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1.
J Phys Chem B ; 2024 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-38845485

RESUMO

This study investigates the nanoscale self-assembly from mixtures of two symmetrical poly(ethylene oxide)-poly(propylene oxide)-pol(ethylene oxide) (PEO-PPO-PEO) block copolymers (BCPs) with different lengths of PEO blocks and similar PPO blocks. The blended BCPs (commercially known as Pluronic F88 and L81, with 80 and 10% PEO, respectively) exhibited rich phase behavior in an aqueous solution. The relative viscosity (ηrel) indicated significant variations in the flow behavior, ranging from fluidic to viscous, thereby suggesting a possible micellar growth or morphological transition. The tensiometric experiments provided insight into the intermolecular hydrophobic interactions at the liquid-air interface favoring the surface activity of mixed-system micellization. Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) revealed the varied structural morphologies of these core-shell mixed micelles and polymersomes formed under different conditions. At a concentration of ≤5% w/v, Pluronic F88 exists as molecularly dissolved unimers or Gaussian chains. However, the addition of the very hydrophobic Pluronic L81, even at a much lower (<0.2%) concentration, induced micellization and promoted micellar growth/transition. These results were further substantiated through molecular dynamics (MD) simulations, employing a readily transferable coarse-grained (CG) molecular model grounded in the MARTINI force field with density and solvent-accessible surface area (SASA) profiles. These findings proved that F88 underwent micellar growth/transition in the presence of L81. Furthermore, the potential use of these Pluronic mixed micelles as nanocarriers for the anticancer drug quercetin (QCT) was explored. The spectral analysis provided insight into the enhanced solubility of QCT through the assessment of the standard free energy of solubilization (ΔG°), drug-loading efficiency (DL%), encapsulation efficiency (EE%), and partition coefficient (P). A detailed optimization of the drug release kinetics was presented by employing various kinetic models. The [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] MTT assay, a frequently used technique for assessing cytotoxicity in anticancer research, was used to gauge the effectiveness of these QCT-loaded mixed nanoaggregates.

2.
ACS Nano ; 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38833572

RESUMO

Amyloid-like fibrils are garnering keen interest in biotechnology as supramolecular nanofunctional units to be used as biomimetic platforms to control cell behavior. Recent insights into fibril functionality have highlighted their importance in tissue structure, mechanical properties, and improved cell adhesion, emphasizing the need for scalable and high-kinetics fibril synthesis. In this study, we present the instantaneous and bulk formation of amyloid-like nanofibrils from human platelet lysate (PL) using the ionic liquid cholinium tosylate as a fibrillating agent. The instant fibrillation of PL proteins upon supramolecular protein-ionic liquid interactions was confirmed from the protein conformational transition toward cross-ß-sheet-rich structures. These nanofibrils were utilized as building blocks for the formation of thin and flexible free-standing membranes via solvent casting to support cell self-aggregation. These PL-derived fibril membranes reveal a nanotopographically rough surface and high stability over 14 days under cell culture conditions. The culture of mesenchymal stem cells or tumor cells on the top of the membrane demonstrated that cells are able to adhere and self-organize in a three-dimensional (3D) spheroid-like microtissue while tightly folding the fibril membrane. Results suggest that nanofibril membrane incorporation in cell aggregates can improve cell viability and metabolic activity, recreating native tissues' organization. Altogether, these PL-derived nanofibril membranes are suitable bioactive platforms to generate 3D cell-guided microtissues, which can be explored as bottom-up strategies to faithfully emulate native tissues in a fully human microenvironment.

