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Gold nanorods (Au NRs) are an exceptionally promising tool in nanotechnology due to three key factors: (i) their strong interaction with electromagnetic radiation, stemming from their plasmonic nature, (ii) the ease with which the resonance frequency of their longitudinal plasmon mode can be tuned from the visible to the near-infrared region of the electromagnetic spect r u m based on their aspect ratio, and (iii) their simple and cost-effective preparation through seed-mediated chemical growth. In this synthetic method, surfactants play a critical role in controlling the size, shape, and colloidal stabi l i t y of Au NRs. For example, surfactants can stabilize specific crystallographic facets during the formation of Au NRs, leading to t h e formation of NRs with specific morphologies. The process of surfactant adsorption onto the NR surface may result in various assemblies of surfactant molecules, such as spherical micelles, elongated micelles, or bilayers. Again, the assembly mode is critical toward determining the further availabi l i t y of the Au NR surface to the surrounding medium. Despite its importance and a great deal of research effort, the interaction between Au NPs and surfactants remains insufficiently understood, because the assembly process is influenced by numerous factors, including the chemical nature of the surfactant, the surface morphology of Au NPs, and solution parameters. Therefore, gaining a more comprehensive understanding of these interactions is essential to unlock the full potential of the seed-mediated growth method and the applications of plasmonic NPs. A plethora of characterization techniques have been applied to reach such an understanding , but many open questions remain. In this Account, we review the current knowledge on the interactions between surfactants and Au NRs. We briefly introduce the state-of-the-art methods for synthesizing Au NRs and highlight the crucial role of cationic surfactants during this process. The self-assembly and organization of surfactants on the Au NR surface is then discussed to better understand their role in seed-mediated growth. Subsequently, we provide examples and elucidate how chemical additives can be used to modulate micellar assemblies, in turn allowing for a finer control over the growth of Au NRs, including chiral NRs. Next, we review the main experimental characterization and computational modeling techniques that have been applied to shed light on the arrangement of surfactants on Au NRs and summarize the advantages and disadvantages for each technique. The Account ends with a "Conclusions and Outlook" section, outlining promising future research directions and developments that we consider are sti l l required, mostly related to the application of electron microscopy in liquid and in 3D. Finally, we remark on the potential of exploiting machine learning techniques to predict synthetic routes for NPs with predefined structures and properties.

Purpose To determine corneal cross-linking (CXL) efficacy and chromophore penetration after excimer laser-assisted patterned de-epithelialization. Methods Two-hundred-twenty porcine eyes were de-epithelialized ex vivo, either fully (mechanical; n = 88) or patterned (excimer laser; n = 132). Consecutively, corneas were impregnated with hypo- or hyperosmolar riboflavin (RF; n = 20, RF-D; n = 40, respectively) or water-soluble taurine (WST11; n = 40, and WST-D; n = 40, respectively), or kept unimpregnated (n = 80). Sixty corneas were subsequently irradiated, inducing CXL, with paired contralateral eyes serving as controls. Outcome measurements included strip extensiometry to assess CXL efficacy, and spectrophotometry and fluorescence microscopy to determine stromal chromophore penetration. Results All tested chromophores induced significant CXL (p < 0.001), ranging from 7.6% to 14.6%, with similar stiffening for all formulations (p = 0.60) and both de-epithelialization methods (p = 0.56). Light transmittance was significantly lower (p < 0.001) after full compared with patterned de-epithelialization. Stromal chromophore penetration was comparable between fully and patterned de-epithelialized samples, with full penetration in RD and RF-D samples and penetration depths measuring 591.7 +/- 42.8 mu m and 592.9 +/- 63.5 mu m for WST11 (p = 0.963) and 504.2 +/- 43.2 mu m and 488.8 +/- 93.1 mu m for WST-D (p = 0.669), respectively. Conclusions Excimer laser-assisted patterned de-epithelialization allows for effective CXL. Stromal chromophore concentration is, however, reduced, which may have safety implications given the need for sufficient UVA attenuation in RF/UVA CXL. The different safety profile of near-infrared (NIR) may allow safe WST11/NIR CXL even with reduced stromal chromophore concentration values. In vivo studies are needed to evaluate the benefits and further assess safety of excimer laser-assisted patterned de-epithelialization for corneal CXL.

International audience; Thymic epithelial tumors are rare neoplastic proliferations of thymic epithelial cells. The aggressiveness of these malignancies increases as higher is the histologic subtype, being thymic carcinoma the most aggressive subtype, with a greater tendency to metastatic spread. In metastatic setting, there is no standard treatment after progression on platinum-based chemotherapy. In this scenario, monotherapy treatment either with lenvatinib, a multi-tyrosine kinase inhibitor with antiangiogenic properties, or pembrolizumab, an immune-checkpoint inhibitor, has reported clinical activity. Potential combination of both agents may have synergistic activity as reported in other cancer types. PECATI trial is a single-arm, investigator-initiated phase II study aiming to assess the activity and safety of the combination of lenvatinib and pembrolizumab in 43 patients with advanced B3-thymoma or thymic carcinoma who progressed on or after at least one previous line of platinum-based chemotherapy. The primary endpoint of the trial is 5-month progression-free survival rate and the secondary endpoints include overall response rate, duration of response, and overall survival.

