Influence of Aging on the Flexural Strength of PLA and PLA-X 3D-Printed Materials.

The three-point bending test is a valuable method for evaluating the mechanical properties of 3D-printed biomaterials, which can be used in various applications. The use of 3D printing in specimen preparation enables precise control over material composition and microstructure, facilitating the investigation of different printing parameters and advanced materials. The traditional approach to analyzing the mechanical properties of a material using a three-point bending test has the disadvantage that it provides only global information about the material's behavior. This means that it does not provide detailed insight into the local strain distribution within the material. However, the 2D Digital Image Correlation (DIC) method offers additional insight, especially in terms of strain localization. DIC is an optical technique that measures full-field displacements and strains on the surface of a sample. PLA and enhanced PLA-X material were utilized to create three-point bending samples. The aim of this paper was to analyze and compare the influence of aging on the mechanical properties of PLA and enhanced PLA-X materials using three-point bending coupled with the DIC method. The results showed statistically significant differences between the PLA and PLA-X, for both the new and aged materials. The aged PLA samples had the highest average value of maximal force around 68 N, which was an increase of 8.8% compared to the new PLA samples. On the other hand, the aged PLA-X material had an increase of 7.7% in the average maximal force compared to the new PLA-X samples. When comparing the two materials, the PLA samples had higher maximal force values, 6.2% for the new samples, and 7.3% for the aged samples. The DIC results showed that both the new PLA and PLA-X samples endured higher strain values at Points 1 and 2 than the aged ones, except for the aged PLA-X sample at Point 2, where the new sample had higher strain values. However, for the first 5 min of the experiment, both materials exhibited identical behavior, after which point significant differences started to occur for both materials, as well as at Points 1 and 2. A more profound comprehension of the biomechanical characteristics of both PLA and PLA-X material is essential to enhance the knowledge for potential biomedical applications. The DIC method was found to be a powerful tool for analyzing the deformation and failure behavior of samples and for complementing the traditional approach to material testing.

Exploring fullerene derivatives for optoelectronic applications: synthesis and characterization study.

In this study, we conducted a comprehensive investigation of newly synthesized fullerene derivatives developed for potential application in perovskite solar cells (PSCs). We explored three novel dihydrofuran-fused C60 fullerene derivatives (13, 14, and 15) that were specifically designed to enhance solubility and interaction with the substrate, fluorine-doped tin oxide (FTO). A comparative analysis was performed, with reference to the widely used phenyl-C61-butyric acid methyl ester (PCBM) and compound 12, from which 13, 14, and 15 are derived, to assess the impact of sugar units on materials properties. The synthesized compounds demonstrated significant solubility in common organic solvents, a critical factor in their potential application in wet-processed PSCs. Our investigation included electrochemical property analysis, thin film deposition, surface characterization, and electrochemical impedance spectroscopy (EIS). EIS measurements unveiled key insights into charge transfer properties at the electrode/electrolyte interface, making the compounds attractive candidates for electron transport layers (ETLs) in PSCs.

Enzymatic functionalization of liquid phase exfoliated graphene using horseradish peroxidase and laccase.

We present a novel approach for the enzymatic functionalization of graphene, utilizing horseradish peroxidase (HPO) and laccase (LC) from Trametes versicolor. This study demonstrates, for the first time, the covalent modification of non-homogeneous graphene with a low surface-to-volume ratio, both in solution and on solid support. Through thermogravimetry analysis, we estimate the degree of functionalization to be 11% with HPO and 4% with LC, attributed to the varying redox potentials of the enzymes. This work highlights the potential of enzymatic reactions for tailored functionalization of graphene under mild conditions.

Sugar-Bridged Fullerene Dumbbells and Their Interaction with the [10]Cycloparaphenylene Nanoring.

The synthesis and characterization of four dumbbell-shaped fullerene molecules connected by isosorbide and isomannide moieties is presented. Additionally, their electrochemical behavior and their ability to form complexes with [10]cycloparaphenylene ([10]CPP) were investigated. The cyclic voltammetry (CV) results of the fullerene dumbbells demonstrate a high electron affinity, indicating their strong interaction with electron-donating counterparts such as carbon nanorings, which possess complementary charge and shape properties. To study the thermodynamic and kinetic parameters of complexation, isothermal titration calorimetry (ITC) was employed. NMR titration experiments provided further insights into the binding stoichiometries. Two distinct approaches were utilized to create bridged structures: one based on cyclopropane and the other based on furan. Regardless of the type of linker used, all derivatives formed conventional 2 : 1 complexes denoted as [10]CPP2 ⊃C60derivative . However, the methano-dumbbell molecules exhibited distinct binding behavior, resulting in the formation of mono- and bis-pseudorotaxanes, as well as oligomers (polymers). The formation of linear polymers holds significant potential for applications in solar energy conversion processes.