3.
Chem Bio Eng ; 1(1): 44-52, 2024 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-38434799

RESUMO

Artemisinin, a drug used to treat malaria, can be chemically synthesized or extracted from Artemisia annua L. However, the extraction method for artemisinin from biomass needs to be more sustainable while maintaining or enhancing its bioactivity. This work investigates the use of aqueous solutions of salts and ionic liquids with hydrotropic properties as alternative solvents for artemisinin extraction from Artemisia annua L. Among the investigated solvents, aqueous solutions of cholinium salicylate and sodium salicylate were found to be the most promising. To optimize the extraction process, a response surface method was further applied, in which the extraction time, hydrotrope concentration, and temperature were optimized. The optimized conditions resulted in extraction yields of up to 6.50 and 6.44 mg·g-1, obtained with aqueous solutions of sodium salicylate and cholinium salicylate, respectively. The extracts obtained were tested for their antimalarial activity, showing a higher efficacy against the Plasmodium falciparum strain compared with pure (synthetic) artemisinin or extracts obtained with conventional organic solvents. Characterization of the extracts revealed the presence of artemisinin together with other compounds, such as artemitin, chrysosplenol D, arteannuin B, and arteannuin J. These compounds act synergistically with artemisinin and enhance the antimalarial activity of the obtained extracts. Given the growing concern about artemisinin resistance, the results here obtained pave the way for the development of sustainable and biobased antimalarial drugs.

4.
ChemSusChem ; : e202301801, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38323919

RESUMO

The economic advantages of H2 SO4 make it the acid of choice for the hydrometallurgical treatment of waste lithium-ion batteries (LIBs). However, to facilitate the full dissolution of the higher valency metal oxides present in the cathode black mass, a suitable reducing agent is required. Herein, the application of industrial black liquor (BL) obtained from the Kraft pulping for papermaking is investigated as a renewable reducing agent for the enhanced leaching of transition metals from LIB powder with H2 SO4 . The addition of acidified BL to H2 SO4 significantly improved the leaching efficiency for a range of LIB cathode chemistries, with the strongest effect observed for manganese-rich active material. Focusing on NMC111 (LiMnx Coy Niz O2 ) material, a linear correlation between the BL concentration and the leaching yield of Mn was obtained, with the best overall leaching efficiencies being achieved for 2.0 mol L-1 H2 SO4 and 50 vol % of BL at 353 K. A quasi-total degradation of oxygenated and aromatic groups from the BL during NMC111 dissolution was observed after leaching, suggesting that these chemical groups are essential for LIB reduction. Finally, the leached transition metals could be easily recovered by pH adjustment and oxalic acid addition, closing the resource loop and fostering resource efficiency.

5.
Phys Chem Chem Phys ; 26(9): 7308-7317, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38351888

RESUMO

The understanding of molecular interactions that control phase separation in polymer/polymer aqueous two-phase systems (ATPS) has been a subject of debate up to this day. In light of this, we set out to investigate the molecular interactions occurring in ternary mixtures composed of polyethylene glycol (PEG600), polypropylene glycol (PPG400) and water. The ternary phase diagram was plotted at two temperatures (298 K and 323 K), revealing a transition from a type 0 to a type I diagram. Molecular dynamics (MD) simulations were performed to elucidate the polymer-polymer and polymer-water interactions occurring at different temperatures and water concentrations. COnductor-like Screening Model for Realistic Solvents (COSMO-RS) was used to assess the thermodynamic properties of the polymer-water binary mixtures and their correlation with ATPS formation. The MD simulations clearly demonstrate the effect of segregation/separation with increasing water content and temperature, highlighting a significant reduction in PPG-water interactions compared to PEG-water counterparts. Polymer-water interactions were identified as those controlling the phase separation mechanism, and the thermodynamic properties determined with COSMO-RS for the polymer-water binary systems further support this view.

6.
Radiol Case Rep ; 19(3): 835-838, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38188946

RESUMO

Biliary injury secondary to trauma is frequently associated with long-term complications. Liver transplantation is rarely indicated but might be the best therapeutic option in severe or intractable cases. We report the case of a 19-year-old male referred for liver transplantation due to biliary injury after abdominal trauma. A Roux-en-Y hepaticojejunostomy was initially performed without immediate complications. Anastomotic stricture developed requiring several trials of biliary dilatation and stenting through a percutaneous approach. The presence of liver cirrhosis and the intractability of this complication culminated in the decision of liver transplantation. The authors present clinical course, complications and interventional procedures that were used in a judicious step-up approach.

