A theoretical and electrochemical impedance spectroscopy study of the adsorption and sensing of selected metal ions by 4-morpholino-7-nitrobenzofuran.

The selectivity of a novel chemosensor, based on a modified nitrobenzofurazan referred to as NBD-Morph, has been investigated for the detection of heavy metal cations (Co2+, Pb2+, Mg2+, Ag+, Cu2+, Hg2+, Ni2+, and Zn2+). The ligand, 4-morpholino-7-nitrobenzofurazan (NBD-Morph), was characterized using spectroscopic techniques including FT-IR and 1H NMR. Vibrational frequencies obtained from FT-IR and proton NMR (1H) chemical shifts were accurately predicted employing the density functional theory (DFT) at the B3LYP level of theory. Furthermore, an examination of the structural, electronic, and quantum chemical properties was conducted and discussed. DFT calculations were employed to explore the complex formation ability of the NBD-Morph ligand with Co2+, Pb2+, Mg2+, Ag+, Cu2+, Hg2+, Ni2+, and Zn2+ metal cations. The comparison of adsorption energies for all possible conformations reveals that NBD-Morph exhibits sensitivity and selectivity towards metal ions, including Pb2+, Cu2+, Ag+, and Ni2+. However, an assessment of their reactivity using QTAIM topological parameters demonstrated the ligand's greater complexation ability toward Cu2+ or Ni2+ than those formed by Pb2+ or Ag+. Additionally, molecular electrostatic potential (MEP), Hirshfeld surfaces, and their associated 2D-fingerprint plots were applied to a detailed study of the inter-molecular interactions in NBD-Morph-X (X = Pb2+, Cu2+, Ag+, Ni2+) complexes. The electron localization function (ELF) and the localized-orbital locator (LOL) were generated to investigate the charge transfer and donor-acceptor interactions within the complexes. Electrochemical analysis further corroborates the theoretical findings, supporting the prediction of NBD-Morph's sensory ability towards Ni2+ metal cations. In conclusion, NBD-Morph stands out as a promising sensor for Ni2+.

Exponential feedback effects in a parametric resonance climate model.

The variations in the distribution of solar radiation due to the ~ 105 years Milankovitch cycle, which is connected to the Earth eccentricity variation, cannot explain the sharp drop in temperature of 6 °C ÷ 10 °C that marks the transition from the interglacial to the glacial age registered in the last ~ 5.5 106 years temperature variation behavior. More specifically, neglecting other effects, only a temperature variation of 0.2 °C ÷ 0.3 °C can be attributed to this cycle and, therefore, positive feedback effects should be taken into account to explain the registered effect. In the present work, a comparative Wavelet-Fourier analysis of the Vostok recontructed temperature record, for which different sampling steps are taken into account, is performed. Then, a study of exponential feedback effects within a climate parametric resonance model is dealt and discussed. The obtained findings put into evidence an exponential amplification of the temperature variation from the interglacial to the glacial age supporting the hypothesis that the system energization be connected to periodic variations in the internal solar system parameters. More in details, it is shown that, following the parametric resonance climate model, even small oscillations increase over time proportionally to the system energy itself, i.e. exponentially, and hence, a series of connected resonances is able to energize the climate system.

Lichenysin-like Polypeptide Production by Bacillus licheniformis B3-15 and Its Antiadhesive and Antibiofilm Properties.

We report the ability of the crude biosurfactant (BS B3-15), produced by the marine, thermotolerant Bacillus licheniformis B3-15, to hinder the adhesion and biofilm formation of Pseudomonas aeruginosa ATCC 27853 and Staphylococcus aureus ATCC 29213 to polystyrene and human cells. First, we attempted to increase the BS yield, optimizing the culture conditions, and evaluated the surface-active properties of cell-free supernatants. Under phosphate deprivation (0.06 mM) and 5% saccharose, the yield of BS (1.5 g/L) increased by 37%, which could be explained by the earlier (12 h) increase in lchAA expression compared to the non-optimized condition (48 h). Without exerting any anti-bacterial activity, BS (300 µg/mL) prevented the adhesion of P. aeruginosa and S. aureus to polystyrene (47% and 36%, respectively) and disrupted the preformed biofilms, being more efficient against S. aureus (47%) than P. aeruginosa (26%). When added to human cells, the BS reduced the adhesion of P. aeruginosa and S. aureus (10× and 100,000× CFU/mL, respectively) without altering the epithelial cells' viability. As it is not cytotoxic, BS B3-15 could be useful to prevent or remove bacterial biofilms in several medical and non-medical applications.