Covalent and non-covalent chemistry of 2D black phosphorus.

The post-graphene era is undoubtedly marked by two-dimensional (2D) sheet polymers, such as black phosphorus (BP). This emerging material has a fascinating structure and outstanding electronic properties and has been postulated for a plethora of applications. The need to circumvent the pronounced oxophilicity of P atoms has dominated the research on this material in recent years, with the objective of finding the most effective method to improve its environmental stability. When it comes to chemical functionalization, the few approaches reported so far involve some drawbacks such as low degree of addition and low production ability. This review presents the concepts and strategies of our studies on the chemical functionalization of BP, both non-covalent and covalent, emphazising the current synthetic challenges. Moreover, we also provide some effective pathways for the chemical activation of the unreactive basal plane, the identification of the effective binding strategies, and the concept to overcome hurdles associated with characterization tools. This work will provide fundamental insights into the controlled chemical functionalization and characterization of BP, fostering the research on this appealing 2D material.

Differential Polarization Imaging of Plant Cells. Mapping the Anisotropy of Cell Walls and Chloroplasts.

Modern light microscopy imaging techniques have substantially advanced our knowledge about the ultrastructure of plant cells and their organelles. Laser-scanning microscopy and digital light microscopy imaging techniques, in general-in addition to their high sensitivity, fast data acquisition, and great versatility of 2D-4D image analyses-also opened the technical possibilities to combine microscopy imaging with spectroscopic measurements. In this review, we focus our attention on differential polarization (DP) imaging techniques and on their applications on plant cell walls and chloroplasts, and show how these techniques provided unique and quantitative information on the anisotropic molecular organization of plant cell constituents: (i) We briefly describe how laser-scanning microscopes (LSMs) and the enhanced-resolution Re-scan Confocal Microscope (RCM of Confocal.nl Ltd. Amsterdam, Netherlands) can be equipped with DP attachments-making them capable of measuring different polarization spectroscopy parameters, parallel with the 'conventional' intensity imaging. (ii) We show examples of different faces of the strong anisotropic molecular organization of chloroplast thylakoid membranes. (iii) We illustrate the use of DP imaging of cell walls from a variety of wood samples and demonstrate the use of quantitative analysis. (iv) Finally, we outline the perspectives of further technical developments of micro-spectropolarimetry imaging and its use in plant cell studies.

Cell wall response to UV radiation in needles of Picea omorika.

The UV-B represents the minor fraction of the solar spectrum, while UV-C is not contained in natural solar radiation, but both radiation types can cause damaging effects in plants. Cell walls (CWs) are one of the targets for external stressors. Juvenile P. omorika trees were treated either with 21 day-high doses UV-B or with 7 day- UV-C in open-top chambers. Using spectroscopic and biochemical techniques, it was shown that the response to UV radiation includes numerous modifications in needle CW structure: relative content of xylan, xyloglucan, lignin and cellulose decreased; cellulose crystallinity changed; yield of lignin monomers with stronger connection of CC in side chain with the ring increased; re-distribution of inter- and intra-polymer H-bonds occurred. The recovery was mediated by an increase in the activities and changes in isoform profiles of CW bound covalent peroxidases (POD) and polyphenol oxidases (PO) (UV-B), and ionic POD and covalent PO (UV-C). A connection between activities of specific POD/PO isoforms and phenolic species (m- and p-coumaric acid, pinoresinol and cinnamic acid derivatives) was demonstrated, and supported by changes in the sRNA profile. In vivo fluorometry showed phenolics accumulation in needle epidermal CWs. These results imply transversal connections between polymers and changed mechanical properties of needle CW as a response to UV. The CW alterations enabled maintenance of physiological functions, as indicated by the preserved chlorophyll content and/or organization. The current study provides evidence that in conifers, needle CW response to both UV-B and UV-C includes biochemical modifications and structural remodeling.

Selective formation of dihydrofuran fused [60] fullerene derivatives by TEMPO mediated [3 + 2] cycloaddition of medium chain ß-keto esters to C60.