7.
Int J Biol Macromol ; 253(Pt 8): 127540, 2023 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-37863128

RESUMO

Although pentraxin-3 holds promise as a diagnosis/prognosis biomarker of microbial infections and lung cancer, its analysis in human serum can be constrained by matrix effects caused by high abundance proteins - human serum albumin and immunoglobulin G. Aqueous biphasic systems composed of polymers and citrate buffer are here proposed as a serum pretreatment step to improve the accuracy of pentraxin-3 analysis. Binodal curves were determined to identify the compositions required to form two phases and to correlate the polymers' properties and performance in serum pretreatment and biomarker extraction. Aqueous biphasic systems were evaluated regarding their ability to deplete human serum albumin and immunoglobulin G at the interphase. Polymers of relatively high to intermediate hydrophobicity were unveiled as efficient components to deplete high abundance serum proteins. Considering the possibility to extract pentraxin-3 from human serum into the polymer-rich phase, the system composed of polyethylene glycol with a molecular weight of 1000 g·mol-1 simultaneously achieved >93 % of human serum albumin and immunoglobulin G depletion and complete biomarker extraction. The accuracy of analysis of pretreated human serum by enzyme-linked immunosorbent assays outperformed that of a non-pretreated sample, with a relative error of 0.8 % compared to 14.6 %, contributing to boost pentraxin-3 usefulness as a biomarker.


Assuntos
Polietilenoglicóis , Polímeros , Humanos , Água , Albumina Sérica Humana , Imunoglobulina G , Biomarcadores
9.
Phys Chem Chem Phys ; 25(38): 26327-26340, 2023 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-37750038

RESUMO

Some ionic liquids (ILs) were shown to display a strong ability to enhance the solubility of phenolic compounds through hydrotropy. However, evidence shows that salt ions in hydrotropic aqueous solutions may change the behavior of molecules by promoting possible interactions between the components of the system, thus causing changes in solubility. Herein, we study the impact of sodium salt anions on the hydrotropic dissolution of syringic acid using 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) as a hydrotrope, with a focus on dicyanamide Na[N(CN)2] and thiocyanate Na[SCN] salts. Dynamic light scattering, Raman spectroscopy, and nuclear magnetic resonance spectroscopy were used to investigate how the mixture of IL-salts affects the solvation. The results obtained show that [C4mim]Cl is able to increase the solubility of syringic acid 80-fold. Despite their structural similarities, the presence of Na[N(CN)2] or Na[SCN] in an aqueous solution of [C4mim]Cl induced opposite solubility trends. The addition of Na[N(CN)2] promotes a higher ability to solubilize syringic acid than in the corresponding IL system due to a pH buffering effect, resulting in the deprotonation of the solute. The addition of Na[SCN], on the other hand, induces a relative decrease in syringic acid solubilization at higher concentrations of ILs due to the negative contribution of the NaCl formed by anion-exchange. These results emphasise the often overlooked pH contribution provided by ILs for biomolecule solubilisation whilst providing experimental insights into the structure of aqueous solutions of ionic liquids and the role it plays in the formation of IL-salt aggregates.

