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Elisabetta Garavaglia,1 Cinzia Sala,2 Manuela Busato,1 Gilberto Bellia,3 Nadia Tamburlin,1 Alberto Massirone1 1Agorà, Italian Scientific Society of Aesthetic Medicine, Milan, Italy; 2Private Practice, Milan, Italy; 3Medical Affair, IBSA Farmaceutici, Italia Srl, Lodi, ItalyCorrespondence: Elisabetta GaravagliaAgorà, Italian Scientific Society of Aesthetic Medicine, Piazza Caiazzo 1, Milan 20124, ItalyTel +39 3382731072Email Garavaglia.Elisabetta@hsr.itObjective: Evaluation of the impact of hyaluronan hybrid cooperative complex (HCC) injections in premenopausal and postmenopausal Italian women affected by vulvar-vaginal atrophy (VVA), one of the symptoms of genitourinary syndrome (GS), on self-reported quality-of-life, vaginal symptoms, and sexual activity, as well as treatment side-effects.Methods: We surveyed a sample of 26 women affected by VVA with follow-up at 6 and 12 months. Deep intradermal injections of HCC were delivered at 1-month intervals. Evaluation of the treatment impacting the VVA patients was assessed by three international validated questionnaires (Visual Analogic Scale, VAS; health-related quality-of-life test, SF12; Female Sexual Function Index, FSFI). The statistically significant differences between pre- and after-treatment responses have been assessed by Wilcoxon signed-rank test and repeated measures ANOVA test.Results: At 6– 12-month follow-up, general quality-of-life (SF12) did not show any significant improvement. On the contrary, VVA patients showed significant improvements of genital symptoms (VAS) and sexual function (FSFI). Global FSFI score increased by 58% and evidenced important satisfaction (P≤ 0.05).Conclusion: Vestibular HCC injection is an office, safe, fast, not expensive, and reproducible procedure effective in vulvar-vaginal atrophy. This study can be used as a pilot for future trials.Keywords: hyaluronic acid, bio-stimulation, vulvovaginal atrophy, genito-urinary syndrome of menopause, hyaluronic acids injection, menopause, hyaluronan hybrid cooperative complexes

Copyright of Brazilian Journal of Biology is the property of Instituto Internacional de Ecologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Brazilian Journal of Biology is the property of Instituto Internacional de Ecologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Molecularly imprinted polymers (MIPs) are high affinity robust synthetic receptors, which can be optimally synthesized and manufactured more economically than their biological equivalents (i.e. antibody). In MIPs production, rational design based on molecular modeling is a commonly employed technique. This mostly aids in (i) virtual screening of functional monomers (FMs), (ii) optimization of monomer-template ratio, and (iii) selectivity analysis. We present MIRATE, an integrated science gateway for the intelligent design of MIPs. By combining and adapting multiple state-of-the-art bioinformatics tools into automated and innovative pipelines, MIRATE guides the user through the entire process of MIPs’ design. The platform allows the user to fully customize each stage involved in the MIPs’ design, with the main goal to support the synthesis in the wet-laboratory. Availability: MIRATE is freely accessible with no login requirement at http://mirate.di.univr.it/. All major browsers are supported.

The evolution of adhesive dentistry and the addition of nanoparticles has heralded an improvement in the mechanical properties of adhesives. Thus, the aim of the present study was to evaluate the effects produced by carbon nanotubes (CN) added to two adhesives used for indirect bonding by an examination of the shear bond strength (SBS) and location of bond failure.

Ionic liquids (ILs) including oxalatoborate anions, like bis(oxalato)borate (BOB) and difluoro(oxalato)borate (DFOB) are extensively used in the battery sector as additives to promote the formation of protective layers on the surface of high-voltage cathode materials. In this work four ILs have been synthesized: N -ethoxyethyl- N -methylpiperidinium bis(oxalato)borate (PIP 1,2O2 BOB), N -ethoxyethyl- N -methylpiperidinium difluoro(oxalato)borate (PIP 1,2O2 DFOB), N -propyl- N -methylpiperidinium bis(oxalato)borate (PIP 1,3 BOB) and N -propyl- N -methylpiperidinium difluoro(oxalato)borate (PIP 1,3 DFOB) and their thermal properties have been linked to their structure. The presence of an oxygen atom in the PIP 1,2O2 lateral chain suppresses crystallization of the ILs. Furthermore, PIP 1,2O2 DFOB shows a lower glass transition temperature than PIP 1,2O2 BOB. These observations have been explained using a combined molecular dynamics and density functional theory approach and an increase in the degree of freedom of the lateral chain of the cation due to the ether oxygen has been found. Comparing PIP 1,2O2 DFOB and PIP 1,2O2 BOB, a notable interaction between different domains of the anions is observed and is stronger in the DFOB case due to the charge-delocalization induced by the fluorine atoms, which generates a relatively positive charge on the boron atom. This is correlated to the weaker cation-anion attraction which hinders the glass transition of PIP 1,2O2 DFOB.

Fridericia chica is widely distributed in Brazil, where it is commonly known as crajiru or pariri in several regions. Despite its popular use for treating inflammations and as an insect repellent, there has been limited assessment of its chemical and biological properties, including its bioinsecticide activities. In this study, we conducted phytochemical analyses and investigated the larvicidal and repellent effects of F. chica against the mosquito Aedes aegypti. The F. chica (HEFc) hydroalcoholic extract was partitioned using column chromatography, and subfractions were analyzed using chromatographic and spectroscopic analyses (ESI-IT-MS n and NMR). In addition, HEFc was evaluated for its larvicidal and repellent activities. Phytochemical analyses revealed the presence of 17 constituents, including 2,4-dihydroxybenzoic and p-coumaric acids, along with umbelliferone, acetovanilone, myricetin-3-O-glucuronide, and cis-isorhapontigenin, which are reported for the first time in this species. Although no larvicidal effect was observed at the doses tested, the HEFc exhibited promising repellent effects against A. aegypti, which aligns with its ethnopharmacological potential. In addition, molecular docking studies demonstrated that the compounds of HEFc interacted efficiently with insect odorant binding proteins (OBPs), providing repellent effects. Consistent with the chemical profile and in silico studies, preparations of F. chica have considerable repellent potential., (© 2024 Wiley-VHCA AG, Zurich, Switzerland.)