In this study, ß-keto esters as readily available bio-based building blocks were used to decorate the C60 sphere. Generally, cyclopropanated fullerene derivatives are obtained by the standard Bingel-Hirsch procedure. Herein, omitting the iodine from the reaction mixture and adding TEMPO afforded dihydrofuran fused C60 fullerene derivatives. The mechanism of the reaction shifted from nucleophilic aliphatic substitution to oxidative [3 + 2] cycloaddition via fullerenyl cations as an intermediate. This mechanism is proposed based on a series of control experiments with radical scavengers. Therefore, dihydrofuran-fused C60 derivatives were selectively obtained in good yields and their structures were established based on UV-Vis, IR, NMR spectroscopy and mass spectrometry. The electrochemical properties of the synthesized compounds were investigated by cyclic voltammetry. DFT calculations were performed in order to investigate the difference in stability, electronic properties and π-electron delocalization between methano and furano fullerenes.

Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts.

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31 P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.

Does beauty capture the eye, even if it's not (overtly) adaptive? A comparative eye-tracking study of spontaneous attention and visual preference with VAST abstract art.

Studies have routinely shown that individuals spend more time spontaneously looking at people or at mimetic scenes that they subsequently judge to be more aesthetically appealing. This "beauty demands longer looks" phenomenon is typically explained by biological relevance, personal utility, or other survival factors, with visual attraction often driven by structural features (symmetry, texture), which may signify fitness and to which most humans tend to respond similarly. However, what of objects that have less overtly adaptive relevance? Here, we consider whether people also look longer at abstract art with little associative/mimetic content that they subsequently rate for higher aesthetic appeal. We employed the "Visual aesthetic sensitivity test" (VAST), which consists of pairs of matched abstract designs with one example of each pair argued to be objectively 'aesthetically better' in regards to low-level features, thus offering a potential contrast between 'objective' (physical feature-based) and 'subjective' (personal taste-based) assessments. Participants (29 women) first looked at image pairs without a specific task and then in three follow-up blocks indicated their preference within the pairs and rated the individual images for liking and for presumed ratings by an art expert. More preferred designs were looked at longer. However, longer looking only occurred in line with participants' subjective tastes. This suggests a general correlation of attention and visual beauty, which-in abstract art-may nonetheless be related to features that are not identified by experts as more generally appealing and thus may not directly map to other (more utility-related) stimuli types.

SR-FTIR spectro-microscopic interaction study of biochemical changes in HeLa cells induced by Levan-C60, Pullulan-C60, and their cholesterol-derivatives.

Objects of the present study are improved fullerene C60 drug carrier properties trough encapsulation by microbial polysaccharides, levan (LEV), pullulan (PUL), and their hydrophobized cholesterol-derivatives (CHL and CHP), that show better interaction with cancer cells. The zeta potential, polydispersity index, and the diameter of particles were determined, and their cytotoxicity against three cancer cell lines were tested. Biochemical changes in HeLa cells are analyzed by synchrotron radiation (SR) FTIR spectro-microscopy combined with the principal component analysis (PCA). The most significant changes occur in HeLa cells treated with LEV-C60 and correspond to the changes in the protein region, i.e. Amide I band, and the changes in the structure of lipid bodies and membrane fluidity are evident. The highest cytotoxicity was also induced by LEV-C60. In HeLa cells, cytotoxicity could not be strictly associated with biochemical changes in lipids, proteins and nucleic acids, but these findings are significant contribution to the study of the mechanism of interaction of C60-based nanoparticles with cellular biomolecules. In conclusion, LEV, PUL, CHL, and CHP enhanced fullerene C60 potential to be used as target drug delivery system with the ability to induce specific intracellular changes in HeLa cancer cells.

Biochemical and histological characterization of succulent plant Tacitus bellus response to Fusarium verticillioides infection in vitro.

We present changes in Tacitus bellus antioxidative system that specifically correspond to subsequent phases of hemibiotroph Fusarium verticillioides infection revealed by histological analysis. T. bellus response to spore germination 6 h post inoculation (hpi), manifested as first oxidative burst, was characterized by transient decrease in malondialdehyde (MDA) content, transient increase in catalase (CAT), low level of superoxide dismutase (SOD) and peroxidase (POD) activity, as well as with transient decrease in total antioxidant capacity (TAC), total phenol content (TPC) and phenylalanine ammonium lyase activity (PAL), and no changes in polyphenol oxidase (PPO) activity, or phenolic profile. During the biotrophic phase of F. verticillioides infection, characterized by hyphae spread intercellularly in epidermal and mesophyll tissue, the host antioxidative system was suppressed. The transition to necrotrophic phase of F. verticillioides infection (inter- and intracellular colonization and sporulation), occurred 3-4 days post inoculation (dpi). During the necrotrophic phase, 5-7 dpi, slowed progression of colonization of T. bellus mesophyll cells occurred and it coincided with sharp increase in MDA content and CAT, SOD and POD activities, but the drop in TAC, TPC content, and PPO activity, as well as the production of phytotoxin fusaric acid. Presented results add to the knowledge of events and mechanisms related to the transition from biotrophy to necrotrophy in F. verticillioides.

