Numerical Design of a Thread-Optimized Gripping System for Lap Joint Testing in a Split Hopkinson Apparatus.

Currently, few experimental methods exist that enable the mechanical characterization of adhesives under high strain rates. One such method is the Split Hopkinson Bar (SHB) test. The mechanical characterization of adhesives is performed using different specimen configurations, such as Single Lap Joint (SLJ) specimens. A gripping system, attached to the bars through threading, was conceived to enable the testing of SLJs. An optimization study for selecting the best thread was performed, analyzing the thread type, the nominal diameter, and the thread pitch. Afterwards, the gripping system geometry was numerically evaluated. The optimal threaded connection for the specimen consists of a trapezoidal thread with a 14 mm diameter and a 2 mm thread pitch. To validate the gripping system, the load-displacement (P-δ) curve of an SLJ, which was simulated as if it were tested on the SHB apparatus, was compared with an analogous curve from a validated drop-weight test numerical model.

Influence of Ethanol Parametrization on Diffusion Coefficients Using OPLS-AA Force Field.

Molecular dynamics simulations employing the all-atom optimized potential for liquid simulations (OPLS-AA) force field were performed for determining self-diffusion coefficients (D11) of ethanol and tracer diffusion coefficients (D12) of solutes in ethanol at several temperature and pressure conditions. For simulations employing the original OPLS-AA diameter of ethanol's oxygen atom (σOH), calculated and experimental diffusivities of protic solutes differed by more than 25%. To correct this behavior, the σOH was reoptimized using the experimental D12 of quercetin and of gallic acid in liquid ethanol as benchmarks. A substantial improvement of the calculated diffusivities was found by changing σOH from its original value (0.312 nm) to 0.306 nm, with average absolute relative deviations (AARD) of 3.71% and 4.59% for quercetin and gallic acid, respectively. The new σOH value was further tested by computing D12 of ibuprofen and butan-1-ol in liquid ethanol with AARDs of 1.55% and 4.81%, respectively. A significant improvement was also obtained for the D11 of ethanol with AARD = 3.51%. It was also demonstrated that in the case of diffusion coefficients of non-polar solutes in ethanol, the original σOH=0.312 nm should be used for better agreement with experiment. If equilibrium properties such as enthalpy of vaporization and density are estimated, the original diameter should be once again adopted.

Different faces, same attitudes: behavioral mimicry and description of a new termitophilous species of the remarkable rove beetle genus Thyreoxenus (Staphylinidae, Aleocharinae, Corotocini) from Brazil with notes on post-imaginal growth.

Among the termite-associated fauna, rove beetles of the subfamily Aleocharinae are distinguished by exhibiting the majority of convergent evolutions to this lifestyle. This phenomenon known as termitophily brings many advantages, including the care of nestmates and the exploitation of resources. While some mechanisms that ensure the integration of the termitophiles into the colony are well known, such as chemical mimicry, others remain unclear. In this article, we discuss the importance of termitophile behavior for the stability of interactions within termite colonies. We address behavioral mimicry as an important integration mechanism between termitophiles and termites. We compare both termitophile's and termite's behavioral repertoires and found no significant differences between them, suggesting that social parasites can mislead their host through their behavior in order to exploit the colony and to keep positive interactions with their hosts. In addition, we describe a new species of termitophile rove beetle from a highland humid forest in northeastern Brazil: Thyreoxenus alakazam sp. nov., with detailed illustrations and comments on post-imaginal growth in the context of our hypothesis of the post-imago phenotype, known as stenogastry, as a recapitulation of ancestral conditions in physogastric rove beetles.

Experimental Measurement and Modeling of Hg(II) Removal from Aqueous Solutions Using Eucalyptus globulus Bark: Effect of pH, Salinity and Biosorbent Dosage.

