Multiscale Modeling Approach to Understand Mechanism of Deposit Control by Sulfonate-Based Lubricant Detergents.

Protecting the material surfaces from deposits and insoluble sludge particles extends the engine life and reduces waste. Lubricant detergents in engine oils are essential additive technologies that prevent deposit formation in internal combustion engines. In this study, the effect of sulfonate detergent on deposit formation in a passenger car engine is investigated with experimental and multiscale molecular modeling methods to present a unified approach. First principles density-functional theory calculations, statistical sampling methods, all-atom molecular dynamics simulations, and coarse-grained simulations are examined to elucidate deposit control mechanism of sulfonate detergents. Analysis of the results reveals that sludge particles in the drain oil are similar in structure to piston deposits, and they might be the precursors of the piston deposits. Main factor for controlling the sludge particle deposition is the prevention of their colloidal aggregation at the microscale in the base oil matrix. Aggregation can be mitigated by the intercalation of detergent polar groups between the particles. This is followed by the extension of hydrophobic tails into the oil phase, which decreases further aggregation via formation of a repulsive layer.

MOLECULAR MECHANISM OF PHYSICAL AND MECHANICAL IMPROVEMENT IN GRAPHENE/GRAPHENE OXIDE-EPOXY COMPOSITE MATERIALS.

The performance provided by graphene (Gr) and graphene oxide (GO) additives can be improved by achieving strong adhesion and uniform dispersion in the epoxy resin matrix. In this study, molecular modeling and simulation of DGEBA/DETA based epoxy nanocomposites containing Gr and GO additives were performed. Density functional theory and molecular dynamics simulations were used to investigate interfacial interaction energies and Young's Modulus. Improvement in the interaction energies was studied by controlling the epoxy:hardener ratio, type and the number of oxygen-containing functional groups on the GO, the mass percentage of Gr/GO filler in the epoxy matrix, size and dispersion of GO in the cell. It was demonstrated that functional groups with up to 10% oxygen content in GO significantly increase interfacial interaction energy for large size Gr/GO. Increasing DETA type amine ratio in the preparation of epoxy polymers increases the interaction energy for high oxygen content while decreasing the interaction energy for low oxygen content in GO for small size GO with edge functional groups. The performance of material dramatically decreased even at high DETA hardener and high GO mass percentages when the aggregation factor of Gr/GO was included in simulations that explain lower Gr/GO percentages in the experimental studies.

Design, Synthesis, and Theoretical Studies on the Benzoxadiazole and Thienopyrrole Containing Conjugated Random Copolymers for Organic Solar Cell Applications.

In this study, six different donor-π-acceptor1-π-donor-acceptor2 type random co-polymers containing benzodithiophene as a donor, benzooxadiazole (BO), and thieno[3,4-c]pyrrole-4,6-dione (TPD) as acceptor, have been synthesized and characterized. In addition to the acceptor core ratio at different values, the effect of aromatic bridge structures on the optical, electronic, and photovoltaic properties of six different random co-polymers is investigated by using thiophene and selenophene structures as aromatic bridge units. To investigate how the acceptor unit ratio and replacement of aromatic bridge units impact the structural, electronic, and optical properties of the polymers, density functional theory (DFT) calculations are carried out for the tetramer models. The open-circuit voltage (VOC), which is strongly correlated with the HOMO levels of the donor material, is enhanced with the increasing ratio of the TPD moiety. On the other hand, the short-circuit current (JSC), which is associated with the absorption ability of the donor material, is improved by the increasing ratio of BO moiety with the π-bridges. BO moiety dominant selenophene π-bridged co-polymer (P4) showed the best performance with a power conversion efficiency (PCE) of 6.26%, a JSC of 11.44 mA cm2, a VOC of 0.80 V, and a fill factor (FF) of 68.81%.

Effects of tDCS on emotion recognition and brain oscillations.

