Microspectroscopic visualization of how biochar lifts the soil organic carbon ceiling.

The soil carbon (C) saturation concept suggests an upper limit to the storage of soil organic carbon (SOC). It is set by the mechanisms that protect soil organic matter from mineralization. Biochar has the capacity to protect new C, including rhizodeposits and microbial necromass. However, the decadal-scale mechanisms by which biochar influences the molecular diversity, spatial heterogeneity, and temporal changes in SOC persistence, remain unresolved. Here we show that the soil C storage ceiling of a Ferralsol under subtropical pasture was raised by a second application of Eucalyptus saligna biochar 8.2 years after the first application-the first application raised the soil C storage ceiling by 9.3 Mg new C ha-1 and the second application raised this by another 2.3 Mg new C ha-1. Linking direct visual evidence from one-, two-, and three-dimensional analyses with SOC quantification, we found high spatial heterogeneity of C functional groups that resulted in the retention of rhizodeposits and microbial necromass in microaggregates (53-250 µm) and the mineral fraction (<53 µm). Microbial C-use efficiency was concomitantly increased by lowering specific enzyme activities, contributing to the decreased mineralization of native SOC by 18%. We suggest that the SOC ceiling can be lifted using biochar in (sub)tropical grasslands globally.

Hierarchical Porous Carbon-PtPd Catalysts and Their Activity toward Oxygen Reduction Reaction.

PtPd bimetallic catalysts supported on hierarchical porous carbon (HPC) with different porous sizes were developed for the oxygen reduction reaction (ORR) toward fuel cell applications. The HPC pore size was controlled by using SiO2 nanoparticles as a template with different sizes, 287, 371, and 425 nm, to obtain three HPC materials denoted as HPC-1, HPC-2, and HPC-3, respectively. PtPd/HPC catalysts were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy. The electrochemical performance was examined by cyclic voltammetry and linear sweep voltammetry. PtPd/HPC-2 turned out to be the most optimal catalyst with an electroactive surface area (ESA) of 40.2 m2 g-1 and a current density for ORR of -1285 A g-1 at 2 mV s-1 and 1600 rpm. In addition, we conducted a density functional theory computational study to examine the interactions between a PtPd cluster and a graphitic domain of HPC, as well as the interaction between the catalyst and the oxygen molecule. These results reveal the strong influence of the porous size (in HPC) and ESA values (in PtPd nanoparticles) in the mass transport process which rules the electrochemical performance.

Rational design of large flat nitrogen-doped graphene oxide quantum dots with green-luminescence suitable for biomedical applications.

Rational synthesis and simple methodology for the purification of large (35-45 nm in lateral size) and flat (1.0-1.5 nm of height) nitrogen-doped graphene oxide quantum dots (GOQDs) are presented. The methodology allows robust metal-free and acid-free preparation of N-GOQDs with a yield of about 100% and includes hydrothermal treatment of graphene oxide with hydrogen peroxide and ammonia. It was demonstrated that macroscopic impurities can be separated from N-GOQD suspension by their coagulation with 0.9% NaCl solution. Redispersible in water and saline solutions, particles of N-GOQDs were characterized using tip-enhanced Raman spectroscopy (TERS), photoluminescent, XPS, and UV-VIS spectroscopies. The size and morphology of N-GOQDs were studied by dynamic light scattering, AFM, SEM, and TEM. The procedure proposed allows nitrogen-doped GOQDs to be obtained, having 60-51% of carbon, 34-45% of oxygen, and up to 7.2% of nitrogen. The N-GOQD particles obtained in two hours of synthesis contain only pyrrolic defects of the graphene core. The fraction of pyridine moieties grows with the time of synthesis, while the fraction of quaternary nitrogen declines. Application of TERS allows demonstration that the N-GOQDs consist of a graphene core with an average crystallite size of 9 nm and an average distance between nearest defects smaller than 3 nm. The cytotoxicity tests reveal high viability of the monkey epithelial kidney cells Vero in the presence of N-GOQDs in a concentration below 60 mg L-1. The N-GOQDs demonstrate green luminescence with an emission maximum at 505 nm and sedimentation stability in the cell culture medium.

