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The lipolytic yeast Yarrowia lipolytica produces cell-wall-associated lipases, namely Lip7p and Lip8p, that could have interesting properties as catalyst either in free (released lipase fraction—RLF) or cell-associated (cell-bound lipase fraction—CBLF) forms. Herein, a mixture of waste soybean frying oil, yeast extract and bactopeptone was found to favor the enzyme production. Best parameters for lipase activation and release from the cell wall by means of acoustic wave treatment were defined as: 26 W/cm2 for 1 min for CBLF and 52 W/cm2 for 2 min for RLF. Optimal pH and temperature values for lipase activity together with storage conditions were similar for both the free enzyme and cell-associated one: pH 7.0; T = 37 °C; and > 70% residual activity for 60 days at 4, − 4 °C and for 15 days at 30 °C.

Organophosphorus poisoning caused by some pesticides and nerve agents is a life-threating condition that must be swiftly addressed to avoid casualties. Despite the availability of medical countermeasures, the clinically available compounds lack a broad spectrum, are not effective towards all organophosphorus toxins, and have poor pharmacokinetics properties to allow them crossing the blood-brain barrier, hampering cholinesterase reactivation at the central nervous system. In this work, we designed and synthesised novel isatin derivatives, linked to a pyridinium 4-oxime moiety by an alkyl chain with improved calculated properties, and tested their reactivation potency against paraoxon- and NEMP-inhibited acetylcholinesterase in comparison to the standard antidote pralidoxime. Our results showed that these compounds displayed comparable in vitro reactivation also pointed by the in silico studies, suggesting that they are promising compounds to tackle organophosphorus poisoning.

Schinus terebinthifolia Raddi, Anacardiaceae, is a Brazilian plant species, with anti-inflammatory and healing properties. This plant is popularly used for the treatment of several disorders, including thyroid dysfunctions. However, its influence on thyroid physiology is not fully understood. This study investigated the effects of a S. terebinthifolia leaf methanolic extract on the proliferation, viability, and reactive oxygen species (ROS) level of rat thyroid follicular cells. For this, PCCL3 cells were treated with different concentrations of the extract (1–100 μg/ml) and times of exposure (24, 48, and 72 h). The 30 μg/ml concentration significantly reduced cell viability. Thyrocytes treated with the extract presented altered cell morphologies and evidence of oxidative stress. The 50 μg/ml concentration of the extract elicited a pronounced increase in ROS level. The results demonstrated that S. terebinthifolia leaf is harmful to thyroid cells after exposure to high concentrations for prolonged periods. These potentially harmful effects should be considered when this medicinal plant is used in humans. This observation is particularly relevant to individuals with an increased risk of thyroid dysfunctions.

Oseltamivir, a pro-drug, is the best option for treatment and chemoprophylaxis for influenza outbreaks. However, many patients treated with oseltamivir developed adverse reactions, including hypersensitivity, gastritis, and neurological symptoms. The aim of this study was to determine the adverse drug reactions (ADRs) in Mexican patients treated with oseltamivir and whether these ADRs are associated with SNPs of the genes involved in the metabolism, transport, and interactions of oseltamivir. This study recruited 310 Mexican patients with acute respiratory diseases and treated them with oseltamivir (75 mg/day for 5 days) because they were suspected to have influenza A/H1N1 virus infection. Clinical data were obtained from medical records and interviews. Genotyping was performed using real-time polymerase chain reaction and TaqMan probes. The association was assessed under genetic models with contingency tables and logistic regression analysis. Out of 310 patients, only 38 (12.25%) presented ADRs to oseltamivir: hypersensitivity (1.9%), gastritis (10%), and depression and anxiety (0.9%). The polymorphism ABCB1-rs1045642 was associated with adverse drug reactions under the recessive model (P = 0.017); allele C was associated with no adverse drug reactions, while allele T was associated with adverse drug reactions. The polymorphisms SLC15A1-rs2297322, ABCB1-rs2032582, and CES1-rs2307243 were not consistent with Hardy–Weinberg equilibrium, and no other associations were found for the remaining polymorphisms. In conclusion, the polymorphism rs1045642 in the transporter encoded by the ABCB1 gene is a potential predictive biomarker of ADRs in oseltamivir treatment.

Lead iodide (PbI2) is a precursor for the preparation of the organolead iodide perovskite (CH3NH3PbI3), which has been used in the fabrication of highly efficient solar cells. In this work, a novel...

Lactoferrin (Lf) is an iron-binding glycoprotein and a component of many external secretions with a wide diversity of functions. Structural studies are important to understand the mechanisms employed by Lf to exert so varied functions. Here, we used guanidine hydrochloride and high hydrostatic pressure to cause perturbations in the structure of bovine Lf (bLf) in apo and holo (unsaturated and iron-saturated, respectively) forms, and analyzed conformational changes by intrinsic and extrinsic fluorescence spectroscopy. Our results showed that the iron binding promotes changes on tertiary structure of bLf and increases its structural stability. In addition, we evaluated the effects of bLf structural change on the kinetics of bLf internalization in Vero cells by confocal fluorescence microscopy, and observed that the holo form was faster than the apo form. This finding may indicate that structural changes promoted by iron binding may play a key role in the intracellular traffic of bLf. Altogether, our data improve the comprehension of bLf stability and uptake, adding knowledge to its potential use as a biopharmaceutical., Bioactive component; Denaturation; Fluorescence spectroscopy; Functionality; Guanidine hydrochloride; Lactoferrin; Microscopy.

