Search Results (54)

The pre-courtship behavior of Proholopterus chilensis on Nothofagus obliqua trees was recorded for the first time, documenting a putative female “calling” behavior and the consequent male “oriented search,” enabling the description of behavioral units, sequences, frequencies, and degrees of stereotypy. Post-resting activity in both sexes began with walking and grooming during the first hour of the scotophase, following a period of daytime inactivity. Subsequently, females extended their ovipositor both horizontally and vertically, alternating between contact with the tree substrate and, simultaneously, walking the surface (=putative calling behavior), while males became active, extending their antennae perpendicularly to the longitudinal body axis. In response to the putative call, males exhibited oriented flight and hasty walking that followed the trajectory and direction previously taken by females on the substrate, ultimately leading to their location. Statistical analysis of behavioral sequences and the stereotypy index indicated that both behaviors were non-random and partially stereotyped. These findings are consistent with previous chemical analyses of female aerations and terminalia performed by our research group, which identified semiochemicals likely functioning as long-range sex pheromones guiding males to the vicinity of the female’s tree, as well as potential trail pheromones facilitating close-range localization. This dual signaling system seems necessary to the high mobility displayed by females during calling behavior, characterized by frequent and extended bidirectional vertical walks along the trunk, which may enhance signal dispersal and/or reduce predation risk. If confirmed, this would represent a novel sexual encounter mechanism within Cerambycidae. Full article

A temporal monitoring of monumental buildings in calcarenite, exposed outdoors in the considered Mediterranean environment of Southern Italy, was performed using XPS, the surface-specific technique. The methodology adopted to monitor the surfaces interacting with atmospheric agents and biotic/abiotic pollutants involved progressive sampling, extended to about five years, from the walls of a new building, specifically installed in the immediate vicinity of an ancient farmhouse in an advanced state of degradation. Taking the ancient building as the final temporal reference, the aim was to obtain adequate information on the degradation processes of calcarenitic stones, from the initial and evolving phases of the new building towards those representative of the old reference. A large set of XPS data was obtained by resolving, through curve-fitting, the acquired spectra into component peaks, identified as ‘indicator’ chemical groups, which trend as a function of time, supported by PCA, demonstrates a close compositional similarity between the samples of the new building analyzed after 52 months from its installation and those of the ancient building dating back to over a century ago. The results obtained can be considered in the diagnostic strategy of the ongoing PNRR programs dedicated to the care of historical monuments and ecosystem sustainability. Full article

Precise control over the morphology of surface-supported supramolecular patterns is a significant challenge, requiring the careful selection of suitable molecular building blocks and the fine-tuning of experimental conditions. In this contribution, we demonstrate the utility of lattice Monte Carlo computer simulations for predicting the topology of adsorbed overlayers formed by star-shaped tetratopic molecules with vicinal interaction centers. The investigated tectons were found to self-assemble into a range of structurally diverse architectures, including two-dimensional crystals, aperiodic mosaics, Sierpiński-like aggregates, and one-dimensional strands. The theoretical insights presented herein deepen our understanding of molecular self-assembly and may aid in the rational design of novel nanomaterials with tunable porosity, chirality, connectivity, and molecular packing. Full article

Azurin is a small blue copper protein that participates in redox reactions during anaerobic respiration in Pseudomonas aeruginosa, and there are a significant number of studies employing this model to investigate the electron transfer (ET) processes or coordination sphere of metal ion in metalloproteins. Azurin naturally contains Cu(II/I) as a central ion and is redox-active for a single electron ET. Moreover, azurin with no central ion (apo-azurin) is capable of binding other metal cofactors—e.g., Zn(II)—forming redox-inactive Zn-form and many others impacting the redox potential and structural variation in the active site’s arrangement. Also, mutations of amino acid residues in the immediate vicinity of the metal ion can influence the structure and functionality of a particular metalloprotein. Therefore, this review aims to summarize the abundant information about selected topics related to redox reactions and blue copper proteins, particularly azurin, and is structured as follows: (i) introduction to the structure, properties, and physiological role of this group of metalloproteins, (ii) the role of the equatorial and axial ligands of the central metal ions, or metal species, in the active site on the metal coordination sphere’s structure and related determination of the particular azurin form’s redox potentials, and (iii) the effects of the particular amino acid’s moiety (Phe, Tyr and Trp residues together with acceleration employing Trp-Trp π-π stacking interactions contrary to ET distance dependence) on the preferable type of long-range ET mechanism in an azurin-mediated model biomolecule. We assume that azurin is a suitable model to study the structural functionality of a particular central metal ion or individual amino acid residues in the central ion coordination sphere for studying the redox potential and ET reactions in metalloproteins. Full article