Phosphorus homeostasis in Populus alba L. under excess phosphate conditions, assessed by 31P nuclear magnetic resonance spectroscopy and X-ray microfluorescence.

The phosphates (Pi) are nowadays recognized as pollutants. We studied the effect of Pi (0.625-12.500 mM KH2PO4) in the culture medium on in vitro grown 2-month-old Populus alba trees. The levels of sugar phosphates and vacuolar and cytoplasmic Pi in cell compartments of roots and stems were determined using 31P NMR, while tissue-specific micro- and macroelements mapping on stem cross-sections were performed using synchrotron-based X-ray microfluorescence. Plants grown on 0.625 mM Pi (MS/2 medium) showed a survival rate of 70%. With the increase in Pi concentrations up to 6.250 mM, plant growth and survival increased, without changes in total P content per mass or in the levels of cytoplasmic and vacuolar phosphates, in both stems and roots, while the levels of Fe, Cu, Zn, Ca and Mn in stems increased. Further increase in Pi to 9.375 and 12.500 mM in the medium resulted in inhibited growth comparable with plants grown on MS/2, with the increase in total P content per mass up to 50%, in both stems and roots, but with no changes in cytoplasmic and vacuolar phosphates; 12.500 mM Pi affected even plant survival (70%) and thus might be considered as mildly toxic. 31P NMR results indicate that the high tolerance of P. alba to increased Pi could result from its ability to maintain an intracellular P homeostasis, despite P accumulation up to 50%, in both stems and roots, indicating P. alba as a promising wood species for dendroremediation.

3D Digital Image Correlation Analysis of the Shrinkage Strain in Four Dual Cure Composite Cements.

The introduction of resin-based cements and an adhesive-bonding system in daily dental practice has given the opportunity to increase the retention of previously conventional cemented restorations and the optimal results in esthetic. This experimental study employed the 3D Digital Image Correlation Method (3D-DIC) for detecting shrinkage strain in four dual cured composite cements. The aim was to visualize measure, analyze, and compare strain fields in four resin-based cements using the 3D-DIC method. A total of 72 samples were divided into 4 groups considering variations in sample types, diameter, and thickness. Four types of composite cements: RelyX U200 (3 M ESPE, St. Paul, MN, USA), MaxCem Elite (Kerr, Orange, CA, USA), Multilink Automix (Ivoclar Vivadent, Schaan, Liechtenstein), and SeT PP (SDI, Australia) were used. Each type had diameters of 3 mm, 4 mm, and 5 mm, respectively, combined with two different values of thickness: 1 mm and 2 mm. Thickness had an important role on strain detected in all tested materials showing higher strain in samples with 2 mm thickness compared to 1 mm samples. Shrinkage strain values were the highest in Set PP samples indicated the possibility of undesirable de-bonding.

Interaction of Carbohydrate Coated Cerium-Oxide Nanoparticles with Wheat and Pea: Stress Induction Potential and Effect on Development.

: Reports about the influence of cerium-oxide nanoparticles (nCeO2) on plants are contradictory due to their positive and negative effects on plants. Surface modification may affect the interaction of nCeO2 with the environment, and hence its availability to plants. In this study, the uncoated and glucose-, levan-, and pullulan-coated nCeO2 were synthesized and characterized. The aim was to determine whether nontoxic carbohydrates alter the effect of nCeO2 on the seed germination, plant growth, and metabolism of wheat and pea. We applied 200 mgL-1 of nCeO2 on plants during germination (Ger treatment) or three week-growth (Gro treatment) in hydroponics. The plant response to nCeO2 was studied by measuring changes in Ce concentration, total antioxidative activity (TAA), total phenolic content (TPC), and phenolic profile. Our results generally revealed higher Ce concentration in plants after the treatment with coated nanoparticles compared to uncoated ones. Considering all obtained results, Ger treatment had a stronger impact on the later stages of plant development than Gro treatment. The Ger treatment had a stronger impact on TPC and plant elongation, whereas Gro treatment affected more TAA and phenolic profile. Among nanoparticles, levan-coated nCeO2 had the strongest and positive impact on tested plants. Wheat showed higher sensitivity to all treatments.