The high ionic conductivity in lithium lanthanum titanate perovskite ceramics, Li3xLa(2/3)-xTiO3 (LLTO), is well-known for the x ≈ 0.11 lithium concentration. The grain conductivity is approximatel...

Liposomes are used in synthetic biology as cell‐like compartments and their microfluidic production through double emulsions allows for efficient encapsulation of various components. However, residual oil in the membrane remains a critical bottleneck for creating pristine phospholipid bilayers. It has been discovered that osmotically driven shrinking leads to detachment of the oil drop. Separation inside a microfluidic chip has been realized to automate the procedure, which allows for controlled continuous production of monodisperse liposomes., Shrinking away turns useful: Polydimethylsiloxane‐based droplet microfluidics are used for the high‐throughput formation of double emulsions. Afterwards, the oleic acid phase can be removed through control of osmotic gradients. The method provides a technological platform for the production of monodisperse vesicles for bottom‐up synthetic biology applications.

Injections of insulin are the main treatment for diabetes, but in the long run this therapy can induce serious drawbacks. This has inspired new drugs able to decrease insulin requirements. For instance, human amylin (hIAPP) is a small hormone cosecreted by pancreatic β-cells with insulin to which is a synergistic partner. However, the high amyloidogenicity of hIAPP precluded it as a therapeutics and led to the design of pramlintide (sIAPP), a chimeric analogue with substitutions (A25P, S28P, and S29P) inherited from the aggregation-resistant rat isoform (rIAPP). Despite sIAPP advantages, it still shares with hIAPP a poorly soluble profile at physiological pH that hampers its mixture with insulin. Recent improvements, as charge-enhanced mutants, have been proposed. For instance, sIAPP+ was screened in silico by purely microcanonical thermostatistical methods and adds to sIAPP an S20R mutation to uplift its solubility. This suggests that such physically inspired computational approach may also be auspicious on devising effective coformulations of insulin with amylin analogues. In this seminal attempt, we make comparative multicanonical simulations of regular acting human insulin coformulated with hIAPP, sIAPP, or sIAPP+. To assess the respective physicochemical stabilities against aggregation, we characterize the structural-phase transitions through the microcanonical thermodynamic formalism and evaluate their time lags using the classical nucleation theory. These results are then correlated with estimates of solvation free energies, modeled by the Poisson-Boltzmann equation, and structural propensities. Experimental essays are compared to our simulations and support our methodology.

Quantum dots (QDs) have attracted considerable attention as fluorescent probes for life sciences. The advantages of using QDs in fluorescence-based studies include high brilliance, a narrow emission band allowing multicolor labeling, a chemically active surface for conjugation, and especially, high photostability. Despite these advantageous features, the size of the QDs prevents their free transport across the plasma membrane, limiting their use for specific labeling of intracellular structures. Over the years, various methods have been evaluated to overcome this issue to explore the full potential of the QDs. Thus, in this review, we focused our attention on physical and biochemical QD delivery methods—electroporation, microinjection, cell-penetrating peptides, molecular coatings, and liposomes—discussing the benefits and drawbacks of each strategy, as well as presenting recent studies in the field. We hope that this review can be a useful reference source for researches that already work or intend to work in this area. Graphic Abstract: Strategies for the intracellular delivery of quantum dots discussed in this review (electroporation, microinjection, cell-penetrating peptides, molecular coatings, and liposomes).[Figure not available: see fulltext.]

Glycerol is a byproduct of biodiesel production and, as such, it is of limited economic value. By means of electrooxidation, glycerol can be used as a feedstock for scalable hydrogen production, in addition to conversion to value-added products. The development of novel and efficient catalytic electrode materials for the anodic side of the reaction is a key towards a hydrogen-based energy economy. In the present study, a computational screening protocol combining DFT, scaling relations, and microkinetic modeling allows for a rational selection of novel catalysts that can deliver efficient glycerol electrooxidation, low cost of production, and environmental sustainability. Activity and chemical selectivity towards hydrogen production on pure metal catalysts is discussed in terms of volcano-shaped plots. We find that the selectivity in the glycerol oxidation reaction is influenced by a different energy landscape when in the presence of water and best classified by a comparison of O-H and C-H bond-breaking barriers. In addition, we screened 3570 bi-metallic catalysts in the AB (L1(0)) and A(3)B (L1(2)) ordered structures for activity, stability, price, and toxicity. By filtering based on the criteria for toxicity, resistance to oxidation, miscibility, and price, we have identified 5 L1(0) structured catalysts (AgPd, AuPd, PtSb, CuPt, and AgPt) and 20 L1(2) catalysts (Ga3Ta, In3Ta, Ir3W, Ir3Mo, Cu3Pt, Ir3Ta, Ir3Re, Pd3Bi, Pd3Cu, Pd3W, Pd3Co, Pd3Sn, Pd3Mo, Pd3Ag, Pd3Ga, Pd3Ta, Au3Ru, Pd3In, Au3Ir, and Pd3Au) that are all predicted to show high activity. We also identify an additional 37 L1(0) and 92 L1(2) structured electrocatalysts with an anticipated medium-high activity. (C) 2021 The Author(s). Published by Elsevier Ltd.

