Near-edge X-ray Absorption Fine Structure Spectroscopy Research Articles

Electronic structure of multi-layered graphene oxide membrane moderately reduced in vacuum

Graphene oxide (GO) has recently attracted more attention for its own physical and chemical properties regardless of being initially seen only as an ideal candidate for the production process of single/few graphene layers. One of the most interesting forms of this material is a multilayer structure, sometimes called graphene paper, with a thickness approaching a value up to a few micrometers. We present and discuss the results of investigation on electronic structure of such a thick material produced by the improved Hummer's method and deposited on a metallic mesh. The samples were investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) around the carbon absorption edge. The NEXAFS results are supplemented with the output of the X-ray photoelectron spectroscopy (XPS) analysis for C1s and O1s lines and with the micro-Raman spectroscopy. There are still some discrepancies concerning the electronic structure of graphene oxide (GO), especially, when many individual GO sheets are stacked together as in the case under consideration. The samples were heavily functionalized by oxidation (the presence of carbonyl, epoxy, and hydroxyl groups). There are indications that the prepared samples tended towards the turbostratic form of stacking when annealed in vacuum at moderate temperatures between 100 °C and 500 °C. These changes were observed in both π* and σ* resonance areas. Surprisingly, the features of the NEXAFS spectrum of both the annealed and non-annealed samples resemble reasonably the theoretically determined structure of the density of states (DOS) of monocrystalline carbon. It could suggest a strong “graphitisation” process already in the sample preparation phase. The observed increase in the sample amenability to the environmental water with annealing temperature is discussed briefly. The results also deliver a clear support for the claims of room-temperature metastability of multilayer GO.

Reversible and Irreversible Redox Processes in Li-Rich Layered Oxides

Reversible and irreversible charge exchange reactions of Li- and Mn-rich layered oxides (Li1.15Ni0.2Co0.1Mn0.55O2, LLO) are investigated with bulk and surface-sensitive near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the Ni L2,3, Co L2,3, Mn L2,3, and O K edges; mass spectrometry (MS); and operando synchrotron X-ray powder diffraction (SXPD). The present work shows the relation between O–O formation in the bulk and Ni, Co, and Mn reduction/oxidation processes, which in turn deliver outstanding capacities of Li-rich layered oxides (LLO). Moreover, the reversibility of charge compensation reactions is discussed and differences between O–O formation and oxygen release, both occurring mainly upon the first charge (so-called activation), are identified.

On the Origin of Reversible and Irreversible Reactions in LiNixCo(1−x)/2Mn(1−x)/2O2

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO2, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNixCo(1−x)/2Mn(1−x)/2O2 (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g−1), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes.

Identification and characterisation of individual nanoplastics by scanning transmission X-ray microscopy (STXM)

Nanoplastics (NP) are of environmental and human health concern. We tested a novel NP extraction method and scanning transmission X-ray spectro-microscopy (STXM) in combination with near-edge X-ray absorption fine-structure spectroscopy (NEXAFS) to image and identify individual NP in environmental and food matrices. We (1) discussed the potential of STXM compared to other methods potentially suitable for NP analysis, (2) applied the method on NP suspensions of eight of the most common polymers, (3) analyzed environmental water and soil samples spiked with NP and (4) characterized NP in tea water infused in plastic teabags and unspiked soil samples. Here we show that STXM has methodological advantages and that polymers give characteristic spectra, which allows NP identification in environmental and food matrices. For soils we deliver a visual and spectroscopic characterization of NP, proving their presence and highlighting their diversity. Thus, STXM, can be used for the detection and characterisation of NP in different types of matrices.

The Identification of Cu-O-C Bond in Cu/MWCNTs Hybrid Nanocomposite by XPS and NEXAFS Spectroscopy.

The results of the research of a composite based on multi-walled carbon nanotubes (MWCNTs) decorated with CuO/Cu2O/Cu nanoparticles deposited by the cupric formate pyrolysis are discussed. The study used a complementary set of methods, including scanning and transmission electron microscopy, X-ray diffractometry, Raman, and ultrasoft X-ray spectroscopy. The investigation results show the good adhesion between the copper nanoparticles coating and the MWCNT surface through the oxygen atom bridge formation between the carbon atoms of the MWCNT outer graphene layer and the oxygen atoms of CuO and Cu2O oxides. The formation of the Cu–O–C bond between the coating layer and the outer nanotube surface is clearly confirmed by the results of the O 1s near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) of the Cu/MWCNTs nanocomposite. The XPS measurements were performed using a laboratory spectrometer with sample charge compensation, and the NEXAFS studies were carried out using the synchrotron radiation of the Russian–German dipole beamline at BESSY-II (Berlin, Germany) and the NanoPES station at the Kurchatov Center for Synchrotron Radiation and Nanotechnology (Moscow, Russia).