We have carried out a comparative study on three sets of eutectic mixtures based on choline chloride (ChCl) and hydroxyphenol isomers having two hydroxyl groups in the ortho -, meta -, and para -positions of the aromatic ring, namely catechol (Cate), resorcinol (Reso), and hydroquinone (Hydro), respectively. Differential scanning calorimetry highlighted a different thermal behavior of the mixtures depending on the composition and precursor isomerism. These systems behave as deep eutectic solvents (DESs) with the exception of the ChCl/Cate mixture at a 1 : 0.75 molar ratio, the ChCl/Reso mixtures at 1 : 2 and 1 : 3 molar ratios, and the ChCl/Hydro mixture at a 1 : 3 molar ratio. Infrared spectroscopy measurements and molecular dynamics simulations show that the stronger hydrogen-bonding (H-bonding) in the mixed states compared to the pure precursors is key for the formation of a DES. This interaction is mostly reliant on interconnected chloride anion coordination shells thanks to the two hydroxyl groups of the hydroxyphenol molecules, which can bridge between different anions to form an extended H-bond network. This structural arrangement maximizes the interactions and is enhanced by the 1 : 0.75 and 1 : 1 molar ratios, while increasing the hydroxyphenol concentration translates into a lowering of the total number of H-bonds formed in the mixture. This is the basis for the different thermal behavior and points to nearly equimolar compositions between the components, as ideally suited to achieve a DES from these precursors. The obtained insights are able to explain the structure-property relationships for the studied systems and are deemed useful for more conscious development of these inherently tuneable solvents.

X-ray absorption near-edge structure (XANES) spectroscopy has been used, in conjunction with extended X-ray absorption fine structure (EXAFS), to determine the coordination structure of the Ag + ion in a dimethyl sulfoxide (DMSO) solution. From the EXAFS data analysis, the Ag-O first shell distance in DMSO was found to be 2.31(3) Å, with 4.1(5) oxygen atoms surrounding the Ag + ion, in fair agreement with previous results. This technique did not allow us to determine the geometry of the 4-fold coordination complex and a quantitative analysis of the XANES region was carried out to shed light on this issue. The XANES data analysis confirmed the presence of a four-coordinated complex, unambiguously showing that a regular tetrahedral [Ag(DMSO) 4 ] + complex is formed when silver triflate is dissolved in DMSO solution.

Oscillating reactions are among the most intriguing phenomena in chemistry, but many questions on their mechanisms still remain unanswered, due to their intrinsic complexity and to the low sensitivity of the most common spectroscopic techniques toward the reaction brominated species. In this work, we investigate the cerium ion-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction by means of time-resolved X-ray absorption spectroscopy (XAS), in combination with UV-vis spectroscopy and unsupervised machine learning, multivariate curve resolution, and kinetic analyses. Altogether, we provide new insights into the collective oscillatory behavior of the key brominated species involved in the classical BZ reaction and measure previously unreported oscillations in their concentrations through Br K-edge XAS, while simultaneously tracking the oscillatory Ce 4+ -to-Ce 3+ transformation by coupling XAS with UV-vis spectroscopy. Our work evidences the potential of the XAS technique to investigate the mechanisms of oscillatory chemical systems whose species are often not detectable with conventional experimental methods.

The cyclometalated terpyridine complexes [Ru(η 2 -OAc)(NC-tpy)(PP)] (PP = dppb 1 , ( R , R )-Skewphos 4 , ( S , S )-Skewphos 5 ) are easily obtained from the acetate derivatives [Ru(η 2 -OAc) 2 (PP)] (PP = dppb, ( R , R )-Skewphos 2 , ( S , S )-Skewphos 3 ) and tpy in methanol by elimination of AcOH. The precursors 2 , 3 are prepared from [Ru(η 2 -OAc) 2 (PPh 3 ) 2 ] and Skewphos in cyclohexane. Conversely, the NNN complexes [Ru(η 1 -OAc)(NNN-tpy)(PP)]OAc (PP = ( R , R )-Skewphos 6 , ( S , S )-Skewphos 7 ) are synthesized in a one pot reaction from [Ru(η 2 -OAc) 2 (PPh 3 ) 2 ], PP and tpy in methanol. The neutral NC-tpy 1 , 4 , 5 and cationic NNN-tpy 6 , 7 complexes catalyze the transfer hydrogenation of acetophenone (S/C = 1000) in 2-propanol with NaO i Pr under light irradiation at 30 °C. Formation of ( S )-1-phenylethanol has been observed with 4 , 6 in a MeOH/ i PrOH mixture, whereas the R -enantiomer is obtained with 5 , 7 (50-52% ee ). The tpy complexes show cytotoxic activity against the anaplastic thyroid cancer 8505C and SW1736 cell lines (ED 50 = 0.31-8.53 µ M), with the cationic 7 displaying an ED 50 of 0.31 µ M, four times lower compared to the enantiomer 6 .