In this paper, we demonstrate that torsional surface elastic waves can propagate along the curved surface of a metamaterial elastic rod (cylinder) embedded in a conventional elastic medium. The crucial parameter of the metamaterial rod is its elastic compliance $s_{44}^{\left(1\right)}\left(\omega \right),$ which varies as a function of frequency $\omega$ analogously to the dielectric function $\epsilon \left(\omega \right)$ in Drude’s model of metals. As a consequence, the elastic compliance $s_{44}^{\left(1\right)}\left(\omega \right)$ can take negative values $s_{44}^{\left(1\right)}\left(\omega \right)<0$ as a function of frequency $\omega$. Negative elastic compliance ($s_{44}^{\left(1\right)}\left(\omega \right)<0$) enables the emergence of new surface states, i.e., new types of surface elastic waves. In fact, the proposed torsional elastic surface waves can be considered as an elastic analog of Surface Plasmon Polariton (SPP) electromagnetic (optical) waves propagating along a metallic rod (cylinder) embedded in a dielectric medium. Consequently, we developed the corresponding analytical equations, for the dispersion relation and group velocity of the new torsional elastic surface wave. The newly discovered torsional elastic surface waves exhibit virtually all extraordinary properties of their electromagnetic SPP counterparts, such as strong subwavelength concentration of the wave energy in the vicinity of the cylindrical surface $(r=a$) of the guiding rod, very low phase and group velocities, etc. Therefore, the new torsional elastic surface waves can be used in: (a) near-field subwavelength acoustic imaging (super-resolution), (b) acoustic wave trapping (zero group and phase velocity), etc. Importantly, the newly discovered torsional elastic surface waves can form a basis for the development of a new generation of ultrasonic sensors (e.g., viscosity sensors), biosensors, and chemosensors with a very high mass sensitivity. Full article

This publication reports a facile and convenient preparation of tri-O-acetyl-glucopyranoses, derived from the corresponding 2-deoxyaminosugar, where the vicinal anomeric and C2 positions are decorated by azido and (thio)ureido groups, respectively. This double functionalization leads to an inherently chiral core incorporating the versatile azido and (thio)ureido linkages prone to further manipulation. The latter also provides a structural element for hydrogen-bonded donor-acceptor (HB-DA) sites, which are of immense value in organocatalytic pursuits. A computation-aided conformational analysis unveils the landscape of available conformers and their relative stability. N-aryl (thio)ureas bearing substituents at ortho positions exist as mixtures of M- and P-atropisomeric conformers. Full article

Considering the role of phytoplankton in the functioning and health of marine systems, it is important to characterize its responses to a changing environment. The central Adriatic Sea, as a generally oligotrophic area, is a suitable environment to distinguish between regular fluctuations in phytoplankton and those caused by anthropogenic or climatic influences. This study provides a long-term perspective of phytoplankton assemblage in the central eastern Adriatic Sea, with 14 years of continuous time series data collected at two coastal and two offshore stations. The predominant phytoplankton groups were diatoms and phytoflagellates, but their proportion varied depending on the vicinity of the coast, as evidenced also by the distribution of chlorophyll a. In the coastal environment, the phytoplankton biomass was substantially higher, with a higher proportion of microphytoplankton, while small phytoplankton accounted for the majority of biomass in the offshore area. In addition, a decreasing trend in diatom abundance was observed in the coastal waters, while such trend was not so evident in the offshore area. Using a neural gas algorithm, five clusters were defined based on the contribution of the major groups. The observed increase in diversity, especially in dinoflagellates, which outnumber diatom taxa, could be a possible adaptation of dinoflagellates to the increased natural solar radiation in summer and the increased sea surface temperature. Full article