Characterizing porous microaggregates and soil organic matter sequestered in allophanic paleosols on Holocene tephras using synchrotron-based X-ray microscopy and spectroscopy

Allophanic tephra-derived soils can sequester sizable quantities of soil organic matter (SOM). However, no studies have visualized the fine internal porous structure of allophanic soil microaggregates, nor studied the carbon structure preserved in such soils or paleosols. We used synchrotron radiation-based transmission X-ray microscopy (TXM) to perform 3D-tomography of the internal porous structure of dominantly allophanic soil microaggregates, and carbon near-edge X-ray absorption fine-structure (C NEXAFS) spectroscopy to characterize SOM in ≤ 12,000-year-old tephra-derived allophane-rich (with minor ferrihydrite) paleosols. The TXM tomography showed a vast network of internal, tortuous nano-pores within an allophanic microaggregate comprising nanoaggregates. SOM in the allophanic paleosols at four sites was dominated by carboxylic/carbonyl functional groups with subordinate quinonic, aromatic, and aliphatic groups. All samples exhibited similar compositions despite differences between the sites. That the SOM does not comprise specific types of functional groups through time implies that the functional groups are relict. The SOM originated at the land/soil surface: ongoing tephra deposition (intermittently or abruptly) then caused the land-surface to rise so that the once-surface horizons were buried more deeply and hence became increasingly isolated from inputs by the surficial/modern organic cycle. The presence of quinonic carbon, from biological processes but vulnerable to oxygen and light, indicates the exceptional protection of SOM and bio-signals in allophanic paleosols, attributable both to the porous allophane (with ferrihydrite) aggregates that occlude the relict SOM from degradation, and to rapid burial by successive tephra-fallout, as well as strong Al-organic chemical bonding. TXM and C NEXAFS spectroscopy help to unravel the fine structure of soils and SOM and are of great potential for soil science studies.

Thermal stability studies of plasma deposited hydrogenated carbon nitride nanostructures

Thermally stable carbon nitride nanostructures have potential applications in surface coatings and automotive fields. In this work, hydrogenated nitrogen-rich carbon nitride nanoparticles have been synthesised via low-pressure low-power plasma vapour deposition technique from methane/nitrogen gas mixture in a dry process. Thermal stability of the initially prepared hydrogenated carbon nitride structures has been analysed by near-edge X-ray absorption fine-structure spectroscopy (NEXAFS, in-situ), Raman spectroscopy, scanning and transmission electron microscopy and nuclear reaction analysis (NRA). Thermal studies reveal the excellent stability of the material and nitrogen-rich characteristics (N/C ratio 0.5–0.2 ± 0.01). The obtained results suggest transformation of sp3-rich as-deposited carbon nitride into sp2-carbon phase with more graphitic features upon thermal annealing. Such in-situ thermal studies of plasma deposited carbon nitrides confirm the conversion of sp3-rich phase to sp2-rich carbon phase at the critical temperature (about 450 K), without a huge loss in nitrogen content. The analysis revealed that the material is a stable plasma deposit after this critical temperature up to >1100 K. Additionally, super hydrophilic carbon nitride nanostructure transforms into a hydrophobic surface after thermal annealing. These thermally stable hydrophobic carbon nitride nanoparticles could be used as a promising material for the hydrophobic coatings for various applications, especially for harsh conditions.

Effect of HF treatment on the bonding strength of laser-bonded Mg alloy/carbon fiber-reinforced plastic joint: XPS and NEXAFS study

This study investigated the effect of hydrofluoric acid treatment on the bonding strength of AZ31 carbon-fiber-reinforced plastic (CFRP) joints produced by thermal laser joining. Surface modification was performed to generate reactive sites for the promotion of chemical interaction with the CFRP, resulting in an enhanced interfacial adhesion. The improved interfacial adhesion and joint strength were determined by contact angle and tensile shear strength tests, respectively. Scanning electron microscopy (SEM) was used to investigate the joint interface and the fracture surfaces. The fracture surfaces were further analyzed using X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure spectroscopy (NEXAFS). The formation of C-F and MgO chemical bonds at the HF-treated AZ31/CFRP joint interface were found to be key factors influencing joint strength.