Different experimental conditions were tested in order to optimize the Hg(II) removal by Eucalyptus globulus bark. Response surface methodology was applied to extract information about the significance of the factors and to obtain a model describing the sorption. The results were generated through the design of experiments by applying the methodology of a three-factor and three-level Box-Behnken design. The factors tested were pH (4.0, 6.5, and 9.0), salinity (0, 15, and 30), and biosorbent dosage (0.2, 0.5, and 0.8 g dm-3) to evaluate the Hg(II) removal using realistic conditions, such as contaminated natural waters with an initial Hg(II) concentration of 50 µg dm-3. The optimum response provided by the model was 81% of the metal removal under the optimal operating conditions: a pH value of 6.0, no salinity, and a biosorbent dosage of 0.55 g dm-3. Concerning the kinetic, the pseudo-second-order equation fitted better to the experimental results with R 2 between 0.973 and 0.996. This work highlights the promising valorization of this biomass, which is an industrial byproduct and makes available information about the influence of the variables for Hg(II) removal in water treatment processes.

The role of ammonia oxide in the reaction of hydroxylamine with carboxylic esters.

Theoretical calculations indicate that hydroxylamine can exist in both neutral and zwitterionic (ammonia oxide) forms in aqueous solution, the former being 3.5 kcal mol(-1) more stable. In this report, we have studied the reaction mechanism of hydroxylamine with phenyl acetate and analyzed the role of the zwitterionic isomer. We have observed that the main reaction pathway takes place through the zwitterionic form with a concerted mechanism, not involving the classical tetrahedral intermediate. Attack by the nitrogen atom (via neutral isomer) has a minor contribution and it is also a concerted process. The activation free energy barriers in aqueous solution were calculated at the MP4/TZVPP + diff level for gas phase energies, CPCM for optimization and frequencies, and through single point calculation of the solvation free energy using the SM8 method. Our theoretically predicted barriers are 20.8 and 23.8 kcal mol(-1) for O and N attack, respectively, in very good agreement with the experimental values of 20.4 and 22.3 kcal mol(-1), respectively. Our results support the view that hydroxylamine is a very special nucleophile and the reactivity of this functional group should be further investigated.

Urinary neurotrophic factors in healthy individuals and patients with overactive bladder.

PURPOSE: We investigated urinary levels of nerve growth factor, brain-derived neurotrophic factor and glial cell line-derived neurotrophic factor in healthy individuals and patients with overactive bladder. MATERIALS AND METHODS: Urine from 40 healthy volunteers, half of them male and half female, was collected in the morning, afternoon and evening on 2 occasions 3 months apart. Morning urine samples were collected from 37 female naïve patients with overactive bladder. A total of 24 patients were followed. Urine was collected after a 3-month lifestyle intervention and after 3-month antimuscarinic treatment (oxybutynin 10 mg, extended release). Urinary nerve growth factor, brain-derived neurotrophic factor and glial cell line-derived neurotrophic factor concentrations were measured by enzyme-linked immunosorbent assay and normalized to creatinine. Patients completed a 7-day bladder diary combined with an urgency severity scale. The number of urgency episodes per week was counted. RESULTS: In healthy individuals urinary levels of neurotrophic factors were stable. In patients with overactive bladder the nerve growth factor-to-creatinine (mean ± SD 488.5 ± 591.8 vs 188.3 ± 290.2, p = 0.005) and brain-derived neurotrophic factor-to-creatinine (mean 628.1 ± 590.5 vs 110.4 ± 159.5, p <0.001) ratios were significantly higher than in healthy women. No significant differences were found in the glial cell line-derived neurotrophic factor-to-creatinine ratio. After lifestyle intervention the nerve growth factor-to-creatinine and brain-derived neurotrophic factor-to-creatinine ratios decreased to a mean of 319.7 ± 332.3 and 432.5 ± 589.0 (vs baseline p = 0.318 and 0.033, respectively). After antimuscarinic treatment the nerve growth factor-to-creatinine and brain-derived neurotrophic factor-to-creatinine ratios further decreased to a mean of 179.8 ± 237.9 and 146.6 ± 264.9 (vs baseline p = 0.008 and <0.001, respectively). There was no significant variation in the glial cell line-derived neurotrophic factor-to-creatinine ratio at any time point. The reduction in the number of urgency episodes per week correlated with the brain-derived neurotrophic factor-to-creatinine variation (Pearson product-moment correlation coefficient r = 0.607, p = 0.006) but not with the nerve growth factor-to-creatinine ratio (r = 0.396, p = 0.094). CONCLUSIONS: The urinary nerve growth factor-to-creatinine and brain-derived neurotrophic factor-to-creatinine ratios are increased in patients with overactive bladder. These findings may have pathophysiological and clinical implications.