Structural characterization and plasmonic properties of manganese oxide-coated gold nanorods.

The preparation of metal@(dielectric or semiconductor) core@shell hybrid materials have been shown promising for both SERS and SEF applications due to improved stability in the presence of ions and the adsorbate compared to non-covered metallic nanoparticles. However, fine control over the thickness of the covering layer is essential to maximize the intrinsic trade-off between the plasmonic enhancement and the chemical stability improvement. Here, the preparation of manganese dioxide ultrathin layers covered gold nanorods (AuNR@MnO2) with varying thicknesses of the MnO2 layer is reported, and the characterization and evaluation of the resulting materials as SERS and SEF substrate. The MnO2 layer over the AuNR was prepared by reducing potassium permanganate by sodium oxalate in a basic medium. The AuNR@MnO2 hybrid material was characterized by UV-Vis spectroscopy, transmission electron microscopy, X-ray powder diffraction, and cyclic voltammetry. It was studied the SEF effect of the cyanine dye IR-820 excited at 785 nm with high performance for several thicknesses of the MnO2 ultrathin film. The enhancement factor increased for thicker oxide layers. The SERS effect of the IR-820 dye excited at 633 nm showed the most significant enhancement factor for thinner layers. The seemly opposite behavior of the two plasmonic effects may be assigned to the distance dependence of the electromagnetic field generated in the AuNR, which results in decreasing SERS performance. For SEF, the thinner layers resulted in the Au nanoparticles' emission quenching, so a more significant distance was necessary to observe enhancement.

Nanofabrication of plasmon-tunable nanoantennas for tip-enhanced Raman spectroscopy.

Plasmon-tunable tip pyramids (PTTPs) are reproducible and efficient nanoantennas for tip-enhanced Raman spectroscopy (TERS). Their fabrication method is based on template stripping of a segmented gold pyramid with a size-adjustable nanopyramid end, which is capable of supporting monopole localized surface plasmon resonance (LSPR) modes leading to high spectral enhancement when its resonance energy is matched with the excitation laser energy. Here, we describe in detail the PTTP fabrication method and report a statistical analysis based on 530 PTTPs' and 185 ordinary gold micropyramids' templates. Our results indicate that the PTTP method generates probes with an apex diameter smaller than 30 nm on 92.4% of the batch, which is a parameter directly related to the achievable TERS spatial resolution. Moreover, the PTTPs' nanopyramid edge size L, a critical parameter for LSPR spectral tuning, shows variability typically smaller than 12.5%. The PTTP's performance was tested in TERS experiments performed on graphene, and the results show a spectral enhancement of up to 72-fold, which is at least one order of magnitude higher than that typically achieved with gold micropyramids. Imaging resolution is in the order of 20 nm.

Impact of nanoconfinement on acetylacetone Equilibria in Ordered Mesoporous Silicates.

Nanoconfinement is one of the most intriguing nanoscale effects and affects several physical and chemical properties of molecules and materials, including viscosity, reaction kinetics, and glass transition temperature. In this work, liquid nuclear magnetic resonance (NMR) was used to analyze the behavior of 2,4-pentadienone in ordered mesoporous materials with a pore diameter of between 3 and 10 nm. The liquid NMR results showed meaningful changes in the hydrogen chemical shift and the keto-enol chemical equilibrium, which were associated with the pore diameter, allowing the authors to observe the effects of nanoconfinement. An interesting phenomenon was observed where the chemical equilibria of 2,4-pentadienone confined in a mesoporous material with a pore diameter of 3.5 nm was similar to that obtained with free (bulk) 2,4-pentadienone in larger pore materials. Another interesting result was observed for the enthalpy and entropy of the tautomeric equilibria of 2,4-pentadienone confined in mesoporous materials with a 5.5 nm pore diameter being -7.9 kJ mol-1 and -15.9 J mol-1.K. These values are similar to those obtained by dimethyl sulfoxide. This phenomenon indicates the possible use of ordered mesoporous materials as a reaction substitute in organic solvents. It was further observed that while the values of enthalpy (ΔH) and entropy (ΔS) had been modified by confinement, the Gibbs free energy (ΔG) value remained closer to that observed in free (bulk) 2,4-pentadienone. It is expected that this study will help in understanding the effects of nanoconfinement and provide a simple method to employ NMR techniques to analyze these phenomena.

