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The rapid implementation of membrane processes in the industry requires novel membrane materials. One of the promising ways to obtain a membrane material with improved properties is to combine the advantages of a polymer and a modifier (in particular, carbon nanoparticles). In the present work, novel pervaporation membranes based on hydroxyethyl cellulose (HEC)/polyvinyl alcohol (PVA) blend and HEC/PVA/fullerene derivative (polyhydroxylated fullerene, carboxyfullerene, and fullerene derivative with l-arginine) composites were developed for dehydration. The membrane composition and the cross-linking with maleic acid were optimized. The membranes were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, thermogravimetric analysis, contact angle and swelling measurements. Transport properties of the membranes were studied in the pervaporation dehydration of isopropanol. The cross-linked dense HEC/PVA(30/70 wt%)/carboxyfullerene (5 wt%) membrane had the optimal transport properties in pervaporation dehydration of isopropanol (12–100 wt% water) at 22 °C: permeation flux of 24–1633 g/(m2 h), 99.99–98.3 wt% water in permeate.

Light fullerenes, C60 and C70, have significant potential in biomedical applications due to their ability to absorb reactive oxygen species, inhibit the development of tumors, inactivate viruses and bacteria, and as the basis for developing systems for targeted drug delivery. However, the hydrophobicity of individual fullerenes complicates their practical use; therefore, creating water-soluble derivatives of fullerenes is increasingly important. Currently, the most studied soluble adducts of fullerenes are polyhydroxy fullerenes or fullerenols. Unfortunately, investigations of fullerenol biocompatibility are fragmental. They often lack reproducibility both in the synthesis of the compounds and their biological action. We here investigate the biocompatibility of a well-defined fullerenol C60(OH)24 obtained using methods that minimize the content of impurities and quantitatively characterize the product's composition. We carry out comprehensive biochemical and biophysical investigations of C60(OH)24 that include photodynamic properties, cyto- and genotoxicity, hemocompatibility (spontaneous and photo-induced hemolysis, platelet aggregation), and the thermodynamic characteristics of C60(OH)24 binding to human serum albumin and DNA. The performed studies show good biocompatibility of fullerenol C60(OH)24, which makes it a promising object for potential use in biomedicine.

Biopolymer sodium alginate (SA) is actively used as a green membrane material. To improve the pervaporation properties of the SA membrane in the isopropanol dehydration, different water-soluble fullerene derivatives with L-amino acids (threonine, hydroxyproline, and arginine) were used. In this study, fullerene–arginine derivative (C60-Arg) was shown to be an optimal filler acting both as a modifier and a cross-linking agent for SA. Different cross-linking agents (phosphoric and citric acids, calcium chloride) were tested for dense membrane cross-linking to reinforce the membranes for the separation of diluted solutions. Two types of membranes based on SA and SA/C60-Arg (5%) were developed: dense and supported on polyacrylonitrile substrate. The structural features of obtained membranes were investigated by the following methods: FTIR spectroscopy, scanning electron (SEM), and atomic force (AFM) microscopies. The optimal transport properties in dehydration of isopropanol (12–100 wt.% water) were found for the cross-linked SA/C60-Arg (5%) membrane supported on PAN substrate. The following parameters were obtained: 0.5–4.7 kg/(m2h) permeation flux and constant 99.99 wt.% water content in the permeate.

The effect of the addition of triblock copolymer polyethylene glycol (PEG)–polypropylene glycol (PPG)–polyethylene glycol (PEG) (Pluronic F127) and polyethylene glycol (PEG-4000, Mn = 4000 g mol−1) to the polysulfone (PSF) casting solution on the membrane structure and performance was studied. The phase state, viscosity and turbidity of PSF solutions in N,N-dimethylacetamide (DMAc) with the addition of block copolymer Pluronic F127 were investigated. It was found that 18–22 wt.% PSF solutions in DMAc with Pluronic F127 content ≥ 5 wt.% feature a lower critical solution temperature (LCST). Membrane structure was investigated using scanning electron and atomic force microcopies. It was revealed that average pore size and pore amount on the surface of the membrane selective layer increase and pore size distribution becomes wider with an increase in Pluronic F127 content in the casting solution. It was found that the average surface roughness parameters of the membrane selective layer for PSF/Pluronic F127 membranes significantly exceed those for PSF/PEG-4000 membranes. It was shown that the increase in the membrane flux and the decrease in polyvinylpyrrolidone (PVP K-30, Mn = 40,000 g mol−1) rejection are a result of the addition of both Pluronic F127 and PEG-4000 into the casting solution. It was revealed that PSF/Pluronic F127 membranes are characterized by higher pressure resistance in ultrafiltration process, a lower total flux decrease during ultrafiltration of bovine serum albumin solutions. The antifouling performance of PSF/Pluronic F127 membranes was found to exceed significantly the antifouling performance of PSF/PEG-4000 membranes.

