Acetone-water Mixtures Research Articles

SYNTHESIS OF NEW FRAMEWORK PHOSPHONATES BY THE INTERACTION OF 2-ETHOXYVINYL DICHLOROPHOSPHONATE WITH 4-ETHYLRESORCINOL

A simple, new and promising approach to obtaining previously unknown phosphorus-containing framework compounds by the developed original synthesis method is proposed. The proposed method is based on the condensation reaction of 2-ethoxyvinylphosphonic acid dichloride with resorcinol and its derivatives in toluene in the presence of trifluoroacetic acid. The article presents the results of a study of the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol. It was found that this reaction results in the formation of a mixture of two regioisomers. The structure and construction of the obtained regioisomeric framework phosphonates were studied using 31P and 1H NMR. The regioisomeric framework phosphonates obtained as a result of the reaction of vinylphosphonate with 4-ethylresorcinol were separated by acylation of the mixture with acetic anhydride, using as a medium and a reagent. One functionalized regioisomer was isolated as an individual product, which was white crystals with good solubility in acetone-water and DMSO mixtures. The structure and composition of the obtained regioisomer were confirmed by 1H, 31P, 13C NMR, IR spectroscopy, mass spectrometry (MALDI) and elemental analysis. It was found that the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol in the presence of an equimolar amount of trifluoroacetic acid in toluene resulted in the formation of a regioisomeric mixture of framework phosphonates in a 4:1 ratio. It was shown that acylation of this regioisomeric mixture with acetic anhydride allowed one of the regioisomers to be isolated individually.

Interactions between small organic molecules and water measured using pressure perturbation calorimetry

Aqueous liquid mixtures play a critical role in many biological and chemical processes. Solutes including sugars, sugar alcohols, carboxylic acids, alcohols and acetone can affect the hydrogen-bonded structure of water and this can be measured using pressure perturbation calorimetry (PPC). In binary water–solute mixtures, Δ(∂CP/∂P)T is a measure of the structure of the water component. At low alcohol concentrations, negative Δ(∂CP/∂P)T values are consistent with clathrate-like water cages around the alkyl moieties. Conversely, when solutes hydrogen bond with water it interferes in the formation of “ice-like” water and is observable as a positive Δ(∂CP/∂P)T. The Δ(∂CP/∂P)T at increasing concentrations of ethanol, acetone and acetic acid in water displayed very different behaviors. Ethanol–water mixtures had three distinct concentration dependent phases; the first, with ethanol surrounded by water molecules, followed by the ethyl groups self-associating breaking the clathrate-like cages, and the ethanol–water network displacing all of the bulk water. Acetic acid–water mixtures display nonlinearity in Δ(∂CP/∂P)T versus acetic acid concentration consistent with acetic acid self-interaction which interferes with acetic acid capacity to disrupt water structure. Acetone-water mixtures display linearity in Δ(∂CP/∂P)T versus acetone concentration which is consistent with acetone’s inability to hydrogen bond with other acetone molecules. The lack of negative Δ(∂CP/∂P)T values in acetic acid-water and acetone-water mixtures suggests there is sufficient self-association between these solutes to prevent clathrate-like water cage formation. PPC can provide invaluable insight into the behavior of aqueous binary mixtures.

Benign and Selective Amination of Lignins towards Aromatic Biobased Building Blocks with Primary Amines.

Lignin is a widely available second-generation biopolymer and the main potential source of renewable aromatic building blocks. Lignin-based polyamines offer great potential in applications based on chemical and materials sciences. However, common aminations techniques for lignin usually involve toxic chemicals and generate hindered and low reactivity amines. In this study, we developed two new, simple, and benign 2-step methodologies for the elaboration of lignin-based polyamines from different technical lignins (kraft, soda and organosolv) with a selectivity towards reactive primary amines. These methods involve grafting amide groups onto lignin followed by a hydrolysis step. Non-toxic heterocyclic compounds N-acetyl-2-oxazolidinone and 2-methyl-2-oxazoline were used as amidation agents. Hydrolysis was performed in acetone-water mixtures. Reactions were studied on model compounds and optimized on lignins. Aminated lignins were fully characterized and primary amines were quantified using quantitative 19F NMR. Our methods generated aminated lignins with low apparent molar masses and high solubility in water and solvents. Nitrogen contents of the products ranged between 2.0 and 3.5 mmol/g with reactive primary amines counts up to 1.7 mmol/g. These soluble and reactive lignin-based polyamines offer great potential as a replacement for fossil-based polyamines in e.g., the synthesis of aromatic polymer materials or as potential chelating, antibacterial agents.

