nano and submicrometric fibers of poly( D , L ‐lactide) (PDLLA or PLA) were spun from solutions using a solution blow spinning (SBS) apparatus. Fiber morphology and diameter were investigated by scanning electron microscopy as a function of polymer concentration, feed rate, and air pressure. A more systematic understanding of the SBS process parameters was obtained, and a quantitative relationship between these parameters and average fiber diameter was established by design of experiments and response surface methodology. It was observed that polymer concentration played an important role in fiber diameter, which ranges from 70 to 2000 nm, and its distribution. Lower polymer concentration tended to increase the formation of bead‐on‐string structures, whereas smooth fibers were formed at higher concentrations. Fiber diameter tended to increase with polymer concentration and decrease with feed rate. Based on these results, optimal conditions could be obtained for solution‐blow spun fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.

The structure of the infectious prion protein (PrPSc), which is responsible for Creutzfeldt-Jakob disease in humans and bovine spongiform encephalopathy, has escaped all attempts at elucidation due to its insolubility and propensity to aggregate. PrPSc replicates by converting the non-infectious, cellular prion protein (PrPC) into the misfolded, infectious conformer through an unknown mechanism. PrPSc and its N-terminally truncated variant, PrP 27-30, aggregate into amorphous aggregates, 2D crystals, and amyloid fibrils. The structure of these infectious conformers is essential to understanding prion replication and the development of structure-based therapeutic interventions. Here we used the repetitive organization inherent to GPI-anchorless PrP 27-30 amyloid fibrils to analyze their structure via electron cryomicroscopy. Fourier-transform analyses of averaged fibril segments indicate a repeating unit of 19.1 Å. 3D reconstructions of these fibrils revealed two distinct protofilaments, and, together with a molecular volume of 18,990 Å3, predicted the height of each PrP 27-30 molecule as ~17.7 Å. Together, the data indicate a four-rung β-solenoid structure as a key feature for the architecture of infectious mammalian prions. Furthermore, they allow to formulate a molecular mechanism for the replication of prions. Knowledge of the prion structure will provide important insights into the self-propagation mechanisms of protein misfolding.

Abstract A pectin‐based hydrogel was used as a remover of Cu 2+ and Pb 2+ ions from water and wastewater and in the release of phosphate, potassium, and urea. The swelling studies in either aqueous or saline solutions were analyzed at different pressures, and the prediction of profile of water and solute transports was further analyzed on basis of transport process by diffusion in swellable polymer networks. The hydrogel composed of 0.10 g mL −1 final polymer concentration showed an excellent absorption capacity for removal of Cu 2+ and Pb 2+ from the solution: 120 mg Cu 2+ and 130 mg Pb 2+ per g hydrogel, both at pH 5.5. The hydrogel help to conserve water in a pressure range in which a variety of horticultural plants can absorb it. The release process of urea, phosphate, and potassium from the hydrogels is controlled by non‐Fickian mechanism with a tendency to macromolecular relaxation. This type of hydrogel is an interesting system for applications in which the efficient use of water is required and release of fertilizers for agriculture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The increasing interest and research on two-dimensional (2D) materials has not yet translated into a reality of diverse materials applications. To go beyond graphene and transition metal dichalcogenides for several applications, suitable candidates with desirable properties must be proposed. Here we use machine learning techniques to identify thermodynamically stable 2D materials, which is the first essential requirement for any application. According to the formation energy and energy above the convex hull, we classify materials as having low, medium, or high stability. The proposed approach enables the stability evaluation of novel 2D compounds for further detailed investigation of promising candidates, using only composition properties and structural symmetry, without the need for information about atomic positions. We demonstrate the usefulness of the model generating more than a thousand novel compounds, corroborating with DFT calculations the classification for five of these materials. To illustrate the applicability of the stable materials, we then perform a screening of electronic materials suitable for photoelectrocatalytic water splitting, identifying the potential candidate Sn2SeTe generated by our model, and also PbTe, both not yet reported for this application.

A major challenge exists in the preparation of scaffolds for bone regeneration, namely, achieving simultaneously bioactivity, biocompatibility, mechanical performance and simple manufacturing. Here, cellulose nanofibrils (CNF) are introduced for the preparation of scaffolds taking advantage of their biocompatibility and ability to form strong 3D porous networks from aqueous suspensions. CNF are made bioactive for bone formation through a simple and scalable strategy that achieves highly interconnected 3D networks. The resultant materials optimally combine morphological and mechanical features and facilitate hydroxyapatite formation while releasing essential ions for in vivo bone repair. The porosity and roughness of the scaffolds favor several cell functions while the ions act in the expression of genes associated with cell differentiation. Ion release is found critical to enhance the production of the bone morphogenetic protein 2 (BMP-2) from cells within the fractured area, thus accelerating the in vivo bone repair. Systemic biocompatibility indicates no negative effects on vital organs such as the liver and kidneys. The results pave the way towards a facile preparation of advanced, high performance CNF-based scaffolds for bone tissue engineering.