Novel membranes based on polyphenylene isophthalamide (PA) modified by fullerene derivatives (5 wt% with respect to PA weight) (polyhydroxylated fullerene (fullerenol), carboxyfullerene and fullerene derivative with L-arginine) were developed. The presence of PA/fullerene and PA/fullerene derivative composites and distribution of carbon nanoparticles after ultrasonic treatment in polymer solution was investigated by dynamic light scattering. The influence of carbon modifier on structural characteristics of PA was examined by nuclear magnetic resonance, small-angle X-ray scattering, scanning electron microscopy, atomic force microscopy, sorption experiments, density investigation and contact angle measurements of water. The transport properties were examined by pervaporation separation of industrially important methanol/toluene mixtures in two regimes (1. a series of experiments of different concentrations including azeotropic mixture and 2. only azeotropic mixture) to assess the effect of residual solvent in the PA membranes on their parameters. It was found that all membranes containing fullerene derivatives possessed improved permeation flux compared to pristine PA membrane. The optimal transport characteristics for the separation of methanol/toluene mixtures containing 10–72 wt% methanol were noticed for PA membrane modified by 5 wt% fullerenol due to the highest permeation fluxes (0.084–0.214 kg/(m2h)) and high level of selectivity (95.9 wt% methanol content in the permeate).

Novel porous and dense membranes based on polysulfone (PSF) modified by poly(ethylene glycol)–b–poly(propylene glycol)–b– poly(ethylene glycol) (Pluronic F127) were developed. The influence of Pluronic F127 introduction to the casting solution on different types of polymer membrane formation via two different phase inversion techniques—non-solvent induced phase separation (NIPS) for porous membranes and evaporation induced phase separation (EIPS) for dense membranes—was investigated. According to the triangular phase diagram obtained, PSF-Pluronic F127-N,N-dimethylacetamide (DMAc) systems feature lower critical solution temperature and have a tendency to micelle formation due to Pluronic F127 self-assembly. The structure, hydrophilic-hydrophobic balance and physicochemical properties of PSF-Pluronic F127 membranes were characterized by water contact angle measurements, scanning electron microscopy, nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy. The performance of dense membranes in pervaporation separation of water-ethyl acetate mixtures was investigated to reveal the effect of Pluronic F127 on the structure and free volume of the PSF-Pluronic F127 membranes. It was shown that Pluronic F127 introduction to the casting solution during membrane formation via two different techniques (NIPS and EIPS) leads to the increase in the pore size of the porous membranes and free volume of the dense membranes, as well as the increase in flux and surface hydrophilicity for both membrane types. Pluronic F127 was found to improve the antifouling performance of porous PSF-Pluronic F127 membranes in the BSA solution ultrafiltration. The introduction of 3 wt% Pluronic F127 into dense PSF membrane improved permeation flux in 1.7 and 2.7 times (15.1 and 27.3 g/(m2h)) at high selectivity level (100 wt% water in the permeate) during the separation of ethyl acetate-water mixtures (2 and 4 wt% ethyl acetate) compared to pristine PSF membrane.

International audience; The so-called Graftfast reaction in water and at room temperature (RT) was applied to graft polyethylene glycol (PEG) at the surface of the microporous zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) using acrylPEG of different chain lengths (480 Da and 5 kDa). In comparison to non-modified ZIF-8 NPs, both chemical and colloidal stabilities of PEGylated ZIF-8 NPs are significantly enhanced in water. A series of colloidal complex fluids by mixing PEG grafted ZIF-8 (i. e. PEG-g-ZIF-8) NPs with different amounts of polyvinylalcohol (PVA) was prepared and characterized by advanced characterization tools such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) thereby showing their long-term colloidal stability. Finally, dense and supported mixed matrix membranes were cast from PEG-g-ZIF-8/PVA solutions and have shown high performance in isopropanol (IPA) dehydration by pervaporation. The permeation flux of the supported MMM (i. e. 0.091 kg/(m$^2$h) is eleven times higher than that of the pure PVA membrane and these MMMs present a high separation factor (i. e. 7326). These transport properties are presumably due to the molecular sieving effects induced by ZIF-8 and the good interfacial properties of the membrane. The computational exploration of the ZIF-8/PVA and PEG/PVA interfaces provides a microscopic scale explanation for the enhanced compatibility of PVA with the PEGylated MOF when compared to that for the composite based on the bare ZIF-8 as a filler.