Vitis vinifera L. cv. Falanghina Seed Extracts: Antioxidant Effect of Bioactive Compounds on HepG2 Cells.

Vitis vinifera L. is a natural source of bioactive compounds that is already used for cosmeceutical and nutraceutical approaches. However, their phytochemical and antioxidant properties, although studied, have not been fully explored. We aimed to characterize V. vinifera L. cv. Falanghina seed extracts in different polarity solvents (hexane, ethyl acetate, ethanol, and a mixture of acetone-water) for their phytochemical contents, including the total phenolic compound content (TPC), free radical scavenging capacities, and antioxidant ability on HepG2 cells. We directly profiled the functional quality of V. vinifera seed extracts against H2O2-induced oxidative stress in HepG2 cells, focusing on mitochondrial functions. The content of bioactive compounds was characterized by LC-MS. To assess the cytocompatibility of the extracts, a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was conducted. Results showed that extraction with ethyl acetate (18.12 mg GAE·g-1) and ethanol solvents (18.07 mg GAE·g-1), through Soxhlet, and with an acetone-water mixture (14.17 mg GAE·g-1), through maceration, yielded extracts rich in (poly)phenols, with good scavenging and antioxidant activity (98.32 I% for ethanol solvents and 96.31 I% for acetone-water mixture). The antioxidant effect of polyphenols is at least partially due to their capacity to maintain mitochondrial biogenesis and mitophagy, which elevates mitochondrial efficiency, resulting in diminished ROS production, hence re-establishing the mitochondrial quality control. These findings highlight the valorization of Vitis by-products to improve food functional characteristics.

Thermodynamic studies on the formation of ion-pair cobalt complexes in acetone–water mixtures

Dicarboxylic acids are stronoger acids than moncraboxylic acids and more soluble in water due to the presence of two carboxylic (–COOH) groups which are industrially important in producing polyester, polyamides, and polyols and as a pioneer to pharmaceutical additives. Succinic acid is one of the most prosperous chemicals that can be generated from renewable resources which can be used in the industries of antiseptics, cosmetics, sutures, drugs, solvents, detergents, herbicides, fungicides, synthetic resins, and inks. The ion–pair formation is very important in diferent applications, used widely for inorganic analysis by liquid chromatography and used for the heavy metal removal from waste water, so studing the ion-pair association constant (KA) formed between chloropentamminecobalt(III) cation [CpX2+] and a different ligands of dicarboxylate anions (AC2-), have been determined by EMF technique in different compositions of acetone aqueous media (0–44.20 wt% acetone) for succinic acid and for the other dicarboxylic acids (Maleic, Malonic and Malic) in the same solvent composition (40 wt% acetone) with in temperature range (30 – 60 °C). The thermodynamic association properties (ΔGA°, ΔHA° and ΔSA°) have been estimated and discussed. Extra thermodynamic correlations like ΔHA°- ΔSA° and ΔGA°- ΔGI(orII)° (where I and II are mentioned for the first and second dissociation constant of the dicarboxylic acids) in different compositions of acetone aqueous media for succinic acid and in fixed solvent composition for the other dicarboxylic acids were examined in order to give more information about the behavior of solvent molecules and its effect on formation of the ion-pair molecules. In addition, The Gibbs free energy of transfer for the association process ΔGA°(t) from water to acetone mixed solvents were calculated for succinic acid in order to indicate the spontaneous nature and the stabilization of the ion-pair by increasing the acetone weight percent in the mixed acetone – aqueous media. The linear correlation between pKD values and the relative permittivity of acetone aqueous medium is in accordance to Born’s equation.