INTRODUCTION: Emotion recognition, the ability to interpret the emotional state of individuals by looking at their facial expressions, is essential for healthy social interactions and communication. There is limited research on the effects of tDCS on emotion recognition in the literature. This study aimed to investigate the effects of anodal stimulation of the ventromedial prefrontal cortex (vmPFC), a key region for emotion recognition from facial expressions, on emotion recognition and brain oscillations. METHOD: A single-blind randomized-controlled study was conducted with 54 healthy participants. Before and after brain stimulation emotion recognition tasks were administered and resting-state EEG were recorded. The changes in task performances and brain oscillations were analyzed using repeated-measures two-way ANOVA analysis. RESULTS: There was no significant difference in the emotion recognition tasks between groups in pre-post measurements. The changes in delta, theta, alpha, beta and gamma frequency bands in the frontal, temporal, and posterio-occipital regions, which were determined as regions of interest in resting state EEG data before and after tDCS, were compared between groups. The results showed that there was a significant difference between groups only in delta frequency before and after tDCS in the frontal and temporal regions. While an increase in delta activity was observed in the experimental group in the frontal and temporal regions, a decrease was observed in the control group. CONCLUSIONS: The tDCS may not have improved emotion recognition because it may not have had the desired effect on the vmPFC, which is in the lower part of the prefrontal lobe. The changes in EEG frequencies observed section tDCS may be similar to those seen in some pathological processes, which could explain the lack of improvement in emotion recognition. Future studies to be carried out for better understand this effect are important.

Optical Properties of Cationic Perylenediimide Nanowires in Aqueous Medium: Experimental and Computational Studies.

Cationic perylenediimide derivative, namely N,N'-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI), has been synthesized and characterized in an aqueous medium by using dynamic light scattering (DLS), X-ray diffraction (XRD), fourier-transform infrared (FTIR), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The optical absorption and fluorescence spectra of TAIPDI revealed the formation of aggregated TAIPDI nanowires in water, but not in organic solvents. In order to control the aggregation behavior, the optical properties of TAIPDI have been examined in different aqueous media, namely cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS). Furthermore, the utilization of the examined TAIPDI for constructing supramolecular donor-acceptor dyad has been achieved by combining the electron accepting TAIPDI with the electron donating 4,4'-bis (2-sulfostyryl)-biphenyl disodium salt (BSSBP). The formed supramolecular dyad TAIPDI-BSSBP through the ionic and electrostatic π-π interactions have been well examined by various spectroscopic techniques, e.g., steady-state absorption and fluorescence, cyclic voltammetry, and time-correlated single-photon counting (TCSPC), and first principle computational chemistry methods. Experimental results suggested the occurring of intra-supramolecular electron transfer from BSSBP to TAIPDI with rate constant and efficiency of 4.76 × 109 s-1 and 0.95, respectively. The ease of construction, absorption in the UV-Visible region, and fast electron transfer process render the supramolecular TAIPDI-BSSBP complex as a donor-acceptor material for optoelectronic devices.

Depression affects working memory performance: A Functional Near Infrared Spectroscopy (fNIRS) Study.

Depression is a complex disorder that can be caused by psychosocial and biological conditions, and it not only affects to emotional life, but also cognitive functions, specifically the executive functions, attention, psychomotor speed, and memory. Some results of the studies in the literature show that depressed individuals perform worse on cognitive tasks than healthy individuals, while others indicate that there is no difference. Moreover, there is also no consensus about the depressed people brain functionalities. We aimed to compare the people who has high and low depression score measured with Beck Depression Inventory in terms of their working memory performance by using n-back paradigm and their brain activity by using optical imaging with this study. The age of lower BDI group (n = 11) is 23,9 ± 3,04 and higher BDI group (n = 23) is 22,2 + 2,28. The fNIRS were recorded from each subject while neutral words-faces and emotional words-faces are given to the subjects in the visuospatial 2-back WM task. There are no significant differences between the two groups behaviorally during the working memory performance, however, the high BDI group's PFC activation in right hemisphere is founded to be higher than the lower group. Our findings support the literature who is claiming the difference brain activity in depressed brain but not cognitive performance. Though, the small group size and the task difficulty (easy) could be the explanation of the behavioral results.