10.
Genes (Basel) ; 14(8)2023 08 14.
Artigo em Inglês | MEDLINE | ID: mdl-37628675

RESUMO

Malaria in pregnancy (MiP) is a public health problem in malaria-endemic areas, contributing to detrimental outcomes for both mother and fetus. Primigravida and second-time mothers are most affected by severe anemia complications and babies with low birth weight compared to multigravida women. Infected erythrocytes (IE) reach the placenta, activating the immune response by placental monocyte infiltration and inflammation. However, specific markers of MiP result in poor outcomes, such as low birth weight, and intrauterine growth restriction for babies and maternal anemia in women infected with Plasmodium falciparum are limited. In this study, we identified the plasma proteome signature of a mouse model infected with Plasmodium berghei ANKA and pregnant women infected with Plasmodium falciparum infection using quantitative mass spectrometry-based proteomics. A total of 279 and 249 proteins were quantified in murine and human plasma samples, of which 28% and 30% were regulated proteins, respectively. Most of the regulated proteins in both organisms are involved in complement system activation during malaria in pregnancy. CBA anaphylatoxin assay confirmed the complement system activation by the increase in C3a and C4a anaphylatoxins in the infected plasma compared to non-infected plasma. Moreover, correlation analysis showed the association between complement system activation and reduced head circumference in newborns from Pf-infected mothers. The data obtained in this study highlight the correlation between the complement system and immune and newborn outcomes resulting from malaria in pregnancy.


Assuntos
Malária , Placenta , Recém-Nascido , Gravidez , Lactente , Feminino , Humanos , Animais , Camundongos , Camundongos Endogâmicos CBA , Ativação do Complemento , Biomarcadores
11.
ChemSusChem ; 16(15): e202300455, 2023 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-37317672

RESUMO

The recovery of critical metals from spent lithium-ion batteries (LIBs) is rapidly growing. Current methods are energy-intensive and hazardous, while alternative solvent-based strategies require more studies on their 'green' character, metal dissolution mechanism and industrial applicability. Herein, we bridged this gap by studying the effect of dilute HCl solutions in hydroxylated solvents to dissolve Co, Ni and Mn oxides. Ethylene glycol emerged consistently as the most effective solvent, dissolving up to four times more Co and Ni oxides than using aqueous acidic media, attributed to improved chloro-complex formation and solvent effects. These effects had a significant contribution compared to acid type and concentration. The highest Co dissolution (0.27 M) was achieved in 0.5 M HCl in 25 % (v/v) glycerol in water, using less acid and a significant amount of water compared to other solvent systems, as well as mild temperatures (40 °C). This solvent was applied to dissolve battery cathode material, achieving 100 % dissolution of Co and Mn and 94 % dissolution of Ni, following what was concluded to be a mixed mechanism. These results offer a simple alternative to current leaching processes, reducing acid consumption, enhancing atomic efficiency, and paving the way for optimized industrial hydrometallurgical processes leaning to 'greener' strategies.

12.
Phys Chem Chem Phys ; 25(16): 11227-11236, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37039782

RESUMO

The solid-liquid phase behaviour of two tertiary alcohols, perfluoro-tert-butanol and tert-butanol, was studied here using experimental (ITC, DSC and density measurements) and theoretical (MD simulations) approaches. The phase diagram of the binary mixture reveals highly negative deviations from ideality at low concentrations, as well as the formation of co-crystals and is characterized by two eutectic points, a congruent melting point and a peritectic reaction corresponding to TBH : TBF stoichiometries of 2 : 1 and 1 : 1 respectively. Excess molar enthalpies and volumes were calculated, showing negative and positive deviations from ideality, respectively. The effect of acidity, stereochemical hindrance and phobic effects and how they affect intermolecular interactions in these binary mixtures is discussed, with the aim of designing and fine-tuning type V deep eutectic solvents. The results showed that the fluorination of tertiary alcohols can be used for the tuning of the mixing properties and solid-liquid phase diagrams.

13.
Ind Eng Chem Res ; 62(12): 5326-5335, 2023 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-37014371

RESUMO

The Abraham and NRTL-SAC semipredictive models were employed to represent the solubility of (-)-borneol, (1R)-(+)-camphor, l-(-)-menthol, and thymol in water and organic solvents, using data measured in this work and collected from the literature. A reduced set of solubility data was used to estimate the model parameters of the solutes, and global average relative deviations (ARDs) of 27% for the Abraham model and 15% for the NRTL-SAC model were obtained. The predictive capability of these models was tested by estimating the solubilities in solvents not included in the correlation step. Global ARDs of 8% (Abraham model) and 14% (NRTL-SAC model) were obtained. Finally, the predictive COSMO-RS model was used to describe the solubility data in organic solvents, with ARD of 16%. These results show the overall better performance of NRTL-SAC in a hybrid correlation/prediction approach, while COSMO-RS can produce very satisfactory predictions even in the absence of any experimental data.

