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1.
Braz. J. Anesth. (Impr.) ; 73(6): 718-724, Nov.Dec. 2023. tab, graf
Artigo em Inglês | LILACS | ID: biblio-1520379

RESUMO

Abstract Introduction and objectives: Myofascial Pain Syndrome (MPS) of the Quadratus Lumborum muscle (QL) is a frequent cause of chronic low back pain. With this study, we aimed to assess the efficacy of ultrasound-guided infiltration with 0.25% levobupivacaine and 40 mg triamcinolone for MPS of the QL. Methods: Observational and retrospective study of participants submitted to ultrasound-guided infiltration of the QL muscle from January 1, 2015 to June 31, 2019. Pain intensity was assessed using the five-point pain Numeric Rating Scale (NRS): pre-intervention, at 72 hours, 1 month, 3 months and 6 months post-intervention. Additional data collected were demographic characteristics, opioid consumption, and adverse effects. Results: We assessed 90 participants with mean age of 55.2 years. Sixty-eight percent of participants were female. Compared to the pre-intervention assessment, there was an improvement in pain at 72 hours (Mean Difference [MD = 3.085]; 95% CI: 2.200-3.970, p < 0.05), at the 1st month (MD = 2.644; 95% CI: 1.667-3.621, p < 0.05), at the 3rdmonth (MD = 2.017; 95% CI: 0.202-2.729, p < 0.05) and at the 6th month (MD = 1.339; 95% CI 0.378-2.300, p < 0.05), post-intervention. No statistically significant differences in opioid consumption were observed. No adverse effects associated with the technique were reported. Conclusions: Ultrasound-guided infiltration of the QL muscle is a safe and effective procedure for the treatment of pain in the QL MPS within 6 months post-intervention.


Assuntos
Humanos , Masculino , Feminino , Pessoa de Meia-Idade , Neuralgia Facial/tratamento farmacológico , Bloqueio Nervoso/métodos , Dor , Triancinolona , Estudos Retrospectivos , Ultrassonografia de Intervenção/métodos , Levobupivacaína , Analgésicos Opioides
2.
Int J Biol Macromol ; 248: 125947, 2023 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-37482163

RESUMO

Phenolic foams are typically produced from phenolic resins, using phenol and formaldehyde precursors. Therefore, common phenolic foams are non-sustainable, comprising growing environmental, health, and economic concerns. In this work, lignin extracted from pine wood residues using a "green" levulinic acid-based solvent, was used to partially substitute non-sustainable phenol. The novel engineered foams were systematically compared to foams composed of different types of commercially available technical lignins. Different features were analyzed, such as foam density, microstructure (electron microscopy), surface hydrophilicity (contact angle), chemical grafting (infrared spectroscopy) and mechanical and thermal features. Overall, it was observed that up to 30 wt% of phenol can be substituted by the new type of lignin, without compromising the foam properties. This work provides a new insights on the development of novel lignin-based foams as a very promising sustainable and renewable alternative to petrol-based counterparts.


Assuntos
Lignina , Pinus , Lignina/química , Fenóis/química , Fenol/química , Madeira/química
3.
Biomacromolecules ; 24(7): 3094-3104, 2023 07 10.
Artigo em Inglês | MEDLINE | ID: mdl-37288956

RESUMO

The high potential use of lignin in novel biomaterials and chemicals represents an important opportunity for the valorization of the most abundant natural resource of aromatic molecules. From an environmental perspective, it is highly desirable replacing the hazardous methods currently used to extract lignin from lignocellulosic biomass and develop more sustainable and environmentally friendly approaches. Therefore, in this work, levulinic acid (a "green" solvent obtained from biomass) was successfully used, for the first time, to selectively extract high-quality lignin from pine wood sawdust residues at 200 °C for 6 h (at atmospheric pressure). Moreover, the addition of catalytic concentrations of inorganic acids (i.e., H2SO4 or HCl) was found to substantially reduce the temperature and reaction times needed (i.e., 140 °C, 2 h) for complete lignin extraction without compromising its purity. NMR data suggests that condensed OH structures and acidic groups are present in the lignin following extraction. Levulinic acid can be easily recycled and efficiently reused several times without affecting its performance. Furthermore, excellent solvent reusability and performance of extraction of other wood residues has been successfully demonstrated, thus making the developed levulinic acid-based procedure highly appealing and promising to replace the traditional less sustainable methodologies.