There is an increasing shift from dissolution testing to dissolution-permeation testing of formulations during formulation development and this has led increasing application of permeability measurements using parallel artificial membrane permeability assay (PAMPA) membranes. However, there is a lack of thorough analysis of the impact of variabilities in the PAMPA setup on the mass flow rate outcomes, particularly for complex solubility-enabling formulations. In this study, we investigated the impact of amorphous drug-rich nanodroplets, formed in supersaturated solutions by liquid-liquid phase separation, on membrane transport by measuring mass flow rate across PAMPA membranes. In addition, we explored the impact of PAMPA variants such as lipid composition, hydrophobicity and pore size of the filter support, as well as receiver sink properties on membrane mass flow rates of solutions containing amorphous nanodroplets. Filter properties and lipid composition did not show a notable influence on the mass flow rates for lipophilic molecules, while a marked impact was observed for hydrophilic molecules. High sink conditions in the receiver compartment, arising from addition of micellar surfactant, altered the membrane integrity for lipid-impregnated hydrophilic membranes. In contrast, no such effect was observed for a hydrophobic filter support. Membrane integrity tests also suggested that monitoring water transport may be an improved approach over using Lucifer yellow. Furthermore, high sink conditions in the receiver compartment resulted in an increase in the overall mass flow rate. This was due to the effect of asymmetric conditions, generated across the membrane, on mass transport kinetics. Linearity between mass flow rate and donor concentration was observed until the donor concentration reached the amorphous solubility. Above the amorphous solubility, a gradual increase in mass flow rate was observed i.e., with an increasing number of nanodroplets in the solution. This was attributed to decrease in the permeability barrier across unstirred water layer due to reduction of the concentration gradient as nanodroplets dissolved to replenish absorbed drug. Observations made in this study provide insights into the mechanisms associated with mass transport of supersaturated solutions across PAMPA membranes, which are critical for improved evaluation of enabling formulations.

Summary Objective The aim of this study was to evaluate nitric oxide (NO) levels and lipid peroxidation (Malondialdehyde: MDA) in plasma of dogs naturally infected by Ehrlichia canis, and to determine the effect of doxycycline on clinical, hematological, and oxidative parameters. Methods Clinical and hematological parameters and positive serology for E. canis were used to diagnose the disease. Plasma samples were obtained from infected animals (n = 15) before and after doxycycline treatment (10 mg/kg, daily for 28 days) and from healthy dogs (n = 8). The concentrations of NO and MDA were determined by Griess’ assay and thiobarbituric acid assay, respectively. Results Increased plasmatic levels of NO and MDA were observed in infected dogs compared to healthy animals (P Conclusion This study shows that dogs infected by E. canis develop oxidative stress that might be involved in the pathophysiology of the disease and highlights the beneficial effect of doxycycline in this infection.

The effect of salinity on aerobic granular sludge treating fish-canning wastewater was evaluated through a one-dimensional biofilm model. Salt inhibition of heterotrophic and nitrifying bacteria was described by a non-competitive inhibition term, for which the value of the half-saturation coefficient was estimated based on data from literature. The model was calibrated and validated with experimental lab-scale data regarding COD and nitrogen removal from industrial wastewater. Two dynamic operating periods with salinities of 13 and 5 g NaCl L-1 were used for calibration and validation, respectively. The prevailing feast-famine regime necessitated simultaneous growth and storage processes to accurately describe COD removal. The presence of salt caused nitrite accumulation, as well as unusually low estimated maximum growth rates of nitrifying bacteria. The addition of a salinity inhibition term to the model could accurately describe the COD and nitrogen species experimentally measured along the cycles with different salinities.

In the first results from an ongoing global cancer screening data repository, screening program organization was better overall in Europe compared to other continents; however, there were substantial gaps in implementation across both high- and low-resource settings. The CanScreen5 project is a global cancer screening data repository that aims to report the status and performance of breast, cervical and colorectal cancer screening programs using a harmonized set of criteria and indicators. Data collected mainly from the Ministry of Health in each country underwent quality validation and ultimately became publicly available through a Web-based portal. Until September 2022, 84 participating countries reported data for breast (n = 57), cervical (n = 75) or colorectal (n = 51) cancer screening programs in the repository. Substantial heterogeneity was observed regarding program organization and performance. Reported screening coverage ranged from 1.7% (Bangladesh) to 85.5% (England, United Kingdom) for breast cancer, from 2.1% (Cote d'Ivoire) to 86.3% (Sweden) for cervical cancer, and from 0.6% (Hungary) to 64.5% (the Netherlands) for colorectal cancer screening programs. Large variability was observed regarding compliance to further assessment of screening programs and detection rates reported for precancers and cancers. A concern is lack of data to estimate performance indicators across the screening continuum. This underscores the need for programs to incorporate quality assurance protocols supported by robust information systems. Program organization requires improvement in resource-limited settings, where screening is likely to be resource-stratified and tailored to country-specific situations.