Corn starch films as a long-term drug delivery system for chlorhexidine gluconate.

The present study describes the development of a chlorhexidine long-term drug delivery system using starch as a biodegradable polymer base. Three batches of thermoplastic starch films, containing starch particles/nanoparticles and chlorhexidine (CHX), were manufactured by casting. Morphological characterization showed an irregular surface with particles incorporated with chlorhexidine agglomerated in a starch matrix. Nanoindentation showed that the control film (without chlorhexidine) presented a more plastic and rigid behavior in relation to the films containing CHX. CHX was partially bounded to starch and prevented starch crystallization. Starch nanoparticles formed by precipitation were observed through transmission electron microscopy. By incorporating CHX into the solution, the nanoparticles presented different morphology, suggesting absorption of the drug. In vitro drug release was observed for 21 days by UV-vis spectrophotometry and released CHX amounted up to 19 mg/100 ml. Films presented microbiological potential for inhibiting Staphylococcus aureus growth as evaluated by the disk diffusion test in agar. It has been concluded that the developed film met the main requirements for a drug delivery system and that it is possible to be produced from a simple, cheap and reproduceable process.

The two faces of titanium dioxide nanoparticles bio-camouflage in 3D bone spheroids.

Titanium (Ti) and its alloys are widely used in dental implants and hip-prostheses due to their excellent biocompatibility. Growing evidence support that surface degradation due to corrosion and wear processes, contribute to implant failure, since the release of metallic ions and wear particles generate local tissue reactions (peri-implant inflammatory reactions). The generated ions and wear debris (particles at the micron and nanoscale) stay, in a first moment, at the interface implant-bone. However, depending on their size, they can enter blood circulation possibly contributing to systemic reactions and toxicities. Most of the nanotoxicological studies with titanium dioxide nanoparticles (TiO2 NPs) use conventional two-dimensional cell culture monolayers to explore macrophage and monocyte activation, where limited information regarding bone cells is available. Recently three-dimensional models have been gaining prominence since they present a greater anatomical and physiological relevance. Taking this into consideration, in this work we developed a human osteoblast-like spheroid model, which closely mimics bone cell-cell interactions, providing a more realistic scenario for nanotoxicological studies. The treatment of spheroids with different concentrations of TiO2 NPs during 72 h did not change their viability significantly. Though, higher concentrations of TiO2 NPs influenced osteoblast cell cycle without interfering in their ability to differentiate and mineralize. For higher concentration of TiO2 NPs, collagen deposition and pro-inflammatory cytokine, chemokine and growth factor secretion (involved in osteolysis and bone homeostasis) increased. These results raise the possible use of this model in nanotoxicological studies of osseointegrated devices and demonstrate a possible therapeutic potential of this TiO2 NPs to prevent or reverse bone resorption.

Controlling burst effect with PLA/PVA coaxial electrospun scaffolds loaded with BMP-2 for bone guided regeneration.

Biocompatible scaffolds have been used to promote cellular growth and proliferation in order to develop grafts, prostheses, artificial skins and cartilage. Electrospinning is widely studied as a method capable of producing nanofibers which enables cell attachment and proliferation, generating a functional scaffold that is suitable for many types of organs or tissues. In this study, electrospinning was used to obtain core-shell and monolithic fibers from the biocompatible poly (lactic acid) and poly (vinyl alcohol) polymers. The main purpose of this work is to produce core-shell nanofiber based scaffolds that works as a sustained delivery vehicle for BMP-2 protein, allowing those fibers to be used in the recovery of alveolar bone tissue without further bone surgery. Then, polymer nanofibers were manufactured by optimizing process parameters of coaxial electrospinning with emphasis on the most relevant ones: voltage, internal and external flows in an attempt to correlate fibers properties with protein releasing abilities. All nanofibers were characterized according to its morphology, thermal behaviour, crystallinity and release profile. For the release tests, bovine albumin was added into internal fiber for future periodontal restorage application. Obtained results demonstrate that fibers were formed with diameters up to 250 nm. According to electronic microscopy images, one could observe surface of nanofibers, thickness and core-shell morphology confirmed. X-ray diffraction analysis and contact angle tests showed fibers with low crystal degree and low hydrophobicity. Nanofibers structure affected in vitro release model tests and consequently the cellular assays.