Effects of liking on visual attention in faces and paintings.

The visual aesthetics of an object increases visual attention towards the object. It is argued that this relation between liking and attention is an evolutionary adaptation in sexual and natural selection. If this is the case, we would expect this relation to be domain specific, and thus, stronger for biological than for non-biological objects. To test this hypothesis, we conducted two eye-tracking studies, in which we compared the relation between liking and gaze patterns in images of biological (faces) and non-biological (paintings) stimuli. In Study 1, we presented randomly combined image pairs for 20 s in a free-viewing paradigm. Participants then selected the image they liked more in a 2-AFC task and rated the liking of each image on a Likert-scale. In Study 2, we employed the same paradigm but this time, images were combined based on pre-rated liking to ensure that images in each pair were clearly different. In both studies, we found a strong relation between liking and visual attention. Against our expectations, these effects were of similar magnitude for faces as for paintings. We conclude that the relation between liking and visual attention is not limited to biological objects but that its effects are domain general. The evolutionary function of the relation between liking and visual attention might stem from evolutionary adaptations, nonetheless, this link seems to be a rather basic phenomenon that applies across domains.

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus.

The chemical bulk reductive covalent functionalization of thin-layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes.

How relationship status and sociosexual orientation influence the link between facial attractiveness and visual attention.

Facial attractiveness captures and binds visual attention, thus affecting visual exploration of our environment. It is often argued that this effect on attention has evolutionary functions related to mating. Although plausible, such perspectives have been challenged by recent behavioral and eye-tracking studies, which have shown that the effect on attention is moderated by various sex- and goal-related variables such as sexual orientation. In the present study, we examined how relationship status and sociosexual orientation moderate the link between attractiveness and visual attention. We hypothesized that attractiveness leads to longer looks and that being single as well as being more sociosexually unrestricted, enhances the effect of attractiveness. Using an eye-tracking free-viewing paradigm, we tested 150 heterosexual men and women looking at images of urban real-world scenes depicting two people differing in facial attractiveness. Participants additionally provided attractiveness ratings of all stimuli. We analyzed the correlations between how long faces were looked at and participants' ratings of attractiveness and found that more attractive faces-especially of the other sex-were looked at longer. We also found that more sociosexually unrestricted participants who were single had the highest attractiveness-attention correlation. Our results show that evolutionary predictions cannot fully explain the attractiveness-attention correlation; perceiver characteristics and motives moderate this relationship.

Understanding the mechanisms behind the sexualized-body inversion hypothesis: The role of asymmetry and attention biases.

A controversial hypothesis, named the Sexualized Body Inversion Hypothesis (SBIH), claims similar visual processing of sexually objectified women (i.e., with a focus on the sexual body parts) and inanimate objects as indicated by an absence of the inversion effect for both type of stimuli. The current study aims at shedding light into the mechanisms behind the SBIH in a series of 4 experiments. Using a modified version of Bernard et al.´s (2012) visual-matching task, first we tested the core assumption of the SBIH, namely that a similar processing style occurs for sexualized human bodies and objects. In Experiments 1 and 2 a non-sexualized (personalized) condition plus two object-control conditions (mannequins, and houses) were included in the experimental design. Results showed an inversion effect for images of personalized women and mannequins, but not for sexualized women and houses. Second, we explored whether this effect was driven by differences in stimulus asymmetry, by testing the mediating and moderating role of this visual feature. In Experiment 3, we provided the first evidence that not only the sexual attributes of the images but also additional perceptual features of the stimuli, such as their asymmetry, played a moderating role in shaping the inversion effect. Lastly, we investigated the strategy adopted in the visual-matching task by tracking eye movements of the participants. Results of Experiment 4 suggest an association between a specific pattern of visual exploration of the images and the presence of the inversion effect. Findings are discussed with respect to the literature on sexual objectification.

Cycloaddition Reactions of Azomethine Ylides and 1,3-Dienes on the C2v-Symmetrical Pentakisadduct of C60.

The reactivity of the C2v-symmetric pentakisadduct of C60 with azomethine ylides and conjugated dienes was studied experimentally and computationally. This derivative possesses four [6,6] double bonds, each with unique electrophilicity. The Diels-Alder reaction studied is a regiospecific, kinetically and thermodynamically guided [4 + 2] process producing [5:1]-hexaadducts with an octahedral addition pattern. The kinetically controlled Prato reaction gives a mixture of regioisomeric [5:1]-hexaadducts. The synthesis of geometrically well-defined supramolecular architectures may benefit from these new types of highly functionalized [5:1]-hexaadducts.