Green synthesis of gold nanoparticles (AuNPs) using microorganisms has been generally studied aiming for high-yield production and morphologies appropriated for various applications, such as bioremediation, (bio)sensors, and (bio)catalysis. Numerous approaches showed the individual effect of factors influencing the synthesis of AuNPs with limited analysis of the governing factors enhancing the production and desired quality of the precipitates. This study proposes a fractional-factorial design to investigate the simultaneous influence of seven environmental factors (cell concentration, temperature, anoxic/oxic conditions, pH, gold concentration, electron donor type, and bacterial species) on the recovery yield and synthesis of targeted AuNPs. Various sizes and morphologies of the AuNPs were obtained by varying the environmental factors studied. The factors with significant effects (i.e., 0.2 mM Au and pH 5) were selected according to statistical analysis for optimal removal of 88.2 ± 3.5% of gold and with the production of valuable 50 nm AuNPs, which are known for their enhanced sensitivity. Implications of the cytochrome-C on the bacterial mechanisms and the provision of electron donors via an electrochemical system are further discussed. This study helps develop gold recovery and nanoparticle synthesis methods, focusing on the determining factor(s) for efficient, low-cost, green synthesis of valuable materials.

[Abstract] The use of supramolecular polymers to construct functional biomaterials is gaining more attention due to the tunable dynamic behavior and fibrous structures of supramolecular polymers, which resemble those found in natural systems, such as the extracellular matrix. Nevertheless, to obtain a biomaterial capable of mimicking native systems, complex biomolecules should be incorporated, as they allow one to achieve essential biological processes. In this study, supramolecular polymers based on water-soluble benzene-1,3,5-tricarboxamides (BTAs) were assembled in the presence of hyaluronic acid (HA) both in solution and hydrogel states. The coassembly of BTAs bearing tetra(ethylene glycol) at the periphery (BTA-OEG4) and HA at different ratios showed strong interactions between the two components that led to the formation of short fibers and heterogeneous hydrogels. BTAs were further covalently linked to HA (HA-BTA), resulting in a polymer that was unable to assemble into fibers or form hydrogels due to the high hydrophilicity of HA. However, coassembly of HA-BTA with BTA-OEG4 resulted in the formation of long fibers, similar to those formed by BTA-OEG4 alone, and hydrogels were produced with tunable stiffness ranging from 250 to 700 Pa, which is 10-fold higher than that of hydrogels assembled with only BTA-OEG4. Further coassembly of BTA-OEG4 fibers with other polysaccharides showed that except for dextran, all polysaccharides studied interacted with BTA-OEG4 fibers. The possibility of incorporating polysaccharides into BTA-based materials paves the way for the creation of dynamic complex biomaterials. The authors acknowledge the ICMS Animation Studio for providing the artwork. S.V.-A. and G.M. acknowledge the funding received by Gravitation Program “Materials Driven Regeneration,” funded by the Netherlands Organization for Scientific Research (024.003.013). J.M. acknowledges a Marie Skłodowska-Curie postdoctoral fellowship (794016) for financial support. G.M. acknowledges the funding received by the Swiss National Science Foundation (SNSF “Early PostDoc Mobility” P2EZP2-178435). R.C. acknowledges TA Instruments for providing the DHR-3 rheometer under the Young Distinguished Rheologist Award instrument grant. S.S. and E.W.M acknowledge the European Research Council (H2020-EU.1.1., SYNMAT project, ID 788618). Netherlands Organisation for Scientific Research; 024.003.013 Swiss National Science Foundation; P2EZP2-178435

This work reports on the use of gallium aminotrisphenolate compounds as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The results show that they are highly active, and more so than the corresponding aluminium congeners. The catalyst system is applicable at low and elevated temperatures across a wide substrate scope including terminal, internal, multiple and fully deuterated epoxides. Applying low catalyst loadings has allowed for a TON of 344,000 to be obtained, highlighting their stability. A DFT investigation has confirmed that the gallium catalysts have lower energetic profiles compared to the aluminium congeners. Measurement of the Lewis acidity of both the gallium and aluminium aminotrisphenolate compounds using the Gutmann‐Beckett method provides the experimental proof that the gallium compounds are more Lewis acidic than their aluminium congeners. Finally, Ab‐Initio Molecular Dynamic (AIMD) simulations have investigated and quantified the dynamic behaviour of the catalytic systems, highlighting an important increase in fluxionality in some cases which helps to explain the increase in catalytic activity.

Polymers are essential materials in our daily life. The synthesis of value-added polymers is mainly performed from fossil fuel-derived monomers. However, the adoption of the circular economy model based on the bioeconomy will reduce the dependence on fossil fuels. In this context, biorefineries have emerged to convert biomass into bioenergy and produce high value-added products, including molecules that can be further used as building blocks for the synthesis of biopolymers and bioplastics. The achievement of catalytic systems able to polymerize the natural monomer counterparts, such as terpenes or terpenoids, is still a challenge in the development of polymers with good mechanical, thermal, and chemical properties. This review describes the most common types of bioplastics and biopolymers and focuses specifically on the polymerization of terpenes and terpenoids, which represent a source of promising monomers to create bio-based polymers and copolymers.