Assuntos
Ácidos , Lignina , Lignina/química , Solventes/química , Ácidos Levulínicos , Biomassa
4.
Environ Sci Pollut Res Int ; 30(13): 39258-39271, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36598726

RESUMO

The architecture of hydrophobically modified polymers can be tailored to produce variants with different levels of functionality. This allows industry to apply rational design methods for the development of more environmentally friendly materials. In the present work, the ecotoxicity of six variants of hydrophobically modified poly(acrylic) acids (HMPAA), obtained by changing the crosslinked conformation, insertion position, and length of the hydrophobic groups, was assessed for the (i) bioluminescence production of Aliivibrio fischeri; (ii) population growth rate of Raphidocelis subcapitata and Chlorella vulgaris; (iii) mortality of Brachionus calyciflorus; (iv) feeding inhibition, somatic growth rate, reproduction, and mortality of Daphnia magna; and (iv) mortality and somatic growth rate of Pelophylax perezi tadpoles. The concentrations causing 50% and 20% of effects (L(E)C50 and 20, respectively) ranged from 9.64 up to > 2000 mg·L-1 for all six HMPAA and species. The bacterium A. fischeri and tadpoles of P. perezi were the most sensitive and most tolerant organisms to the six tested HMPAA, respectively. The computed 5% hazard concentrations (computed on the basis of L(E)C50 s) showed that HMPAA1 (13.0 mg·L-1) and HMPAA2 (26.1 mg·L-1) were the most toxic variants, while HMPAA6 (233 mg·L-1) the least one. These results suggest HMPAA6 (with low crosslink percentage modified by the addition of long and short hydrophobic groups at the surface) to be the most environmentally friendly variant and should be preferentially considered to be used in consumer products, compared to the other five studied variants.


Assuntos
Chlorella vulgaris , Rotíferos , Poluentes Químicos da Água , Animais , Poluentes Químicos da Água/farmacologia , Ecotoxicologia , Aliivibrio fischeri , Daphnia , Larva
5.
Int J Biol Macromol ; 228: 594-603, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36563812

RESUMO

The aim of the present work was to modify the exuded gum of Sterculia striata tree by an amination reaction. The viscosity and zero potential of the chicha gum varied as a function of pH. The modification was confirmed by X-ray diffraction (XRD), infrared spectroscopy (FTIR), size exclusion chromatography (SEC), zeta potential, thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). Furthermore, the chemical modification changed the molar mass and surface charge of the chicha gum. In addition, the gums were used in tests for ex vivo mucoadhesion strength, antibacterial activity against the standard strain of Staphylococcus aureus (ATCC 25923), inhibitory activity of α-glucosidase, antioxidant capacity, and viability of Caco-2 cells. Through these tests, it was found that amination caused an increase in the mucoadhesive and inhibitory activity of chicha gum against the bacterium Staphylococcus aureus. In addition, the gums (pure and modified) showed antioxidant capacity and an inhibitory effect against the α-glucosidase enzyme and did not show cytotoxic potential.


Assuntos
Antioxidantes , alfa-Glucosidases , Humanos , Antioxidantes/farmacologia , Células CACO-2 , Antibacterianos/farmacologia , Antibacterianos/química , Difração de Raios X , Gomas Vegetais/farmacologia , Gomas Vegetais/química , Espectroscopia de Infravermelho com Transformada de Fourier
6.
Braz J Anesthesiol ; 73(6): 718-724, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-34411624