14.
PLoS Negl Trop Dis ; 17(3): e0011167, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36877732

RESUMO

BACKGROUND: Snakebites represent a significant health problem in tropical countries, with an annual incidence of 2.7 million cases worldwide. The incidence of secondary infections after snake bites is also high and is usually caused by bacteria from the oral cavity of snakes. Morganella morganii has been identified as an important cause of infections and has been guiding antibiotic therapy in several regions of Brazil and the world. METHODOLOGY/PRINCIPAL FINDINGS: We performed a retrospective cross-sectional evaluation of snakebites in hospitalized patients between January 2018 and November 2019 and selected those with secondary infection in their medical records. During the period, 326 cases of snakebites were treated, and 155 (47.5%) of them eventually had secondary infections. However, only seven patients underwent culture of soft tissue fragments, in which three cases were negative culture results, while Aeromonas hydrophila was identified in four cases. Of these, 75% were resistant to ampicillin/sulbactam, 50% had intermediate sensitivity to imipenem, and 25% had intermediate sensitivity to piperacillin/tazobactam. Trimethoprim/sulfamethoxazole (TMP-SMX) was not tested on any strain. Of the 155 cases that progressed to secondary infections, 48.4% (75) were empirically treated with amoxicillin/clavulanate, 41.9% (65) with TMP-SMX, and 32 (22%) of these 144 cases required a change to a second regimen, and 10 of these 32 patients required a third therapeutic regimen. CONCLUSION: Wild animals act as reservoirs of resistant bacteria because their oral cavity favors biofilm formation, which explains the finding of A. hydrophila with a reduced sensitivity profile in this study. This fact is essential for the appropriate choice of empirical antibiotic therapy.


Assuntos
Coinfecção , Mordeduras de Serpentes , Animais , Mordeduras de Serpentes/complicações , Mordeduras de Serpentes/epidemiologia , Mordeduras de Serpentes/microbiologia , Combinação Trimetoprima e Sulfametoxazol/uso terapêutico , Coinfecção/tratamento farmacológico , Brasil/epidemiologia , Estudos Retrospectivos , Estudos Transversais , Antibacterianos/farmacologia , Antibacterianos/uso terapêutico
15.
Annu Rev Chem Biomol Eng ; 14: 141-163, 2023 06 08.
Artigo em Inglês | MEDLINE | ID: mdl-36888992

RESUMO

Are deep eutectic solvents (DESs) a promising alternative to conventional solvents? Perhaps, but their development is hindered by a plethora of misconceptions. These are carefully analyzed here, beginning with the very meaning of DESs, which has strayed far beyond its original scope of eutectic mixtures of Lewis or Brønsted acids and bases. Instead, a definition that is grounded on thermodynamic principles and distinguishes between eutectic and deep eutectic is encouraged, and the types of precursors that can be used to prepare DESs are reviewed. Landmark works surrounding the sustainability, stability, toxicity, and biodegradability of these solvents are also discussed, revealing piling evidence that numerous DESs reported thus far, particularly those that are choline based, lack sufficient sustainability-related traits to be considered green solvents. Finally, emerging DES applications are reviewed, emphasizing their most remarkable feature: the ability to liquefy a solid compound with a target property, allowing its use as a liquid solvent.