Hydrogen peroxide produced in the cathode of a bioelectrochemical system (BES) enables on-site disinfection of water using electrons derived from the wastewater organics at the microbial anode. While a proof of concept has been established, the long-term performance and putative impact of H2O2 on the anodic microbial community have not been studied extensively. Here, the performance of three BESs was monitored for a 28-day operation period with different concentrations of H2O2 (1 g L−1 and 5 g L−1) flowing in a compartment separated from the anolyte by a cation exchange membrane, which allowed H2O2 diffusion. The reactors exposed to 1 g L−1 H2O2 did not show any significant (p > 0.05) deterioration in catalytic activity during the studied period. Contrastingly, a notable drop in current production was observed in the reactors that were challenged with 5 g L−1 H2O2 in the adjacent chamber. There were no significant differences in the beta diversity of the anodic microbial community from the BESs exposed to H2O2 when compared with the control reactor (0 g L−1 H2O2). Even so, a relative decrease in putative electroactive microorganisms was observed in the reactors exposed to 5 g L−1 H2O2. A stainless-steel anodic current collector was corroded when the BESs were under open circuit and in the presence of H2O2, illustrating the risk of this oxidant during downtimes. These results indicate that whereas BESs are promising in this context, their stability can be compromised at higher peroxide concentrations, thereby limiting the attainable product in routine applications.

Nanoparticles of zinc oxide and of ZnO doped with MgO in different concentrations (1, 2 and 4 mol%) were synthesized in a controlled and reproducible way, using the Pechini polymer precursor method. To determine the physicochemical and structural characteristics of the synthesized nanoparticles, Fourier transform IR (FTIR), X-ray diffraction (XRD), UV–Vis spectroscopy and transmission and scanning electron microscopy (TEM and SEM) were used. Characterization revealed the particles obtained to be nanometric in size (

Copolymerization of xylitol usually yields cross-linked materials. In this work, microwave-assisted polyesterification of xylitol and succinic acid produced materials with diverse molecular weights and different branching degrees, and more importantly, no cross-linking was observed, as supported by the solubility behavior and spectroscopic data. Reactions were carried out for short times, less than 20 min, which is not common for production of industrial polyesters. Control over the branching degree was achieved by tuning the reaction conditions, such as temperature, time of exposure, and monomer ratio, during microwave irradiation. No solvent or catalyst was employed during the step-growth polymerization.

Este trabajo de investigación tuvo como propósito evidenciar la producción de biogás generado por medio de una digestión anaerobia de las aguas residuales producidas por la industria procesadora de café instantáneo, ya que debido a la elaboración de este producto se obtienen altos volúmenes de aguas residuales, encontrando en su composición compuestos recalcitrantes. Una de las posibles alternativas en el tratamiento de efluentes recalcitrantes es la aplicación de procesos oxidativos avanzados (POA), influyendo en la disminución de la demanda química de oxígeno (DQO) y del carbono orgánico total; siendo valorado el sustrato del agua residual sintética de café instantáneo mediante el potencial bioquímico del metano (BMP) como principal componente en la generación de biogás. Se caracterizó el inoculo en función de los sólidos volátiles suspendidos, El potencial Bioquímico de metano se realizó a temperatura mesofílica y Termofílica (35 ºC y 55 ºC) con cargas orgánicas de 0,1; 0,2; 0,35 y 0,5 gDQO/gSSV con la presencia de taninos y en cargas orgánicas de 0,2 y 0,35 gDQO/gSSV con remoción de taninos, ambas durante un periodo de 25 días; el agua residual de café instantáneo utilizada presentó concentraciones de DQO que oscilaron entre ≥4000 mg/L y ≥4478 mg/L, aplicando un inóculo procedente de un reactor anaerobio de la industria de pescado EUROFISH. Los procesos fueron monitoreados a través de parámetros como DQO, DBO, SSV, pH, temperatura y rendimiento de metano, mostrando comportamientos diferentes en la degradación de la materia orgánica acorde a las cargas aplicadas.

The use of two solvent-casted film methods to select optimal polymer compositions for amorphous solid dispersions prepared to support preclinical pharmacokinetic and toxicology studies is described. Evaporation of solvent from cover slips by using nitrogen flow, and solvent removal from vials by using rotary evaporation were employed. The films prepared on cover slips were evaluated under the microscope to determine crystallinity. The methods were validated by scaling up corresponding SDDs, evaluating SDD’s dissolution, and comparing those results to the dissolution of drug-polymer films. Subsequently, SDD suspensions were prepared and dosed orally to rats to determine pharmacokinetic parameters. This was done by using three compounds from our pipeline and evaluating multiple polymers. The dissolution of generated films showed good agreement with the dissolution of spray dried dispersions when the films were fully amorphous (Compound A and B). In contrast, there was disagreement between film and SDD dissolution when the films had crystallized (Compound C). The in vivo exposure results indicated that the polymer choice based on the film screening methods would have been accurate for drug-polymer films that were amorphous (Compound A and B). Two additional case studies (Compound D and E) are presented, showing good agreement between in vivo and in vitro results. This study established the ability of two film casting screening methods to predict the in vitro and in vivo performance of corresponding SDDs, provided that the films are fully amorphous.

This study aimed to evaluate the influence of a magnetic field (MF) intensity of 25 mT on Chlorella fusca cultivation in outdoor and indoor conditions, and evaluate the changes in the macromolecules, pigment content and protein profile. C. fusca was cultivated for 15 d in raceway photobioreactor. MF was applied for 24 h d−1 and 1 h d−1. In outdoor cultivation, MF applied for 24 h d−1 increased 23% in the biomass concentration, while indoor assays resulted in an increase in both modes, with biomass production increasing between 70 and 85%. Biomass composition was altered when MF was applied for 1 h d−1 in indoor assays; the highest protein content was achieved (32.7%). Nitrate consumption was higher in outdoor assays, while MF application did not alter the protein profile. The results showed that combining the outdoor conditions with MF is advantageous, as higher biomass concentration can be achieved with lower energy expenditure.