RESUMO

INTRODUCTION AND OBJECTIVES: Myofascial Pain Syndrome (MPS) of the Quadratus Lumborum muscle (QL) is a frequent cause of chronic low back pain. With this study, we aimed to assess the efficacy of ultrasound-guided infiltration with 0.25% levobupivacaine and 40.ßmg triamcinolone for MPS of the QL. METHODS: Observational and retrospective study of participants submitted to ultrasound-guided infiltration of the QL muscle from January 1, 2015 to June 31, 2019. Pain intensity was assessed using the five-point pain Numeric Rating Scale (NRS): pre-intervention, at 72.ßhours, 1 month, 3 months and 6 months post-intervention. Additional data collected were demographic characteristics, opioid consumption, and adverse effects. RESULTS: We assessed 90 participants with mean age of 55.2 years. Sixty-eight percent of participants were female. Compared to the pre-intervention assessment, there was an improvement in pain at 72.ßhours (Mean Difference [MD.ß=.ß3.085]; 95% CI: 2.200...3.970, p.ß<.ß0.05), at the 1st month (MD.ß=.ß2.644; 95% CI: 1.667...3.621, p.ß<.ß 0.05), at the 3rdmonth (MD.ß=.ß2.017; 95% CI: 0.202...2.729, p.ß<.ß0.05) and at the 6th month (MD.ß=.ß1.339; 95% CI 0.378...2.300, p.ß<.ß0.05), post-intervention. No statistically significant differences in opioid consumption were observed. No adverse effects associated with the technique were reported. CONCLUSIONS: Ultrasound-guided infiltration of the QL muscle is a safe and effective procedure for the treatment of pain in the QL MPS within 6 months post-intervention.


Assuntos
Síndromes da Dor Miofascial , Bloqueio Nervoso , Humanos , Feminino , Pessoa de Meia-Idade , Masculino , Levobupivacaína , Triancinolona , Estudos Retrospectivos , Analgésicos Opioides , Bloqueio Nervoso/métodos , Ultrassonografia de Intervenção/métodos , Dor , Síndromes da Dor Miofascial/tratamento farmacológico
7.
J Funct Biomater ; 13(2)2022 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-35645271

RESUMO

Tissue engineering using scaffolds is a promising strategy to repair damaged articular cartilage, whose self-repair is inefficient. Cellulose properties have been recognized for their application in the biomedical field. The aim of this study was to fabricate and characterize novel scaffolds based on poly(ɛ-caprolactone) (PCL) and sustainable cellulose. Thus, the performance of corncob-derived cellulose (CC) in scaffolds as an alternative to wood cellulose (WC) was also investigated to reduce the environmental footprint. Two concentrations of CC in scaffolds were tested, 1% and 2% (w/w), and commercial WC using the same concentrations, as a control. Morphologically, all the developed scaffolds presented pore sizes of ~300 µm, 10 layers, a circular shape and well-dispersed cellulose. Thus, all of these characteristics and properties provide the manufactured scaffolds suitable for use in cartilage-replacement strategies. The use of 2% CC results in higher porosity (54.24%), which promotes cell infiltration/migration and nutrient exchange, and has similar mechanical properties to WC. As for the effects of enzymatic degradation of the scaffolds, no significant changes (p > 0.05) were observed in resistance over time. However, the obtained compressive modulus of the scaffold with 2% CC was similar to that of WC. Overall, our results suggest that the integration of 2% corncob cellulose in PCL scaffolds could be a novel way to replace wood-cellulose-containing scaffolds, highlighting its potential for cartilage-replacement strategies.

8.
Molecules ; 27(9)2022 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-35566176

RESUMO

Resole resins have many applications, especially for foam production. However, the use of phenol, a key ingredient in resoles, has serious environmental and economic disadvantages. In this work, lignin extracted from pine wood using a "green" solvent, levulinic acid, was used to partially replace the non-sustainable phenol. The physicochemical properties of this novel resin were compared with resins composed of different types of commercial lignins. All resins were optimized to keep their free formaldehyde content below 1 wt%, by carefully adjusting the pH of the mixture. Substitution of phenol with lignin generally increases the viscosity of the resins, which is further increased with the lignin mass fraction. The addition of lignin decreases the kinetics of gelification of the resin. The type and amount of lignin also affect the thermal stability of the resins. It was possible to obtain resins with higher thermal stability than the standard phenol-formaldehyde resins without lignin. This work provides new insights regarding the development of lignin-based resoles as a very promising sustainable alternative to petrol-based resins.