Candidatus Liberibacter asiaticus (CLas) is a phloem-limited bacterium that is associated with the Huanglongbing (HLB) disease of citrus and transmitted by the psyllid, Diaphorina citri. There are no curative methods to control HLB and the prevention of new infections is essential for HLB management. Therefore, the objective of our study was to determine the effects of systemic insecticides, such as the neonicotinoids imidacloprid, thiamethoxam, and a mixture of thiamethoxam and chlorantraniliprole (diamide) on the probing behavior of CLas-infected D. citri and their effect on CLas transmission. The electrical penetration graph (EPG-DC) technique was used to monitor the stylet penetration activities of CLas-infected D. citri on sweet orange [Citrus sinensis (L.) Osbeck] &lsquo, Valencia&rsquo, treated with systemic insecticides. Systemic insecticides disrupted the probing behavior of CLas-infected D. citri, in a way that affected CLas transmission efficiency, particularly by negatively affecting the stylet activities related to the phloem phase. All insecticides reduced (by 57&ndash, 73%) the proportion of psyllids that exhibited sustainable phloem ingestion (waveform E2 &gt, 10 min), with significant differences observed on plants treated with thiamethoxam and thiamethoxam + chlorantraniliprole. The transmission rate of CLas with high inoculum pressure (five CLas-infected D. citri per plant and a seven-day inoculation access period) to untreated control plants was 93%. In contrast, CLas transmission was reduced to 38.8% when test plants were protected by systemic insecticides. Our results indicated that all insecticides tested presented a potential to reduce CLas inoculation by an average of 59%, therefore, these insecticides can be used to reduce the spread of HLB.

Significance Analogous to phospholipids, some polymers assemble into vesicles and can mimic cellular membranes. Apart from enabling compartmentalization in the context of artificial cells, amphiphiles may serve as interface for proteins. However, complex transmembrane proteins were reconstituted in polymers with limited success so far. We functionally integrated the proton pump bo3 oxidase (part of the bacterial respiratory chain) in synthetic membranes made of PDMS-g-PEO and demonstrated lumen acidification. We provided mechanistic insights into the interplay between the protein and the (semi)synthetic membrane by measuring bending rigidity, lateral diffusion and disorder, proton permeability, and protein partitioning. Polymer and hybrid membranes displayed favorable properties for the construction of artificial cells such as membrane rearrangement, enhanced stability and fluidity, while keeping the compartments proton-tight., Cytochrome bo3 ubiquinol oxidase is a transmembrane protein, which oxidizes ubiquinone and reduces oxygen, while pumping protons. Apart from its combination with F1Fo-ATPase to assemble a minimal ATP regeneration module, the utility of the proton pump can be extended to other applications in the context of synthetic cells such as transport, signaling, and control of enzymatic reactions. In parallel, polymers have been speculated to be phospholipid mimics with respect to their ability to self-assemble in compartments with increased stability. However, their usability as interfaces for complex membrane proteins has remained questionable. In the present work, we optimized a fusion/electroformation approach to reconstitute bo3 oxidase in giant unilamellar vesicles made of PDMS-g-PEO and/or phosphatidylcholine (PC). This enabled optical access, while microfluidic trapping allowed for online analysis of individual vesicles. The tight polymer membranes and the inward oriented enzyme caused 1 pH unit difference in 30 min, with an initial rate of 0.35 pH·min−1. To understand the interplay in these composite systems, we studied the relevant mechanical and rheological membrane properties. Remarkably, the proton permeability of polymer/lipid hybrids decreased after protein insertion, while the latter also led to a 20% increase of the polymer diffusion coefficient in polymersomes. In addition, PDMS-g-PEO increased the activity lifetime and the resistance to free radicals. These advantageous properties may open diverse applications, ranging from cell-free biotechnology to biomedicine. Furthermore, the presented study serves as a comprehensive road map for studying the interactions between membrane proteins and synthetic membranes, which will be fundamental for the successful engineering of such hybrid systems.