Exploration of intramolecular charge transfer in para-substituted nitrobenzofurazan: Experimental and theoretical analyses.

The present work aims at exploring the high electrophilic character of 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) toward the morpholine group by an SNAr reaction in acetonitrile or water (thereafter referred to as NBD-Morph). The electron-donating ability of the morpholine causes intra-molecular charge transfer (ICT). In this report, we present a comprehensive study on the optical characteristics using UV-Vis, photoluminescence (cw-PL) and its time-resolved (TR-PL) to determine the properties of the emissive intramolecular charge transfer (ICT) in the NBD-Morph donor-acceptor system. An exhaustive theoretical investigation utilizing the density functional theory (DFT) and its extension TD-DFT methods is an essential complement of experiments to rationalize and understand the molecular structure and related properties. The findings from QTAIM, ELF, and RDG analyses establish that the bonding between morpholine and NBD moieties is of the electrostatic or hydrogen bond type. In addition, the Hirshfeld surfaces have been established to explore the types of interactions. Further, the non-linear optical (NLO) responses of the compound have been examined. The structure-property relationships obtained through the combined experimental and theoretical offer valuable insights for designing efficient NLO material.

Investigation of Glucose-Water Mixtures as a Function of Concentration and Temperature by Infrared Spectroscopy.

The main aim of the present paper is to characterize the hydration properties of glucose and the hydrogen bond network in glucose-water mixtures. For these purposes, temperature scans on ten concentration values of glucose-water mixtures were performed by means of Fourier Transform InfraRed (FTIR) spectroscopy. More specifically, in order to get this information an analysis of the intramolecular OH stretching mode, investigating the 3000-3700 cm-1 spectral range, was performed by means of an innovative approach based on the evaluation of the Spectral Distance (SD). The adopted procedure allows evaluating the glucose hydration number as well as characterizing the temperature behavior of the hydrogen bond network in the glucose-water mixtures. The obtained results for the hydration number are in excellent agreement with literature data and suggest the existence of a particular concentration value for which the hydrogen bond network shows a maximum strength.

Multiscale Spectral Analysis on Lysozyme Aqueous Solutions in the Presence of PolyEthyleneGlycol.

Infrared spectroscopy measurements were performed on Lysozyme aqueous solutions also in the presence of PolyEthylene Glycol (PEG 400) as a function of an increasing temperature from T = 27 °C to 90 °C, and, successively in sequence, by decreasing temperatures from T = 90 °C to 27 °C. Data were analyzed by evaluating the spectral difference with respect to the initial spectrum collected at 27 °C. This procedure allows to quantitatively evaluate the thermal restraint related to the thermal scan from T = 27 °C to 90 °C, as well as to introduce a spectral resilience concerning the entire increasing and decreasing thermal paths which allow to highlight the bioprotectant effectiveness of low molecular weight PEG. In particular, the main purpose of the present work is to highlight the effects of a thermal treatment on a mixture of Lysozyme/water and of Lysozyme/water/PEG 400 during an increasing temperature scan, and then after a successive decreasing temperature scan, in order to highlight the bioprotectant role of PEG 400. On that score, an evaluation of the spectral distances of the registered spectra as a function of increasing and decreasing temperatures has been performed and analyzed.

Stabilization Effects Induced by Trehalose on Creatine Aqueous Solutions Investigated by Infrared Spectroscopy.