Assuntos
Colina , Solventes Eutéticos Profundos , Solventes
16.
Surg Endosc ; 37(4): 3215-3223, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36922427

RESUMO

OBJECTIVES: We aimed to analyze the efficacy and safety of endoscopic sleeve gastroplasty at 3 months as well as to determine factors influencing post-procedural weight loss. METHODS: Seventy-three patients with obesity classes I, II and III (BMI 31.1-46.6 kg/m2) underwent ESG between September 2021 and April 2022 at a tertiary care hospital using Overstitch (Apollo Endosurgery, Austin, TX). ESG's efficacy and safety was evaluated at 1 and 3 months post-procedure with regard to excess weight loss (EWL) and total weight loss (TWL). Categorical variables were expressed as percentages and compared with chi-square test while continuous variables were expressed as mean ± standard deviation and compared with paired t test and analysis of variance (ANOVA) as applicable. Pearson's correlation was used to determine association between factors at baseline and weight loss. RESULTS: Mean age was 49.2 ± 9.7 years with 61 (83.6%) patients being female. Mean initial weight was 105.7 ± 15.7 kg, and mean BMI was 38.6 ± 3.5 kg/m2. Median hospitalization was 2.0 ± 1.8 days with 62 (84.9%) patients discharged after 24 h. One patient had accidental suturing of the stomach to the abdominal wall and diaphragm which was managed laparoscopically. Mean %EWL was 25.4 ± 7.1 and 36.3 ± 11.4, and %TBWL was 11.2 ± 2.6 and 15.8 ± 4.2 at 1 and 3 months, respectively. Significant excess weight loss at 3 months was only observed in patients with BMI < 40 kg/m2 (p = 0.001). CONCLUSIONS: ESG is safe and effective to manage obesity. Significant weight loss at 3 months was only observed in patients with obesity class I and class II.


Assuntos
Gastroplastia , Obesidade Mórbida , Humanos , Feminino , Adulto , Pessoa de Meia-Idade , Masculino , Gastroplastia/métodos , Resultado do Tratamento , Obesidade/complicações , Obesidade/cirurgia , Endoscopia/métodos , Redução de Peso , Obesidade Mórbida/cirurgia
17.
J Chromatogr A ; 1691: 463812, 2023 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-36738573

RESUMO

A study on the formation of ternary biphasic systems composed of heptane, 1-butanol or ethyl acetate and type III or type V deep eutectic solvents based on levulinic acid and choline chloride or thymol was carried. Binodal curves and densities and phase compositions of phases in equilibrium for seven systems are reported. The partition coefficients of six natural compounds, namely quercetin, apigenin, coumarin, ß-ionone, retinol, and α-tocopherol, in these systems were measured. Results show that the influence of choline chloride on the partition coefficients is more significant in systems with 1-butanol or ethyl acetate than previously reported for ethanol, and that the separation of natural compounds is worst when using DES containing thymol instead of choline chloride. Based on these partition coefficients, one system composed of heptane, 1-butanol and the DES choline chloride:levulinic acid at molar ratio 1:3 was selected to be applied in centrifugal partition chromatography, and the results obtained confirmed that it allows a good separation of apigenin, coumarin, ß-ionone and α-tocopherol.


Assuntos
Timol , alfa-Tocoferol , Solventes/química , 1-Butanol , Apigenina , Cromatografia Líquida/métodos , Cumarínicos
18.
Molecules ; 28(4)2023 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-36838595

RESUMO

Anthocyanins from juçara fruits were extracted by pressurized liquid extraction (PLE) or ultrasound-assisted extraction (UAE), using aqueous solutions of 1,2-alkanediols and glycerol ethers as biobased solvents. The PLE (100 bar, 13 min, 1 mL/min flow rate) in the optimal extraction conditions originated 23.1 mganthocyanins·gdry biomass-1. On the other hand, the UAE was 10 min long, and the optimal conditions using 1,2-propanediol were 42.6 wt%, 160 W, and pH 7.0, leading to 50 mganthocyanins·gdry biomass-1. Extractions at the UAE optimized conditions, with aqueous solutions of five different 1,2-alkanediols and three glycerol ethers were performed, and compared to water and ethanolic extracts. The biobased solvent solutions presented anthocyanin yields up to 33% higher than water, and were shown to be as efficient as ethanol/water, but generated extracts with higher antioxidant capacity. The anthocyanin-rich extract of juçara, obtained with 1,2-propanediol, was used in the production of a natural soap and incorporated into a cream, showing that the addition of the juçara extract resulted in an antioxidant capacity in both products.