Producción Científica, Arbutus unedo L., commonly known as the strawberry-tree fruit, is an endemic species of the Mediterranean flora. Microwave extraction technology has been considered as a fast and “green” method for the production of extracts rich in bioactive compounds, although the energy consumption is high. To overcome this bottleneck, microwave was used as a pretreatment procedure in short time periods. This technique promotes the burst of intracellular vacuoles leading to an increase in the lixiviation of phenolic compounds. Different approaches were tested, namely a solvent-free irradiation (SFI), a solvent-assisted irradiation (SAI) and a pressurized solvent-assisted irradiation (PSAI). After irradiation, a solid–liquid extraction procedure was performed using a mixture of water and ethanol. A kinetic evaluation of the total phenolic content (TPC) was performed using the Folin–Ciocalteu method. For the total anthocyanin content, a UV-spectrophotometric method was used. HPLC-UV and LC-MS were used for TPC and identification of present compounds. Microwave irradiation led to an increase in TPC of extracts after SAI (52%) and PSAI (66%) along with a reduction in time of extraction from 30 min to less than 2 min. The anthocyanin content also increased by 66% for the SAI and PSAI extractions., Fundação para Ciência e Tecnologia (fellowship SFRH/BD/52532/2014), Fundação para a Ciência e Tecnologia/Ministério da Educação e Ciência - Fondo Europeo de Desarrollo Regional (partnership PT2020), Portuguese National Mass Spectrometry Network (contracts RNEM—REDE/1518/REM/2005, ROTEIRO/0028/2013 and LISBOA-01-0145-FEDER-022125), Marie Curie Industry - Academia Partnerships and Pathways (project FP7-PEOPLE-2013-IAPP-612208)

We investigate the prevalence, and so the role in the amyloidogenesis, of biased conformations in large ensembles of monomeric forms for Aβ42 and Aβ40 that can trigger the formation and growth of f...

Bismuth triiodide (BiI3) has been studied aiming the development of lead-free photovoltaic materials. It can also be used as X-ray detectors due to the high density of its elements (bismuth and iodine). We investigate the mechanical stress, hardness, and elastic properties of BiI3 thin films deposited by thermal evaporation. The stress was determined by the bending beam technique using the Stoney equation. The films are tensile with stress of approximately 27 MPa. The hardness and the elastic modulus were determined by nanoindentation technique using a Berkovich diamond tip. The hardness of the films is approximately 0.8 GPa and the reduced Young´s modulus is ∼28 GPa for maximum penetration depth of 10% of the film thickness.

Bismuth triiodide (BiI3) is a potential candidate for application in solar cell due to its good optoelectronic properties and because it is free of toxic elements. It can be used as the absorber material in solar cells or converted into the perovskite-like material MA3Bi2I9, suitable also for photovoltaic applications. Bismuth triiodide has been prepared by physical vapour transport (PVT) and by solution process through spin coating. In this work we present optical and structural/topological properties of BiI3 deposited by thermal evaporation under high vacuum. The films are slightly tensile, polycrystalline, homogenously distributed and with good adherence on several substrates, with an indirect bandgap of 1.81 eV, index of refraction of 3.3 (630 nm), photoluminescence centered at 1.74 eV and a Raman peak at 118cm-1 associated with the Ag mode.

Structural properties of Aβ(16-35) fragment are investigated as a model for the amyloid-β peptide excluding its coil-inducing terminals. Our replica-exchange molecular dynamics simulations using all-atom and explicit aqueous solvation widely reduce any structural bias. The principal folding pathway shows direct conversion of coil to β-sheet, without the long proposed helix intermediates. Our principal component analysis indicates that the fragment is also intrinsically disordered, as the full amyloid-β peptide. Thus, the observed folding mechanism lacks free-energy barriers and any peaks in the thermal capacity.

Carbohydrates and glycoconjugates are involved in numerous natural and pathological metabolic processes, and the precise elucidation of their biochemical functions has been supported by smart technologies assembled with lectins, i.e., ubiquitous proteins of nonimmune origin with carbohydrate-specific domains. When lectins are anchored on suitable electrochemical transducers, sensitive and innovative bioanalytical tools (lectin-based biosensors) are produced, with the ability to screen target sugars at molecular levels. In addition to the remarkable electroanalytical sensitivity, these devices associate specificity, precision, stability, besides the possibility of miniaturization and portability, which are special features required for real-time and point-of-care measurements. The mentioned attributes can be improved by combining lectins with biocompatible 0-3D semiconductors derived from carbon, metal nanoparticles, polymers and their nanocomposites, or employing labeled biomolecules. This systematic review aims to substantiate and update information on the progress made with lectin-based biosensors designed for electroanalysis of clinically relevant carbohydrates and glycoconjugates (glycoproteins, pathogens and cancer biomarkers), highlighting their main detection principles and performance in highly complex biological milieus. Moreover, particular emphasis is given to the main advantages and limitations of the reported devices, as well as the new trends for the current demands. We believe that this review will support and encourage more cutting-edge research involving lectin-based electrochemical biosensors.

The relative strength of noncovalent interactions between a thioether sulfur atom and various π systems in designed top pan molecular balances was determined by NMR spectroscopy. Compared to its oxygen counterpart, the sulfur atom displays a remarkable ability to interact with almost equal facility over the entire range of π systems studied, with the simple alkene emerging as the most powerful partner. With the exception of the O⋅⋅⋅heteroarene interaction, all noncovalent interactions of sulfur with π systems are favoured over oxygen.

The ubiquity of silicon in the semiconductor industry and its unique charge transport features has consistently fueled interest in this element and recent realization 2D silicene is a new feather i ...