Selective Vapor Condensation for the Synthesis and Assembly of Spherical Colloids with a Precise Rough Patch.

Patchy particles occupy an increasingly important space in soft matter research due to their ability to assemble into intricate phases and states. Being able to fine-tune the interactions among these particles is essential to understanding the principles governing the self-assembly processes. However, current fabrication techniques often yield patches that deviate chemically and physically from the native particles, impeding the identification of the driving forces behind self-assembly. To overcome this challenge, we propose a new approach to synthesizing spherical colloids with a well-defined rough patch on their surface. By treating polystyrene microspheres with vapors of a good solvent, here an acetone-water mixture, we achieve selective polymer corrugation on the particle surface resulting in a chemically similar yet rough surface patch. The key step is the selective condensation of the acetone-water vapors on the apex of the polystyrene microparticles immobilized on a substrate, which leads to rough patch formation. We leverage the ability to tune the vapor-liquid equilibrium of the volatile acetone-water mixture to precisely control the polymer corrugation on the particle surface. We demonstrate the dependence of patch formation on particle and substrate wettability, with the condensation occurring on the particle apex only when it is more wettable than the substrate, which is consistent with Volmer's classical nucleation theory. By combining experiments and molecular dynamics simulations, we identify the role of the rough patch in the depletion interaction-driven self-assembly of the microspheres, which is crucial for designing programmable supracolloidal structures.

Getting the phase consistent: The importance of phase description in balanced steady-state free precession MRI of multi-compartment systems.

Determine the correct mathematical phase description for balanced steady-state free precession (bSSFP) signals in multi-compartment systems. Based on published bSSFP signal models, different phase descriptions can be formulated: one predicting the presence and the other predicting the absence of destructive interference effects in multi-compartment systems. Numerical simulations of bSSFP signals of water and acetone were performed to evaluate the predictions of these different phase descriptions. For experimental validation, bSSFP profiles were measured at 3T using phase-cycled bSSFP acquisitions performed in a phantom containing mixtures of water and acetone, which replicates a system with two signal components. Localized single voxel MRS was performed at 7T to determine the relative chemical shift of the acetone-water mixtures. Based on the choice of phase description, the simulated bSSFP profiles of water-acetone mixtures varied significantly, either displaying or lacking destructive interference effects, as predicted theoretically. In phantom experiments, destructive interference was consistently observed in the measured bSSFP profiles of water-acetone mixtures, supporting the theoretical description that predicts such interference effects. The connection between the choice of phase description and predicted observation enables unambiguous experimental identification of the correct phase description for multi-compartment bSSFP profiles, which is consistent with the Bloch equations. The study emphasizes that consistent phase descriptions are crucial for accurately describing multi-compartment bSSFP signals, as incorrect phase descriptions result in erroneous predictions.

By-products of the cocoa agribusiness: high valueadded materials based on their bromatological and chemical characterization

Worldwide, cocoa agribusiness generates about 48 million tons of cocoa pod husk residues annually, and 700 thousand tons of cocoa bean shell, by-products of the pulping and roasting processes. These residues, if not used, can represent an environmental problem. The aim of this research was to identify the potential and use of these by-products through their bromatological composition, lignocellulosic content, aromatic compounds, fatty acid profile, polyphenol and methylxanthine content, and antioxidant capacity. Extraction was made from cocoa husk and shell with a mixture of acetone-water (70:30), applying sonication (40 kHz 15 min-1) and maceration (4 h). Total polyphenols (Folin-Ciocalteau method), antioxidant capacity (DPPH and ABTS), catechin, epicatechin, caffeine, and theobromine (HPLC) were quantified. Aromatic compounds and fatty acid quantifications were evaluated through GC/MS-QP. Cocoa husk and shell stood out for their content of fiber, protein, lignocellulosic material, and fatty acids (oleic, linoleic, elaidic, and stearic). Volatile compounds such as pyrazines, esters, alcohols, and aldehydes were identified in the residues. The results showed that the husk had a higher content of total polyphenols than the shell (26.64 mg GAE g-1 vs. 19.18 mg GAE g-1). The shell exhibited higher values of epicatechin (21.64 mg g-1), theobromine (15.41 mg g-1), and caffeine (4.96 mg g-1) compared to the husk (6.07, 0.53, and 0.52 mg g-1, respectively). Due to their composition, these by-products can be used by different industries, and contribute to obtaining a higher added value and to the solution of environmental problems due to their use.