Organic Charge Transfer Cocrystals as Additives for Dissipation of Contact Charges on Polymers.

Common polymers can accumulate surface charges through contact, a phenomenon known since ancient times. This charge accumulation can have detrimental consequences in industry. It causes accidents and yields enormous economic losses. Many empirical methods have been developed to prevent the problems caused by charge accumulation. However, a general chemical approach is still missing in the literature since the charge accumulation and discharging mechanisms have not been completely clarified. The current practice to achieve charge mitigation is to increase materials conductivity by high doping of conductive additives. A recent study showed that using photoexcitation of some organic dyes, charge decay can be started remotely, and the minute amount of additive does not change the material's conductivity. Here, we show the contact charging and charge decay behavior of polydimethylsiloxane doped with a series of organic charge transfer cocrystals (CTC) of TCNQ acceptor and substituted pyrene donors (CTC-PDMS). The results show that the CTC-PDMS are antistatic, and the discharging propensity of the composites follows the calculated charge transfer degree of the complexes. On the other hand, the CTC-PDMS are still insulators, as shown by their high surface resistivities. Kelvin probe force microscopy images of the contact-charged and discharged samples show a quick potential decay in CTC domains upon illumination. Combined with the fast overall decay observed, the antistatic behavior in these insulators can be attributed to an electron transfer between the mechanoions in the polymer and the CTC frontier orbitals. We believe our results will help with the general understanding of the molecular mechanism of contact charging and discharging and help develop insulator antistatics.

Design Principles for the Acceptor Units in Donor-Acceptor Conjugated Polymers.

More than 50 different acceptor units from the experimental literature have been modeled, analyzed, and compared by using the computationally extracted data from the density functional theory (DFT) perspective for tetramer structures in the form of (D-B-A-B)4 (D, donor; A, acceptor; B, bridge) with fixed donor and bridge units. Comparison of dihedral angle between acceptor, donor, and bridge units, bond order, and hyperpolarizability reveals that these three structural properties have a dominant effect on the frontier electronic energy levels of the acceptor units. Systematic investigation of the structural properties has demonstrated the band gap energy dependency of the acceptor units on the planarity, conjugation, and the electron delocalization. Substitution effect, morphological alternation, and insertion of π-electron deficient atoms in A unit have also an important role to determine physical properties of the donor-acceptor conjugated polymers. This benchmark study will be beneficial for the band gap engineering and molecular design of the donor-acceptor copolymers using different acceptor units for the organic electronic applications.

Organocatalytic enantioselective synthesis of dihydronaphthofurans and dihydrobenzofurans: reaction development and insights into stereoselectivity.

Squaramide/cinchona alkaloid-derived bifunctional organocatalysts are in high demand in asymmetric transformations. Bifunctional quinine-derived sterically encumbered squaramide (H-bond donor) organocatalysts were used to catalyze the asymmetric Friedel-Crafts/SN2 type domino reaction of (Z)-α-bromonitroalkenes and α/ß-naphthols and phenol derivatives to generate enantiomerically enriched dihydronaphthofuran (DHN) and dihydrobenzofuran (DHB) derivatives, respectively. The target adducts were obtained in up to >99% ee under mild conditions with a relatively low catalyst loading (5 mol%) compared to the methods known in the literature. In addition, density functional theory (DFT) calculations were performed to establish a possible outcome, explaining the origin of the stereoselectivity. It was discovered that π-stacked interactions for the trans-conformation in the Friedel-Crafts step are 0.79 kcal mol-1 more stable than the cis-conformation.

Does anxiety have an impact on temporomandibular disorders? A study in a Turkish sample by using specific questionnaires.