Creatine is a very popular amino acid widely utilized in the sports world due to its functions mainly related to muscle building and increasing performance. The present work investigates the behavior of creatine aqueous solutions and of creatine aqueous in the presence of trehalose as a function of time changes by means of Infrared spectroscopy. Infrared spectra have been gathered and studied over time for both the full spectrum and the intramolecular OH-stretching region for the two mixtures. This latter region was studied more specifically using a cutting-edge technique called Spectral Distance (SD). From this analysis of the spectral features of the investigated samples, it emerges that trehalose has a significant stabilizing effect on creatine aqueous solutions.

Hydrating Capabilities of the Biopolymers Produced by the Marine Thermophilic Bacillus horneckiae SBP3 as Evaluated by ATR-FTIR Spectroscopy.

The surfactin-like lipopeptide (BS-SBP3) and the exopolysaccharide (EPS-SBP3) produced by the polyextremophilic Bacillus horneckiae SBP3 (DSM 103063) have been recently described as valuable biopolymers useful in biotechnological applications. To investigate the hydrating capabilities of BS-SBP3 and EPS-SBP3, here we evaluated (i) their wetting properties, measuring the contact angle; (ii) their moisture uptake abilities using the gravimetric method; and (iii) their hydrating states (from 0 to 160% w/w of water content) using ATR-FTIR spectroscopy. BS-SBP3 reduced the water contact angle on a hydrophobic surface from 81.7° to 51.3°, whereas the contact angle in the presence of EPS-SBP3 was 72.9°, indicating that BS-SBP3 improved the wettability of the hydrophobic surface. In the moisture uptake tests, EPS-SBP3 absorbed more water than BS-SBP3, increasing its weight from 10 mg to 30.1 mg after 36 h of 100% humidity exposure. Spectral distance and cross-correlation analyses were used to evaluate the molecular changes of the two biopolymers during the hydration process. As the water concentration increased, BS-SBP3 spectra changed in intensity in the two contributions of the OH-stretching band named "closed" and "open" (3247 and 3336 cm-1, respectively). Differently, the spectra of EPS-SBP3 exhibited a broader peak (3257 cm-1), which shifted at higher water concentrations. As evaluated by the spectral distance and the wavelet cross-correlation analysis, the OH-stretching bands of the BS-SBP3 and EPS-SBP3 changed as a function of water content, with two different sigmoidal trends having the inflection points at 80% and 48%, respectively, indicating peculiar water-properties of each biopolymer. As wetting agents, these biopolymers might replace industrially manufactured additives in agriculture and the food and cosmetic industries.

Experimental Investigation on the Bioprotective Role of Trehalose on Glutamine Solutions by Infrared Spectroscopy.

Glutamine plays a significant role in several basic metabolic processes and is an important regulator of heat shock protein response. The present work is focused on the analysis of the thermal response of aqueous solutions of Glutamine and aqueous solutions of Glutamine in the presence of Trehalose by means of infrared absorption technique. The performed study shows how in the case of a multicomponent system, characterized by a huge number of spectral contributions whose assignment are questionable, the Spectral Distance (SD) and the Cross Wavelet Correlation (XWT) approaches are able to furnish explanatory parameters that can characterize the variations in the spectra behaviour, which is an efficient tool for quantitative comparisons. With this purpose, the analysis has been performed by evaluating the SD and the XWT parameters for the whole investigated spectral range, i.e., 4000-400 cm-1, for scans collected as a function of temperature in the range 20 °C ÷ 60 °C both for Glutamine/Water compounds and for Glutamine /Water/Trehalose mixtures. By means of these analyses, it is found that in aqueous solutions of Glutamine, with respect to aqueous solutions of Glutamine in the presence of Trehalose, the SD and XWT temperature trends follow a linear behaviour where the angular coefficient for Glutamine /Water/Trehalose compounds are lower than that of the Glutamine-Water system in both cases. The obtained findings suggest that Trehalose stabilizes Glutamine against heat treatment.

Molecular Basis of Interactions between the Antibiotic Nitrofurantoin and Human Serum Albumin: A Mechanism for the Rapid Drug Blood Transportation.