With the notable achievements attained through the implementation of steam-assisted gravity drainage (SAGD), the vertical–horizontal steam drive (VHSD) emerges as a pivotal technological advancement aimed at significantly enhancing the efficiency of thin reservoir heavy oil recovery subsequent to steam cyclic stimulation. The inclusion of nitrogen assistance has proven effective in enhancing the efficacy of gravity drainage techniques in reservoir development. However, it is noteworthy that this method has only led to improvements in approximately 50% of the well groups within the observed field. The comprehensive evaluation index of VHSD was proposed, and as the objective function, it was determined that the greatest contribution to the VHSD technique lies in oil saturation, accounting for 40% of the overall evaluations. This differs from conventional SAGD operations, where reservoir thickness serves as the primary determinant. Building upon an enhanced physical simulation similarity criterion, two comparative injection scheme experiments were conducted to explore the impact of nitrogen injection on the performance of VHSD and the characteristics of the steam chamber. Nitrogen is distributed in the vicinity of the steam chamber, leading to the formation of a dual mechanism characterized by ‘top heat insulation and lateral traction’ on the steam chamber. The lateral traction accounts for approximately 25% of the team chamber volume. Additionally, the inducement of nitrogen causes a downward displacement of crude oil, resulting in its accumulation within the high-temperature region of the steam chamber. This, in turn, enhances the contact area between the high-temperature steam and the crude oil, ultimately leading to improvement in production efficiency. Further validation of the impact of nitrogen on steam lateral traction and interlayer steam drainage within the reservoir was confirmed using Xinjiang oilfield testing. The well temperature increased from 75 °C to 130 °C. Full article

This paper uses a very effective way for surface modification of thermoplastic polymers during moulding. It is based on a grafting reaction between a thin layer of a functional polymer, deposited on a substrate in advance, and a polymer melt. In this paper, a glycol-modified polyethylene terephthalate (PETG) that was brought in contact with a polyethyleneimine layer during fused filament fabrication is investigated. The focus of this paper is the investigation of the reaction product. Grafting was realised by the formation of stable amide bonds by amidation of ester groups in the main chain of a PETG. XPS investigations revealed that the conversion of amino groups was very high, the distribution was even, and the quantity of amino groups per polyester surface area was still very high. The surface properties of the produced polyester part were mainly characterised by polyethyleneimine. The grafting was able to resist several cycles of extraction in alkaline solutions. The stability was only limited by saponification of the polyester. The degree of surface modification was dependent on the molar mass of polyethyleneimine. This could be rationalised, because grafting only occurred with the one polyethyleneimine molecule that is in close vicinity to the polyester surface when both components come in contact. Fused deposition modelling was chosen as the model process with control over each processing step. However, any other moulding process may be applied, particularly injection moulding for mass production. Full article

Swarm intelligence (SI) methods are nature-inspired metaheuristics for global optimization that exploit a coordinated stochastic search strategy by a group of agents. Particle swarm optimization (PSO) is an established SI method that has been applied successfully to the optimization of rugged high-dimensional likelihood functions, a problem that represents the main bottleneck across a variety of gravitational wave (GW) data analysis challenges. We present results from the first application of PSO to one of the most difficult of these challenges, namely the search for the Extreme Mass Ratio Inspiral (EMRI) in data from future spaceborne GW detectors such as LISA, Taiji, or Tianqin. We use the standard Generalized Likelihood Ratio Test formalism, with the minimal use of restrictive approximations, to search 6 months of simulated LISA data and quantify the search depth, signal-to-noise ratio (SNR), and breadth, within the ranges of the EMRI parameters, that PSO can handle. Our results demonstrate that a PSO-based EMRI search is successful for a search region ranging over ≳10σ for the majority of parameters and ≳200σ for one, with $\sigma$ being the SNR-dependent Cramer–Rao lower bound on the parameter estimation error and $30\le \mathrm{SNR}\le 50$. This is in the vicinity of the search ranges that the current hierarchical schemes can identify. Directions for future improvement, including computational bottlenecks to be overcome, are identified. Full article