OBJECTIVE: The aim of the study is to verify the impact of anxiety on temporomandibular disorders (TMD) by using specific questionnaires in a Turkish sample. METHODS: This survey was conducted on 292 patients with a mean age of 38.59 ± 10.38 using Helkimo index, Oral Health Impact Profile (OHIP-14), and State Trait Anxiety Inventory (STAI). Spearman Correlation and Fisher Freeman Halton analyses were used for the statistical analysis. RESULTS: There was no statistically significant difference between the Helkimo anamnestic dysfunction (HAD) levels in terms of OHIP-14 total scores or STAI state scores. There was, however, a statistically positive correlation between STAI state and OHIP-14 total values at 18.4%, a positive correlation between the STAI trait and OHIP-14 total values at 29.8%. CONCLUSION: No significant correlation was observed between OHIP-14 total scores, STAI state scores, and HAD levels. Therefore, this study did not find a significant relationship between TMDs and anxiety.

Hydrolytic Degradation of Polylactic Acid Fibers as a Function of pH and Exposure Time.

Polylactic acid (PLA) is a widely used bioresorbable polymer in medical devices owing to its biocompatibility, bioresorbability, and biodegradability. It is also considered a sustainable solution for a wide variety of other applications, including packaging. Because of its widespread use, there have been many studies evaluating this polymer. However, gaps still exist in our understanding of the hydrolytic degradation in extreme pH environments and its impact on physical and mechanical properties, especially in fibrous materials. The goal of this work is to explore the hydrolytic degradation of PLA fibers as a function of a wide range of pH values and exposure times. To complement the experimental measurements, molecular-level details were obtained using both molecular dynamics (MD) simulations with ReaxFF and density functional theory (DFT) calculations. The hydrolytic degradation of PLA fibers from both experiments and simulations was observed to have a faster rate of degradation in alkaline conditions, with 40% of strength loss of the fibers in just 25 days together with an increase in the percent crystallinity of the degraded samples. Additionally, surface erosion was observed in these PLA fibers, especially in extreme alkaline environments, in contrast to bulk erosion observed in molded PLA grafts and other materials, which is attributed to the increased crystallinity induced during the fiber spinning process. These results indicate that spun PLA fibers function in a predictable manner as a bioresorbable medical device when totally degraded at end-of-life in more alkaline conditions.

Mechanically robust hybrid hydrogels of photo-crosslinkable gelatin and laminin-mimetic peptide amphiphiles for neural induction.

Self-assembling bio-instructive materials that can provide a biomimetic tissue microenvironment with the capability to regulate cellular behaviors represent an attractive platform in regenerative medicine. Herein, we develop a hybrid neuro-instructive hydrogel that combines the properties of a photo-crosslinkable gelatin methacrylate (GelMA) and self-assembling peptide amphiphiles (PAs) bearing a laminin-derived neuro-inductive epitope (PA-GSR). Electrostatic interaction and ultraviolet light crosslinking mechanisms were combined to create dual-crosslinked hybrid hydrogels with tunable stiffness. Spectroscopic, microscopic and theoretical techniques show that the cationic PA-GSR(+) electrostatically co-assembles with the negatively charged GelMA to create weak hydrogels with hierarchically ordered microstructures, which were further photo-crosslinked to create mechanically robust hydrogels. Dynamic oscillatory rheology and micromechanical testing show that photo-crosslinking of the co-assembled GelMA and PA-GSR(+) hydrogel results in robust hydrogels displaying improved stiffness. Gene expression analysis was used to show that GelMA/PA-GSR(+) hydrogels can induce human mesenchymal stem cells (hMSCs) into neural-lineage cells and supports neural-lineage specification of neuroblast-like cells (SH-SY5Y) in a growth-factor-free manner. Also, metabolomics analysis suggests that the hydrogel alters the metabolite profiles in the cells by affecting multiple molecular pathways. This work highlights a new approach for the design of PA-based hybrid hydrogels with robust mechanical properties and biological functionalities for nerve tissue regeneration.