Physical Structure and Electrochemical Response of Diamond-Graphite Nanoplatelets: From CVD Synthesis to Label-Free Biosensors.

Hybrid diamond-graphite nanoplatelet (DGNP) thin films are produced and applied to label-free impedimetric biosensors for the first time, using avidin detection as a proof of concept. The DGNPs are synthesized by microwave plasma chemical vapor deposition through H2/CH4/N2 gas mixtures in a reproducible and rapid single-step process. The material building unit consists of an inner two-dimensional-like nanodiamond with preferential vertical alignment covered by and covalently bound to nanocrystalline graphite grains, exhibiting {111}diamond||{0002}graphite epitaxy. The DGNP films' morphostructural aspects are of interest for electrochemical transduction, in general, and for Faradaic impedimetric biosensors, in particular, combining enhanced surface area for biorecognition element loading and facile Faradaic charge transfer. Charge transfer rate constants in phosphate buffer saline/[Fe(CN)6]4- solution are shown to increase up to 5.6 × 10-3 cm s-1 upon N2 addition to DGNP synthesis. For the impedimetric detection of avidin, biotin molecules are covalently bound as avidin specific recognition elements on (3-aminopropyl)triethoxysilane-functionalized DGNP surfaces. Avidin quantification is attained within the 10-1000 µg mL-1 range following a logarithmic dependency. The limits of detection and of quantitation are 1.3 and 6.4 µg mL-1 (19 and 93 nM), respectively, and 2.3 and 13.8 µg mL-1 (33 and 200 nM) when considering the nonspecific response of the sensors.

Copper Nanocrystals Encapsulated in Zr-based Metal-Organic Frameworks for Highly Selective CO2 Hydrogenation to Methanol.

We show that the activity and selectivity of Cu catalyst can be promoted by a Zr-based metal-organic framework (MOF), Zr6O4(OH)4(BDC)6 (BDC = 1,4-benzenedicarboxylate), UiO-66, to have a strong interaction with Zr oxide [Zr6O4(OH)4(-CO2)12] secondary building units (SBUs) of the MOF for CO2 hydrogenation to methanol. These interesting features are achieved by a catalyst composed of 18 nm single Cu nanocrystal (NC) encapsulated within single crystal UiO-66 (Cu⊂UiO-66). The performance of this catalyst construct exceeds the benchmark Cu/ZnO/Al2O3 catalyst and gives a steady 8-fold enhanced yield and 100% selectivity for methanol. The X-ray photoelectron spectroscopy data obtained on the surface of the catalyst show that Zr 3d binding energy is shifted toward lower oxidation state in the presence of Cu NC, suggesting that there is a strong interaction between Cu NC and Zr oxide SBUs of the MOF to make a highly active Cu catalyst.

Assessment of a High-Throughput Methodology for the Study of Alloy Oxidation using AlxFeyNi1-x-y Composition Gradient Thin Films.

The high-temperature oxidation of multicomponent metal alloys exhibits complex dependencies on composition, which are not fully understood for many systems. Combinatorial screening of the oxidation of many different compositions of a given alloy offers an ideal means for gaining fundamental insights into such systems. We have previously developed a high-throughput methodology for studying AlxFeyNi1-x-y alloy oxidation using ∼100 nm thick composition spread alloy films (CSAFs). In this work, we critically assess two aspects of this methodology: the sensitivity of CSAF oxidation behavior to variations in AlxFeyNi1-x-y composition and the differences between the oxidation behavior of ∼100 nm thick CSAFs and that of bulk AlxFeyNi1-x-y alloys. This was done by focusing specifically on AlxFe1-x and AlxNi1-x oxidation in dry air at 427 °C. Transitions between phenomenologically distinguishable types of oxidation behavior are found to occur over CSAF compositional ranges of <2 at. %. The oxidation of AlxFe1-x CSAFs is found to be very similar to that of bulk AlxFe1-x alloys, but some minor differences between CSAF and bulk behavior are observed for AlxNi1-x oxidation. On the basis of our assessment, high-throughput studies of CSAF oxidation appear to be an effective method for gaining fundamental insights into the composition dependence of the oxidation of bulk alloys.