Water for human consumption is the main source of fluoride exposure. The concentration in water should not exceed 1 mg/L of fluoride since, at higher levels; it increases the risk of dental fluorosis, among other adverse effects. The fluoride content of 149 water samples from different aqueducts in Cauca (Colombia) has been determined by ion exchange chromatography with the aim of fluoride risk assessment. The rural area of the Municipality of Santander de Quilichao registered fluoride concentrations between 0.012 and 0.150 mg/L. The urban area of Santander de Quilichao recorded lower fluoride levels than the rural area (0.027-0.068 mg/L). The urban area of the Municipality of Cajibío registered fluoride levels of 0.082-0.186 mg/L. The highest levels of fluoride were found in Timbío (0.121-0.210 mg/L). The fluoride levels recorded in this study are not considered sufficient to trigger dental fluorosis. Likewise, optimal levels are not considered to protect the child population against dental caries. However, a monitoring plan of fluoride concentrations in water should be implemented to assure the quality and safe of the water.

Lead-free hybrid perovskites have attracted significant attention due to the toxicity of lead and poor stability of lead hybrid perovskites. Among them, bismuth-based hybrid perovskites are currently being developed as they possess negligible toxicity, moderate price and great stability. Herein, we report the synthesis of two stable organic–inorganic perovskites based on one-dimensional iodobismuthates and the benzimidazolium cation (BzlmH)+. Firstly, the BzImH[BiI]4·H2O structure (IEF-4 RT-phase) was prepared using a simple and fast synthetic method at room temperature, leading to the dehydrated BzImH[BiI]4 (IEF-4 HT-phase) upon the removal of water by soft heating. This dehydration-hydration process, which has never been reported for Bi-based perovskites, is fully reversible, affecting the optoelectronic properties of the solid, with an optical bandgap of ∼2 eV. Furthermore, this perovskite material formed stable and homogeneous thin films, which exhibited a high absorption coefficient (1.5 × 105 cm−1) comparable to that of the CH3NH3PbI3 lead perovskite. Thus, both the optoelectronic properties and air stability of these perovskites make them suitable as absorber materials in solar cells.

We report a series of azobenzene boronic acids that reversibly control the extent of diol binding via photochemical isomerization. When the boronic acid is ortho to the azo group, the thermodynamically-favored E isomer binds weakly with diols to form boronic esters. Isomerization of the E azobenzene to its Z isomer enhances diol binding, and the magnitude of this enhancement is affected by the azobenzene structure. 2,6-Dimethoxy azobenzene boronic acids show over 20-fold enhancement in binding upon E–Z isomerization, which can be triggered with red light. Competition experiments and computational studies suggest that the changes in binding affinity originate from stabilization of the E boronic acids and destabilization of the E boronic esters. We demonstrate a correlation between diol binding and photostationary state: different wavelengths of irradiation yield different quantities of bound diol. Higher binding constants for the Z isomer relative to the E isomer was observed with all diols investigated, including cyclic diols, nitrocatechol, biologically relevant compounds, and polyols. This photoswitch was employed to “catch and release” a fluorescently tagged diol in buffered water. By tethering this photoswitch to a poly(ethylene glycol) star polymer, we can tune the stiffness of covalent adaptable hydrogels using different wavelengths of visible light. This work establishes photoswitchable equilibria as a tool for the reversible ligation of molecular and macromolecular species.

Background and objective Cellular damage related to oxidative stress (OS) is implicated in periodontal diseases (PD). Melatonin (MEL) has multiple functions, and it has been described as a potential treatment for PD. We aim at evaluating the protective effects of MEL on an in vitro model of cellular damage triggered by glutamate (GLUT) and DL-buthionine sulfoximine (BSO), on gingival cells (GCs) in culture. Material and methods A primary culture of GCs from Wistar rats was developed in order to test the protective property of MEL; BSO and GLUT were administered alone as well as in combination with MEL. The viability and apoptosis were measured with MTT assay and TUNEL, respectively, and the concentration of superoxide anion ( O 2 - ) was measured with the NBT method. Results The combination of BSO and GLUT treatment resulted in a decreased viability of GCs. This was evidenced by the increase in both the production of superoxide anion and apoptosis. After MEL administration, the oxidant and pro-apoptotic effects of BSO and GLUT were totally counteracted. Conclusions These findings demonstrated that MEL has an effective protective role on GCs subjected to cellular damage in a model of OS and cytotoxicity triggered by BSO and GLUT. Consequently, MEL could be used as a therapeutic agent in PD which begin with a significative loss of GCs.

Background: Encrusted uropathy (EU) is a rare disease caused by urea-splitting bacteria, most commonly Corynebacterium urealyticum, whose incidence is increasing. Standard treatment is based on pathogen-directed antibiotic therapy, urinary diversion, bladder instillations, and surgical resection of urinary calcifications. Case Presentation: We present the case of a 60-year-old man with symptomatic bilateral encrusted pyelitis and cystitis with acute renal failure. We initially treated the patient with antibiotic therapy, urinary diversion, and oral acidification with acetohydroxamic acid, achieving negative urinary cultures. Because of the persistence of encrusted pyelitis, the patient was discharged on oral l-methionine 500 mg bid and 12 months later the encrustations had almost disappeared. Finally, we performed right retrograde intrarenal surgery to remove a persistent small calcification. Conclusion: Oral urinary acidification with l-methionine is a valid treatment for urinary encrustations in EU, with no complications reported. Complete resolution of the calcifications may be achieved without the need for invasive processes and unnecessary manipulation of the urinary system.

Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical penetration, higher spatial resolution, and lower optical scattering compared with other optical materials. Herein, a convenient and efficient supramolecular approach is used to synthesize a two-photon excited near-infrared emissive co-crystalline material. A naphthalenediimide-based triangular macrocycle and coronene form selectively two co-crystals. The triangle-shaped co-crystal emits deep-red fluorescence, while the quadrangle-shaped co-crystal displays deep-red and near-infrared emission centered on 668 nm, which represents a 162 nm red-shift compared with its precursors. Benefiting from intermolecular charge transfer interactions, the two co-crystals possess higher calculated two-photon absorption cross-sections than those of their individual constituents. Their two-photon absorption bands reach into the NIR-II region of the electromagnetic spectrum. The quadrangle-shaped co-crystal constitutes a unique material that exhibits two-photon absorption and near-infrared emission simultaneously. This co-crystallization strategy holds considerable promise for the future design and synthesis of more advanced optical materials., Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical properties compared with other optical materials. Here, the authors use a convenient and efficient supramolecular approach to synthesize a two-photon excited near-infrared emissive co-crystalline material.

The purpose of this study was to evaluate the capability of Aspergillus tubingensis and Talaromyces islandicus to solubilize inorganic phosphorus sources, their activity under abiotic stress, and the enhancement of P availability in soils and plant growth. The P-solubilizing capability and acidification mechanism of the strains were assessed in vitro using tricalcium phosphate and rock phosphate. Independent assays were conducted with rock phosphate under NaCl and fungicides carbendazim, chlorothalonil, and propamocarb hydrochloride using a factorial design. Thereafter, the effects of fungal inoculations in rock phosphate–amended soil and P nutrition of Zea mays were assessed in a greenhouse experiment. Both fungi solubilized P in vitro via acidification through the exudation of acetic, citric, lactic, malic, quinic, and succinic acids. The P-solubilizing efficiency of A. tubingensis was maintained above 97.5% under 0.5 to 3.0% NaCl, up to 28.7% in the treatment with carbendazim, up to 5.3% with chlorothalonil, and above 96.5% with propamocarb hydrochloride; while T. islandicus efficiency decreased to 45.2% in a NaCl concentration-dependent trend, and maintained it above 80% in the fungicide treatments. The inoculation with A. tubingensis increased the available P in the amended soil by up to 65% after 30 days and resulted in 87% higher foliar P content, 111% greater plant height, and 25% greater dry weight of maize shoots. Similarly, T. islandicus contributed to these parameters in 55, 67, 90, and 17%, respectively. These findings suggest their potential as qualified phosphorus solubilizing microorganisms to develop novel and sustainable approaches for P fertilization in agriculture.

An improved methodology of achieving an accurate separation of pure fractions of betacyanins and betaxanthins from Ullucus tuberosus Caldas has been carried out. For that purpose, an in-depth chemical identification of each betalain fraction using HPLC-DAD-ESI-MS was developed. This procedure allowed to evaluate the fractionation efficiency and also identify a large number of betalains, most of which have not been described so far in this raw material: betanidin- and isobetanidin-5-O-(4'-O-malonyl-β-glucoside), 2-decarboxy-phyllocactin, betanidin- and isobetanidin-6-O-(6'-O-feruloyl)-β-glucoside (gomphrenin and isogomphrenin III), dehydro-phyllocactin and isophyllocactin, and arginine and glycine-betaxanthins (portulacaxanthin III). Moreover, the availability of pure betalain fractions by the proposed methodology permitted to establish the total betalain content and the antioxidant activity of both separated betacyanin and betaxanthin fractions of ulluco for the first time. The results suggest Ullucus tuberosus as an underutilized food bioactive source with a high concentration of total betaxanthins (21.8 μg indicaxanthin/g fresh ulluco) and betacyanins (44.5 μg betanin/g fresh ulluco), strongly correlated to the Folin-Ciocalteau reduction capacity.

BACKGROUND Small cell neuroendocrine (NE) carcinomas of the prostate classically lose androgen receptor (AR) expression, may harbor loss of the RB1, TP53, and PTEN tumor suppressor genes, and are associated with a poor prognosis. However usual-type adenocarcinomas may also contain areas of NE differentiation, and in this context the molecular features and biological significance are less certain. METHODS We examined the molecular phenotype and oncologic outcomes of primary prostate adenocarcinomas with ≥5% NE differentiation (≥5% chromogranin A-positive NE cells in any given tumor spot on tissue microarray) using three independent study sets: a set of tumors with paneth cell-like NE differentiation (n = 26), a retrospective case-cohort of intermediate- and high-risk patients enriched for adverse outcomes (n = 267), and primary tumors from a retrospective series of men with eventual castration-resistant metastatic prostate cancer (CRPC) treated with abiraterone or enzalutamide (n = 55). RESULTS Benign NE cells expressed significantly lower quantified AR levels compared with paired benign luminal cells (P