Influence of the coagulation bath on the nanostructure of cellulose films regenerated from an ionic liquid solution.

Cellulose membranes were prepared from an EMIMAc ionic liquid solution by nonsolvent-induced phase separation (NIPS) in coagulation baths of water-acetone mixtures, ethanol-water mixtures and water at different temperatures. High water volume fractions in the coagulation bath result in a highly reproducible gel-like structure with inhomogeneities observed by small-angle neutron scattering (SANS). A structural transition of cellulose takes place in water-acetone baths at very low water volume fractions, while a higher water bath temperature increases the size of inhomogeneities in the gel-like structure. These findings demonstrate the value of SANS for characterising and understanding the structure of regenerated cellulose films in their wet state. Such insights can improve the engineering and structural tuning of cellulose membranes, either for direct use or as precursors for carbon molecular sieve membranes.

Extraction of Bioactive Compounds from Spent Coffee Grounds Using Ethanol and Acetone Aqueous Solutions.

Given global coffee consumption, substantial quantities of spent coffee grounds (SCGs) are generated annually as a by-product of brewing coffee. SCG, although rich in bioactive compounds, is nowadays disposed of. The objective of this study is to compare, for the first time and from the same SCG, the efficiency of ethanol-water mixtures and acetone-water mixtures for the recovery of total polyphenols, chlorogenic acid, and caffeine. Acetone at 20% (m/m) was the most convenient solvent to extract all three bioactive compounds simultaneously, yielding 4.37 mg of GAE/g SCG for total polyphenols, chlorogenic acid (0.832 mg 5-CQA/g SCG), and caffeine (1.47 mg/g SCG). Additionally, this study aims to address some challenges associated with the industrial-scale utilization of SCG as a raw material, encompassing factors such as pre-treatment conditions (natural drying and oven drying), storage duration, and the kinetics of the extraction process. No significant difference was observed between the natural drying and oven drying of SCG. In terms of storage duration, it is advisable to process the SCG within less than 3-4 months of storage time. A significant decline of 82% and 70% in chlorogenic acid (5-CQA) and caffeine contents, respectively, was observed after eight months of storage. Furthermore, the kinetic study for the recovery of total polyphenols revealed that the optimal extraction times were 10 min for acetone at 20% and 40 min for water, with a yield increase of 28% and 34%, respectively. What is remarkable from the present study is the approach considered, using the simplest operating conditions (minimal time and solvent-to-solid ratio, and ambient temperature); hence, at an industrial scale, energy and resource consumption and equipment dimensions can be together reduced, leading to a more industrially sustainable extraction process.

Thermodynamic functions of succinic acid in acetone–water binary mixtures based on computation of KI & KII constants

Succinic acid is commonly used in various chemical, pharmaceutical, environmental and industrial activities and its reactivity is principally determined by the pK(I & II) values. Therefore, the dissociation constants of succinic acid have been determined in this study on the basis of emf measurements in both different acetone mole fractions and temperature range. The pK(I or II) values of the studied acids in acetone aqueous media were found higher than those obtained in other organic aqueous media with the same conditions (temperature and mole fraction of solvent). Moreover, (KI/KII) in 40 wt% acetone–water mixture was identified to follow succinic acid < malic acid < malonic acid < maleic acid owing to the stabilization of intramolecular hydrogen bonding. The free energy of transfer (ΔG0I or II) for succinic acid was increased with the increasing of pKI or pKII values due to the decrease in relative permittivity (εr) via increment of the acetone fraction in the aqueous medium. The trend of ΔS°I value among the studied acids were found to follow maleic < malic < succinic < malonic. ΔS°II values were characterized lower than ΔS°I due to possible solvent interactions with the acid anion (L2-). Therefore, ΔH°II values of the second dissociation process were identified lower than ΔH°I to favor an exothermic reaction.

