Multimodal Spectroscopic Studies to Evaluate the Effect of Nod-Factor-Based Fertilizer on the Maize (Zea mays) Stem.

Maize (Zea mays) is one of the most cultivated plants in the world. Due to the large area, the scale of its production, and the demand to increase the yield, there is a need for new environmentally friendly fertilizers. One group of such candidates is bacteria-produced nodulation (or nod) factors. Limited research has explored the impact of nodulation, factors on maize within field conditions, with most studies restricted to greenhouse settings and early developmental stages. Additionally, there is a scarcity of investigations that elucidate the metabolic alterations in the maize stem due to nod-factor exposure. It was therefore the aim of this study. Maize stem's metabolites and fibers were analyzed with various imaging analytical techniques: matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI), Raman spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR), and diffuse reflectance infrared Fourier transform spectroscopy. Moreover, the biochemical analyses were used to evaluate the proteins and soluble carbohydrates concentration and total phenolic content. These techniques were used to evaluate the influence of nod factor-based biofertilizer on the growth of a non-symbiotic plant, maize. The biofertilizer increased the grain yield and the stem mass. Moreover, the spectroscopic and biochemical investigation proved the appreciable biochemical changes in the stems of the maize in biofertilizer-treated plants. Noticeable changes were found in the spatial distribution and the increase in the concentration of flavonoids such as maysin, quercetin, and rutin. Moreover, the concentration of cell wall components (fibers) increased. Furthermore, it was shown that the use of untargeted analyses (such as Raman and ATR FT-IR, spectroscopic imaging, and MALDI-MSI) is useful for the investigation of the biochemical changes in plants.

Developing Benign Ni/g-C3N4 Catalysts for CO2 Hydrogenation: Activity and Toxicity Study.

This research discusses the CO2 valorization via hydrogenation over the non-noble metal clusters of Ni and Cu supported on graphitic carbon nitride (g-C3N4). The Ni and Cu catalysts were characterized by conventional techniques including XRD, AFM, ATR, Raman imaging, and TPR and were tested via the hydrogenation of CO2 at 1 bar. The transition-metal-based catalyst designed with atom-economy principles presents stable activity and good conversions for the studied processes. At 1 bar, the rise in operating temperature during CO2 hydrogenation increases the CO2 conversion and the selectivity for CO and decreases the selectivity for methanol on Cu/CN catalysts. For the Ni/CN catalyst, the selectivity to light hydrocarbons, such as CH4, also increased with rising temperature. At 623 K, the conversion attained ca. 20%, with CH4 being the primary product of the reaction (CH4 yield >80%). Above 700 K, the Ni/CN activity increases, reaching almost equilibrium values, although the Ni loading in Ni/CN is lower by more than 90% compared to the reference NiREF catalyst. The presented data offer a better understanding of the effect of the transition metals' small metal cluster and their coordination and stabilization within g-C3N4, contributing to the rational hybrid catalyst design with a less-toxic impact on the environment and health. Bare g-C3N4 is shown as a good support candidate for atom-economy-designed catalysts for hydrogenation application. In addition, cytotoxicity to the keratinocyte human HaCaT cell line revealed that low concentrations of catalysts particles (to 6.25 µg mL-1) did not cause degenerative changes.

Surface Chemical and Morphological Analysis of Chitosan/1,3-ß-d-Glucan Polysaccharide Films Cross-Linked at 90 °C.

The cross-linking temperature of polymers may affect the surface characteristics and molecular arrangement, which are responsible for their mechanical and physico-chemical properties. The aim of this research was to determine and explain in detail the mechanism of unit interlinkage of two-component chitosan/1,3-ß-d-glucan matrices gelled at 90 °C. This required identifying functional groups interacting with each other and assessing surface topography providing material chemical composition. For this purpose, various spectroscopic and microscopic approaches, such as attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were applied. The results indicate the involvement mainly of the C-C and C-H groups and C=O⋯HN moieties in the process of biomaterial polymerization. Strong chemical interactions and ionocovalent bonds between the N-glucosamine moieties of chitosan and 1,3-ß-d-glucan units were demonstrated, which was also reflected in the uniform surface of the sample without segregation. These unique properties, hybrid character and proper cell response may imply the potential application of studied biomaterial as biocompatible scaffolds used in regenerative medicine, especially in bone restoration and/or wound healing.

Amyloid ß interaction with model cell membranes - What are the toxicity-defining properties of amyloid ß?