Ring fusion and conjugated bridge length dependent exciton dynamics and electronic coupling in a series of perylenediimide dimers with acceptor–donor–acceptor arrangement are investigated by ultrafast optical spectroscopy and TDDFT calculations., Perylenediimide (PDI) derivatives have been widely studied as electron acceptor alternatives to fullerenes in organic photovoltaics (OPVs) because of their tunable absorption in the visible range, inexpensive synthesis, and photochemical stability. A common motif for improving device efficiency involves joining multiple PDIs together through electron-rich linkers to form a twisted acceptor–donor–acceptor molecule. Molecular features such as ring fusion are further employed to modify the structure locally and in films. These synthetic efforts have greatly enhanced OPV device efficiencies, however it remains unclear how the increasingly elaborate structural modifications affect the photophysical processes integral to efficient photon-to-charge conversion. Here we carry out a systematic study of a series of PDI dimers with thienoacene linkers in which the twist angle, linker length, and degree of ring fusion are varied to investigate the effects of these structural features on the molecular excited states and exciton recombination dynamics. Spectroscopic characterization of the dimers suggest that ring fusion causes greater coupling between the donor and acceptor components and greatly enhances the lifetime of a thienoacene to PDI charge transfer state. The lifetime of this CT state also correlates well with the linker–PDI dihedral angle, with smaller dihedral angle resulting in longer lifetime. DFT and two-photon absorption TDDFT calculations were developed in-house to model the ground state and excited transitions, providing theoretical insight into the reasons for the observed photophysical properties and identifying the charge transfer state in the excited state absorption spectra. These results highlight how the longevity of the excited state species, important for the efficient conversion of excitons to free carriers in OPV devices, can be chemically tuned by controlling ring fusion and by using steric effects to control the relative orientations of the molecular fragments. The results provide a successful rationalization of the behavior of solar cells involving these acceptor molecules.

Nine partially halogenated benzylphosphanes ArXCH2PR2 (ArX = 3,6-dichlorophenyl, 3,6- difluorophenyl and 3,4,5-trifluorophenyl; R = Ph, Cy, iPr) have been prepared and reacted with palladium acetate to obtain the cyclometallated dimers [Pd(μ-OAc)(κ2-C,P-ArXCH2PR2)]2. The acetate bridge has been exchanged by bromide using lithium bromide and the obtained dimers have been thoroughly characterised. The dimers with the non-halogenated phosphanes PhCH2PR2 (R = Ph, iPr) have also been prepared. Treatment with norbornadiene in the presence of silver tetrafluoroborate has furnished the cationic mononuclear complexes [Pd(κ2-C,P-ArXCH2PR2)(nbd)]BF4 as stable solids. These complexes and some of the bromide dimers have been used as catalytic precursors in the Mizoroki- Heck reaction between bromobenzene and butyl acrylate. The complexes efficiently catalyse this transformation and important differences of activity are found depending on the ligand. In general, fluorinated phosphanes give more active systems than chlorinated analogues.

Alkali metal compounds 1–12, with terpene-derived oximate ligands, have been prepared and fully spectroscopically characterized. For derivatives 1–9 aggregation processes are observed in solution. ...

When partial nitritation-anammox (PN-AMX) processes are applied to treat the mainstream in wastewater treatment plants (WWTPs), it is difficult to fulfil the total nitrogen (TN) quality requirements established by the European Union (

Superhydrophobic surfaces present promising applications in the protection of building materials, such as the self-cleaning effect promoted by their high water-repellent properties. However, these surfaces easily lose their properties when exposed to oil contaminants. This is a critical weak point for their application in building facades, which are exposed to environmental pollutants such as hydrocarbons and vandalism (e.g., grafitti). A viable strategy to remove oils is to produce superhydrophilic surfaces, which present underwater superoleophobic behavior. In the case of buildings, the use of this strategy can be considered counterproductive because it promotes their interaction with water, the main vehicle of most decay agents. In this work, we have successfully combined the advantages of a superhydrophilic coating with a hydrophobic impregnation treatment, which prevents water ingress into the porous structure of the substrate. Specifically, a photoinduced superhydrophilic surface was produced on concrete by simple spraying of a starting sol containing TiO2NPs, which create a Cassie-Baxter state, a silica oligomer, producing a compatible matrix promoting good adhesion to the substrate and polydimethylsiloxane as a hydrophobic agent. After being exposed to sunlight, the treated surfaces switched from superhydrophobic (SCA 160°) to superhydrophilic (SCA 85% reduction). The treatment showed suitable adhesion to the substrate and good resistance to rainfall and outdoor exposure due to the presence of the hydrophobic silica matrix in the concrete pore structure.

Ozone (O3) therapy has been used for medical procedures for centuries; however, there are no extensive studies on its utilization in horses. This study aimed to evaluate the application of transrectal O3 on horses by physical and laboratorial evaluation, and production of reactive oxygen species (ROS). Sixteen healthy horses were separated in two groups: a control group (CG) and a group treated with O3 (TG). The TG animals received 1L of an oxygen and O3 mixture transrectally. The initial dose was 10µg/ml for the first two applications, 15μg/ml for the following two applications, and 20μg/ml for the next six applications. The CG animals received 1L of oxygen transrectally. In TG animals no variations in the physical examination were detected; furthermore, TG animals did not exhibit changes in biochemical evaluation results, fibrinogen concentrations, or ROS production. TG animals had increased red blood cell counts, hemoglobin concentrations, and packet cell volume values in comparison to the baseline and CG values. We could infer that O3 affected the red blood cell counts and improved rhetological properties of the blood. The transrectal application of O3 in horses is safe and can indirectly improve the oxygenation and metabolism of tissues.