Shoulder pain is a serious clinical disease frequently related to absence from work. It is characterized by pain and stiffness, probably connected to the presence of an inflammatory substrate involving gleno-humeral capsule and collagen tissues. A physiotherapy program has shown to be effective for the conservative treatment of this disorder. Our aim is to assess if a manual treatment directed to fascial tissues could obtain better improvement regarding pain, strength, mobility, and function. A total of 94 healthcare workers with recurrent shoulder pain were recruited and then randomized in two groups: the control group (CG) underwent a five-session physiotherapy program; the study group (SG) underwent three sessions of physiotherapy and two sessions of fascial manipulation (FM) technique. At the end of the treatment phase, both groups improved every outcome. Despite few statistical differences between groups, at the follow-up visit, a greater percentage of subjects in SG overcame the minimal clinical important difference (MCID) in every outcome. We conclude that FM is effective for treatment of shoulder pain and further studies should better assess how to manage this treatment to obtain better results.

Magnesium chloride is a prototypical deliquescent material whose surface properties, although central for Ziegler-Natta cataysis, have so far remained elusive to experimental characterization. In this work, we use surface-selective X-ray absorption spectroscopy (XAS) at ambient pressure in combination with multivariate curve resolution, molecular dynamics, and XAS theoretical methods to track in real time and accurately describe the interaction between water vapor and the MgCl 2 surface. By exposing MgCl 2 to water vapor at temperatures between 595 and 391 K, we show that water is preferentially adsorbed on five-coordinated Mg 2+ sites in an octahedral configuration, confirming previous theoretical predictions, and find that MgCl 2 is capable of retaining a significant amount of adsorbed water even under prolonged heating to 595 K. As a consequence, our work provides first experimental insights into the unique surface affinity of MgCl 2 for atmospheric water. The developed technique is proven highly sensitive to the modifications induced by adsorbates on a given low-Z metal based surface and may be useful in the toolbox required to disentangle the mechanisms of interfacial chemical processes.

An approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) has been used to carry out a comparative study about the solvation properties of dilute La(NO 3 ) 3 solutions in water and methanol, with the aim of elucidating the still elusive coordination of the La 3+ ion in the latter medium. The comparison between these two systems enlightened a different behavior of the nitrate counterions in the two environments: while in water the La(NO 3 ) 3 salt is fully dissociated and the La 3+ ion is coordinated by water molecules only, the nitrate anions are able to enter the metal first solvation shell to form inner-sphere complexes in methanol solution. The speciation of the formed complexes showed that the 10-fold coordination is preferential in methanol solution, where the nitrate anions coordinate the La 3+ cations in a monodentate fashion and the methanol molecules complete the solvation shell to form an overall bicapped square antiprism geometry. This is at variance with the aqueous solution where a more balanced situation is observed between the 9- and 10-fold coordination. An experimental confirmation of the MD results was obtained by La K-edge XAS measurements carried out on 0.1 M La(NO 3 ) 3 solutions in the two solvents, showing the distinct presence of the nitrate counterions in the La 3+ ion first solvation sphere of the methanol solution. The analysis of the extended X-ray absorption fine structure (EXAFS) part of the absorption spectrum collected on the methanol solution was carried out starting from the MD results and confirmed the structural arrangement observed by the simulations.

Interfaces between water and materials are ubiquitous and are crucial in materials sciences and in biology, where investigating the interaction of water with the surface under ambient conditions is key to shedding light on the main processes occurring at the interface. Magnesium oxide is a popular model system to study the metal oxide-water interface, where, for sufficient water loadings, theoretical models have suggested that reconstructed surfaces involving hydrated Mg 2+ metal ions may be energetically favored. In this work, by combining experimental and theoretical surface-selective ambient pressure X-ray absorption spectroscopy with multivariate curve resolution and molecular dynamics, we evidence in real time the occurrence of Mg 2+ solvation at the interphase between MgO and solvating media such as water and methanol (MeOH). Further, we show that the Mg 2+ surface ions undergo a reversible solvation process, we prove the dissolution/redeposition of the Mg 2+ ions belonging to the MgO surface, and we demonstrate the formation of octahedral [Mg(H 2 O) 6 ] 2+ and [Mg(MeOH) 6 ] 2+ intermediate solvated species. The unique surface, electronic, and structural sensitivity of the developed technique may be beneficial to access often elusive properties of low-Z metal ion intermediates involved in interfacial processes of chemical and biological interest.

X-ray absorption spectroscopy (XAS) has been employed to carry out structural characterization of the local environment around mercury after the dissolution of the HgCl 2 molecule. A combined EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) data analysis has been performed on the Hg L 3 -edge absorption spectra recorded on 0.1 M HgCl 2 solutions in water, methanol (MeOH), acetone and acetonitrile. The Hg-Cl distance determined by EXAFS (2.29(2)-2.31(2) Å) is always comparable to that found in the HgCl 2 crystal (2.31(2) Å), demonstrating that the HgCl 2 molecule dissolves in these solvents without dissociating. A small sensitivity of EXAFS to the solvent molecules interacting with HgCl 2 has been detected and indicates a high degree of configurational disorder associated with this contribution. XANES data analysis, which is less affected by the disorder, was therefore carried out for the first time on these systems to shed light into the still elusive structural arrangement of the solvent molecules around HgCl 2 . The obtained results show that, in aqueous and MeOH solutions, the XANES data are compatible with three solvent molecules arranged around the HgCl 2 unit to form a trigonal bipyramidal structure. The determination of the three-body Cl-Hg-Cl distribution shows a certain degree of uncertainty around the average 180° bond angle value, suggesting that the HgCl 2 molecule probably vibrates in the solution around a linear configuration.