Transformation of copper oxide and copper oxide nanoparticles in the soil and their accumulation by Hordeum sativum.

In recent years, the study of the influence of nanoparticles (NPs) on the environment has attracted much interest as nanotechnology is becoming the key technology of the future generation. The comparative studies on the effects of macro- and nanosized copper oxide (CuO) on plants rarely cover the state and behaviour of CuO in the soil-plant system. This work considers the transformation of CuO in Haplic Chernozem depending on the degree of dispersion and its toxic effects on spring barley (Hordeum sativum) growth. To investigate the transformation of the studied particles of metal oxide in the soil and plant, both chemical method of analysis and synchrotron radiation X-ray powder diffraction, X-ray absorption near-edge structure spectroscopy (XANES) and X-ray absorption fine-structure spectroscopy (EXAFS) were used. It was shown that CuO NPs underwent a stronger transformation due to the high reactivity of smaller particles. The Cu mobility was observed to increase within the soil profile as confirmed by the model pollution experiment. This is mainly due to the formation of complex forms of metal with organic matter. A dose of 300mg/kg of macro- and nanosized CuO did not significantly affect the development and productivity of spring barley. The effect of high doses of macro- and nanosized CuO (2000 and 10,000mg/kg) had a negative impact on the growth of spring barley. The application of nanosized CuO had a greater toxic effect than the macrosized CuO on the plants. The XANES and EXAFS data revealed that CuO NPs accumulated in the soil and plants. The linear combination fit shown that Cu atoms, incorporated into the plants, have environment typical of CuO. This indicates a high environmental risk when soil is contaminated with CuO NPs compared with its arrival as CuO.

Selective retention of extracellular polymeric substances induced by adsorption to and coprecipitation with ferrihydrite

Recent work shows that microbially-derived compounds constitute a significant fraction of the soil organic matter (OM) pool. These compounds include extracellular polymeric substances (EPS) whose mass can far exceed total microbial cell biomass. Sorption of EPS to soil minerals occurs via adsorption and coprecipitation and contributes to the preservation of OM in the soil environment. Little is known, however, about the sorption mechanisms of EPS and selective retention of different EPS constituents on iron (oxyhydr)oxides, especially during EPS adsorption versus coprecipitation with these reactive soil phases. This study examines how EPS interacts with the ubiquitous soil iron (oxyhydr)oxide ferrihydrite during EPS adsorption and coprecipitation and whether these different EPS-mineral association pathways affect EPS sorption and selective retention, and thus the mobility and fate of microbially-derived OM in the soil environment. We use several complimentary techniques to i) examine EPS-carbon, EPS-nitrogen and EPS-phosphorus sorption and fractionation, ii) visualize spatial relationships between EPS biomolecular classes and ferrihydrite using confocal laser scanning microscopy (CLSM), iii) determine EPS-C speciation and chemical fractionation with ferrihydrite using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and iv) determine functional group interactions with ferrihydrite using Fourier transform infrared spectroscopy (FTIR) combined with two-dimensional correlation spectroscopy (2D-COS) analysis. Results show that the coprecipitation of EPS does not change the ferrihydrite mineralogy, as the main mineral phase for EPS association, but it substantially increases the particle size of EPS-ferrihydrite. A substantial difference in the EPS mass fraction associated with the ferrihydrite is observed between the adsorption and coprecipitation experiments at an initial molar C/Fe ratio >1. The EPS-N is relatively enriched during the adsorption process, while more EPS-C and near-complete EPS-P are fixed in the coprecipitation process. XPS results show that the surface of the ferrihydrite formed through EPS adsorption is preferentially enriched with protein-like components, whereas, the surface of the ferrihydrite formed through EPS coprecipitation is enriched with polysaccharide-like components, which is visually confirmed with CLSM images. NEXAFS results reveal that the carboxylic/amide C-containing components are selectively retained during adsorption, with the aliphatic and O-alkyl C-containing components relatively enriched during coprecipitation. 2D-FTIR-COS results indicate that during EPS adsorption on ferrihydrite the PO functional groups are adsorbed faster than the amide and carboxylate functional groups, while during EPS coprecipitation with ferrihydrite the opposite trend is observed. The findings from this study indicate that the formation pathway of EPS-ferrihydrite associations substantially effects the sorption mechanisms and selective retention of EPS and may thus affect the mobility and fate of microbially-derived carbon (C), nitrogen (N) and phosphorus (P) in soils. These new insights on EPS behaviour at the mineral–water interface might be used to evaluate how microbially-derived compounds like EPS are stabilized by iron (oxyhydr)oxides and how EPS-iron (oxyhydr)oxide couplings might affect the reactivity and cycling of OM in natural environments.