Disruption of the neuronal membrane by toxic amyloid ß oligomers is hypothesized to be the major event associated with Alzheimer's disease's neurotoxicity. Misfolding of amyloid ß is followed by aggregation via different pathways in which structurally different amyloid ß oligomers can be formed. The respective toxic actions of these structurally diverse oligomers can vary significantly. Linking a particular toxic action to a structurally unique kind of amyloid ß oligomers and resolving their toxicity-determining feature remains challenging because of their transient stability and heterogeneity. Moreover, the lipids that make up the membrane affect amyloid ß oligomers' behavior, thus adding to the problem's complexity. The present review compares and analyzes the latest results to improve understanding of amyloid ß oligomers' interaction with lipid bilayers.

Fingermark detection using upconverting nanoparticles and comparison with cyanoacrylate fuming.

This paper reports the synthesis of high-quality upconverting nanoparticles (UCNPs) - sodium yttrium tetrafluoride doped with ytterbium and erbium (NaYF4:Yb,Er) with a silica shell and capped with phenyl functional groups. The main goal of this research was to design tailor-made UCNPs for fingermark detection, to test and validate a nanoparticle-based detection technique and to compare their performance against a benchmark method to assess potential implementation in routine practice by law enforcement agencies. The water-based UCNPs solution was applied to natural fingermarks on a number of substrates. This is the first ever systematic comparative study between UCNPs and a benchmark fingermark detection technique - cyanoacrylate fuming (CAF) followed by luminescent dye staining. Fingermark detection effectiveness was studied by treating 300 latent fingermark specimens on aluminium foil, polyethylene, polypropylene and glass slides. It was concluded that, on average, CAF performed better across the substrates tested. Nevertheless, UCNPs can be advantageous for fingermark detection on multicoloured, patterned or luminescent substrates due to their unique optical properties. There are, however, shortfalls associated with their synthesis and use that need to be addressed before they can be considered for operational purposes.

Interaction of LL-37 human cathelicidin peptide with a model microbial-like lipid membrane.

The only representative of cathelicidin peptides in humans is LL-37, a multifunctional antimicrobial peptide (AMP) that is a part of the innate immune response. Details of the LL-37 direct activity against pathogens are not well understood at the molecular level. Here, we present research on the mechanism of interaction between LL-37 and a model multicomponent bilayer lipid membrane (BLM), mimicking microbial cell membrane. Electrochemical impedance spectroscopy (EIS), high-resolution atomic force microscopy (AFM) imaging, and polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) were applied to study the peptide influence on a model microbial-like membrane. We show that LL-37 causes changes in the phospholipid molecules conformation and orientation, leading to membrane disintegration, significantly affecting the membrane electrical parameters, such as capacitance and resistance. High-resolution AFM imaging shows topographical and mechanical effects of such disintegration, while PM-IRRAS data indicates that introduction of LL-37 causes changes in the phospholipid acyl chains from all-trans to gauche conformations. Moreover, the presence of LL-37 significantly alters the value of the phospholipid tilt angle. Altogether, our results suggest a "carpet" membrane dissolution followed by a detergent-like membrane disruption mechanism upon LL-37 activity. This research gives a novel insight into the understanding of LL-37 influence on multicomponent model membranes and a promising contribution to the development of LL-37-derived therapeutic agents against drug-resistant bacteria.

Inhibition of Amyloid ß-Induced Lipid Membrane Permeation and Amyloid ß Aggregation by K162.

Alzheimer's disease (AD) is characterized by progressive neurodegeneration associated with amyloid ß (Aß) peptide aggregation. The aggregation of Aß monomers (AßMs) leads to the formation of Aß oligomers (AßOs), the neurotoxic Aß form, capable of permeating the cell membrane. Here, we investigated the effect of a fluorene-based active drug candidate, named K162, on both Aß aggregation and AßO toxicity toward the bilayer lipid membrane (BLM). Electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), and molecular dynamics (MD) were employed to show that K162 inhibits AßOs-induced BLM permeation, thus preserving BLM integrity. In the presence of K162, only shallow defects on the BLM surface were formed. Apparently, K162 modifies Aß aggregation by bypassing the formation of toxic AßOs, and only nontoxic AßMs, dimers (AßDs), and fibrils (AßFs) are produced. Unlike other Aß toxicity inhibitors, K162 preserves neurologically beneficial AßMs. This unique K162 inhibition mechanism provides an alternative AD therapeutic strategy that could be explored in the future.

Physicochemical changes of the chitosan/ß-1,3-glucan/hydroxyapatite biocomposite caused by mesenchymal stem cells cultured on its surface in vitro.