Euryachen seuzei, a new genus and species of Placusini (Coleoptera: Staphylinidae: Aleocharinae) from Brazil.

The tribe Placusini (Coleoptera: Staphylinidae) consists five genera with worldwide distribution. Despite great morphological diversity, the species are easily recognized by their 4-4-5 tarsal formula and the two-articulated labial palpi, along with a broad and rounded ligula. Several synapomorphies proposed by earlier authors, both for larvae and adults, have led to the conclusion that the tribe now is considered monophyletic within Aleocharinae. Herein, a new genus and species of Placusini from Brazil is described and illustrated. Euryachen seuzei gen. et sp. nov. presents all the proposed synapomorphies for the tribe, in addition to unique characters. An updated key for the genera in Placusini is also provided.

Two new species of the termitophilous rove beetle genus Xenogaster Wasmann from Brazil (Staphylinidae, Aleocharinae, Corotocini).

Xenogaster Wasmann, 1891, is a Neotropical beetle genus of termitophilous beetles, comprising ten species disjunctly distributed. During the study of specimens of the Museu de Zoologia da Universidade de São Paulo, collected during expeditions to Southeastern Brazil, two new species were discovered. Xenogaster pseudonuda sp. nov. and X. kymopoleia sp. nov., are described and illustrated. A discussion is provided regarding the tarsal condition in Xenogaster and the coeloconic sensilla on antennomere III, constituting the first record for the subtribe Termitogastrina.

A new species and morphological notes on the remarkable termitophilous genus Austrospirachtha Watson from Australia (Coleoptera: Staphylinidae: Aleocharinae).

Termitophilous rove beetles in Australia encompass diverse genera and species from several tribes in Aleocharinae. While some taxa have been well-documented, others remain poorly known due to the scarcity of available material. The existing knowledge of Austrospirachtha Watson for instance, is based solely on Austrospirachtha mimetes, described from two specimens collected in an old termite mound. The genus is known for its highly developed physogastry and potential mimicry adaptations. Herein, we present the description of a new species, Austrospirachtha carrijoi sp. nov., representing the second known species for the genus.

A New Termitophilous Rove Beetle from Brazil Suggests an Undersampling Scenario and Cospeciation between Termites and their Termitophiles in the Neotropical region (Coleoptera: Staphylinidae: Aleocharinae).

Numerous staphylinid species can be found in termite nests. While the distributional range of termite hosts has been well studied, the same cannot be said for their associated fauna. There is a lack of comprehensive sampling even in areas where termite fauna has been well-sampled. In recent surveys in Southeastern Brazil, we collected a new species of termitophilous rove beetle from the tribe Termitohospitini (Aleocharinae): Termitosocius boraceiensis sp. nov., is herein described. The new species is the first termitophile found in Boracéia, SP, Brazil, even with decades of termite sampling in the place. Additionally, we discuss the diversity and description rate of neotropical Termitohospitini, and investigate the potential of cospeciation between termites and their termitophilous beetles on the Emerson-Kistner principle. Our findings suggest that the neotropical Termitohospitini may be more diverse than previously believed and that Termitosocius species are present in host species that are geographically separated, implying a cospeciation scenario. Additional sampling is required to fully comprehend the relationships between termitophiles and their termite hosts. The outcomes of this study provide new insights into the undersampling scenario and possibly cospeciation between termites and their termitophiles in the Neotropical region.