On the Structural and Chemical Characteristics of Co/Al2O3/graphene Interfaces for Graphene Spintronic Devices.

We report a detailed investigation of the structural and chemical characteristics of thin evaporated Al2O3 tunnel barriers of variable thickness grown onto single-layer graphene sheets. Advanced electron microscopy and spectrum-imaging techniques were used to investigate the Co/Al2O3/graphene/SiO2 interfaces. Direct observation of pinhole contacts was achieved using FIB cross-sectional lamellas. Spatially resolved EDX spectrum profiles confirmed the presence of direct point contacts between the Co layer and the graphene. The high surface diffusion properties of graphene led to cluster-like Al2O3 film growth, limiting the minimal possible thickness for complete barrier coverage onto graphene surfaces using standard Al evaporation methods. The results indicate a minimum thickness of nominally 3 nm Al2O3, resulting in a 0.6 nm rms rough film with a maximum thickness reaching 5 nm.

All-Diamond Microelectrodes as Solid State Probes for Localized Electrochemical Sensing.

The fabrication of an all-diamond microprobe is demonstrated for the first time. This ME (microelectrode) assembly consists of an inner boron doped diamond (BDD) layer and an outer undoped diamond layer. Both layers were grown on a sharp tungsten tip by chemical vapor deposition (CVD) in a stepwise manner within a single deposition run. BDD is a material with proven potential as an electrochemical sensor. Undoped CVD diamond is an insulating material with superior chemical stability in comparison to conventional insulators. Focused ion beam (FIB) cutting of the apex of the ME was used to expose an electroactive BDD disk. By cyclic voltammetry, the redox reaction of ferrocenemethanol was shown to take place at the BDD microdisk surface. In order to ensure that the outer layer was nonelectrically conductive, a diffusion barrier for boron atoms was established seeking the formation of boron-hydrogen complexes at the interface between the doped and the undoped diamond layers. The applicability of the microelectrodes in localized corrosion was demonstrated by scanning amperometric measurements of oxygen distribution above an Al-Cu-CFRP (Carbon Fiber Reinforced Polymer) galvanic corrosion cell.

Tuning Localized Surface Plasmon Resonance in Scanning Near-Field Optical Microscopy Probes.

A reproducible route for tuning localized surface plasmon resonance in scattering type near-field optical microscopy probes is presented. The method is based on the production of a focused-ion-beam milled single groove near the apex of electrochemically etched gold tips. Electron energy-loss spectroscopy and scanning transmission electron microscopy are employed to obtain highly spatially and spectroscopically resolved maps of the milled probes, revealing localized surface plasmon resonance at visible and near-infrared wavelengths. By changing the distance L between the groove and the probe apex, the localized surface plasmon resonance energy can be fine-tuned at a desired absorption channel. Tip-enhanced Raman spectroscopy is applied as a test platform, and the results prove the reliability of the method to produce efficient scattering type near-field optical microscopy probes.

Chemical analysis and molecular models for calcium-oxygen-carbon interactions in black carbon found in fertile Amazonian anthrosoils.

Carbon particles containing mineral matter promote soil fertility, helping it to overcome the rather unfavorable climate conditions of the humid tropics. Intriguing examples are the Amazonian Dark Earths, anthropogenic soils also known as "Terra Preta de Índio'' (TPI), in which chemical recalcitrance and stable carbon with millenary mean residence times have been observed. Recently, the presence of calcium and oxygen within TPI-carbon nanoparticles at the nano- and mesoscale ranges has been demonstrated. In this work, we combine density functional theory calculations, scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transformed infrared spectroscopy, and high resolution X-ray photoelectron spectroscopy of TPI-carbons to elucidate the chemical arrangements of calcium-oxygen-carbon groups at the molecular level in TPI. The molecular models are based on graphene oxide nanostructures in which calcium cations are strongly adsorbed at the oxide sites. The application of material science techniques to the field of soil science facilitates a new level of understanding, providing insights into the structure and functionality of recalcitrant carbon in soil and its implications for food production and climate change.