Thermal behavior, magnetic properties, ESR, XPS, Mössbauer and NEXAFS study of Fe-doped CaCu3Ti4O12 ceramics

The methods of magnetic dilution, thermal analysis, ESR (Electron Spin Resonance), Mössbauer and NEXAFS (Near-Edge X-ray Absorption Fine Structure) spectroscopy were used to study iron-doped solid solutions of calcium copper titanate CaCu3Ti4-4xFe4xO12-δ (0.005 ≤ x ≤ 0.08, 0.2) and CaCu3-3xFe3xTi4O12+δ (0.005 ≤ x ≤ 0.06) synthesized by the standard ceramic method by replacing copper or titanium ions with iron. According to X-ray diffraction data, the samples of the both series contained no iron-based impurity phases. A characteristic feature of the Mössbauer spectra of the samples of both series was the doublet part in the form of an asymmetric triplet with an intensity ratio of 1:3:1. The analysis of the Mössbauer spectra of the samples of the both series showed the presence of three doublets in them with different quadrupole splitting and isomeric shift values of 0.3–0.4 mm/s, which is typical for Fe3+ ions in an octahedral coordination with varying degrees of distortion. According to the Mössbauer data and ESR spectroscopy, in the both series of solid solutions, the substitution (Fe→Ti or Fe→Cu) occurred mainly in the octahedral positions of titanium by means of heterovalent substitution Fe3+→Ti4+. In the ESR spectra, the increase in the iron content in the samples of the both series led to broadening of the Lorentz absorption line of Cu(II) ions with g ≈ 2.15 and to decrease in the g-factor. NEXAFS and XPS revealed that the doping of CaCu3Ti4O12 (CCTO) with iron ions had no significant effect on the electronic state and polyhedral environment of Ca, Cu and Ti ions in CCTO, regardless of the degree and nature of the doping. The charge state of iron ions in the solid solutions corresponded to Fe(III), iron ions predominantly occupy the positions of titanium. According to the magnetic dilution data, the antiferromagnetic exchange appeared between the nearest iron (III) ions in the solid solutions of calcium copper titanate. The clusters of iron (III) ions interacted with Cu(II) ions through the formation of ferromagnetic exchange. There were no significant differences in the magnetic behavior of the iron-doped solid solutions of both series. According to the thermogravimetric data, there was no mass loss of the samples below the melting temperature (∼1033 °C). The DSC (Differential Scanning Calorimetry) curves of the both series of the solid solutions revealed the exothermic effect at 233–300 °C and a number of endothermic processes at temperatures above 946 °C, near the melting temperature of the samples.

Controlling the flux of reactive species: a case study on thin film deposition in an aniline/argon plasma

The plasma based synthesis of thin films is frequently used to deposit ultra-thin and pinhole-free films on a wide class of different substrates. However, the synthesis of thin films by means of low temperature plasmas is rather complex due to the great number of different species (neutrals, radicals, ions) that are potentially involved in the deposition process. This contribution deals with polymerization processes in a capacitively coupled discharge operated in a mixture of argon and aniline where the latter is a monomer, which is used for the production of plasma-polymerized polyaniline, a material belonging to the class of conductive polymers. This work will present a particular experimental approach that allows to (partially) distinguish the contribution of different species to the film growth and thus to control to a certain extent the properties of the resulting material. The control of the species flux emerging from the plasma and contributing to the film growth also sheds new light on the deposition process, in particular with respect to the role of the ion component. The analysis of the produced films has been performed by means of Fourier Transform Infrared spectroscopy (FTIR) and Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS).

Charge transfer controlled hydrogenation of graphene on an electronically modified Pt(111) surface

The interfaces of graphene and hydrogenated graphene with 3d atom embedded Pt(111) [Pt-3d-Pt(111), 3d: Fe, Co] substrates have comparatively been investigated utilizing X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and temperature-programmed XPS (TPXPS) and desorption (TPD). 3d atoms in the subsurface layer of Pt(111) change the electronic properties of graphene via modifying its p-doping level. Hydrogenation makes graphene pinned to the Pt(111) and Pt-3d-Pt(111) substrates and induces surface segregation of 3d atoms from the subsurface layer into the interface of HGr and Pt-3d-Pt(111). Such a mechanism changes the desorption energetics of hydrogen significantly.