Microlia cayaponia, a new pollen-feeder species from Brazil (Staphylinidae: Aleocharinae: Hoplandriini) and its potential competitionin pollinator activity in Cayaponia plants (Cucurbitaceae).

Microlia Casey is a genus of small rove beetles from the New World and Australasia. Many species are recorded to be associated with the flowers of Cucurbitaceae, Solanaceae, Asteraceae, and Monimiaceae. In this work, a new species from Brazil associated with flowers of Cayaponia (Cucurbitaceae), Microlia cayaponia Zilberman & Pires-Silva sp. nov., is described and illustrated. Aspects of its natural history are also investigated, with insights on foraging, reproduction, and the supposed impact on the plant and pollinator's fitness.

Supercritical fluid extraction of Eucalyptus globulus bark-A promising approach for triterpenoid production.

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold.

Modeling Tracer Diffusion Coefficients of Any Type of Solutes in Polar and Non-Polar Dense Solvents.

In this work, a simple two-parameters correlation based on the Rice and Gray, Lennard-Jones, and Stockmayer theories was devised for the calculation of binary diffusion coefficients (D12) of any type of solutes at infinite dilution in polar and non-polar solvents. This equation can be relevant for systems with polar solvents, since most models in the literature fail when strong intermolecular forces predominate in solution. The new correlation embodies the Stockmayer potential without requiring the dipole moments of any component, which significantly enlarges its application. It was validated with the largest D12 database of polar and non-polar dense systems, with 8812 data points (NDP) spanning 553 systems, of which 133 have water as solvent (NDP = 1266), 89 contain polar solvents excluding water (NDP = 1405), 177 have supercritical carbon dioxide (SC-CO2) as solvent (NDP = 5028), and 154 have non-polar or weakly polar solvents excluding SC-CO2 (NDP = 1113). Overall, the model achieved an average deviation of only 3.43%, with accurate and unbiased behavior even for polar systems.

Production and Upgrading of Recovered Carbon Black from the Pyrolysis of End-of-Life Tires.

Increasing awareness regarding fossil fuel dependence, waste valorization, and greenhouse gas emissions have prompted the emergence of new solutions for numerous markets over the last decades. The tire industry is no exception to this, with a global production of more than 1.5 billion tires per year raising environmental concerns about their end-of-life recycling or disposal. Pyrolysis enables the recovery of both energy and material from end-of-life tires, yielding valuable gas, liquid, and solid fractions. The latter, known as recovered carbon black (rCB), has been extensively researched in the last few years to ensure its quality for market applications. These studies have shown that rCB quality depends on the feedstock composition and pyrolysis conditions such as type of reactor, temperature range, heating rate, and residence time. Recent developments of activation and demineralization techniques target the production of rCB with specific chemical, physical, and morphological properties for singular applications. The automotive industry, which is the highest consumer of carbon black, has set specific targets to incorporate recycled materials (such as rCB) following the principles of sustainability and a circular economy. This review summarizes the pyrolysis of end-of-life tires for the production of syngas, oil, and rCB, focusing on the process conditions and product yield and composition. A further analysis of the characteristics of the solid material is performed, including their influence on the rCB application as a substitute of commercial CB in the tire industry. Purification and modification post-treatment processes for rCB upgrading are also inspected.

Impact of a Pretreatment Step on the Acidogenic Fermentation of Spent Coffee Grounds.