Long-range crystalline order in spicules from the calcareous sponge Paraleucilla magna (Porifera, Calcarea).

We investigated the ultrastructure and crystallographic orientation of spicules from the calcareous sponge Paraleucilla magna (subclass Calcaronea) by transmission and scanning electron microscopy using two different methods of sample preparation: ultramicrotomy and focused ion beam (FIB). It was found that the unpaired actine from the spicules was oriented in the [211] zone axis. The plane that contains the unpaired actine and divides symmetrically the paired actines is the (-120). This plane is a mirror plane of the hexagonal lattice system. All the spicule types analyzed presented the same crystallographic orientation. Electron nanodiffraction maps from 4µm×4µm regions prepared by FIB showed disorientation of <2° between diffraction patterns obtained from neighbor regions, indicating the presence of a unique, highly aligned calcite crystalline phase. Among the eight FIB sections obtained, four presented high pore density. In one section perpendicular to the actine axis pores were observed only in the center of the spicule aligned in a circular pattern and surrounded by a faint circular contour with a larger radius. The presence of amorphous carbon representative of organic molecules detected by electron energy loss spectroscopy was correlated neither with porosity nor with specific lattice planes.

Characterizing inorganic crystals grown on organic self-assembled bilayers with scanning probe and electron microscopies.

Combined microscopy techniques are used to establish the usability of phosphonic acid layers as promoters of hydroxyapatite (HAp) growth. Using spread coating, octadecylphosphonic acid (OPA) self-assembled bilayers are delivered to the thin natural oxide layer of a titanium film surface with no prior treatment. These bilayers aggregate two major advantages of phosphonic moieties to titanium surfaces: nucleation of hydroxyapatite crystals from ionic solution and affinity for both titanium oxide surface and HAp crystals. The functionalized substrates and bare titanium (control) samples are immersed in an aqueous solution containing calcium and phosphorus ions. Over a 4-week immersion time, OPA-functionalized substrates present numerous large agglomerates of inorganic crystals, in contrast to control samples, with no significant amount of deposits. Initial sample characterization was performed with atomic force microscopy (AFM). Compositional and structural characterization of these agglomerates (using TEM, EDS, and electron diffraction), revealed that they are indeed HAp, the main component of the inorganic bone matrix.

Dynamic negative compressibility of few-layer graphene, h-BN, and MoS2.

We report a novel mechanical response of few-layer graphene, h-BN, and MoS(2) to the simultaneous compression and shear by an atomic force microscope (AFM) tip. The response is characterized by the vertical expansion of these two-dimensional (2D) layered materials upon compression. Such effect is proportional to the applied load, leading to vertical strain values (opposite to the applied force) of up to 150%. The effect is null in the absence of shear, increases with tip velocity, and is anisotropic. It also has similar magnitudes in these solid lubricant materials (few-layer graphene, h-BN, and MoS(2)), but it is absent in single-layer graphene and in few-layer mica and Bi(2)Se(3). We propose a physical mechanism for the effect where the combined compressive and shear stresses from the tip induce dynamical wrinkling on the upper material layers, leading to the observed flake thickening. The new effect (and, therefore, the proposed wrinkling) is reversible in the three materials where it is observed.

Fabrication of gas nanosensors and microsensors via local anodic oxidation.

A nanosensor and microsensor fabrication method employing scanning probe microscopy (SPM) is demonstrated. Within such process, nano- or microscale metal oxide (MoO(x) or TiO(x)) structures, constituting the active region of a sensor, are directly fabricated onto a microscopic metal track via SPM-assisted local anodic oxidation (LAO). Two distinct LAO routes, a slow (conventional) or a fast (unusual) one, are employed to produce nano- and microsensors, which are tested at different temperatures using CO2 and H2 as test gases. Sensitivities down to ppm levels are demonstrated, and the possibility of easy integration into microfabrication processes is also discussed.