The metal-based deep eutectic solvent (MDES) formed by NiCl 2 ·6H 2 O and urea in 1:3.5 molar ratio has been prepared for the first time and characterized from a structural point of view. Particular accent has been put on the role of water in the MDES formation, since the eutectic could not be obtained with the anhydrous form of the metal salt. To this end, mixtures at different water/MDES molar ratios ( W ) have been studied with a combined approach exploiting molecular dynamics and ab initio simulations, UV-vis and near-infra-red spectroscopies, small- and wide-angle X-ray scattering, and X-ray absorption spectroscopy measurements. In the pure MDES, a close packing of Ni 2+ ion clusters forming oligomeric agglomerates is present thanks to the mediation of bridging chloride anions and water molecules. Conversely, urea poorly coordinates the metal ion and is mostly found in the interstitial regions among the Ni 2+ ion oligomers. This nanostructure is disrupted upon the introduction of additional water, which enlarges the Ni-Ni distances and dilutes the system up to an aqueous solution of the MDES constituents. In the NiCl 2 ·6H 2 O 1:3.5 MDES, the Ni 2+ ion is coordinated on average by one chloride anion and five water molecules, while water easily saturates the metal solvation sphere to provide a hexa-aquo coordination for increasing W values. This multidisciplinary study allowed us to reconstruct the structural arrangement of the MDES and its aqueous mixtures on both short- and intermediate-scale levels, clarifying the fundamental role of water in the eutectic formation and challenging the definition at the base of these complex systems.

The satisfactory rationalization of complex reactive pathways in solution chemistry may greatly benefit from the combined use of advanced experimental and theoretical complementary methods of analysis. In this work, we combine X-Ray Absorption and 1 H NMR spectroscopies with state-of-the-art Multivariate Curve Resolution and theoretical analyses to gain a comprehensive view on a prototypical reaction involving the variation of the oxidation state and local structure environment of a selected metal ion coordinated by organic ligands. Specifically, we investigate the 2-cyano-2-phenylpropanoic acid reduction of the octahedral complex established by the Cu 2+ ion with terpyridine to the tetrahedral complex formed by Cu + and neocuproine. Through our interdisciplinary approach we gain insights into the nature, concentration time evolution and structures of the key metal (XAS measurements) and organic ( 1 H NMR measurements) species under reaction. We believe our method may prove to be useful in the toolbox necessary to understand the mechanisms of reactive processes of interest in solution., (© 2021 Wiley-VCH GmbH.)

The changes upon methanol (MeOH) addition in the structural arrangement of the highly eco-friendly deep eutectic solvent (DES) formed by choline chloride (ChCl) and sesamol in 1:3 molar ratio have been studied by means of attenuated total reflection Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering (SWAXS), and molecular dynamics simulations. The introduction of MeOH into the DES promotes the increase of the number of Cl-MeOH hydrogen bonds (HBs) through the replacement of sesamol and choline molecules from the chloride anion coordination sphere. This effect does not promote the sesamol-sesamol, choline-choline, and sesamol-choline interactions, which remain as negligible as in the pure DES. Differently, the displaced sesamol and choline molecules are solvated by MeOH, which also forms HBs with other MeOH molecules, so that the system arranges itself to keep the overall amount of HBs maximized. SWAXS measurements show that this mechanism is predominant up to MeOH/DES molar ratios of 20-24, while after this ratio value, the scattering profile is progressively diluted in the cosolvent background and decreases toward the signal of pure MeOH. The ability of MeOH to interplay with all of the DES components produces mixtures with neither segregation of the components at nanoscale lengths nor macroscopic phase separation even for high MeOH contents. These findings have important implications for application purposes since the understanding of the pseudophase aggregates formed by a DES with a dispersing cosolvent can help in addressing an efficient extraction procedure., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

A thorough structural characterization of the La(NO 3 ) 3 salt dissolved into several mixtures of ethyl ammonium nitrate (EAN) and methanol (MeOH) with EAN molar fraction χ EAN ranging from 0 to 1 has been carried out by combining molecular dynamics (MD) and X-ray absorption spectroscopy (XAS). The XAS and MD results show that changes take place in the La 3+ first solvation shell when moving from pure MeOH to pure EAN. With increasing the ionic liquid content of the mixture, the La 3+ first-shell complex progressively loses MeOH molecules to accommodate more and more nitrate anions. Except in pure EAN, the La 3+ ion is always able to coordinate both MeOH and nitrate anions, with a ratio between the two ligands that changes continuously in the entire concentration range. When moving from pure MeOH to pure EAN, the La 3+ first solvation shell passes from a 10-fold bicapped square antiprism geometry where all the nitrate anions act only as monodentate ligands to a 12-coordinated icosahedral structure in pure EAN where the nitrate anions bind the La 3+ cation both in mono- and bidentate modes. The La 3+ solvation structure formed in the MeOH/EAN mixtures shows a great adaptability to changes in the composition, allowing the system to reach the ideal compromise among all of the different interactions that take place into it.

Molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) have been combined to study the coordination of the Co 2+ and Ni 2+ ions in ionic liquids (ILs) based on the bis(trifluoromethylsulfonyl)imide ([Tf 2 N] - ) anion and having different organic cations, namely, 1-butyl-3-methylimidazolium ([C 4 mim] + ), 1,8-bis(3-methylimidazolium-1-yl)octane ([C 8 (mim) 2 ] 2+ ), N , N , N -trimethyl- N -(2-hydroxyethyl)ammonium ([choline] + ), and butyltrimethylammonium ([BTMA] + ). Co and Ni K-edge XAS data have been collected on 0.1 mol L -1 Co(Tf 2 N) 2 and Ni(Tf 2 N) 2 solutions and on the metallic salts. MD simulations have been carried out to obtain structural information on the metal ion coordination. The analysis of the extended X-ray absorption fine structure (EXAFS) spectra of the solutions has been carried out based on the atomistic description provided by MD, and the studied ILs have been found to be able to dissolve both the Co(Tf 2 N) 2 and Ni(Tf 2 N) 2 salts giving rise to a different structural arrangement around the metal ions as compared to the solid state. The combined EXAFS and MD results showed that the Co 2+ and Ni 2+ ions are surrounded by a first solvation shell formed by six [Tf 2 N] - anions, each coordinating in a monodentate fashion by means of the oxygen atoms. The nature of the IL organic cation has little or no influence on the overall spatial arrangement of the [Tf 2 N] - anions, so that stable octahedral complexes of the type [M(Tf 2 N) 6 ] 4- (M = Co, Ni) have been observed in all the investigated ILs.