This study examined computed tomography findings in patients with cerebrovascular disease and determined predictors for falls. Images of the head were divided into 13 regions, and the relationships between computed tomography findings and the presence or absence of falls were investigated. A total of 138 patients with cerebrovascular disease (66% men, aged 73.8 ± 9.6 years) were included. A comparison between the fall and non-fall groups revealed a significant difference in the total functional independence measure scores and imaging findings at admission. Logistic regression analysis showed that the thalamus (p < 0.001), periventricular lucency (p < 0.001), lateral hemisphere room enlargement (p < 0.05), and age (p < 0.05) were related to the presence or absence of falls. For the 42 patients with cerebral hemorrhage, the thalamus (p < 0.01), periventricular lucency (p < 0.05), lateral ventricle vicinity (p < 0.05), and posterior limb of the internal capsule (p < 0.05) were extracted as factors related to the presence or absence of falls. For the 96 patients with cerebral infarction, the thalamus (p < 0.001), periventricular lucency (p < 0.01), and anterior limb of the internal capsule (p < 0.05) were extracted as factors related to the presence or absence of falls. This study found a relationship between the thalamus, lateral ventricle enlargement, periventricular lucency, and falls. Fall prognosis can potentially be predicted from computed tomography findings at admission. Full article

Favipiravir (6-fluoro-3-hydroxypyrazine-2-carboxamide, FPV), an active pharmaceutical component of the drug discovered and registered in March 2014 in Japan under the name Avigan, with an indication for pandemic influenza, has been studied. The study of this compound was prompted by the idea that effective processes of recognition and binding of FPV to the nucleic acid are affected predominantly by the propensity to form intra- and intermolecular interactions. Three nuclear quadrupole resonance experimental techniques, namely ¹H-¹⁴N cross-relaxation, multiple frequency sweeps, and two-frequency irradiation, followed by solid-state computational modelling (density functional theory supplemented by the quantum theory of atoms in molecules, 3D Hirshfeld Surfaces, and reduced density gradient) approaches were applied. The complete NQR spectrum consisting of nine lines indicating the presence of three chemically inequivalent nitrogen sites in the FPV molecule was detected, and the assignment of lines to particular sites was performed. The description of the nearest vicinity of all three nitrogen atoms was used to characterize the nature of the intermolecular interactions from the perspective of the local single atoms and to draw some conclusions on the nature of the interactions required for effective recognition and binding. The propensity to form the electrostatic N−H···O, N−H···N, and C−H···O intermolecular hydrogen bonds competitive with two intramolecular hydrogen bonds, strong O−H···O and very weak N−H···N, closing the 5-member ring and stiffening the structure, as well as π···π and F···F dispersive interactions, were analysed in detail. The hypothesis regarding the similarity of the interaction pattern in the solid and the RNA template was verified. It was discovered that the -NH₂ group in the crystal participates in intermolecular hydrogen bonds N–H···N and N–H···O, in the precatalytic state only in N–H···O, while in the active state in N–H···N and N–H···O hydrogen bonds, which is of importance to link FVP to the RNA template. Our study elucidates the binding modes of FVP (in crystal, precatalytic, and active forms) in detail and should guide the design of more potent analogues targeting SARS-CoV-2. Strong direct binding of FVP-RTP to both the active site and cofactor discovered by us suggests a possible alternative, allosteric mechanism of FVP action, which may explain the scattering of the results of clinical trials or the synergistic effect observed in combined treatment against SARS-CoV-2. Full article