The Effect of the Oğuzlar Walnut Extract as a Green Corrosion Inhibitor on AISI 1010 Mild Steel

Mild steel is primarily used in reinforced concrete structures, because it has a low corrosion rate due to the formation of a passive oxide film in the alkaline environment. However, when exposed to acidic and atmospheric environments or aqueous environments containing dissolved salts such as sea water, the protective film deteriorates and corrosion occurs due to contamination caused by chloride and carbonation. It is possible to obtain corrosion inhibitors by extraction of bioactive compounds from plants. Thus, inexpensive and environmentally friendly new effective inhibitors are obtained as an alternative to environmentally harmful inhibitors. In this context, the subject of the study was determined as the investigation of the inhibition efficiency of the vanillin phenolic compound in the Çorum Oğuzlar walnut shell extract, which is a local product, on the corrosion of AISI 1010 mild steel in acidic, alkaline and salty environments. The walnut shells, which were cleaned, ground and pre-sieved with a certain grain size, were extracted in seven different solvents. In order to find the appropriate solvent, the total phenolic content (TPC) in the extracts was determined by both the Folin Ciocalteu method and the liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) system. Cyclic voltammetry (CV) and Tafel polarization methods were applied to determine the effect of the extract on the electrochemical behavior of AISI 1010 and its corrosion rate. LC-MS/MS analysis showed the presence of compounds containing p electrons, N and O heteroatoms responsible for the corrosion inhibition. The best inhibition effectiveness was obtained with 86.1% acetone-water mixture in acidic environment (0.2 M HCl).

Evaluation of Helichrysum arenarium flower exudate as an inhibitor on Lolium perrene seed germination under laboratory conditions

Abstract Compounds accumulated on the surface of plant tissues and structures like glandular trichomes and thin epicuticular layer are defined as exudate, external, superficial. They exhibited important protective activities - antifungal, antibacterial, insect antifeedant, larvicidal, antiplasmodial, and UV protective. The exudate obtained from Helichrysum arenarium flowers was evaluated for its inhibitory activity on germination and initial radicle elongation of Lollium perrene seeds. The experiment was done in vitro in Petri dishes. The exudate, in water–acetone mixture (99.5:0.5), was assayed at concentrations of 1, 3, 5, 7, and 10 mg/mL. The chemical composition of the exudate was analyzed by GC/MS. Exudate solution with 5 mg/mL concentration was found to cause more than 90% of seed germination inhibition. At the same concentration, complete inhibition of root growth was observed. The main bioactive component of exudate was identified as flavonoid aglycone–naringenin. The inhibitory activity of H. arenarium on seed germination was investigated for the first time in the present study.

Measurement of Complex Permittivity for Rapid Detection of Liquid Concentration Using a Reusable Octagon-Shaped Resonator Sensor

Substrate-integrated waveguides (SIWs) are widely used in microwave systems owing to their low cost and ease of integration. In this study, an SIW-based resonator that reacts to the complex permittivity variation of solutions with dimensions of 79.2 mm × 59.8 mm is introduced. This octagon-shaped sensor can be installed on a preliminary monitoring system to test water quality by observing the parameter variations caused by external factors. The resonant structure was used to test different concentrations of ethanol-water and acetone-water mixtures for verification. The resonant frequency and quality factor (Q-factor) were found to vary with the relative complex permittivity of the liquid in the S-band, and the electric field distribution varied when liquid droplets were placed in the center of the substrate. The designed sensor operates at 2.45 GHz in the air, and the observed minimum resonant frequency shift with liquid was 15 MHz. The measurement error was approximately 3.1%, and the results reveal a relationship between the resonant frequency and temperature as well. Considering the observed sources of error, the measured relative permittivity is consistent with the actual values. The proposed sensor is economically convenient and suitable for various test environments.