Nitrofurantoin is an antimicrobial agent obtained through the addition of a nitro group and a side chain containing hydantoin to a furan ring. The interactions of the antibiotic with human serum albumin (HSA) have been investigated by fluorescence, UV-VIS, Fourier transform infrared spectroscopy (FTIR) spectroscopy, and protein-ligand docking studies. The fluorescence studies indicate that the binding site of the additive involves modifications of the environment around Trp214 at the level of subdomain IIA. Fluorescence and UV-VIS spectroscopy, displacement studies, and FTIR experiments show the association mode of nitrofurantoin to HSA, suggesting that the primary binding site of the antibiotic is located in Sudlow's site I. Molecular modeling suggests that nitrofurantoin is involved in the formation of hydrogen bonds with Trp214, Arg218, and Ser454, and is located in the hydrophobic cavity of subdomain IIA. Moreover, the curve-fitting results of the infrared Amide I' band indicate that the binding of nitrofurantoin induces little change in the protein secondary structure. Overall, these data clarify the blood transportation process of nitrofurantoin and its rapid transfer to the kidney for its elimination, hence leading to a better understanding of its biological effects and being able to design other molecules, based on nitrofurantoin, with a higher biological potential.

Effects of Heavy Ion Particle Irradiation on Spore Germination of Bacillus spp. from Extremely Hot and Cold Environments.

Extremophiles are optimal models in experimentally addressing questions about the effects of cosmic radiation on biological systems. The resistance to high charge energy (HZE) particles, and helium (He) ions and iron (Fe) ions (LET at 2.2 and 200 keV/µm, respectively, until 1000 Gy), of spores from two thermophiles, Bacillushorneckiae SBP3 and Bacilluslicheniformis T14, and two psychrotolerants, Bacillus sp. A34 and A43, was investigated. Spores survived He irradiation better, whereas they were more sensitive to Fe irradiation (until 500 Gy), with spores from thermophiles being more resistant to irradiations than psychrotolerants. The survived spores showed different germination kinetics, depending on the type/dose of irradiation and the germinant used. After exposure to He 1000 Gy, D-glucose increased the lag time of thermophilic spores and induced germination of psychrotolerants, whereas L-alanine and L-valine increased the germination efficiency, except alanine for A43. FTIR spectra showed important modifications to the structural components of spores after Fe irradiation at 250 Gy, which could explain the block in spore germination, whereas minor changes were observed after He radiation that could be related to the increased permeability of the inner membranes and alterations of receptor complex structures. Our results give new insights on HZE resistance of extremophiles that are useful in different contexts, including astrobiology.

Self-assembly of Organic Nanomaterials and Biomaterials: The Bottom-Up Approach for Functional Nanostructures Formation and Advanced Applications.

In this paper, we survey recent advances in the self-assembly processes of novel functional platforms for nanomaterials and biomaterials applications. We provide an organized overview, by analyzing the main factors that influence the formation of organic nanostructured systems, while putting into evidence the main challenges, limitations and emerging approaches in the various fields of nanotechology and biotechnology. We outline how the building blocks properties, the mutual and cooperative interactions, as well as the initial spatial configuration (and environment conditions) play a fundamental role in the construction of efficient nanostructured materials with desired functional properties. The insertion of functional endgroups (such as polymers, peptides or DNA) within the nanostructured units has enormously increased the complexity of morphologies and functions that can be designed in the fabrication of bio-inspired materials capable of mimicking biological activity. However, unwanted or uncontrollable effects originating from unexpected thermodynamic perturbations or complex cooperative interactions interfere at the molecular level with the designed assembly process. Correction and harmonization of unwanted processes is one of the major challenges of the next decades and requires a deeper knowledge and understanding of the key factors that drive the formation of nanomaterials. Self-assembly of nanomaterials still remains a central topic of current research located at the interface between material science and engineering, biotechnology and nanomedicine, and it will continue to stimulate the renewed interest of biologist, physicists and materials engineers by combining the principles of molecular self-assembly with the concept of supramolecular chemistry.

Editorial-Special Issue "Macromolecular Self-Assembly Materials: From Modeling to Advanced Applications".

Materials self-assembly represents a key strategy for the design and fabrication of nanostructured systems and has become a fundamental approach for the construction of advanced nanomaterials [...].

The inverse relation between mitochondrial transmembrane potential and proteins α-helix in neuronal-like cells under static magnetic field and the role of VDAC.