Three new species of Agenioideus Ashmead, 1902 and Priocnemis Schioedte, 1837 (Hymenoptera: Pompilidae) from Turkey.

Agenioideus (Mimochares) karsensis sp. nov. (female), Priocnemis (Umbripennis) diyarbakirensis sp. nov. (females and a male) and Priocnemis (Umbripennis) bingolensis sp. nov. (female) are described from eastern Turkey.

Ammonia Sensing Performance of Polyaniline-Coated Polyamide 6 Nanofibers.

To understand the properties of polyaniline (PANI), aim gas, and the interaction between them in PANI-based gas sensors and help us to design sensors with better properties, direct calculations with molecular dynamics (MD) simulations were done in this work. Polyamide 6/polyaniline (PA6/PANI) nanofiber ammonia gas sensors were studied as an example here, and the structural, morphological, and ammonia sensing properties (to 50-250 ppm ammonia) of PA6/PANI nanofibers were tested and evaluated by scanning electron microscopy, Fourier transform infrared spectroscopy, and a homemade test system. The PA6/PANI nanofibers were prepared by in situ polymerization of aniline with electrospun PA6 nanofibers as templates and hydrochloric acid (HCl) as a doping agent for PANI, and the sensors show rapid response, ideal selectivity, and acceptable repeatability. Then, complementary molecular dynamics simulations were performed to understand how ammonia molecules interact with HCl-doped PANI chains, thus providing insights into the molecular-level details of the ammonia sensing performances of this system. Results of the radial distribution functions and mean square displacement analysis of the MD simulations were consistent with the dedoping mechanism of the PANI chains.

First checklist of Tunisian sphecid wasps (Hymenoptera: Sphecidae) with new and additional records.

The first checklist of Sphecidae of Tunisia is established. It is based on literature, on examination of Tunisian specimens present in the Muséum National d'Histoire Naturelle, Paris, France), and on specimens recently collected in Tunisia. Fifty-three species and subspecies belonging to 10 genera, 3 tribes and 4 subfamilies are listed. Three species: Parapsammophila errabunda (Kohl, 1901), Eremochares luteus (Taschenberg, 1869) and Prionyx macula (Fabricius, 1804) are recorded for the first time from Tunisia.

Correlating charge and thermoelectric transport to paracrystallinity in conducting polymers.

The conceptual understanding of charge transport in conducting polymers is still ambiguous due to a wide range of paracrystallinity (disorder). Here, we advance this understanding by presenting the relationship between transport, electronic density of states and scattering parameter in conducting polymers. We show that the tail of the density of states possesses a Gaussian form confirmed by two-dimensional tight-binding model supported by Density Functional Theory and Molecular Dynamics simulations. Furthermore, by using the Boltzmann Transport Equation, we find that transport can be understood by the scattering parameter and the effective density of states. Our model aligns well with the experimental transport properties of a variety of conducting polymers; the scattering parameter affects electrical conductivity, carrier mobility, and Seebeck coefficient, while the effective density of states only affects the electrical conductivity. We hope our results advance the fundamental understanding of charge transport in conducting polymers to further enhance their performance in electronic applications.

Physical Characterization of Inclusion Complexes of Triphenyl Phosphate and Cyclodextrins in Solution.

The goal of this work is to provide physical insights into the formation and stability of inclusion complexes (ICs) in aqueous solution between cyclodextrins (CDs) and a common flame retardant, triphenyl phosphate (TPP). Quantum chemistry calculations reveal the possible energetically favorable geometries of TPP in their 1:1 IC form with α-, ß-, and γ-CDs as well as their associated complexation, conformational, and interaction energies. High-resolution mass spectrometry (MS) and tandem MS were used with electrospray ionization to study the soluble ICs formed between TPP and CDs. Successful formation of TPP ICs with both ß- and γ-CD in solution was detected in the ratio of 1:1 using high-resolution MS in the positive ion mode. Collision-induced dissociation confirmed the formation of TPP ICs with ß- and γ-CDs by generating two product ions, TPP and ß- or γ-CD, in both cases. Although quantum chemistry calculations suggest that IC formation with α-CD is energetically possible, an IC with α-CD is not observed in aqueous solution using MS, which aligns with what we also previously observed in the solid state. Since TPP forms stable ICs with ß- and γ-CDs both in the solid state and in solution suggests that complexation could be a safer alternative than applying TPP directly to a substrate. In addition, complexation with CDs in solution also opens up new processing methods to create flame-retardant fabrics and foams with TPP.