The knowledge of ant assemblages that occurs in Conservation Units in the Atlantic Forest domain is a priority, considering the number of endemic species and the impacts that this biome has been suffering. The aim of this study was to evaluate ant assemblages in the Turvo State Park, which is the largest conservation unit in the State of Rio Grande do Sul and presents an important role on biodiversity protection. Two samplings were conducted in 2019, one in the summer (January) and the other in the spring (November and December), at five sites 2 km apart, with pitfall traps (soil and canopy), sardine baits, glucose, beating net, sweeping net and manual collection. We sampled 121 species in the summer and 120 in the spring, totaling 163 ant species. A total of 78 species (47.8%) occurred in both sampling seasons. The richest genera in the study were Camponotus (S = 30), Pheidole (S = 23) and Linepithema (S = 11). Seventeen species were recorded for the first time for Rio Grande do Sul state. The results indicate that this is one of the most species-rich assemblages of ants ever surveyed in a conservation unit in southern Brazil. The study highlights the importance of Conservation Units as protected environments against habitat loss for ant biodiversity. The results of this study contribute to myrmecofauna knowledge and serve as a basis for environmental impact studies, management plans and conservation of Atlantic Forest remnants.

The structural properties of the deep eutectic solvent (DES) formed by choline chloride (ChCl) and sesamol in 1 : 3 ratio have been investigated and compared to those of reline (ChCl : urea 1 : 2). An integrated approach combining small and wide angle X-ray scattering with molecular dynamics simulations has been employed and the simulation protocol has been validated against the experimental data. In the ChCl : sesamol DES, strong hydrogen bonds (HBs) are formed between the chloride anion and the hydroxyl groups of the choline and of sesamol molecules. Conversely, choline-choline, choline-sesamol and sesamol-sesamol interactions are negligible. A more extended interplay between the constituents is observed in reline where, besides the HBs involving the chloride anion, the eutectic formation is favored also by strong choline-urea and urea-urea interactions. The three-dimensional arrangement around the individual components shows that, in the ChCl : sesamol DES, the cholinium cations and the sesamol molecules are packed in such a way to maximize the interactions with the chlorine anion. This structural arrangement may favor the π-π interactions between the sesamol molecules and the aromatic species mediated by the chloride ions, providing an interpretation for the high separation rates previously observed for phenolic DESs towards aromatic compounds.

Background: Queensland, Australia has been successful in containing the COVID-19 pandemic. Underpinning that response has been a highly effective virus containment strategy which relies on identification, isolation, and contact tracing of cases. The dramatic emergence of the COVID-19 pandemic rendered traditional paper-based systems for managing contact tracing no longer fit for purpose. A rapid digital transformation of the public health contact tracing system occurred to support this effort., Objectives: The objectives of the digital transformation were to shift legacy systems (paper or standalone electronic systems) to a digitally enabled public health system, where data are centered around the consumer rather than isolated databases. The objective of this paper is to outline this case study and detail the lessons learnt to inform and give confidence to others contemplating digitization of public health systems in response to the COVID-19 pandemic., Methods: This case study is set in Queensland, Australia. Universal health care is available. A multidisciplinary team was established consisting of clinical informaticians, developers, data strategists, and health information managers. An agile "pair-programming" approach was undertaken to application development and extensive change efforts were made to maximize adoption of the new digital workflows. Data governance and flows were changed to support rapid management of the pandemic., Results: The digital coronavirus application (DCOVA) is a web-based application that securely captures information about people required to quarantine and creates a multiagency secure database to support a successful containment strategy., Conclusion: Most of the literature surrounding digital transformation allows time for significant consultation, which was simply not possible under crisis conditions. Our observation is that staff was willing to adopt new digital systems because the reason for change (the COVID-19 pandemic) was clearly pressing. This case study highlights just how critical a unified purpose, is to successful, rapid digital transformation., Competing Interests: None declared., (Thieme. All rights reserved.)

X-ray absorption spectroscopy (XAS) has been employed to study the coordination of the Ag + ion in aqueous solution. The conjunction of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) data analysis provided results suggesting the preference for a first shell linear coordination with a mean Ag-O bond distance of 2.34(2) Å, different from the first generally accepted tetrahedral model with a longer mean Ag-O bond distance. Ab initio molecular dynamics simulations with the Car-Parrinello approach (CPMD) were also performed and were able to describe the coordination of the hydrated Ag + ion in aqueous solution in very good agreement with the experimental data. The high sensitivity for the closest environment of the photoabsorber of the EXAFS and XANES techniques, together with the long-range information provided by CPMD and large-angle X-ray scattering (LAXS), allowed us to reconstruct the three-dimensional model of the coordination geometry around the Ag + ion in aqueous solution. The obtained results from experiments and theoretical simulations provided a complex picture with a certain amount of water molecules with high configurational disorder at distances comprised between the first and second hydration spheres. This evidence may have caused the proliferation of the coordination numbers that have been proposed so far for Ag + in water. Altogether these data show how the description of the hydration of the Ag + ion in aqueous solution can be complex, differently from other metal species where hydration structures can be described by clusters with well-defined geometries. This diffuse hydration shell causes the Ag-O bond distance in the linear [Ag(H 2 O) 2 ] + ion to be ca. 0.2 Å longer than in isolated ions in solid state.