Modern society strives for the development of sustainable processes that are aimed at meeting human needs while preserving the environment. Membrane technologies satisfy all the principles of sustainability due to their advantages, such as cost-effectiveness, environmental friendliness, absence of additional reagents and ease of use compared to traditional separation methods. In the present work, novel green membranes based on sodium alginate (SA) modified by a FeBTC metal–organic framework were developed for isopropanol dehydration using a membrane process, pervaporation. Two kinds of SA-FeBTC membranes were developed: (1) untreated membranes and (2) cross-linked membranes with citric acid or phosphoric acid. The structural and physicochemical properties of the developed SA-FeBTC membranes were studied by spectroscopic techniques (FTIR and NMR), microscopic methods (SEM and AFM), thermogravimetric analysis and swelling experiments. The transport properties of developed SA-FeBTC membranes were studied in the pervaporation of water–isopropanol mixtures. Based on membrane transport properties, 15 wt % FeBTC was demonstrated to be the optimal content of the modifier in the SA matrix for the membrane performance. A membrane based on SA modified by 15 wt % FeBTC and cross-linked with citric acid possessed optimal transport properties for the pervaporation of the water–isopropanol mixture (12–100 wt % water): 174–1584 g/(m2 h) permeation flux and 99.99 wt % water content in the permeate.

Transport characteristics of sodium alginate (SA) membranes cross-linked with CaCl2 and modified with fullerenol and fullerene derivative with L-arginine for pervaporation dehydration were improved applying various approaches, including the selection of a porous substrate for the creation of a thin selective SA-based layer, and the deposition of nano-sized polyelectrolyte (PEL) layers through the use of a layer-by-layer (Lbl) method. The impacts of commercial porous substrates made of polyacrylonitrile (PAN), regenerated cellulose, and aromatic polysulfone amide were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), standard porosimetry method, and water filtration. The effects of PEL combinations (such as poly(sodium 4-styrene sulfonate) (PSS)/SA, PSS/chitosan, PSS/polyacrylic acid, PSS/poly(allylamine hydrochloride)) and the number of PEL bilayers deposited with the Lbl technique on the properties of the SA and SA/fullerene derivative membranes were studied by SEM, AFM, and contact angle measurements. The best characteristics were exhibited by a cross-linked PAN-supported SA/fullerenol (5%) membrane with five PSS/SA bilayers: permeation flux of 0.68–1.38 kg/(m2h), 0.18–1.55 kg/(m2h), and 0.50–1.15 kg/(m2h), and over 99.7, 99.0, and 89.0 wt.% water in the permeate for the pervaporation dehydration of isopropanol (12–70 wt.% water), ethanol (4–70 wt.% water), and tetrahydrofuran (5.7–70 wt.% water), respectively. It was demonstrated that the mutual application of bulk and surface modifications essentially improved the membrane’s characteristics in pervaporation dehydration.

The aim of the study is to improve the performance of thin-film composite (TFC) membranes with a thin selective layer based on chitosan (CS) via different approaches by: (1) varying the concentration of the CS solution, (2) changing the porosity of substrates from polyacrylonitrile (PAN), (3) deposition of the additional ultrathin layers on the surface of the selective CS layer using interfacial polymerization and layer-by-layer assembly. The developed membranes were characterized by different methods of analyses (SEM and AFM, IR spectroscopy, measuring of water contact angles and porosity). The transport characteristics of the developed TFC membranes were studied in pervaporation separation of isopropanol/water mixtures. It was found that the application of the most porous PAN-4 substrate with combination of formation of an additional polyamide selective layer by interfacial polymerization on the surface of a dense selective CS layer with the subsequent layer-by-layer deposition of five bilayers of poly (sodium 4-styrenesulfonate)/CS polyelectrolyte pair led to the significant improvement of permeance and high selectivity for the entire concentration feed range. Thus, for TFC membrane on the PAN-4 substrate the optimal transport characteristics in pervaporation dehydration of isopropanol (12&ndash, 90 wt.% water) were achieved: 0.22&ndash, 1.30 kg/(m2h), 99.9 wt.% water in the permeate.