Assuntos
Lignina , Pinus , Formaldeído/química , Ácidos Levulínicos , Lignina/química , Fenol/química , Fenóis/química , Polímeros , Solventes , Madeira
9.
Sci Total Environ ; 806(Pt 2): 150560, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34607099

RESUMO

Better performances of cellulose-based polymers can be achieved by adjust their architecture including the density of cationic modifications. In this study, the influence of cationic substitution on the ecotoxicity of four quaternized hydroxyethyl cellulose polymers (SK-H, SK-L, SK-M, SK-MH) was studied, using an aquatic biota acute ecotoxicity classification, and rheological and physicochemical characterization. The ecotoxicity characterization was achieved by performing standard ecotoxicity assays with seven key trophic level species: Vibrio fischeri, Raphidocelis subcapitata, Chlorella vulgaris, Daphnia magna, Brachionus calyciflorus, Heterocypris incongruens, and Danio rerio. Median effective concentrations were used to compute hazard concentrations, through the species sensitive distribution curves method. The microalga C. vulgaris and rotifer B. calyciflorus were the most sensitive species to the studied polymers. The SK-H variant was highly toxic to the rotifer. Overall, variants with intermediate levels of cationic charge (SK-M, SK-MH) presented the lowest toxicity. The SK-M variant showed the lowest value of maximum acceptable concentration (0.00354 mg/L), thus being indicated as the least toxic variant. Therefore, the obtained results suggest that industry could direct the development of this type of polymers by tailoring its cationic substitution to moderate levels, in such a way that both functionality and environmental toxicity could be maximized.


Assuntos
Chlorella vulgaris , Poluentes Químicos da Água , Aliivibrio fischeri , Animais , Organismos Aquáticos , Biota , Celulose/toxicidade , Daphnia , Polímeros/toxicidade , Poluentes Químicos da Água/toxicidade
10.
Int J Pharm ; 609: 121139, 2021 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-34592397

RESUMO

Emergent diseases caused by viral and bacterial infections have proven to be a current and future challenge. The occurrence of these diseases is usually accompanied by the lack of vaccines and dedicated therapies leaving prevention as the best strategy to adopt. In that context, and apart from confinement and physical distancing measures, an increase in hygiene actions, namely hand and surface cleaning and disinfection can reduce the infection spread originated from our day-to-day routines. However, during crisis situations the high disinfectants demand can very likely lead to having them running out of stock. This impels many individuals and companies to produce their own disinfectants. Here, we explore the main components of a disinfection formulation, both for hand-rub and surface cleaning. Alcohol and non-alcohol based formulations are described, including the possibility to fine tune the properties of the final product in order to increase public acceptance while maintaining product efficacy. The action mechanisms of the main active principles are also described conjugating information from experimental and theoretical data. Overall, the main aspects to develop a disinfectant formulation are addressed, as well as their function, helping formulation developers to better understand the impact of their choices.


Assuntos
Desinfetantes , Higienizadores de Mão , Antibacterianos/farmacologia , Antivirais , Desinfetantes/farmacologia , Desinfecção , Etanol , Humanos
11.
Pain Ther ; 10(2): 1427-1437, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34455548

RESUMO

INTRODUCTION: Chronic pain (CP) negatively impacts the lives of almost 2 billion people worldwide, including approximately 37% of adults in Portugal. As most of these patients are followed by a general practitioner, identifying the prevalence and characterizing the pain of patients who visit primary care units will provide valuable insights into the CP landscape in Portugal. METHODS: To achieve this goal, an observational, cross-sectional study was conducted in 58 primary care units of mainland Portugal between June 2017 and March 2018. Interviews were conducted with 8445 patients, and 578 CP patients were characterized. RESULTS: We observed that one third of patients suffered from CP, and of these, approximately one third felt that their pain management was insufficient. Most of the population was 55 years old or older, retired, and had more than three comorbidities. However, age and the number and type of comorbidities were not predictors of pain intensity. Additionally, most of the population had pain or discomfort that hindered their mobility and the performance of their everyday activities. This decrease in the quality of life led to feelings of anxiety and depression, which were associated with pain intensity. CONCLUSION: Given the high prevalence of CP, strategies to improve the quality of life of these patients and decrease the negative impacts, as well as awareness campaigns to increase the populations' knowledge of this condition, are essential for the suitable and timely treatment of CP.