In the present study structural characteristics and physicochemical properties of tri-component biomaterial (consisting of chitosan, ß-1,3-glucan and hydroxyapatite) seeded with mesenchymal stem cells were investigated with the use of diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). In this study we use non-conventional approach of DRIFT spectroscopy for investigating biomaterial changes under simulated physiological conditions. Particular cell-induced changes were intended to be properly evaluated with analytical methods. Abovementioned techniques allowed to precisely assess the changes on the surface of the biomaterial caused by two kinds of stem cells (ADSCs - Adipose tissue-Derived Stem Cells and BMDSCs - Bone Marrow-Derived Stem Cells) cultured directly on the surface of bioceramic-based biomaterial. The bioactivity and biocompatibility of designed bone biomaterial were demonstrated and hence it seems to be a promising scaffold used in tissue engineering. Designed chitosan, ß-1,3-glucan, and hydroxyapatite biomaterial was proven to be non-toxic, surgically handy with cellular compatibility. The obtained results are interesting and promising in terms of spectroscopic methods suitability for qualitative assessment of material-cell interactions.

Bimetallic nanocatalysts supported on graphitic carbon nitride for sustainable energy development: the shape-structure-activity relation.

The catalytic performance of metal nanoparticles (NPs), including activity, selectivity, and durability, depends on their shape and structure at the molecular level. Consequently, metal NPs of different size and shape, e.g., nanobelts, nanocubes, nanoflakes, and nanowires, demonstrate different reactivity and provide different reaction rates depending on the facet exposed. In this context, the present review aims to summarize the shape-structure-activity relation of metallic nanocatalysts. Moreover, keeping in mind that the application of noble metal catalysts is expensive, we would like to draw the reader's attention to bimetallic nanocatalysts supported on graphitic carbon nitride. One of the advantages of these systems is the possibility to minimize the use of noble metals by introducing another metal either to the parent NPs and/or modifying the support materials. The development and optimization of bimetallic nanocatalysts might provide the new class of materials with superior, tunable performance, thermal stability and reduced costs compared to presently available commercial catalysts. Therefore, further application of these bimetallic composites for sustainable development in energy, green chemicals/fuels and environmental protection will be discussed.

Correction: Bimetallic nanocatalysts supported on graphitic carbon nitride for sustainable energy development: the shape-structure-activity relation.

[This corrects the article DOI: 10.1039/D0NA01063D.].

Toxicity of selected airborne nitrophenols on eukaryotic cell membrane models.

Nitroaromatics belong to the group of toxic components of aerosol particles and atmospheric hydrometeors that enter the atmosphere through biomass burning and fuel combustion. In the present work, we report on the cytotoxic effects of a 2-, 3- and 4-nitrophenol mixture on a model eukaryotic-like cell membrane and compared it with in vitro cellular models BEAS-2B (immortalized bronchial epithelial cells) and A549 (cancerous alveolar epithelial cells). A selected model biomembrane comprised of DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine), DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) and POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine) was studied. The electrochemical-based method, combined with atomic force microscopy (AFM) and phase-contrast microscopy imaging, allowed to get insights into the mechanism of cellular function disruption caused by airborne nitrophenols. The efficacy of the method is supported by the data obtained from in vitro experiments performed on cell models. The nitrophenol mixture exhibited cytotoxic effects at concentrations above 100 µg mL-1, as demonstrated by phase-contrast microscopy in real lung cell lines. Electrochemical impedance spectroscopy (EIS) revealed the formation of membrane defects at a nitrophenol concentration of 200 µg mL-1. AFM imaging confirmed the model membrane disintegration and phospholipids rearrangement in the presence of nitrophenols. These observations indicate that particle-bound nitrophenols induce substantial changes in cell membranes and make them more permeable to aerosol, resulting in major cellular damage in the lungs when inhaled. The study provides initial evidence of cellular membrane damage induced by three important nitrated phenols present in the environment.

In Situ Interactions of Eu(TTA)3(H2O)2 with Latent Fingermark Components-A Time-Gated Visualization of Latent Fingermarks on Paper.

We introduce a new latent fingermark (LFM) development method, where compounds showing long lifetime luminescence are generated in situ by the reactions of Eu(TTA)3(H2O)2 with LFM components. Until now, time-gated imaging could not be used to develop LFM on porous surfaces due to the difficulties with selective binding of the developing agents to the fingermark ridges. The nature of the interactions of Eu(TTA)3(H2O)2 with the LFM material has been investigated for three model compounds commonly found in the LFM composition-oleic acid, l-serine, and squalene. The LFMs developed with the europium ß-diketonate complex have been successfully photographed using a time-gated imaging scheme. The presented new approach has been demonstrated to give similar or better results than developing agents commonly used for paper samples (ninhydrin and 1,2-indanedione). Moreover, contrary to the methods mentioned above, the new approach allows for the development of amino acid-poor LFM on paper.