A novel method for one-step preparation of antifouling ultrafiltration membranes via a non-solvent induced phase separation (NIPS) technique is proposed. It involves using aqueous 0.05&ndash, 0.3 wt.% solutions of cationic polyelectrolyte based on a copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride (Praestol 859) as a coagulant in NIPS. A systematic study of the effect of the cationic polyelectrolyte addition to the coagulant on the structure, performance and antifouling stability of polysulfone membranes was carried out. The methods for membrane characterization involved scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), contact angle and zeta-potential measurements and evaluation of the permeability, rejection and antifouling performance in human serum albumin solution and surface water ultrafiltration. It was revealed that in the presence of cationic polyelectrolyte in the coagulation bath, its concentration has a major influence on the rate of &ldquo, solvent&ndash, non-solvent&rdquo, exchange and thus also on the rate of phase separation which significantly affects membrane structure. The immobilization of cationic polyelectrolyte macromolecules into the selective layer was confirmed by FTIR spectroscopy. It was revealed that polyelectrolyte macromolecules predominately immobilize on the surface of the selective layer and not on the bottom layer. Membrane modification was found to improve the hydrophilicity of the selective layer, to increase surface roughness and to change zeta-potential which yields the substantial improvement of membrane antifouling stability toward natural organic matter and human serum albumin.

Novel mixed-matrix membranes based on polyvinyl alcohol and its composites with carboxyfullerene were developed. Carboxyfullerene was simultaneously used as a modifier and a cross-linker for polyvinyl alcohol. The structural properties of the developed composites were studied by nuclear magnetic resonance, X-ray diffraction analysis, scanning electron microscopy, and sorption experiments. Thermal properties and stability were investigated by thermogravimetric analysis and differential scanning calorimetry. Surface features were studied by measuring the contact angles by water. The transport properties of the developed membranes were studied in ethanol-water mixtures separation by pervaporation (4.4–90 wt.% water in the feed) at different temperatures (22, 35, 50 °C). All membranes were selective with respect to water. The optimal transport properties were obtained for the PVA-carboxyfullerene (3.5 wt.%) membranes containing catalyst p-toluenesulfonic acid.

International audience; Novel supported membranes based on polyvinyl alcohol (PVA) were developed using two strategies: first, by the modification of the PVA network, via so-called bulk modification, with the formation of the selective layer accomplished through the introduction of fullerenol and/or poly(allylamine hydrochloride), and second, by the functionalization of the surface with successive depositions of multilayered films of polyelectrolytes, such as poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on the PVA surface. The membrane surface modifications were characterized by scanning electron microscopy and contact angle measurements. The modified PVA membranes were examined for their dehydration transport properties by the perva-poration of isopropyl alcohol-water (80/20% w/w), which was chosen as a model mixture. Compared with the pristine PVA membrane, the main improvement was a marked increase in permeance. It was found that the surface modifications mainly gave rise to a higher global flux but with a strong reduction in selectivity. Only the combination of both bulk and surface modifications with PEL could significantly increase the flux with a high water content in the permeate (over 98%). Lastly, it should be noted that this study developed a green procedure to prepare innovative membrane layers for dehydration, making use of only water as a working medium.

Fullerenol C60(OH)22–24 was incorporated into the polyamide (PA) selective layer to develop novel thin film nanocomposite (TFN) hollow fiber membranes for low molecular weight cut-off ultrafiltration. TFN membranes were fabricated via interfacial polymerization technique by alternately pumping fullerenol dispersion in triethylenetetramine (TETA) aqueous solution and isophthaloyl chloride solution in hexane through polysulfone hollow fiber membranes. Developed TFN PA/fullerenol membranes were investigated by FTIR, Raman spectroscopy, SEM, TEM, AFM, contact angle measurements and evaluated by determining the permeability, rejection and antifouling performance. Introduction of fullerenol to the PA skin layer was revealed to yield in the decrease of pure water flux and slight increase of lysozyme rejection which is attributed to the increase of the thickness of PA layer. Water contact angle of the skin layer was found to decrease sharply from 34° to 21° when the concentration of fullerenol increased up to 0.5 wt% in the TETA aqueous solution. Antifouling properties of the PA/fullerenol membranes were found to be superior to initial membrane. Fouling recovery ratio increased from 54% for the pristine membrane to 93% for the membrane with 0.5 wt% of fullerenol in the TETA aqueous solution. Irreversible fouling ratio was found to decrease from 38% to 6%, respectively. A correlation between surface properties and fouling behavior of TFN membranes upon increase of fullerenol concentration was established.