In this study, a correlation between cell channel α-helices displacement and the mitochondrial transmembrane potential after exposure of 3, 7, 15 and 24 h of neuronal-like cells to a uniform magnetic field at the intensity of 2 mT was shown. Fourier Transform Infrared (FTIR) Spectroscopy and fluorescence techniques were used to analyze the secondary structure of protein content and mitochondrial transmembrane potential, respectively. The main result of this study was represented by a significant inverse relation between the mitochondrial transmembrane potential and the intensity of the Amide I band that can be associated with time exposure. Given that mitochondrial transmembrane potential should be related to the gating state of voltage-dependent anion channel (VDAC) in mitochondrial membrane, this result could have a relevant role in medicine. Indeed, VDAC's irregular behavior can be associated with several varieties of mitochondria-associated pathologies and various forms of cancer and neurodegeneration.

Modulation of Maillard reaction and protein aggregation in bovine meat following exposure to microwave heating and possible impact on digestive processes: An FTIR spectroscopy study.

The aim of this study was to highlight the existence of a correlation between Maillard reaction and protein aggregation in bovine meat as a function of power level and exposure time used by microwave heating. The obtained results are compared with those of convective heating. For this, Fourier Transform-Infrared Spectroscopy was used to analyze the effects of microwave heating on different samples of bovine meat cooked in microwave ovens at three power levels of 700, 900 and 1100 W, and in conventional electric oven at the temperature of 170°C. An increase in intensity of methylene vibration bands after microwave cooking at 700 W for 3 min was more than that which occurred after microwave cooking at 900 and 1100 W for 2 min, showing that Maillard reaction depends on exposure time to microwaves. Also, the ß-sheet contents at 1695 and 1635 cm-1 in meat samples heated for 2 min by microwave oven increased with increase in power level from 700 to 1100 W, showing that protein aggregation is strictly related to the power level of microwave heating. This result showed that an extended exposure time to microwave heating can significantly alter gastrointestinal digestive processes.

Chromosome aberration in typical biological systems under exposure to low- and high-intensity magnetic fields.

The aim of this study was to investigate the response of chromosomes in typical human and plant cells under applied low-frequency magnetic fields at low and high intensities. Neuronal-like cells and roots of Allium sativum and Vicia faba were used to investigate chromosome's response to a static and 50 Hz magnetic fields at intensities ranging from 1 mT to 0.8 T, generated by two Helmholtz coils driven by direct current or alternate current voltage. Vertex spectrometer and Olympus microscope with camera were used. A significant decrease in intensity of the phosphate bands in the DNA infrared region was observed by FTIR spectroscopy analysis after exposure of neuronal-like cells to static and 50 Hz magnetic field at low intensity of 1 mT, which can be explained assuming that uncoiling and unpackaging of chromatin constituents occurred after exposure. This effect was directly observed by microscope in roots of Allium sativum and Vicia faba under exposure to a static magnetic field at high intensity of 0.8 T. These findings can be explained assuming that exposure to both low- and high-intensity magnetic fields of chromosomes in typical human and plant cells induces uncoiling and unpackaging of chromatin constituents, followed by chromosome alignment towards the direction of applied magnetic field, providing further demonstration that magnetic fields can induce the orientation of organic macromolecules even at low-intensity values.

Self-assembly Processes in Hydrated Montmorillonite by FTIR Investigations.

Experimental findings obtained by FTIR and Raman spectroscopies on montmorillonite-water mixtures at three concentration values are presented. To get some insight into the hydrogen bond network of water within the montmorillonite network, FTIR and Raman spectra have been collected as a function of time and then analyzed following two complementary approaches: An analysis of the intramolecular OH stretching mode in the spectral range of 2700-3900 cm-1 in terms of two Gaussian components, and an analysis of the same OH stretching mode by wavelet cross-correlation. The FTIR and Raman investigations have been carried as a function of time for a montmorillonite-water weight composition (wt%) of 20%-80%, 25%-75%, and 35%-65%, until the dehydrated state where the samples appear as a homogeneous rigid layer of clay. In particular, for both the FTIR and Raman spectra, the decomposition of the OH stretching band into a "closed" and an "open" contribution and the spectral wavelet analysis allow us to extract quantitative information on the time behavior of the system water content. It emerges that, the total water contribution inside the montmorillonite structure decreases as a function of time. However, the relative weight of the ordered water contribution diminishes more rapidly while the relative weight of the disordered water contribution increases, indicating that a residual water content, characterized by a highly structural disorder, rests entrapped in the montmorillonite layer structure for a longer time. From the present study, it can be inferred that the montmorillonite dehydration process promotes the layer self-assembly.