Ambient-pressure endstation of the Versatile Soft X-ray (VerSoX) beamline at Diamond Light Source.

The ambient-pressure endstation and branchline of the Versatile Soft X-ray (VerSoX) beamline B07 at Diamond Light Source serves a very diverse user community studying heterogeneous catalysts, pharmaceuticals and biomaterials under realistic conditions, liquids and ices, and novel electronic, photonic and battery materials. The instrument facilitates studies of the near-surface chemical composition, electronic and geometric structure of a variety of samples using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy in the photon energy range from 170 eV to 2800 eV. The beamline provides a resolving power hν/Δ(hν) > 5000 at a photon flux > 1010 photons s-1 over most of its energy range. By operating the optical elements in a low-pressure oxygen atmosphere, carbon contamination can be almost completely eliminated, which makes the beamline particularly suitable for carbon K-edge NEXAFS. The endstation can be operated at pressures up to 100 mbar, whereby XPS can be routinely performed up to 30 mbar. A selection of typical data demonstrates the capability of the instrument to analyse details of the surface composition of solid samples under ambient-pressure conditions using XPS and NEXAFS. In addition, it offers a convenient way of analysing the gas phase through X-ray absorption spectroscopy. Short XPS spectra can be measured at a time scale of tens of seconds. The shortest data acquisition times for NEXAFS are around 0.5 s per data point.

Geometric and electronic structures of pyrazine molecule chemisorbed on Si(100) surface by XPS and NEXAFS spectroscopy

The geometric and electronic structures of several possible adsorption configurations of the pyrazine (C4H4N2) molecule covalently attached to Si(100) surface, which is of vital importance in fabricating functional nano-devices, have been investigated using X-ray spectroscopies. The Carbon K-shell (1s) X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations. Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations. In contrast to the XPS spectra, it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100) systems can be well utilized for structural identification. In addition, according to the classification of carbon atoms, the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.

Studies of Buried Layers and Interfaces of Tungsten Carbide Coatings on the MWCNT Surface by XPS and NEXAFS Spectroscopy

Currently, X-ray photoelectron spectroscopy (XPS) is widely used to characterize the nanostructured material surface. The ability to determine the atom distribution and chemical state with depth without the sample destruction is important for studying the internal structure of the coating layer several nanometers thick, and makes XPS the preferable tool for the non-destructive testing of nanostructured systems. In this work, ultra-soft X-ray spectroscopy methods are used to study hidden layers and interfaces of pyrolytic tungsten carbide nanoscale coatings on the multi-walled carbon nanotube (MWCNT) surfaces. XPS measurements were performed using laboratory spectrometers with sample charge compensation, and Near Edge X-ray Absorption Fine Structure (NEXAFS) studies using the Russian–German dipole beamline (RGBL) synchrotron radiation at BESSY-II. The studied samples were tested by scanning and transmission electron microscopy, X-ray diffractometry, Raman scattering and NEXAFS spectroscopy. It was shown that the interface between MWCNT and the pyrolytic coating of tungsten carbide has a three-layer structure: (i) an interface layer consisting of the outer graphene layer carbon atoms, forming bonds with oxygen atoms from the oxides adsorbed on the MWCNT surface, and tungsten atoms from the coating layer; (ii) a non-stoichiometric tungsten carbide WC1-x nanoscale particles layer; (iii) a 3.3 nm thick non-stoichiometric tungsten oxide WO3-x layer on the WC1-x/MWCNT nanocomposite outer surface, formed in air. The tungsten carbide nanosized particle’s adhesion to the nanotube outer surface is ensured by the formation of a chemical bond between the carbon atoms from the MWCNT upper layer and the tungsten atoms from the coating layer.

The effect of post-deposition annealing conditions on structural and thermoelectric properties of sputtered copper oxide films.