12.
Soft Matter ; 17(30): 7086-7098, 2021 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-34155497

RESUMO

The use of enzymes as biocatalysts in industrial applications has received much attention during the last few years. Lipases are widely employed in the food and cosmetic industry, for the synthesis of novel biomaterials and as a greener solution for the treatment of waste cooking oils (WCO). The latter topic has been widely explored with the use of enzymes from several origins and types, for the treatment of different used and non-used cooking oils. The experimental conditions of such works are also quite broad, hampering the detailed understanding of the process. In this work we present a detailed characterization of the interaction of several commonly used lipases with different types of vegetal oils and food fats through coarse-grained molecular dynamics simulations. First, the molecular details of the oil/water (O/W) mixtures, namely at the O/W interface, are described. The O/W interface was found to be enriched in triglyceride molecules with higher polarity. Then, the interaction of lipases with oil mixtures is characterized from different perspectives, including the identification of the most important protein residues for this process. The lipases from Thermomyces lanuginosus (TLL), Rhizomucor miehei (RML) and Candida antarctica (CALB) were found to bind to the O/W interface in a manner that makes the protein binding site more available for the oil molecules. These enzymes were also found to efficiently bind to the O/W interface of all oil mixtures, which in addition to reactivity factors, may explain the efficient applicability of these enzymes to a large variety of edible oils and WCO.


Assuntos
Enzimas Imobilizadas , Óleos , Basidiomycota , Eurotiales , Rhizomucor , Água
13.
Polymers (Basel) ; 13(5)2021 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-33652842

RESUMO

The dissolution and extraction of lignin from biomass represents a great challenge due to the complex structure of this natural phenolic biopolymer. In this work, several surfactants (i.e., non-ionic, anionic, and cationic) were used as additives to enhance the dissolution efficiency of model lignin (kraft) and to boost lignin extraction from pine sawdust residues. To the best of our knowledge, cationic surfactants have never been systematically used for lignin dissolution. It was found that ca. 20 wt.% of kraft lignin is completely solubilized using 1 mol L-1 octyltrimethylammonium bromide aqueous solution. A remarkable dissolution efficiency was also obtained using 0.5 mol L-1 polysorbate 20. Furthermore, all surfactants used increased the lignin extraction with formic acid, even at low concentrations, such as 0.01 and 0.1 mol L-1. Higher concentrations of cationic surfactants improve the extraction yield but the purity of extracted lignin decreases.

14.
Int J Biol Macromol ; 177: 294-305, 2021 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-33607141

RESUMO

Lignocellulosic biomass is a renewable and sustainable feedstock, mainly composed of cellulose, hemicellulose, and lignin. Lignin, as the most abundant natural aromatic polymer occurring on Earth, has great potential to produce value-added products. However, the isolation of highly pure lignin from biomass requires the use of efficient methods during lignocellulose fractionation. Therefore, in this work, novel acidic deep eutectic solvents (DESs) were prepared, characterized and screened for lignin extraction from maritime pine wood (Pinus pinaster Ait.) sawdust. The use of cosolvents and the development of new DES were also evaluated regarding their extraction and selectivity performance. The results show that an 1 h extraction process at 175 °C, using a novel DES composed of lactic acid, tartaric acid and choline chloride, named Lact:Tart:ChCl, in a molar ratio of 4:1:1, allows the recovery of 95 wt% of the total lignin present in pine biomass with a purity of 89 wt%. Such superior extraction of lignin with remarkable purity using a "green" solvent system makes this process highly appealing for future large-scale applications.


Assuntos
Colina/química , Ácido Láctico/química , Lignina/isolamento & purificação , Pinus/química , Tartaratos/química , Madeira/química , Lignina/química , Solventes/química
15.
J Hazard Mater ; 409: 124966, 2021 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-33418294