The establishment of an invasive species depends on reproductive success and dispersion capability in the new environment. One of the striking examples of invasion in urban environments is the mosquito Aedes aegypti Linnaeus, 1762 (Culicidae). The success of this species is primarily attributed to its ability to colonize urban environments, and some of the important adaptive strategies associated with this ability is the preference for humans as a blood source and intense occupation of residential (indoor) environments. This study evaluated the effects of location (indoor vs. outdoor) and water nutrient level (% organic matter) on the oviposition preference of A. aegypti in an urban environment. We used oviposition choice experiments to evaluate mosquito oviposition in containers holding 1:1 vs 1:0 ratios of water: organic matter placed indoors and outdoors. Eggs were sampled once per week for nine weeks. Our results revealed a strong oviposition preference for outdoor containers, with a significant preference for containers with higher concentrations of organic matter during the fifth to ninth weeks. However, mosquitoes occupying indoor environments did not prefer to lay eggs in containers with lower levels of organic matter. A better understanding of the preferences of A. aegypti regarding the nutrient level and location of oviposition containers can increase our understanding of the behavioral factors allowing mosquitoes to utilize anthropogenic environments.

Molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) were employed to study the solvation of Zn2+ ion in dry [Cnmim][Tf2N] (n = 2, 4; 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) room temperature ionic liquids (RTILs). For [C4mim][Tf2N] also a water-saturated system was considered. The thermodynamic parameters of single ion solvation and transfer from water to the RTIL, as well as the structural information, were calculated by means of MD simulations and our study evidences that both structural and thermodynamic features can be reproduced by MD in good agreement with the experimental data. In the case of [C4mim][Tf2N], enthalpies and entropies of solvation and transfer from water to the RTIL were also obtained. The Zn2+ ion results more favorably solvated in water than in the RTIL and this seems to be caused by the more negative entropy of solvation in the latter liquid. This can be explained by the higher ordering imposed by the metal ion when solvated in [C4mim][Tf2N] with respect to water. When the transfer of Zn2+ in a water/[C4mim][Tf2N] biphasic system is considered, the results show a positive value for the free energy of transfer and the metal ion always prefers to remain solvated in water than in the water-saturated RTIL phase. This theoretical result was confirmed by the analysis of XANES (X-ray absorption near edge structure) and the EXAFS (extended X-ray absorption fine structure) spectra of Zn(Tf2N)2 solutions in [C4mim][Tf2N] in the presence of water.

In this work the dimerization process of the minor allelic form of human alanine glyoxylate aminotransferase, a pyridoxal 5'-phosphate enzyme, was investigated. Bioinformatic analyses followed by site-directed mutagenesis, size exclusion chromatography and catalytic activity experiments allowed us to identify Arg118, Phe238 and Phe240 as interfacial residues not essential for transaminase activity but important for dimer-monomer dissociation. The apo and the holo forms of the triple mutant R118A-Mi/F238S-Mi/F240S-Mi display a dimer-monomer equilibrium dissociation constant value at least ~260- and 31-fold larger, respectively, than the corresponding ones of AGT-Mi. In the presence of PLP, the apomonomer of the triple mutant undergoes a biphasic process: the fast phase represents the formation of an inactive PLP-bound monomer, while the slow phase depicts the monomer-monomer association that parallels the regain of transaminase activity. The latter events occur with a rate constant of ~0.02 μM -1 min -1 . In the absence of PLP, the apomonomer is also able to dimerize but with a rate constant value ~2700-fold lower. Thereafter, the possible interference with the dimerization process of AGT-Mi exerted by the mutated residues in the I244T-Mi and F152I-Mi variants associated with Primary Hyperoxaluria type 1 was investigated by molecular dynamics simulations. On the basis of the present and previous studies, a model for the dimerization process of AGT-Mi, I244T-Mi and F152I-Mi, which outlines the structural defects responsible for the complete or partial mistargeting of the pathogenic variants, was proposed and discussed., (Copyright © 2016 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.)

Molecularly imprinted polymer (MIP) synthetic receptors have proposed and applied applications in chemical extraction, sensors, assays, catalysis, targeted drug delivery, and direct inhibition of harmful chemicals and pathogens. However, they rely heavily on effective design for success. An algorithm has been written which mimics radical polymerization atomistically, accounting for chemical and spatial discrimination, hybridization, and geometric optimization. Synthetic ephedrine receptors were synthesized in silico to demonstrate the accuracy of the algorithm in reproducing polymers structures at the atomic level. Comparative analysis in the design of a synthetic ephedrine receptor demonstrates that the new method can effectively identify affinity trends and binding site selectivities where commonly used alternative methods cannot. This new method is believed to generate the most realistic models of MIPs thus produced. This suggests that the algorithm could be a powerful new tool in the design and analysis of various polymers, including MIPs, with significant implications in areas of biotechnology, biomimetics, and the materials sciences more generally., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Postsurgical physiotherapy programs after total hip arthroplasty (THA) show important differences between types and numbers of treatment sessions. To increase functional recovery in postsurgical patients, manual therapy can be added to traditional physiotherapy programs. Fascial manipulation (FM) has been demonstrated to be effective in decreasing pain and increasing muscular capacity., Objective: To compare the effectiveness of FM when added to a standard protocol of care., Design: Randomized controlled trial., Setting: Rehabilitation center., Patients: A total of 51 patients were recruited after total hip arthroplasty. Inclusion criteria were first THA surgery, posterior-lateral access, and onset of pain within a maximum 2 years. Exclusion criteria were previous hip or knee prosthesis, congenital hip dysplasia, elective THA secondary to trauma, real leg-length discrepancy (≥1.5 cm), cognitive impairment, concomitant rheumatic pathology in acute phase, and serious comorbidities such as cardiac, respiratory, and/or neuromuscular pathologies., Methods: Patients were randomized into 2 groups; both followed a standard protocol based on 2 daily sessions of active exercises for 45 minutes. In the study group, 2 sessions were replaced by FM. The clinical trial was registered at clinicaltrials.gov (NCT02576028)., Main Outcome Measures: Functional outcome measures were collected before and after treatment and at the end of the rehabilitation program. The measures included the Harris Hip Score; Timed Up-and-Go test; articular range of motion in abduction, flexion, extension, and bilateral external rotation with heels together; and verbal numerical scale., Results: Statistically significant differences were observed in degrees of flexion between the study and control group with 25.4 (±11.3) and 18.7 (±9.5), respectively (P = .04); for abduction with 16.8 (±7.0) and 11.1 (±6.1), respectively (P = .005); for extension with 16.2 (±4.9) and 9.3 (±3.8), respectively (P = .001); for bilateral external rotation with heels together with 8.3 (±4.3) and 5.5 (±4.6), respectively (P = .04); for the Harris Hip Score 23.3 (±8.9) and 14.5 (±8.5), respectively (P = .002); and for verbal numerical scale score 1.1 (±2.1) and 0.5 (±1.1), respectively., Conclusions: This study demonstrates that 2 FM sessions are able to significantly improve several functional outcomes in patients compared to usual treatment after THA., Level of Evidence: II., (Copyright © 2016 American Academy of Physical Medicine and Rehabilitation. Published by Elsevier Inc. All rights reserved.)