Detergents are amphiphilic molecules widely used to solubilize biological membranes and/or extract their components. Nevertheless, because of the complex composition of biomembranes, their solubilization by detergents has not been systematically studied. In this review, we address the solubilization of erythrocytes, which provide a relatively simple, robust and easy to handle biomembrane, and of biomimetic models, to stress the role of the lipid composition on the solubilization process. First, results of a systematic study on the solubilization of human erythrocyte membranes by different series of non-ionic (Triton, CxEy, Brij, Renex, Tween), anionic (bile salts) and zwitterionic (ASB, CHAPS) detergents are shown. Such quantitative approach allowed us to propose Re sat—the effective detergent/lipid molar ratio in the membrane for the onset of hemolysis as a new parameter to classify the solubilization efficiency of detergents. Second, detergent-resistant membranes (DRMs) obtained as a result of the partial solubilization of erythrocytes by TX-100, C12E8 and Brij detergents are examined. DRMs were characterized by their cholesterol, sphingolipid and specific proteins content, as well as lipid packing. Finally, lipid bilayers of tuned lipid composition forming liposomes were used to investigate the solubilization process of membranes of different compositions/phases induced by Triton X-100. Optical microscopy of giant unilamellar vesicles revealed that pure phospholipid membranes are fully solubilized, whereas the presence of cholesterol renders the mixture partially or even fully insoluble, depending on the composition. Additionally, Triton X-100 induced phase separation in raft-like mixtures, and selective solubilization of the fluid phase only.

Polymer degradation by the catalytic cracking process has been investigated as an important way of hydrocarbon recovery with high added value. In addition, the effects of the catalyst properties and their behavior during the catalytic degradation of polyolefins have been studied using thermogravimetric analysis. In this context, the present work compares the interactions between the polymeric molecules and the contact surface of zeolitic catalysts (hierarchical and standard Beta zeolites, Y zeolite, ZSM-5, ZSM-12 and MCM-22) with different properties, in the catalytic cracking reactions of low-density polyethylene. It was also possible to evaluate distinct reaction mechanisms in function of the thermal homogenization procedure employed by thermogravimetric analysis. Among the zeolites with large pore diameters, the hierarchical Beta showed superior external area due to the use of a bulky silanized agent (phenylaminopropyl-trimethoxysilane) in the synthesis. In cracking reactions, the polymeric macromolecules mainly react in the external surface of the catalysts due to the several diffusional limitations imposed. Thus, the zeolitic catalysts exhibited behaviors respective to a combination of accessibility to the active centers and selectivity in function of the acid strength of the centers. So, based on this process, zeolites with larger external area values (hierarchical Beta, standard Beta, ZSM-5 and MCM-22) promoted the lower values of degradation temperature with high efficiency of conversion.

In the current emerging sustainable organic battery field, quinones are seen as one of the prime candidates for application in rechargeable battery electrodes. Recently, C6Cl4O2, a modified quinone, has been proposed as a high voltage organic cathode. However, the sodium insertion mechanism behind the cell reaction remained unclear due to the nescience of the right crystal structure. Here, the framework of the density functional theory (DFT) together with an evolutionary algorithm was employed to elucidate the crystal structures of the compounds NaxC6Cl4O2 (x = 0.5, 1.0, 1.5 and 2). Along with the usefulness of PBE functional to reflect the experimental potential, also the importance of the hybrid functional to divulge the hidden theoretical capacity is evaluated. We showed that the experimentally observed lower specific capacity is a result of the great stabilization of the intermediate phase Na1.5C6Cl4O2. The calculated activation barriers for the ionic hops are 0.68, 0.40, and 0.31 eV, respectively, fo...

Borophene, single atomic-layer sheet of boron (Science 2015, 350, 1513), is a rather new entrant into the burgeoning class of 2D materials. Borophene exhibits anisotropic metallic properties whereas its hydrogenated counterpart borophane is reported to be a gapless Dirac material lying on the same bench with the celebrated graphene. Interestingly, this transition of borophane also rendered stability to it considering the fact that borophene was synthesized under ultrahigh vacuum conditions on a metallic (Ag) substrate. On the basis of first-principles density functional theory computations, we have investigated the possibilities of borophane as a potential Li/Na-ion battery anode material. We obtained a binding energy of −2.58 (−1.08 eV) eV for Li (Na)-adatom on borophane and Bader charge analysis revealed that Li(Na) atom exists in Li+(Na+) state. Further, on binding with Li/Na, borophane exhibited metallic properties as evidenced by the electronic band structure. We found that diffusion pathways for Li/...

Organic compounds evolve as a promising alternative to currently used inorganic materials in rechargeable batteries due to their low-cost, environmental friendliness and flexibility. One of the strategies to reach acceptable energy densities and to deal with the high solubility of known organic compounds is to combine small redox active molecules, acting as capacity carrying centres, with conducting polymers. Following this strategy, it is important to achieve redox matching between the chosen molecule and the polymer backbone. Here, a synergetic approach combining theory and experiment has been employed to investigate this strategy. The framework of the density functional theory connected with the reaction field method has been applied to predict the formal potential of 137 molecules and identify promising candidates for the referent application. The effects of including different ring types, e.g. fused rings or bonded rings, heteroatoms, and π bonds, as well as carboxyl groups on the formal potential, have been rationalized. Finally, we have identified a number of molecules with acceptable theoretical capacities that show redox matching with thiophene-based conducting polymers which, hence, are suggested as pendent groups for the development of conducting redox polymer based electrode materials.