The development of thin-film thermoelectric applications in sensing and energy harvesting can benefit largely from suitable deposition methods for earth-abundant materials. In this study, p-type copper oxide thin films have been prepared on soda lime silicate glass by direct current (DC) magnetron sputtering at room temperature from a pure copper metallic target in an argon atmosphere, followed by subsequent annealing steps at 300 °C under various atmospheres, namely air (CuO:air), nitrogen (CuO:N) and oxygen (CuO:O). The resultant films have been studied to understand the influence of various annealing atmospheres on the structural, spectroscopic and thermoelectric properties. X-ray diffraction (XRD) patterns of the films showed reflexes that could be assigned to those of crystalline CuO with a thin mixed Cu(I)Cu(II) oxide, which was also observed by near edge X-ray absorption fine structure spectroscopy (NEXAFS). The positive Seebeck coefficient (S) reached values of up to 204 μV K−1, confirming the p-type behavior of the films. Annealing under oxygen provided a significant improvement in the electrical conductivity up to 50 S m−1, resulting in a power factor of 2 μW m−1 K−2. The results reveal the interplay between the intrinsic composition and the thermoelectric performance of mixed copper oxide thin films, which can be finely adjusted by simply varying the annealing atmosphere.

Theoretical identification of buckyonion fullerene C20@C60 isomers by XPS and NEXAFS spectroscopy.

The C 1s X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of two buckyonion fullerene C20@C60 isomers were theoretically simulated by density functional theory (DFT) method. In this paper, we mainly investigated the relationship between spectroscopy and structure and obtained the spectral dependence on the structures with different symmetries. Our results showed that both XPS and NEXAFS spectra exhibited remarkable dependence on the molecular structures, thus these two spectroscopic techniques could be adopted to identify the two C20@C60 isomers effectively. Additionally, we found that the building block approach could not predict the spectra for C20@C60 isomers due to the strong interaction between the two layer cages. Finally, we studied the decompositions of the total spectra from carbon atoms in different local environments to analyse the origins of the main features.

Fibrillar Self-Assembly of a Chimeric Elastin-Resilin Inspired Engineered Polypeptide.

In the field of tissue engineering, recombinant protein-based biomaterials made up of block polypeptides with tunable properties arising from the functionalities of the individual domains are appealing candidates for the construction of medical devices. In this work, we focused our attention on the preparation and structural characterization of nanofibers from a chimeric-polypeptide-containing resilin and elastin domain, designed on purpose to enhance its cell-binding ability by introducing a specific fibronectin-derived Arg-Gly-Asp (RGD) sequence. The polypeptide ability to self-assemble was investigated. The molecular and supramolecular structure was characterized by Scanning Electronic Microscopy (SEM) and Atomic Force Microscopy (AFM), circular dichroism, state-of-the-art synchrotron radiation-induced techniques X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The attained complementary results allow us to assess as H-bonds influence the morphology of the aggregates obtained after the self-assembling of the chimeric polypeptide. Finally, a preliminary investigation of the potential cytotoxicity of the polypeptide was performed by culturing human fetal foreskin fibroblast (HFFF2) for its use as biomedical device.

Limited Cu(II) binding to biochar DOM: Evidence from C K-edge NEXAFS and EEM-PARAFAC combined with two-dimensional correlation analysis

Multiple spectroscopic technologies and chemometric analyses were combined to explore the compositional characteristics and Cu binding performance of biochar-derived dissolved organic matter (DOM). The DOM samples were extracted from biochars produced from lignocellulose-rich rapeseed cake (RSC) by pyrolysis at 300, 500, and 700 °C (i.e., RSC300, RSC500, RSC700). Fourier transform infrared spectroscopy (FTIR) and carbon K-edge near-edge X-ray absorption fine structure spectroscopy (NEXAFS) analyses were combined to elucidate the molecular-level C species in the DOM. With the increasing pyrolysis temperature, DOM aromaticity increased, whereas the proportion of metal complexing sites (e.g., carboxyl and phenolic groups) decreased. Fluorescence excitation-emission matrix (EEM) spectroscopy with parallel factor analysis (PARAFAC) indicated that biochar DOM, irrespective of pyrolysis temperature, was mostly composed of three types of humic-like components (C1–C3), and a small amount of a protein-like component (C4). As charring temperature increased, DOM concentrations decreased substantially, but the humic-like C3 with abundant aromatic structures became predominant. Fluorescence quenching experiment and two-dimensional correlation spectroscopy (2D-COS) analysis suggested that the preferential Cu(II) binding fractions of the DOM were the humic-like substances. Moreover, the quenching curve fitting results for individual components indicated that despite the Cu(II) binding affinity was slightly enhanced as the pyrolysis temperature increased, the binding capacities of the four components decreased. In general, the DOM components from RSC biochar exhibited limited Cu(II) binding capacities (2.18–17.7 μmol L−1). Results from this study improved understanding of the mechanisms by which biochar DOM interacts with Cu, and provided tools for fast screening of biochars to reduce their environmental risks.