Assuntos
Euterpe , Frutas , Frutas/química , Antocianinas , Antioxidantes/análise , Propilenoglicol , Solventes , Água , Etanol , Extratos Vegetais
19.
Langmuir ; 39(7): 2692-2709, 2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36763753

RESUMO

Aqueous systems comprising polymers and surfactants are technologically important complex fluids with tunable features dependent on the chemical nature of each constituent, overall composition in mixed systems, and solution conditions. The phase behavior and self-assembly of amphiphilic polymers can be changed drastically in the presence of conventional ionic surfactants and need to be clearly understood. Here, the self-aggregation dynamics of a triblock copolymer (Pluronics L81, EO3PO43EO3) in the presence of three cationic surfactants (with a 12C long alkyl chain but with different structural features), viz., dodecyltrimethylammonium bromide (DTAB), didodecyldimethylammonium bromide (DDAB), and ethanediyl-1,2-bis(dimethyldodecylammonium bromide) (12-2-12), were investigated in an aqueous solution environment. The nanoscale micellar size expressed as hydrodynamic diameter (Dh) of copolymer-surfactant mixed aggregates was evaluated using dynamic light scattering, while the presence of a varied micellar geometry of L81-cationic surfactant mixed micelles were probed using small-angle neutron scattering. The obtained findings were further validated from molecular dynamics (MD) simulations, employing a simple and transferable coarse-grained molecular model based on the MARTINI force field. L81 remained molecularly dissolved up to ∼20 °C but phase separated, forming turbid/translucent dispersion, close to its cloud point (CP) and existed as unstable vesicles. However, it exhibited interesting solution behavior expressed in terms of the blue point (BP) and the double CP in the presence of different surfactants, leading to mixed micellar systems with a triggered morphology transition from unstable vesicles to polymer-rich micelles and cationic surfactant-rich micelles. Such an amendment in the morphology of copolymer nanoaggregates in the presence of cationic surfactants has been well observed from scattering data. This is further rationalized employing the MD approach, which validated the effective interactions between Pluronics-cationic surfactant mixed micelles. Thus, our experimental results integrated with MD yield a deep insight into the nanoscale interactions controlling the micellar aggregation (Pluronics-rich micelles and surfactant-rich micelles) in the investigated mixed system.

20.
Chemosphere ; 314: 137675, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36586444

RESUMO

The use of macroalgae, microalgae and cyanobacteria for metal sorption has been widely reported. Still, there are no studies allowing a direct comparison of the performance of these biomasses, especially while evaluating metal competition. The simultaneous sorption of Co2+, Cu2+, Ni2+ and Zn2+ present in a multi-elemental solution by six macroalgae, two microalgae and three cyanobacteria was evaluated. Brown macroalgae were shown to be the most promising biosorbent, with Undaria pinnatifida having a total metal sorption capacity of 0.6 mmol g-1. Overall, macroalgae performed better than microalgae, followed by cyanobacteria. Carboxyl groups were identified as being the main functional groups involved in metal sorption, and all biomass samples were found to be selective to Cu2+. This was linked not only to its higher complexation constant value with relevant functional groups when compared to the remaining metals, but also the Irving-Williams series. The release of K+ and Ca2+ to the aqueous solution during the metal sorption was followed. The obtained results suggest they are readily exchanged with metals in the solution, indicating the occurrence of an ion-exchange mechanism in metal sorption by most biomass. Red macroalgae are an exception to the reported trends, suggesting that their metal sorption mechanism may differ from the other biomass types.


Assuntos
Cianobactérias , Metais Pesados , Poluentes Químicos da Água , Biomassa , Metais , Plantas , Poluentes Químicos da Água/análise , Adsorção , Concentração de Íons de Hidrogênio
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