Constants of Stability of Cobalt(II) Complexes with Glycylglycinate Ions in Aqueous Acetone Solutions

Potentiometric titration is used to determine constants of stability of cobalt(II) glycylglycinate complexes at a temperature of 298 K and the ionic strength of 0.1 M solutions in aqueous acetone solutions. It is established that in contrast to aqueous solutions, cobalt(II) mono-glycylglycinates, bis-glycylglycinates, and tris-ligand complexes can all form in water–acetone mixtures. The stability of cobalt(II) complexes with glycylglycinate ions grows along with the concentration of acetone in a solution.

Computational investigation of explicit solvent effects and specific interactions of hydroxypyrene photoacids in acetone, DMSO, and water.

This work employs the correlated wavefunction-based methods ADC(2) and CC2 in combination with the implicit solvent model COSMO to calculate the UV/Vis absorption and fluorescence emission energies of particularly strong hydroxypyrene photoacids in acetone. According to the Förster cycle, the electronic transition energies are first used to compute , i.e., the pKa change upon excitation and then the excited-state pKa (labeled ) with ground-state pKa values based on COSMO-RS as additional inputs. Furthermore, for the strongest photoacid of that class, namely tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, the need to go beyond implicit solvation and to account for explicit solvent effects on the electronic transition energies and the resulting ΔpKa is investigated in the solvents acetone, dimethyl sulfoxide (DMSO), and water. For this, a hybrid implicit-explicit approach is followed by comparing micro-solvated structures that are generated based on Kamlet-Taft considerations. While implicit solvent effects are mostly sufficient for the aprotic solvent acetone, one explicit solvent molecule seems relevant for DMSO due to its stronger hydrogen-bond (HB) acceptance and hence larger interaction with the photoacid OH group as a HB donor. For the protic solvent water, the situation is more complicated, involving at least one water molecule at the OH group and up to three water molecules at the O- group of the corresponding base. Finally, these results are used to rationalize the experimentally observed spectral evolution of the photoacid absorption band in acetone-water solvent mixtures.

Fractionation and Absolute Molecular Weight Determination of Organosolv Lignin and Its Fractions: Analysis by a Novel Acetone-Based SEC─MALS Method

Accurate and reliable structural characterization of technical lignins is still challenging and inhibits industrial utilization as only poor understanding of structure–property relationship is available. Especially, molar mass analysis of technical lignins is of paramount interest; however, the usage of conventional size exclusion chromatography (SEC) and synthetic polymer standards as a consequence of inaccessible lignin standards is predominantly found in academia. This leads to a huge discrepancy in molecular weight analyses of lignins between different laboratories and consequently to fragile comparability. In this study, organosolv (OS) lignin from beech wood was exemplarily used to develop and evaluate a new acetone–water-based SEC method with the ability to be coupled to an electrospray ionization-mass spectrometer (ESI-MS) or to a multi-angle light scattering detector (MALLS or short MALS). The eluent system used shows very good solubility for the lignins investigated and hence lowers the probability for molecular aggregation of lignin molecules in solution. Solvent fractionation in acetone–water mixtures was conducted to acquire molecular weight classes. The starting lignin (parent lignin) was initially dissolved in 80 wt % acetone–water. Various fractions of the parent lignin were produced by a stepwise reduction of the acetone content. Molecular weights based on narrow polyethylene glycol (PEG)/polyethylene oxide (PEO) standards and absolute molar masses by coupling SEC with MALS were obtained, and the drawback of using polymer standards is discussed in detail. At a lower acetone content, low-molecular-weight fractions were found. Additionally, the specific refractive index increments (dn/dc) were determined for the parent lignin and its fractions. The impact of dn/dc on the final molecular weight (MW) was evaluated considering the chemical composition obtained by nuclear magnetic resonance spectroscopy (NMR) analysis. Furthermore, light scattering revealed that the absorption behavior for this OS lignin is low and neglectable. This article proposes a new acetone-based analytical method for direct determination of absolute molar masses of OS lignin molecules.

Influence of Oxidation and Dialysis of Phlorotannins on Bioactivity and Composition of Ultrasound-Assisted Extracts from Ascophyllum nodosum.