RESUMO

The hydrophobic substitution (HS) of cationic cellulose derivatives may be tuned, promoting their efficiency. This work studied the influence of HS on the acute ecotoxicity of quaternized hydroxyethyl cellulose polymers (SL) to aquatic biota. The ecotoxicity of four SL with different HS (SL-5, SL-30, SL-60, SL-100) was assessed for seven species: Vibrio fischeri, Raphidocelis subcapitata, Chlorella vulgaris, Daphnia magna, Brachionus calyciflorus, Heterocypris incongruens, and Danio rerio. The computed median effective concentrations were used to derive hazard concentrations, by using species sensitive distribution curves. All SL suspensions were characterized for particle size, zeta potential and rheological properties. Results indicated instability of the SL in suspension due to their relatively low zeta potential. Raphidocelis subcapitata, C. vulgaris and B. calyciflorus were the most sensitive to the four SL, suggesting that exposure to these compounds may imbalance the lowest trophic levels. Also, HS influenced the toxicity of SL, with the lowest HS (SL-5) revealing lower ecotoxicity. The maximum acceptable concentrations were 14.0, 2.9, 3.9 and 1.4 mg L-1 for SL-5, SL-30, SL-60, and SL-100, respectively. Accordingly, SL-5 is suggested as the eco-friendliest and is recommended to be used in the production of care products, in detriment of the other three tested variants.


Assuntos
Chlorella vulgaris , Poluentes Químicos da Água , Aliivibrio fischeri , Animais , Organismos Aquáticos , Biota , Celulose/toxicidade , Daphnia , Polímeros/toxicidade , Poluentes Químicos da Água/toxicidade
16.
Polymers (Basel) ; 13(1)2020 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-33374920

RESUMO

Food contamination due to the presence of microorganisms is a serious problem. New food preservation systems are being studied to kill or inhibit spoilage and pathogenic microorganisms that contaminate food and reduce the shelf life of products. Chitosan films with potential application to food preservation have witnessed great developments during the last years. Chitosan is a cationic polysaccharide with the ability to form films and possess antimicrobial properties. It is water-insoluble but can be dissolved in acidic solutions. In the present work, three different acids (acetic, lactic and citric) were used in chitosan dissolution and both, the resultant solutions and formed films were characterized. It was observed that chitosan water-acetic acid systems show the highest antimicrobial activity due to the highest chitosan charge density, compared to the mixtures with lactic and citric acid. This system showed also the higher solution viscosity compared to the other systems. Chitosan-acetic acid films were also the ones presenting better mechanical properties; this can be attributed to the fact that lactic and citric acids remain in the films, changing their properties, which does not happen with acetic acid. Films produced from chitosan dissolved in water/acetic acid system are resistant, while very fragile but elastic films are formed when lactic acid is used. It was demonstrated that a good selection of the type of acid not only facilitates the dissolution of chitosan but also plays a key role in the properties of the formed solutions and films.

17.
Int J Mol Sci ; 21(18)2020 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-32948026

RESUMO

Catanionic vesicles are emerging interesting structures for bioapplications. They self-generate by a pairing of oppositely charged ionic surfactants that assemble into hollow structures. Specifically, the anionic-cationic surfactant pair assumes a double-tailed zwitterionic behavior. In this work, the multilamellar-to-unilamellar thermal transition of several mixed aqueous systems, with a slight excess of the anionic one, were investigated. Interestingly, it was found that the anionic counterion underwent a dissociation as a consequence of a temperature increase, leading to the mentioned thermal transition. The present work proposed the spectroscopic techniques, specifically multinuclear NMR and PGSTE (pulsed gradient stimulated echo), as a key tool to study such systems, with high accuracy and effectiveness, while requiring a small amount of the sample. The results presented herein evidence encouraging perspectives, forecasting the application of the studied vesicular nanoreservoirs, for e.g., drug delivery.


Assuntos
Nanotubos de Carbono/química , Ressonância Magnética Nuclear Biomolecular/métodos , Ânions/química , Cátions/química , Compostos de Cetrimônio/química , Micelas , Microscopia Confocal , Transição de Fase , Dodecilsulfato de Sódio/química , Tensoativos/química , Temperatura
18.
Int J Biol Macromol ; 164: 3454-3461, 2020 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-32827621

RESUMO

Lignin is a natural, renewable resource with potential to be used in biomaterials. Due to its complex structure, its efficient dissolution is still challenging, which hinders its applicability at large scale. This challenge become harder considering the current need of sustainable and environmentally friendly solvents. To the best of our knowledge, this work reports for the first time the dissolution of kraft lignin in levulinic acid, a "green" solvent, and compares its efficiency with common carboxylic acids and sulfuric acid. It has been found that levulinic acid has a high capacity to dissolve kraft lignin at room temperature (40 wt% solubility), and it efficiency is not compromised when diluting the acid with water (up to 40 wt% water content). The Kamlet-Taft π⁎ parameter of the different acidic solvents was estimated and found to correlate well with their solubility performance. Lignins previously dissolved in levulinic and formic acids were selected to be regenerated and minor differences were found in thermal stability and morphological structure, when compared to native kraft lignin. However, an increase in the content of the carbonyl groups in the regenerated lignin material was observed.