Conducting polymers are being considered promising candidates for sustainable organic batteries mainly due to their fast electron transport properties and high recyclability. In this work, the key properties of polythiophene and polypyridine have been assessed through a combined theoretical and experimental study focusing on such applications. A theoretical protocol has been developed to calculate redox potentials in solution within the framework of the density functional theory and using continuous solvation models. Here, the evolution of the electrochemical properties of solvated oligomers as a function of the length of the chain is analyzed and then the polymer properties are estimated via linear regressions using ordinary least square. The predicted values were verified against our electrochemical experiments. This protocol can now be employed to screen a large database of compounds in order to identify organic electrodes with superior properties.

Electrochemical energy storage has recently seen tremendous emphasis being placed on the large-scale (power) grid storage. Sodium-ion batteries are capable of achieving this goal with economic viability. In a recent breakthrough in sodium-ion battery research, the alluaudite framework (Na2Fe2(SO4)3) has been reported, with the highest Fe3+/Fe2+ redox potential (ca. 3.8 V, Barpanda, et al., Nat. Commun., 2014, 5, 4358). Exploring this high-voltage sodium insertion system, we report the discovery of Na2+2xCo2−x(SO4)3 (x = 0.16) as a new member of the alluaudite class of cathode. Stabilized by low-temperature solid-state synthesis (T ≤ 350 °C), this novel Co-based compound assumes a monoclinic structure with C2/c symmetry, which undergoes antiferromagnetic ordering below 10.2 K. Isotypical to the Fe-homologue, it forms a complete family of solid-solution Na2+2x(Fe1−yCoy)2−x(SO4)3 [y = 0–1]. Ab initio DFT analysis hints at potential high voltage operation at 4.76–5.76 V (vs. Na), depending on the degree of desodiation involving a strong participation of the oxygen sub-lattice. With the development of safe organic electrolytes, Na2+2xCo2−x(SO4)3 can work as a cathode material (∼5 V) for sodium-ion batteries.

Amylin, or human islet amyloid polypeptide (hIAPP), is a 37-residue hormone synergistic to insulin and co-secreted with it by β-cells in the pancreas. The deposition of its cytotoxic amyloid fibrils is strongly related to the progression of Type II diabetes (T2D) and islet graft failures. Notably, isoforms from some mammalian species, such as rats (rIAPP) and porcine (pIAPP), present a few key mutations preventing aggregation. This has lead to biotechnological development of drugs for adjunct therapies of T2D, such as pramlintide, a variant of hIAPP inspired by rIAPP whose proline substitutions have β-strand fibril-breaking properties. Ideally, such a drug should be formulated with insulin and co-administered, but this has been prevented by a poor solubility profile at the appropriate pH. Hopefully, this could be improved with appropriate point mutations, increasing the molecular net charge. Despite experimental progress, preliminary screening during rational drug design can greatly benefit from thermodynamic insight derived from molecular simulations. So we introduce microcanonical thermostatistics analysis of multicanonical (MUCA) simulations of wild-type amylin isoforms as a systematic assessment of protein thermostability. As a consequence of this comprehensive investigation, the most suitable single-point mutations able to optimize pramlintide are located among the wild-type amylin isoforms. In particular, we find that aggregation inhibition and increased solubility are inherited by pramlintide through further S20R substitution typical of pIAPP. Thus, we provide a consistent thermostatistical methodology to aid the design of improved adjunct therapies for T2D according to current clinical knowledge.

Casualties caused by organophosphorus pesticides are a burden for health systems in developing and poor countries. Such compounds are potent acetylcholinesterase irreversible inhibitors, and share the toxic profile with nerve agents. Pyridinium oximes are the only clinically available antidotes against poisoning by these substances, but their poor penetration into the blood-brain barrier hampers the efficient enzyme reactivation at the central nervous system. In searching for structural factors that may be explored in future SAR studies, we evaluated neutral aryloximes as reactivators for paraoxon-inhibited Electrophorus eel acetylcholinesterase. Our findings may result into lead compounds, useful for development of more active compounds for emergencies and supportive care.