Improved Alignment of PEDOT:PSS Induced by in-situ Crystallization of "Green" Dimethylsulfone Molecules to Enhance the Polymer Thermoelectric Performance.

Dimethylsulfone (DMSO2), a small organic molecule, was observed to induce the alignment of poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS) via in-situ crystallization in PEDOT:PSS mixture, which was verified by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and atomic force microscopy (AFM). A chemically stable dopant, DMSO2, remarkably raised the electrical conductivity of the PEDOT:PSS film, which was fabricated from pre-mixed solution of PEDOT:PSS and DMSO2, up to 1080 S/cm, and more importantly, such a PEDOT:PSS film showed a long-term humidity stability and it retained near 90% electric conductivity after 60 days, suggesting DMSO2 is promising for an eco-friendly alternative to replace dimethyl sulfoxide (DMSO), ethylene glycol (EG) and various acids dopants that have been widely employed to dope and post-treat PEDOT:PSS. Pairwise interaction energies and free energy of solvation between PEDOT:PSS and DMSO2 were calculated by first-principles and molecular mechanics, respectively, revealing the mechanism of DMSO2 in enhancing the electrical conductivity.

Polymer morphology and interfacial charge transfer dominate over energy-dependent scattering in organic-inorganic thermoelectrics.

Hybrid (organic-inorganic) materials have emerged as a promising class of thermoelectric materials, achieving power factors (S2σ) exceeding those of either constituent. The mechanism of this enhancement is still under debate, and pinpointing the underlying physics has proven difficult. In this work, we combine transport measurements with theoretical simulations and first principles calculations on a prototypical PEDOT:PSS-Te(Cux) nanowire hybrid material system to understand the effect of templating and charge redistribution on the thermoelectric performance. Further, we apply the recently developed Kang-Snyder charge transport model to show that scattering of holes in the hybrid system, defined by the energy-dependent scattering parameter, remains the same as in the host polymer matrix; performance is instead dictated by polymer morphology manifested in an energy-independent transport coefficient. We build upon this language to explain thermoelectric behavior in a variety of PEDOT and P3HT based hybrids acting as a guide for future work in multiphase materials.

Nanoscale considerations responsible for diverse macroscopic phase behavior in monosubstituted isobutyl-POSS/poly(ethylene oxide) blends.

Nanocomposites prepared by incorporating functionalized polyhedral oligomeric silsesquioxane (POSS) into polymer matrices afford a wide range of versatile hybrid materials for use in technologies ranging from cosmetics and pharmaceuticals to sensors and batteries. Here, we investigate the phase behavior of nanocomposites composed of poly(ethylene oxide) (PEO) and monosubstituted isobutyl POSS (iPOSS) modified with different functional moieties. Microscopic analyses of blends containing these iPOSS variants reveal the existence of different macroscopic morphologies and surface topologies. In the presence of octa-iPOSS, a POSS-rich surface cell motif reminiscent of breath patterns develops, whereas addition of allyl-iPOSS promotes the formation of surface plates. While aminopropyl-iPOSS forms dispersed aggregates, maleamic acid-iPOSS disperses in PEO with little effect on PEO crystal morphology. We perform rotational isomeric state Monte Carlo simulations to discern the effect of monosubstitution on the interaction energy between iPOSS and PEO, and establish the molecular-level origin for these observed differences in phase behavior.