We previously reported that Lys175 in the region of the active site of chymotrypsin (Csin) could be site-selectively modified by using an N-hydroxy succinimide (NHS) ester of the peptidyl derivative containing 1-amino-2-ethylphenylphosphonate diphenyl ester [NHS-Suc-Ala-Ala-Phe^P(OPh)₂]. In this study, the Lys175-selective modification method was expanded to incorporate functional groups into Lys 175 in Csin. Two types of peptidyl phosphonate derivatives with the dansyl group (Dan) as a functional molecule, Dan-β-Ala-[Asp(NHS) or Glu(NHS)]-Ala-Ala-(R)-Phe^P(OPh)₂ (DanD and DanE, respectively), were synthesized, and their action was evaluated when modifying Lys175 in Csin. Ion-exchange chromatography (IEC), fluorescence spectroscopy, and LC-MS/MS were used to analyze the products from the reaction of Csin with DanD or DanE. By IEC and LC-MS/MS, the results showed that DanE reacted with Csin more effectively than DanD to produce the modified Csin (DanMCsin) bearing Dan at Lys175. DanMCsin exhibited an enzymatic activity corresponding to 1/120 of Csin against Suc-Ala-Ala-Phe-pNA. In addition, an effect of Lys175 modification on the access of the proteinaceous Bowman–Birk inhibitor to the active site of DanMCsin was investigated. In conclusion, by using a peptidyl derivative containing 1-amino-2-ethylphenylphosphonate diphenyl ester, we demonstrated that a functional group could be incorporated into Lys175 in Csin. Full article

Alginate–gelatin hydrogels mimicking extracellular matrix (ECM) of soft tissues have been generated by static–dynamic double crosslinking, allowing fine control over the physical and chemical properties. Dynamic crosslinking provides self-healing and injectability attributes to the hydrogel and promotes cell migration and proliferation, while the static network improves stability. The static crosslinking was performed by enzymatic coupling of the tyrosine residues of gelatin with tyramine residues inserted in the alginate backbone, catalyzed by horseradish peroxidase (HRP). The dynamic crosslinking was obtained by functionalizing alginate with 3-aminophenylboronic acid which generates a reversible bond with the vicinal hydroxyl groups of the alginate chains. Varying the ratio of alginate and gelatin, hydrogels with different properties were obtained, and the most suitable for 3D soft tissue model development with a 2.5:1 alginate:gelatin molar ratio was selected. The selected hydrogel was characterized with a swelling test, rheology test, self-healing test and by cytotoxicity, and the formulation resulted in transparent, reproducible, varying biomaterial batch, with a fast gelation time and cell biocompatibility. It is able to modulate the loss of the inner structure stability for a longer time with respect to the formulation made with only covalent enzymatic crosslinking, and shows self-healing properties. Full article

Geoheritage studies have different perspectives, among which treatment of geological features in relation to particular areas and settlements seems to be promising for better local planning and tourism organization. The small town of Guzeripl in the Western Caucasus (southwestern Russia) experiences tourism-triggered development. Five localities, which are parts of two earlier established geosites, are found directly in this settlement and in its vicinity. They show representative siliciclastic deposits dominated by shales, which accumulated on the deep bottom of the Caucasian Sea in the Early Middle Jurassic. New field investigations allowed for the collection of information regarding the improvement of the geological knowledge of this study area and the reconsideration of its geoheritage in relation to the settlement’s needs. Particularly, the tentative approach for the functional assessment of the localities was proposed and applied. It is established that the localities represent not only deep-marine siliciclastic deposits, trace fossils, and specific palaeoenvironment, but also the structural elements (anticline, syncline, and fault) of the complex deformed domain. They differ by functional value, with two of the most valuable localities directly in Guzeripl, and all of them can be employed for the settlements’ needs. Geoscientists, guided student groups, and geotourists can choose Guzeripl to collect new data, train, and for new impressions. Importantly, geotourism based on the considered localities can diversify the experience of visitors, and it can be combined with and facilitated by ecotourist activities already offered by the Caucasus State Nature Biosphere Reserve, which is famous for its natural heritage. The study area focuses on the spatial distribution of geoheritage relatively to the touristic patterns. Full article