The USFDA has approved pramlintide, commercially named Symlin (sIAPP), as adjunctive therapy for type 2 diabetes (T2D). This analogue of the human amylin peptide (hIAPP) has triple proline substitutions typical of the rat isoform (rIAPP). Recently, it was proposed that pramlintide solubility and aggregation resistance might be improved by incorporating further mutations, as S20R, screened from the wild-type porcine isoform (pIAPP), which leads to the variant named sIAPP+. To better elucidate how such properties might be systematically induced in rationally designed analogues, we performed comparative assessments of rIAPP, sIAPP, and sIAPP+ using replica-exchange molecular dynamics (REMD) with an accurate combination of force field Charmm22* and explicit aqueous solvation TIP4P/Ew. Our thermo-structural analyses show that sIAPP exhibits a thermal conversion channel of helices[Formula: see text]-sheets resembling hIAPP. This channel is depleted in rIAPP and is absent in sIAPP+. As a consequence, sIAPP+ presents an overall decrease of β-like secondary structures and an overstabilization of α-helices. Additionally, we observed in rIAPP and sIAPP+ an increase in the backbone RMSF of molecular terminals and the exposed area of key residues. These structural features of sIAPP+ suggest a nonamyloidogenic character, which is corroborated by our judicious estimate of the electrostatic component of the solvation free energy using a generalized Born model, and so it may constitute an alternative strategy to sIAPP as a peptide analogue of hIAPP. Furthermore, our findings confirm that different aggregation propensities of amylin and its analogues are synergistically modulated by long-range effects of key mutations. Graphical Abstract S20R-Pramlintide.

Bismuth triiodide (BiI3) has been studied in recent years with the aim of developing lead-free semiconductors for photovoltaics. It has also appeared in X-ray detectors due to the high density of the Bismuth element. This material is attractive as an active layer in solar cells, or may be feasible for conversion into perovskite-like material (MA3Bi2I9), being also suitable for photovoltaic applications. In this study, we report on the thermomechanical properties (stress, hardness, coefficient of thermal expansion, and biaxial and reduced Young’s moduli) of BiI3 thin films deposited by thermal evaporation. The stress was determined as a function of temperature, adopting the thermally induced bending technique, which allowed us to extract the coefficient of thermal expansion (31 × 10−6 °C−1) and Young’s biaxial modulus (19.6 GPa) for the films. Nanohardness (~0.76 GPa) and a reduced Young’s modulus of 27.1 GPa were determined through nanoindentation measurements.

Batteries based on Ca hold the promise to leapfrog ahead regarding increases in energy densities and are especially attractive as Ca is the 5th most abundant element in the Earth's crust. The viability of Ca metal anodes has recently been shown by approaches that either use wide potential window electrolytes at moderately elevated temperatures or THF-based electrolytes at room temperature. This paper provides realistic estimates of the practical energy densities for Ca-based rechargeable batteries at the cell level, calculated using open source models for several concepts. The results from the Ca metal anode batteries indicate that doubled or even tripled energy density as compared to the state-of-the-art Li-ion batteries is viable if a practical proof-of-concept can be achieved.

The aim of this study was to assess the relationship between biochemical analytes and milk fat/protein in high-yield (DIM: 42 ± 10 d postpartum) and low-yield (DIM: 91 ± 11 d postpartum) Holstein cows. Stepwise regression analysis was used to evaluate the relationships of biochemical analytes with the fat and protein content of the milk from 126 Holstein cows belonging to nine intensive housed dairy farms. The comparison between the two groups showed differences (P

Producción Científica, The potential of saffron flowers as a source of polyphenols, and in particular anthocyanins, for the extraction of bioactive compounds and the production of a cyanic colorant was analyzed. A microwave pretreatment, prior to the conventional solid–liquid extraction process, was proposed as a feasible intensification step. The effectiveness of microwave pretreatment was assessed in terms of increased yield and improved quality of the final product. The operational variables studied were the pretreatment temperature (60–120 °C) and the solid–liquid ratio (0.30–0.50 g/mL). It was found that the addition of the microwave pretreatment to the conventional process allowed one to reduce extraction time by up to 12 times and to greatly improve the characteristics of the final product, using microwave energy densities as low as 0.16–0.54 kJ/mL. The extract quality was evaluated in terms of polyphenol richness (25% increase), product composition (80% of the anthocyanins was delphinidin), antioxidant capacity (boosted by the pretreatment) and color (variations in red and blue hue depending on conditions). To conclude, a microwave pretreatment in which the material is heated to a temperature of 65 °C with a solvent ratio of 0.30 g/mL was selected as the optimum to maximize process efficiency and product quality., Junta de Castilla y León - (Project VA040U16)

Background Chemical control is the method most used for management of Diaphorina citri, the vector of the phloem-limited bacteria associated with citrus huanglongbing (HLB) disease. The objectives of this study were to determine the influence of soil-drench applications of neonicotinoids (thiamethoxam and imidacloprid) on the probing behaviour of D. citri on citrus nursery trees, using the electrical penetration graph (EPG) technique, and to measure the D. citri settling behaviour after probing on citrus nursery trees that had received these neonicotinoid treatments. Results The drench applications of neonicotinoids on citrus nursery trees disrupt D. citri probing, mainly for EPG variables related to phloem sap ingestion, with a significant reduction (≈90%) in the duration of this activity compared with untreated plants in all assessment periods (15, 35 and 90 days after application). Moreover, both insecticides have a repellent effect on D. citri, resulting in significant dispersal of psyllids from treated plants. Conclusions This study clearly demonstrates the interference of soil-applied neonicotinoids on the feeding and settling behaviour of D. citri on citrus nursery trees, mainly during the phloem ingestion phase. These findings reinforce the recommendation of drench application of neonicotinoids before planting nursery trees as a useful strategy for HLB management. © 2015 Society of Chemical Industry.