Assuntos
Ácidos Levulínicos/química , Lignina/química , Solventes/química , Fenômenos Químicos , Reologia , Solubilidade , Análise Espectral
19.
J Chem Theory Comput ; 16(7): 4734-4743, 2020 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-32496775

RESUMO

The characterization of the affinity and binding mechanism of specific molecules to a protein active site is scientifically and industrially relevant for many applications. In principle, this information can be obtained using molecular dynamics (MD) simulations by calculating the free energy profile of the process. However, this is a computationally demanding calculation. Currently, coarse-grained (CG) force fields are very well implemented for MD simulations of biomolecular systems. These computationally efficient force fields are a major advantage to the study of large model systems and/or those requiring long simulation times. The Martini model is currently one of the most popular CG force fields for these systems. For the specific case of protein simulations, to correctly maintain the macromolecular three-dimensional structure, the Martini model needs to include an elastic network (EN). In this work, the effect of protein flexibility, as induced by three EN models compatible with the Martini force field, was tested on the calculation of free energy profiles for protein-ligand binding. The EN models used were ElNeDyn, GoMartini, and GEN. The binding of triolein (TOG) and triacetin (TAG) to a lipase protein (thermomyces lanuginosa lipase-TLL) was used as a case study. The results show that inclusion of greater flexibility in the CG parameterization of proteins is of high importance in the calculation of the free energy profiles of protein-ligand systems. However, care must be taken in order to avoid unjustified large protein deformations. In addition, due to molecular flexibility there may be no absolute need for the center of the ligand to reach the center of the protein-binding site. The calculation of the energy profile to a distance of about 0.5 nm from the active site center can be sufficient to differentiate the affinity of different ligands to a protein.


Assuntos
Proteínas Fúngicas/química , Ligantes , Lipase/química , Sítios de Ligação , Eurotiales/enzimologia , Proteínas Fúngicas/metabolismo , Lipase/metabolismo , Simulação de Dinâmica Molecular , Ligação Proteica , Triacetina/química , Triacetina/metabolismo , Trioleína/química , Trioleína/metabolismo
20.
Int J Biol Macromol ; 148: 688-695, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31954786

RESUMO

Lignins are among the most abundant renewable resources on the planet. However, their application is limited by the lack of efficient dissolution and extraction methodologies. In this work, a systematic and quantitative analysis of the dissolution efficiency of different alkaline-based aqueous systems (i.e. lithium hydroxide, LiOH; sodium hydroxide, NaOH; potassium hydroxide, KOH; cuprammonium hydroxide, CuAOH; tetrapropylammonium hydroxide, TPAOH and tetrabutylammonium hydroxide, TBAOH) is reported, for the first time, for kraft lignin. Phase maps were determined for all systems and lignin solubility was found to decrease in the following order: LiOH > NaOH > KOH > CuAOH > TPAOH > TBAOH, thus suggesting that the size of the cation plays an important role on its solubility. The π∗ parameter has an opposite trend to the solubility, supporting the idea that cations of smaller size favor lignin solubility. Dissolution was observed to increase exponentially above pH 9-10 being the LiOH system the most efficient. The soluble and insoluble fractions of lignin in 0.1 M NaOH were collected and analyzed by several techniques. Overall, data suggests a greater amount of simple aromatic compounds, preferentially containing sulfur, in the soluble fraction while the insoluble fraction is very similar to the native kraft lignin.


Assuntos
Hidróxidos/química , Lignina/química , Cátions/química , Compostos de Lítio/química , Compostos de Potássio/química , Hidróxido de Sódio/química , Solubilidade , Água/química
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