Acidogenic fermentation (AF) is often applied to wastes to produce short-chain organic acids (SCOAs)-molecules with applications in many industries. Spent coffee grounds (SCGs) are a residue from the coffee industry that is rich in carbohydrates, having the potential to be valorized by this process. However, given the recalcitrant nature of this waste, the addition of a pretreatment step can significantly improve AF. In this work, several pretreatment strategies were applied to SCGs (acidic hydrolysis, basic hydrolysis, hydrothermal, microwave, ultrasounds, and supercritical CO2 extraction), evaluated in terms of sugar and inhibitors release, and used in AF. Despite the low yields of sugar extracted, almost all pretreatments increased SCOAs production. Milder extraction conditions also resulted in lower concentrations of inhibitory compounds and, consequently, in a higher concentration of SCOAs. The best results were obtained with acidic hydrolysis of 5%, leading to a production of 1.33 gSCOAs/L, an increase of 185% compared with untreated SCGs.

Dilacera, a new astonishing Amazonian genus of termitophilous rove beetle (Staphylinidae: Aleocharinae: Termitonannini) and updated checklist of the subtribe Termitonannina with their termite hosts.

The subtribe Termitonannina consists of eight genera of termitophilous rove beetles from the Neotropical region associated with termites of the subfamilies Apicotermitinae, Nasutitermitinae, Syntermitinae, and Termitinae. A new genus, Dilacera Zilberman & Pires-Silva gen. nov. is established, and a new species, Dilacera exokosmos Zilberman & Pires-Silva gen. et sp. nov., from the Brazilian Amazon, is described and illustrated, with its morphological distinctiveness within the subtribe, discussed. Remarks on the host relationship with Uncitermes teevani (Emerson, 1925) (Termitidae: Syntermitinae) are provided, with an updated checklist of termitophilous species and their associated hosts within Termitonannina, including a discussion on confusing nomenclatural takes on termite hosts.

Enzymatic Potential of Filamentous Fungi as a Biological Pretreatment for Acidogenic Fermentation of Coffee Waste.

Spent coffee grounds (SCGs) are a promising substrate that can be valorized by biotechnological processes, such as for short-chain organic acid (SCOA) production, but their complex structure implies the application of a pretreatment step to increase their biodegradability. Physicochemical pretreatments are widely studied but have multiple drawbacks. An alternative is the application of biological pretreatments that include using fungi Trametes versicolor and Paecilomyces variotii that naturally can degrade complex substrates such as SCGs. This study intended to compare acidic and basic hydrolysis and supercritical CO2 extraction with the application of these fungi. The highest concentration of SCOAs, 2.52 gCOD/L, was achieved after the acidification of SCGs pretreated with acid hydrolysis, but a very similar result, 2.44 gCOD/L, was obtained after submerged fermentation of SCGs by T. versicolor. This pretreatment also resulted in the best acidification degree, 48%, a very promising result compared to the 13% obtained with the control, untreated SCGs, highlighting the potential of biological pretreatments.

Uncovering the Bioactivity of Aurantiochytrium sp.: a Comparison of Extraction Methodologies.

Aurantiochytrium sp. is an emerging alternative source of polyunsaturated fatty acids (PUFAs), docosahexaenoic acid (DHA), and squalene, playing an important role in the phasing out of traditional fish sources for these compounds. Novel lipid extraction techniques with a focus on sustainability and low environmental footprint are being developed for this organism, but the exploration of other added-value compounds within it is still very limited. In this work, a combination of novel green extraction techniques (high hydrostatic pressure extraction (HPE) and supercritical fluid extraction (SFE)) and traditional techniques (organic solvent Soxhlet extraction and hydrodistillation (HD)) was used to obtain lipophilic extracts of Aurantiochytrium sp., which were then screened for antioxidant (DPPH radical reduction capacity and ferric-reducing antioxidant potential (FRAP) assays), lipid oxidation protection, antimicrobial, anti-aging enzyme inhibition (collagenase, elastase and hyaluronidase), and anti-inflammatory (inhibition of NO production) activities. The screening revealed promising extracts in nearly all categories of biological activity tested, with only the enzymatic inhibition being low in all extracts. Powerful lipid oxidation protection and anti-inflammatory activity were observed in most SFE samples. Ethanolic HPEs inhibited both lipid oxidation reactions and microbial growth. The HD extract demonstrated high antioxidant, antimicrobial, and anti-inflammatory activities making, it a major contender for further studies aiming at the valorization of Aurantiochytrium sp. Taken together, this study presents compelling evidence of the bioactive potential of Aurantiochytrium sp. and encourages further exploration of its composition and application.