Sodium ion batteries have emerged as a good alternative to lithium based systems due to their low cost of production. In this scenario, the search for higher voltage, sodium cathodes results in a n ...

2030-12 The influence of the estimated values of the physical constants and vapor pressure of esters in a process simulation using the Aspen Hysys was evaluated from the energy parameters of a methanol/ethanol recovery distillation column of a biodiesel production plant. This study was necessary, because in process simulators most of FAMEs and FAEEs are not originally available in the simulator library, due to the lack of experimental data for these components. Accuracy analyses for the values of reboiler temperature and reboiler heat duty of the simulated column were performed from simulations using different predictive models and experimental data. Results demonstrated that small deviations of the vapor pressure can generate considerable errors in the reboiler temperature and reboiler heat duty. In addition, errors can be even greater if vapor pressure is estimated from inaccurate critical constants. Deviations up to 13% were observed for the reboiler temperature and up to 16% for the reboiler heat duty. It is demonstrated that reliable simulations and process design are strongly dependent on the selected physical properties of the esters, specially vapor pressure, which are generated from available experimental data and using group contribution and corresponding states models

Straightforward, microscale, Ellman's cholinesterase test procedures are presented, useful for screening of novel compounds aiming at neurodegenerative diseases and antidotes towards nerve agents and pesticides. Herein, we detail the different procedure features and set forth guidelines on experimental choices researchers may make. The detailed procedure lowers the costs for Ellman´s test, what is highly desirable for low-budget groups in science-lagging and developing countries.

Background The influenza virus can cause seasonal infections with mild to severe symptoms, circulating worldwide, and it can affect people in any age group. Therefore, this infection is a serious public health problem that causes severe illness and death in high-risk populations. Every year, 0.5% of the world’s population is infected by this pathogen. This percentage can increase up to ten times during pandemics. Influenza vaccination is the most effective way to prevent disease. In addition, anti-influenza drugs are essential for prophylactic and therapeutic interventions. The oseltamivir (OST, a neuraminidase inhibitor) is the primary antiviral used in clinics during outbreaks. However, OST resistant viruses may emerge naturally or due to antiviral pressure, with a prevalence of 1–2% worldwide. Thus, the search for new anti-influenza drugs is extremely important. Currently, several groups have been developing studies describing the biotechnological potential of microalgae and cyanobacteria, including antiviral activity of their extracts. In Brazil, this potential is poorly known and explored. Methods With the aim of increasing the knowledge on this topic, 38 extracts from microalgae and cyanobacteria isolated from marine and freshwater biomes in Brazil were tested against: cellular toxicity; OST-sensitive and resistant influenza replications; and neuraminidase activity. Results For this purpose, Madin-Darby Canine Kidney (MDCK)-infected cells were treated with 200 μg/mL of each extract. A total of 17 extracts (45%) inhibited influenza A replication, with seven of them resulting in more than 80% inhibition. Moreover, functional assays performed with viral neuraminidase revealed two extracts (from Leptolyngbya sp. and Chlorellaceae) with IC50 mean Discussion Our results suggest that extracts of microalgae and cyanobacteria have promising anti-influenza properties. Further chemical investigation should be conducted to isolate the active compounds for the development of new anti-influenza drugs. The data generated contribute to the knowledge of the biotechnological potential of Brazilian biomes that are still little explored for this purpose.

Graphene's emergence can be viewed as a positive upheaval in 2D materials research. Along the same line, the realization of a related elemental 2D material, borophene, is another breakthrough. To circumvent the stability issues of borophene, which is reported to have been synthesized on metallic substrates under extreme conditions, hydrogenation of borophene (otherwise called as borophane or hydrogen boride or boron hydride) has been a plausible solution, but only proposed computationally. A recent report (H. Nishino, T. Fujita, N. T. Cuong, S. Tominaka, M. Miyauchi, S. Iimura, A. Hirata, N. Umezawa, S. Okada, E. Nishibori, A. Fujino, T. Fujimori, S. Ito, J. Nakamura, H. Hosono and T. Kondo, J. Am. Chem. Soc., 2017, 139(39), 13761-13769) brings to fore its experimental realization. Our current study delves into the possibilities of employing this intriguing 2D hydrogen boride as anodes in Li/Na ion batteries. Using first-principles density functional theory methods, we computed relevant properties such as the ion (Li/Na) adsorption behavior, the possible pathways of ionic diffusion with the estimation of barriers as well as the theoretical specific capacities and average voltages to uniquely demonstrate that this material is of particular significance for battery applications. It is noted that the use of hydrogen boride leads to a high specific capacity of 861.78 mA h g-1 for Li ions, which is remarkably higher than the value reported in relation to its computationally predicted structure. Furthermore, Na ion intercalation leads to negative voltage profiles, implying the unsuitability of 2D hydrogen boride for this particular ion. Our findings are timely and pertinent towards adding insightful details relevant to the progress of applications of 2D materials for energy storage.