Thermal properties of an exopolysaccharide produced by a marine thermotolerant Bacillus licheniformis by ATR-FTIR spectroscopy.

The novel exopolysaccharide (EPS-B3-15) produced by the marine thermotolerant Bacillus licheniformis strain B3-15, constituted by mannose and glucose, has been recently reported as a valuable biopolymer in pharmaceutical applications. To dynamically characterize the thermal behavior of the whole EPS-B3-15 system, the Attenuated Total Reflectance Fourier Transform Infra-Red spectroscopy technique was used over a temperature range from ambient to 78.5 °C. The molecular changes of EPS-B3-15 during the heating process were evaluated by the spectral distance (SD) and wavelet cross-correlation (XWT) analysis. The thermal analysis revealed that the EPS-B3-15 possessed high stability until 78.5 °C. As evaluated by SD and XWT, the molecular structure of EPS-B3-15 at 45 °C was partially modified, due to -OH groups and the -COOH and -OH interactions, conferring a new conformational structure to the biopolymer. The thermal characterization provides novel information about the molecular conformations of the whole EPS-B3-15 system at different temperatures. The thermostable EPS-B3-15 can be successfully employed for biotechnological, nanotechnological and material science applications even at high temperatures.

Methyl and methylene vibrations response in amino acids of typical proteins in water solution under high-frequency electromagnetic field.

The aim of this paper was to study the response of methyl (CH3) and methylene (CH2) vibration bands in amino acids of some typical proteins diluted in bidistilled water solution after exposure to a high-frequency electromagnetic fields using Fourier Transform Infrared (FTIR) Spectroscopy. Hemoglobin in H2O solution and bovine serum albumin and myoglobin diluted in different D2O solutions were exposed for 4 h to a power density of 0.95 W/m2 at the frequency of 1750 MHz, emitted by operational mobile phones Nokia model 105 and Samsung model GT-E1270, in order to study the response of stretching vibrations of CH3 and CH2 that are in amino acids of those proteins. The main result was that CH3 stretching bands increased significantly in myoglobin in D2O solution because this protein is represented by a single protein chain so that the torque induced by the applied field is larger than that induced on the other two proteins. Otherwise, CH2 stretching vibrations decreased in intensity significantly for all exposed proteins. This result can be explained as well, assuming that, given a fixed volume, a decrease of population of CH2 occurred after exposure because of the alignment of proteins α-helices along the direction of the applied electromagnetic field.

Infrared spectroscopic demonstration of magnetic orientation in SH-SY5Y neuronal-like cells induced by static or 50 Hz magnetic fields.

Purpose: To study the response of neuronal-like cells to an applied static or low-frequency magnetic field. Materials and methods: Fourier Transform Infrared (FTIR) Spectroscopy was used to investigate the overall behavior of SH-SY5Y neuronal-like cells exposed to a static or 50 Hz magnetic fields at intensities up to 1 mT generated by two Helmholtz coils driven by direct current or alternate current voltage. The Helmholtz coils were placed into an incubator in a 5% CO2/95% air humidified at 37 °C. Results: A significant increase in intensity of the Amide I band and of CH2 stretching vibrations in neuronal-like FTIR spectra appeared after 6 h exposure to static or 50 Hz magnetic fields. Conclusions: These findings can be easily explained assuming that proteins α-helices and lipids contents in cellular membrane aligned toward the direction of the applied magnetic field after exposure, inducing an increase of ions flux across cellular membrane channels after exposure to a magnetic field, changing cellular functions.