Synthesis and catalytic properties of molybdenum(VI) complexes with tris(3,5-dimethyl-1-pyrazolyl)methane.

The complex [MoO(2)Cl{HC(3,5-Me(2)pz)(3)}]BF(4) (1) (HC(3,5-Me(2)pz)(3) = tris(3,5-dimethyl-1-pyrazolyl)methane) has been prepared and examined as a catalyst for epoxidation of olefins at 55 °C using tert-butyl hydroperoxide (TBHP) as the oxidant. For reaction of cis-cyclooctene, epoxycyclooctane is obtained quantitatively within 5 h when water is rigorously excluded from the reaction mixture. Increasing amounts of water in the reaction mixture lead to lower activities (without affecting product selectivity) and transformation of 1 into the trioxidomolybdenum(VI) complex [{HC(3,5-Me(2)pz)(3)}MoO(3)] (4). Complex 4 was isolated as a microcrystalline solid by refluxing a suspension of 1 in water. The powder X-ray diffraction pattern of 4 can be indexed in the orthorhombic Pnma system, with a = 16.7349(5) Å, b = 13.6380(4) Å, and c = 7.8513(3) Å. Treatment of 1 in dichloromethane with excess TBHP led to isolation of the symmetrical [Mo(2)O(4)(µ(2)-O){HC(3,5-Me(2)pz)(3)}(2)](BF(4))(2) (2) and unsymmetrical [Mo(2)O(3)(O(2))(2)(µ(2)-O)(H(2)O){HC(3,5-Me(2)pz)(3)}] (3) oxido-bridged dimers, which were characterized by single-crystal X-ray diffraction. Complex 2 displays the well-known (Mo(2)O(5))(2+) bridging structure where each dioxidomolybdenum(VI) center is coordinated to three N atoms of the organic ligand and one µ(2)-bridging O atom. The unusual complex 3 comprises dioxido and oxidodiperoxo molybdenum(VI) centers linked by a µ(2)-bridging O atom, with the former center being coordinated to the tridentate N-ligand. The dinuclear complexes exhibit a similar catalytic performance to that found for mononuclear 1. For complexes 1 and 2 use of the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate and N-butyl-3-methylpyridinium tetrafluoroborate as solvents allowed the complexes to be completely dissolved, and in each case the catalyst and IL could be recycled and reused without loss of activity.

Predictive Models for the Binary Diffusion Coefficient at Infinite Dilution in Polar and Nonpolar Fluids.

Experimental diffusivities are scarcely available, though their knowledge is essential to model rate-controlled processes. In this work various machine learning models to estimate diffusivities in polar and nonpolar solvents (except water and supercritical CO2) were developed. Such models were trained on a database of 90 polar systems (1431 points) and 154 nonpolar systems (1129 points) with data on 20 properties. Five machine learning algorithms were evaluated: multilinear regression, k-nearest neighbors, decision tree, and two ensemble methods (random forest and gradient boosted). For both polar and nonpolar data, the best results were found using the gradient boosted algorithm. The model for polar systems contains 6 variables/parameters (temperature, solvent viscosity, solute molar mass, solute critical pressure, solvent molar mass, and solvent Lennard-Jones energy constant) and showed an average deviation (AARD) of 5.07%. The nonpolar model requires five variables/parameters (the same of polar systems except the Lennard-Jones constant) and presents AARD = 5.86%. These results were compared with four classic models, including the 2-parameter correlation of Magalhães et al. (AARD = 5.19/6.19% for polar/nonpolar) and the predictive Wilke-Chang equation (AARD = 40.92/29.19%). Nonetheless Magalhães et al. requires two parameters per system that must be previously fitted to data. The developed models are coded and provided as command line program.