Despite the significant efforts and discoveries during the last few years in G protein-coupled receptor (GPCR) expression and crystallization, the receptors with known structures to date are limited only to a small fraction of human GPCRs. The lack of experimental three-dimensional structures of the receptors represents a strong limitation that hampers a deep understanding of their function. Computational techniques are thus a valid alternative strategy to model three-dimensional structures. Indeed, recent advances in the field, together with extraordinary developments in crystallography, in particular due to its ability to capture GPCRs in different activation states, have led to encouraging results in the generation of accurate models. This, prompted the community of modelers to render their methods publicly available through dedicated databases and web-servers. Here, we present an extensive overview on these services, focusing on their advantages, drawbacks and their role in successful applications. Future challenges in the field of GPCR modeling, such as the predictions of long loop regions and the modeling of receptor activation states are presented as well., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

HIV-1 Nef interacts with several cellular proteins, among which the human peroxisomal thioesterase 8 (ACOT8). This interaction may be involved in the endocytosis regulation of membrane proteins and might modulate lipid composition in membrane rafts. Nef regions involved in the interaction have been experimentally characterized, whereas structural details of the ACOT8 protein are unknown. The lack of structural information hampers the comprehension of the functional consequences of the complex formation during HIV-1 infection. We modelled, through in silico predictions, the ACOT8 structure and we observed a high charge complementarity between Nef and ACOT8 surfaces, which allowed the identification of the ACOT8 putative contact points involved in the interaction. The predictions were validated by in vitro assays through the development of ACOT8 deletion mutants. Coimmunoprecipitation and immunofluorescence analyses showed that ACOT8 Arg(45)-Phe(55) and Arg(86)-Pro(93) regions are involved in Nef association. In addition, K91S mutation abrogated the interaction with Nef, indicating that Lys(91) plays a key role in the interaction. Finally, when associated with ACOT8, Nef may be preserved from degradation. These findings improve the comprehension of the association between HIV-1 Nef and ACOT8, helping elucidating the biological effect of their interaction.

Molecularly imprinted polymers (MIPs) were combined to MALDI-TOF-MS to evaluate a selective enrichment (SE) method for the determination of clinically relevant biomarkers from complex biological samples. The concept was proven with the myocardial injury marker Troponin I (cTnI). In a first part, MIP materials entailed for the recognition of cTnI epitopes (three peptides selected) were prepared and characterized in dimensions (0.7-2μm), dissociation constants (58-817 nM), kinetics of binding (5-60 min), binding capacity (ca. 1.5 µg/mg polymer), imprinting factors (3 > IF > 5) and selectivity for the peptide epitope. Then, the MIPs, incubated with cTnI peptides and spotted on the target with the DHB matrix, were assayed for the desorption of the peptides in MALDI-TOF-MS. The measured detection limit was ca. 300 femtomols. Finally, the MIP-SE MALDI-TOF-MS was tested for its ability to enrich in the cTnI peptides from a complex sample, mimic of serum (i.e. 81 peptides of digested albumin). The MIP-SE MALDI-TOF-MS successfully enriched in cTnI peptides from the complex sample proving the technique could offer a flexible platform to prepare entailed materials suitable for diagnostic purposes., (Copyright © 2015 John Wiley & Sons, Ltd.)

Cytosolic proteins do not occur as isolated but are exposed to many interactions within a crowded cellular environment. We investigated the associations between a test cytosolic protein, human ileal bile acid binding protein (IBABP), and model cosolutes mimicking macromolecular and lipid membrane intracellular components. Using fluorescence spectroscopy, heteronuclear NMR, and molecular dynamics, we found that IBABP associated weakly with anionic lipid vesicles and experienced transient unspecific contacts with albumin. Localized dynamic perturbations were observed even in the case of apparent unspecific binding. IBABP and ubiquitin did not display mutually attractive forces, whereas IBABP associated specifically with lysozyme. A structural model of the IBABP-lysozyme complex was obtained by data-driven docking simulation. Presumably, all the interactions shown here contribute to modulating functional communication of a protein in its native environment., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Molecularly imprinted polymer (MIP) technique is a powerful mean to produce tailor made synthetic recognition sites. Here precipitation polymerization was exploited to produce a library of MIP nanoparticles (NPs) targeting the N terminus of the hormone Hepcidin-25, whose serum levels correlate with iron dis-metabolisms and doping. Biotinylated MIP NPs were immobilized to NeutrAvidin™ SPR sensor chip. The response of the MIP NP sensor to Hepcidin-25 was studied., Findings: Morphological analysis showed MIP NPs of 20-50 nm; MIP NP exhibited high affinity and selectivity for the target analyte: low nanomolar Kds for the interaction NP/Hepcidin-25, but none for the NP/non regulative Hepcidin-20. The MIP NP were integrated as recognition element in SPR allowing the detection of Hepcidin-25 in 3 min. Linearity was observed with the logarithm of Hepcidin-25 concentration in the range 7.2-720 pM. LOD was 5 pM. The response for Hepcidin-20 was limited. Hepcidin-25 determination in real serum samples spiked with known analyte concentrations was also attempted., Conclusion: The integration of MIP NP to SPR allowed the determination of Hepcidin-25 at picomolar concentrations in short times outperforming the actual state of art. Optimization is still needed for real sample measurements in view of future clinical applications.