The isolation and chemical characterization of phlorotannins has gained special attention in recent years due to their specific health-promoting benefits. Flow-cell ultrasound-assisted extraction (90 W/cm2 of sonication power, 2 min of retention time and 20 g solvent/g algae of liquid-solid ratio) was carried out by using double-distilled water (WE) and acetone:water mixture (AWE) as extraction solvents. The AWE showed a higher total polyphenols content (TPC), carbohydrates (CHOs) and antioxidant activities than WE. However, when the WE was purified by using Amberlite XAD16 column, the purified WE (PWE) showed similar a TPC, decreased CHOs and increased antioxidant activity compared to WE. The oxidation of the PWE extract was evaluated under natural, forced and severe oxidation condition for 120 h. Only severe oxidation conditions were able to significantly reduce TPC and antioxidant activities. PWE was dialyzed (20, 10, 3.5 and 2 kDa). The main bioactive fraction of phlorotannins was obtained from 10 to 20 kDa. CHOs were distributed in fractions below 20 kDa. MALDI-TOF analysis was performed for PWE, PD20 and PD2 extracts to analyze the degree of polymerization of phlorotannins, which ranged from 4 to 17 phloroglucinol units/molecule. Fragmentation patterns allowed the proximate identification of several phlorotannins in Ascophyllum nodosum extracts.

Molecular Dynamics Simulation for Separation Performance of PDMS/Fluorosilane Membrane with Different Mass Ratios in Acetone–Water Mixture

AbstractPolydimethylsiloxane (PDMS) membrane in suitable‐fluorinated level have excellent pervaporation performance as well as antibiological contamination performance. The pervaporation membranes with different PDMS/fluorosilane mass ratios, the adsorption and dissolution behaviors of acetone molecules on the membrane surface, as well as the diffusion and permeation behaviors in the membranes are studied by all‐atom molecular dynamics simulation (AAMDS). The results show that when the mass ratio of PDMS/fluorosilane is 100/20, the surface solubility of acetone is 11.711 (J cm−3)0.5, and the interfacial interaction is −16897.0415 kcal mol−1, both of which are the highest. The results of wide‐angle X‐ray diffraction (WAXD) showed that there are amorphous regions in the membranes suitable for acetone penetration. The maximum chain spacing of the PDMS/fluorosilane(100/20)_membranes is 10.8482 Å, and the free volume fraction (FFV) is 3.03%, both of which are the largest. The change rate of long‐term mean square displacement (MSD) in PDMS/fluorosilane(100/20)_Membrane with time is 0.45269. The Young's modulus E, shear modulus G, volume modulus K, and Poisson's ratio ν of PDMS/fluorosilane(100/20)_Membrane are 0.3249, 0.4061, 0.0492 GPa and ‐0.5999, respectively. The elasticity of the membrane enhances the diffusion behavior of acetone molecules, and the self‐diffusion coefficient of acetone in the membrane is 0.07545 Å2 ps−1.

External Stimuli-Responsive Characteristics of Poly(N,N'-diethylacrylamide) Hydrogels: Effect of Double Network Structure.

Swelling experiments and NMR spectroscopy were combined to study effect of various stimuli on the behavior of hydrogels with a single- and double-network (DN) structure composed of poly(N,N′-diethylacrylamide) and polyacrylamide (PAAm). The sensitivity to stimuli in the DN hydrogel was found to be significantly affected by the introduction of the second component and the formation of the double network. The interpenetrating structure in the DN hydrogel causes the units of the component, which is insensitive to the given stimulus in the form of the single network (SN) hydrogel, to be partially formed as globular structures in DN hydrogel. Due to the hydrophilic PAAm groups, temperature- and salt-induced changes in the deswelling of the DN hydrogel are less intensive and gradual compared to those of the SN hydrogel. The swelling ratio of the DN hydrogel shows a significant decrease in the dependence on the acetone content in acetone–water mixtures. A certain portion of the solvent molecules bound in the globular structures was established from the measurements of the 1H NMR spin–spin relaxation times T2 for the studied DN hydrogel. The time-dependent deswelling and reswelling kinetics showed a two-step profile, corresponding to the solvent molecules being released and absorbed during two processes with different characteristic times.