Abstract Synthesis and characterization of a new hydrogel were carried out using a chemically modified starch (starch‐M) consisting of coupling CC bounds coming from glycidil methacrylate (GMA) onto the polysaccharide structure. 13 C NMR, 1 H NMR, and FT‐IR spectroscopies were used to confirm the incorporation of such groups onto the starch‐M. The hydrogel was prepared by a crosslinking polymerization of starch‐M using sodium persulfate as an initiating agent. The starch‐M hydrogel shows morphology clearly different from that of the raw starch film due to the presence of voids on its surface. The swelling process of the starch‐M hydrogel was not significantly affected by changes on the temperature or on pH of the surrounding liquid, indicating the such behavior can be then understood by a diffusional process, resulting from its physical–chemical interactions with the solvent. The values of the diffusional exponent n were on the order of 0.45–0.49 for the range of pHs investigated, demonstrating that the water transport mechanism of starch‐M hydrogel is more dependent on Fickian diffusion, that is, controlled by water diffusion. Such starch‐M hydrogel is a promising candidate to be used in transporting and in preserving acid‐responsive drugs, such as corticoids, for the treatment of colon‐specific diseases, for example, Crohn's disease. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2567–2574, 2008

The selective action of drugs in tumor cells is a major problem in cancer therapy. Most chemotherapy drugs act nonspecifically and damage both cancer and healthy cells causing various side effects. In this study, the preparation of a selective drug delivery system, which is able to act as a carrier for hydrophobic and anticancer drugs is reported. Amino-functionalized silica nanoparticles loaded with curcumin were successfully synthesized via sol-gel approach and duly characterized. Thereafter, the targeting ligand, folate, was covalently attached to amino groups of nanoparticle surface through amide bond formation. The cytotoxic effect of nanoparticles on prostate cancer cells line was evaluated and compared to normal cells line (prostate epithelial cell). Cytotoxicity experiments demonstrated that folate-functionalized nanoparticles were significantly cytotoxic to tumor cells, whereas normal cells were much less affected by the presence of these structures.

The coating of fertilizers with polymers is an acknowledged strategy for controlling the release of nutrients and their availability in soil. However, its effectiveness in the case of soluble phosphate fertilizers is still uncertain, and information is lacking concerning the chemical properties and structures of such coatings. Here, an oil-based hydrophobic polymer system (polyurethane) is proposed for the control of the release of phosphorus from diammonium phosphate (DAP) granules. This material was systematically characterized, with evaluation of the delivery mechanism and the availability of phosphate in an acid soil. The results indicated that thicker coatings can change the maximum nutrient availability toward longer periods, such as 4.5-7.5 wt % DAP coated, that presented the highest concentrations at 336 h, as compared to 168 h for uncoated DAP. In contrast, DAP treated with 9.0 wt % began to increase the concentration after 168 h until it results in maximum release at 672 h. These effects could be attributed to the homogeneity of the polymer and the porosity. The strategy successfully provided long-term availability of a phosphate source.

A simple and fast fabrication method to create high-performance pencil-drawn electrochemical sensors is reported for the first time. The sluggish electron transfer observed on bare pencil-drawn surfaces was enhanced using two electrochemical steps: first oxidizing the surface and then reducing it in a subsequent step. The heterogeneous rate constant was found to be 5.1 × 10 –3 cm s –1, which is the highest value reported so far for pencil-drawn surfaces. We mapped the origin of such performance by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Our results suggest that the oxidation process leads to chemical and structural transformations on the electrode surface. As a proof-of-concept, we modified the pencil-drawn surface with Meldola’s blue to electrocatalytically detect nicotinamide adenine dinucleotide (NADH). The electrochemical device exhibited the highest catalytic constant (1.7 × 10 5 L mol –1 s –1 ) and the lowest detection potential for NADH reported so far in paper-based electrodes.

Septins are GTP binding proteins considered to be novel components of the cytoskeleton. They polymerize into filaments based on hexameric or octameric core particles in which two copies of either three or four different septins, respectively, assemble into a specific sequence. Viable combinations of the 13 human septins are believed to obey substitution rules in which the different septins involved must come from distinct subgroups. The hexameric assembly, for example, has been reported to be SEPT7-SEPT6-SEPT2-SEPT2-SEPT6-SEPT7. Here, we have replaced SEPT2 by SEPT5 according to the substitution rules and used transmission electron microscopy to demonstrate that the resulting recombinant complex assembles into hexameric particles which are inverted with respect that predicted previously. MBP-SEPT5 constructs and immunostaining show that SEPT5 occupies the terminal positions of the hexamer. We further show that this is also true for the assembly including SEPT2, in direct contradiction with that reported previously. Consequently, both complexes expose an NC interface, as reported for yeast, which we show to be more susceptible to high salt concentrations. The correct assembly for the canonical combination of septins 2-6-7 is therefore established to be SEPT2-SEPT6-SEPT7-SEPT7-SEPT6-SEPT2, implying the need for revision of the mechanisms involved in filament assembly.

accuracy with the computational efficiency of classical force fields. This allows simulations ranging from atoms, molecules, and biosystems, to solid and bulk materials, surfaces, nanomaterials, and their interfaces and complex interactions. A recent class of advanced MLIPs, which use equivariant representations and deep graph neural networks, is known as universal models. These models are proposed as foundation models suitable for any system, covering most elements from the periodic table. Current universal MLIPs (UIPs) have been trained with the largest consistent data set available nowadays. However, these are composed mostly of bulk materials' DFT calculations. In this article, we assess the universality of all openly available UIPs, namely MACE, CHGNet, and M3GNet, in a representative task of generalization: calculation of surface energies. We find that the out-of-the-box foundation models have significant shortcomings in this task, with errors correlated to the total energy of surface simulations, having an out-of-domain distance from the training data set. Our results show that while UIPs are an efficient starting point for fine-tuning specialized models, we envision the potential of increasing the coverage of the materials space toward universal training data sets for MLIPs.