Background: Previous studies examining the relationship between exercise dose and post-exercise hypotension (PEH) have employed a limited range of exercise duration and subject age. We extended the dose-response curve by studying two intensities of prolonged exercise that may produce a greater magnitude of PEH and reveal age differences in the exercise dose-response relationship for PEH., Methods: Two groups of healthy recreational endurance athletes were studied: Young (n = 17; age 28 ± 1.1 years) and middle-aged participants (n = 18; 52 ± 0.90 years). They performed on separate occasions, 120 min of prolonged exercise (running) at moderate (60% VO2max) and high intensities (80% VO2max)., Results: PEH after 1 hour of recovery was similar within each age group for either exercise intensity, but was significantly greater in the middle-aged group (moderate intensity, -12.3 ± 1.6 mmHg; high intensity, -15.1 ± 1.7 mmHg) compared with the young group (moderate intensity, -1.2 ± 1.7 mmHg; high intensity, -5.7 ± 2.5 mmHg; p < 0.05). Stepwise regression showed that baseline blood pressure but not age was significantly related to the degree of PEH. Thus, the greater PEH seen in the middle-aged group is attributed to their higher baseline blood pressure (124 ± 3.0/79 ± 2.0 mmHg) than the young group (111 ± 2.0/69 ± 1.8 mmHg). A reduced total peripheral resistance following exercise was the primary contributor to PEH across both age groups and exercise intensities., Conclusions: We conclude that prolonged exercise induces a significant PEH regardless of exercise intensity.

In this paper we present a new methodology, based on genetic algorithms and multiple linear regression, for discovering regulation mechanisms responsible for observed time series in biological networks. The modeling framework employed is called Metabolic P systems; they are deterministic and time-discrete dynamical systems proposed as an effective alternative to ordinary differential equations for modeling biochemical systems. Our methodology is here successfully applied to the mitotic oscillator in early amphibian embryos. Starting from the time series of substances involved in this system, we are able to reconstruct an MP system reproducing the observed dynamics, where the regulatory components were discovered by our evolutionary methodology. In particular, genetic algorithms are used as a variable selection technique to identify the best representation of any regulation function in terms of some given primitive functions.

We examined the effect of intensity during prolonged exercise (PE) on left (LV) and right ventricular (RV) function. Subjects included 18 individuals (mean +/- SE: age = 28.1 +/- 1.1 yr, maximal aerobic power = 55.1 +/- 1.6 ml . kg(-1) . min(-1)), who performed 150 min of exercise at 60 and 80% maximal aerobic power on two separate occasions. Transthoracic echocardiography assessed systolic and diastolic performance, and blood sampling assessed hydration status and noradrenaline levels before (pre), during (15 and 150 min), and 60 min following (post) PE. beta-Adrenergic sensitivity pre- and post-PE was assessed by dobutamine stress. High-intensity PE (15 vs. 150 min) induced reductions in LV ejection fraction (69.3 +/- 1.3 vs. 63.5 +/- 1.3%, P = 0.000), LV strain (-23.5 +/- 0.6 vs. -22.3 +/- 0.6%, P = 0.034), and RV strain (-26.3 +/- 0.6 vs. -23.0 +/- 0.6%, P < 0.01). Both exercise intensities induced diastolic reductions (pre vs. post) in the ratio of septal early wave of annular tissue velocities to late/atrial wave of annular tissue velocities (2.15 +/- 0.15 vs. 1.62 +/- 0.09; 2.21 +/- 0.15 vs. 1.48 +/- 0.10), ratio of lateral early wave of annular tissue velocities to late/atrial wave of annular tissue velocities (3.84 +/- 0.42 vs. 2.49 +/- 0.20; 3.56 +/- 0.32 vs. 2.08 +/- 0.18), ratio of early to late LV strain rate (2.42, +/- 0.16 vs. 1.97 +/- 0.13; 2.30 +/- 0.15 vs. 1.81 +/- 0.11), and ratio of early to late RV strain rate (2.03 +/- 0.17 vs. 1.51 +/- 0.09; 2.16 +/- 0.16 vs. 1.44 +/- 0.11) (P < 0.001). Evidence of beta-adrenergic sensitivity was supported by a decreased strain, strain rate, ejection fraction, and systolic pressure-volume ratio response to dobutamine (P < 0.05) with elevated noradrenaline (P < 0.01). PE-induced reductions in LV and RV systolic function were related to exercise intensity and beta-adrenergic desensitization. The clinical significance of exercise-induced cardiac fatigue warrants further research.

A case is reported of malignant mixed mesodermal tumor of the uterus in a postmenopausal 56 year-old woman presenting vaginal bleeding and who was cytologically diagnosed with an endometrial aspirate. The cytologic examination of smears showed the presence of two different cellular types: adenocarcinomatous and sarcomatous (some with evident cross striations). The patient underwent total hysterectomy with lymphadenectomy. Histologically, a malignant mixed Müllerian tumor was confirmed. Cytological, histological, histochemical and immunohistochemical features are described in detail together with the main differential diagnosis.