Collimonas fungivorans Ter331 (CfTer331) is a soil bacterium that produces collimomycin, a secondary metabolite that inhibits the vegetative growth of fungi. Here we show that CfTer331 can also interfere with fungal spore germination and that collimomycin biosynthesis is required for this activity. More specifically, in co-cultures of Aspergillus niger N402 (AnN402) co-nidiospores with CfTer331, the rate of transition from the isotropic to polarized stage of the germination process was reduced and the relatively few AnN402 conidiospores that completed the germination process were less likely to survive than those that were arrested in the isotropic phase. By contrast, a collimomycin-deficient mutant of CfTer331 had no effect on germination: in its presence, as in the absence or delayed presence of CfTer331, unhindered germination of conidiospores allowed rapid establishment of AnN402 mycelium and the subsequent acidification of the culture medium to the detriment of any bacteria present. However, when challenged early enough with CfTer331, the collimomycin-dependent arrest of the AnN402 germination process enabled CfTer331 to prevent AnN402 from forming mycelia and to gain dominance in the culture. We propose that the collimomycin-dependent arrest of spore germination represents an early intervention strategy used by CfTer331 to mitigate niche construction by fungi in nature.

The influence of synthesis parameters using the ultrasonic-assisted sol–gel method on the properties of TiO2 nanostructures was studied. Different synthesis conditions such as long stirring time, type of acid used as the catalyst (weak or strong acid), and calcination temperature were explored and their influences on the morphology, size, crystallinity of nanostructures, and photocatalytic performance were evaluated. TiO2 nanostructures were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray diffraction, and ultraviolet–visible diffuse reflectance spectroscopy. Moreover, degradation photocatalytic tests were performed using methylene blue as the polluting model. Changes in the morphologies and sizes of nanostructures were observed by modification of the stirring time using this sonication process. Moreover, the use of a weak acid, such as acetic acid, produced nanostructures with higher anatase proportion, larger crystallite size, and larger nanoparticle size compared with the use of a strong acid such as nitric acid. In addition, changes in crystalline phases were observed with an increase in the calcination temperature. Finally, the photocatalytic performance was influenced mainly by the changes in the crystalline phases, which were dependent on the type of acid catalyst and the calcination temperature.

Historical records of trace elements in lake sediments provide source-to-sink information about potentially toxic pollutants across space and time. We investigated two lakes located at different elevations in the Ecuadorian Andes to understand how trace element fluxes are related to (i) geology, (ii) erosion in the watersheds, and (iii) local point sources and atmospheric loads. In remote Lake Fondococha (4150 m a.s.l.), total Hg fluxes stay constant between ca. 1760 and 1950 and show an approximately 4.4-fold increase between pre-1950 and post-1950 values. The post-1950 increase in fluxes of other trace elements (V, Cr, Co, Ni, Cu, Zn, As, Cd, and Pb) is lower (2.1–3.0-fold) than for Hg. Mostly lithogenic sources and enhanced soil erosion contribute to their post-1950 increase (lithogenic contribution: > 85%, Hg: ~ 58%). Average post-1950 Hg fluxes are approximately 4.3 times higher in peri-urban Lake Llaviucu (3150 m a.s.l.) than in the remote Lake Fondococha. Post-1950 fluxes of the other trace elements showed larger differences between Lakes Fondococha and Llaviucu (5.2 < 25–29.5-fold increase; Ni < Pb–Cd). The comparison of the post-1950 average trace element fluxes that are derived from point and airborne sources revealed 5–687 (Hg–Pb) times higher values in Lake Llaviucu than in Lake Fondococha suggesting that Lake Llaviucu’s proximity to the city of Cuenca strongly influences its deposition record (industrial emissions, traffic, caged fishery). Both lakes responded with temporary drops in trace element accumulations to park regulations in the 1970s and 1990s, but show again increasing trends in recent times, most likely caused by increase in vehicular traffic and openings of copper and gold mines around Cajas National Park. Supplementary Information The online version contains supplementary material available at 10.1007/s11356-020-11437-0.

Two non-toxic potassium compounds, 1 and 2, with a commercial oximate ligand have been prepared and fully spectroscopically characterized. Their activity as catalysts for the ring-opening polymerization (ROP) process of LLA has been studied, showing that they are extremely active and able to polymerize the monomer in a few minutes. For derivative 2, the presence of a crown ether in the potassium coordination sphere affects the nuclearity of the compound and consequently its solubility, with both aspects having an influence in the polymerization process. Detailed studies of the polymerization mechanism have been performed, and an unusual anionic mechanism was observed in absence of a co-initiator. Indeed, the monomer deprotonation generates a lactide enolate, which initiates the polymerization propagation. On the contrary, when a 1:1 ratio of cat:BnOH is used, a mixture of mechanisms is observed, the anionic mechanism and the activated monomer one, while from a cat:BnOH ratio of 1:2 and over, only the activated monomer mechanism is observed.