Effect of Gelation Temperature on the Molecular Structure and Physicochemical Properties of the Curdlan Matrix: Spectroscopic and Microscopic Analyses.

In order to determine the effect of different gelation temperatures (80 °C and 90 °C) on the structural arrangements in 1,3-ß-d-glucan (curdlan) matrices, spectroscopic and microscopic approaches were chosen. Attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) and Raman spectroscopy are well-established techniques that enable the identification of functional groups in organic molecules based on their vibration modes. X-ray photoelectron spectroscopy (XPS) is a quantitative analytical method utilized in the surface study, which provided information about the elemental and chemical composition with high surface sensitivity. Contact angle goniometer was applied to evaluate surface wettability and surface free energy of the matrices. In turn, the surface topography characterization was obtained with the use of atomic force microscopy (AFM) and scanning electron microscopy (SEM). Described techniques may facilitate the optimization, modification, and design of manufacturing processes (such as the temperature of gelation in the case of the studied 1,3-ß-d-glucan) of the organic polysaccharide matrices so as to obtain biomaterials with desired characteristics and wide range of biomedical applications, e.g., entrapment of drugs or production of biomaterials for tissue regeneration. This study shows that the 1,3-ß-d-glucan polymer sample gelled at 80 °C has a distinctly different structure than the matrix gelled at 90 °C.

Spectroscopic studies on the temperature-dependent molecular arrangements in hybrid chitosan/1,3-ß-D-glucan polymeric matrices.

Chitosan/1,3-ß-D-glucan matrices have been recently used in various biomedical applications. Within this study, the structural changes in hybrid polysaccharide chitosan/1,3-ß-D-glucan matrices cross-linked at 70 °C and 80 °C were detected with Attenuated Total Reflection Fourier Transform Infrared spectroscopy (ATR FT-IR) and Raman spectroscopy enabled thorough insights into molecular structure of studied biomaterials, whereas X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) provided their surface characteristics with confirmation of their effective and non-destructive properties. There are temperature-dependent differences in the chemical interactions between 1,3-ß-D-glucan units and N-glucosamine in chitosan, resulting in surface polarity changes. The second order derivatives and deconvolution revealed the alterations in the secondary structure of studied matrices, along with different sized grain-like structures revealed by AFM. Since surface physicochemical properties of biomaterials have great impact on cell behavior, abovementioned techniques may allow to optimize and modify the preparation of polymeric matrices with desired features.

Zinc oxide quantum dots embedded in hydrophobic silica particles for latent fingermarks visualization based on time-gated luminescence measurements.

In this work we demonstrate a composite material based on silica particles. The particles have been doped with zinc oxide quantum dots which possess long living luminescence. The surface of the particles has been functionalized with phenyl groups using sol-gel process. The new material has been successfully applied for visualization of natural latent fingermarks on several surfaces, in particular, those showing their own luminescence and intensive background staining while using powder dusting, what is of the vital interest of forensic science. The time-gated imaging allows to overcome the background luminescence problem and surface functionalization increases the affinity of the particles to the fingermarks, what improves the selectivity of a new developing agent. The main novelty of the presented approach is the use of composite material that combines two main features-long lifetime luminescence and the ability to preferentially attach to the fingermark, due to hydrophobic interactions. Moreover,the utilization of deposition from the suspension instead of simple powder dusting allows for development of latent fingermarks on the surfaces that are difficult to work with powders (e.g. sticky side of the adhesive tape).

Size-Dependent Interaction of Amyloid ß Oligomers with Brain Total Lipid Extract Bilayer-Fibrillation Versus Membrane Destruction.

Amyloid ß, Aß(1-42), is a component of senile plaques present in the brain of Alzheimer's disease patients and one of the main suspects responsible for pathological consequences of the disease. Herein, we directly visualize the Aß activity toward a brain-like model membrane and demonstrate that this activity strongly depends on the Aß oligomer size. PeakForce quantitative nanomechanical mapping mode of atomic force microscopy imaging revealed that the interaction of large-size (LS) Aß oligomers, corresponding to high-molecular-weight Aß oligomers, with the brain total lipid extract (BTLE) membrane resulted in accelerated Aß fibrillogenesis on the membrane surface. Importantly, the fibrillogenesis did not affect integrity of the membrane. In contrast, small-size (SS) Aß oligomers, corresponding to low-molecular-weight Aß oligomers, created pores and then disintegrated the BTLE membrane. Both forms of the Aß oligomers changed nanomechanical properties of the membrane by decreasing its Young's modulus by ∼45%. Our results demonstrated that both forms of Aß oligomers induce the neurotoxic effect on the brain cells but their action toward the membrane differs significantly.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.