This study focuses on the development of a green pervaporation (PV) process for dehydrating a wide range of commercially significant mixtures such as concentrated (and corrosive) acetic acid blends using mixed-matrix membranes based on polyvinyl alcohol (PVA) cross-linked by low-hydroxylated fullerenol (C 60 (OH) 12 ). The effect of C 60 (OH) 12 and various conditions of physical cross-linking on the structure and internal morphology of composite membranes was investigated by X-ray diffraction and scanning electron microscopy, and the stability and transport properties of the developed membranes were investigated for acetic acid dehydration at a wide range of feed water contents (5–30 wt.%) and temperatures (25–60 °C). The supported mixed-matrix membranes exhibited high permeances and water selectivities, as well as good stability toward feed mixtures, with the best transport properties obtained for a C 60 (OH) 12 (5 wt.%)-PVA supported composite membrane thermally treated at 140 °C for 420 min.

This study focuses first on the preparation of mixed matrix supported membranes of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C60(OH)12 used to create water selective membranes and then on their pervaporation properties for the separation of water-THF mixtures. These novel supported PVA membranes containing nano-carbon particles were prepared to reach high membrane performance for further integration in a dehydration process, such as distillation coupled to pervaporation. The separation of water-THF mixtures was performed with the supported membranes over a wide range of water concentrations in the feed mixture, i.e., from the azeotrope range up to 30 wt%, to evaluate the performance and stability of the thin active layer. SEM was used to visualize the internal morphology of the membrane. The influence of temperature on the transport properties was also investigated. All the membranes were highly water selective and stable up to 30 wt% water in the feed. The best compromise of transport properties was obtained for the C60(OH)12(5%)-PVA supported composite membrane: a permeate enrichment of 99.3 ± 0.3 wt% water and a flux of 0.25 ± 0.02 kg/(m2 h) for the separation of a mixture containing 5.7 wt% water and 94.3 wt% tetrahydrofuran (THF) at 30 °C. Considering its water stability, this supported membrane with a dense layer thinner than 2 μm appears promising for use in hybrid industrial processes to upgrade solvents with a smaller environmental footprint than conventional methods.

Inclusion of fillers and modifiers into the polymer matrix is the well-known way significantly to change the physicochemical properties of membrane materials. Recently, considerable progress in the development of novel membranes have been achieved thanks to the modification of polymeric materials by carbon nanoparticles. In this review the current issues of the development of effective membranes based on composites “polymer–graphene oxide,” which possess enhanced physicochemical properties, high transport properties and improved separation characteristics, are considered. More precisely, we focused on mixed matrix membranes for gas separation and ultrafiltration. It is shown that the change of surface properties and inner morphology of the membrane material due to the incorporation of well dispersed nanoparticles can be significantly improved the maintenance properties of the membranes in different membrane processes.

In this work, dense and supported pervaporation polyvinyl alcohol (PVA)-based membranes modified with poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate)(PSS)/PAH top nanolayers were synthesized. Two main points were investigated: the role of the polyelectrolyte PAH on water selectivity of the selective polymer matrix and the impact of the porous substrate based on polyacrylonitrile (PAN) and aromatic polysulfone amide (UPM-20&reg, ), used to get supported high-performance membranes. Various methods of analysis (fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), porosity, contact angles, ultrafiltration) were applied to study the developed membranes. Transport characteristics of the developed membranes were studied in isopropanol dehydration by pervaporation. Obtained results are discussed in the light of the structure and physicochemical characteristics of these PVA/PAH membranes and the types of porous substrate. It was shown that the PAN-supported membrane with the selective layer based on PVA/PAH modified by 10 polyelectrolyte PSS/PAH bilayers possessed ~4.5 times higher permeation flux with the same high selectivity level (99.9 wt % water in the permeate) for the dehydration of the isopropanol (20 wt % water) at 60 &deg, C compared to the commercial analog PERVAPTM 1201.

Pervaporation has been applied for tetrahydrofuran (THF) dehydration with novel composite membranes advanced by a thin selective layer composed of chitosan (CS) modified by copolymerization with vinyl monomers, acrylonitrile (AN) and styrene, in order to improve the chemical and mechanical stability of CS-based membranes. Composite membranes were developed by depositing a thin selective layer composed of CS copolymers onto a commercially-available porous support based on aromatic polysulfonamide (UPM-20&reg, ). The topography and morphology of the obtained materials were studied by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Thermal properties and stability were determined by coupled evolved gas analysis (EGA-MS). Transport properties were estimated in pervaporation dehydration of THF. The effect of operating parameters for the pervaporation dehydration of THF such as feed compositions and temperatures (295, 308 and 323 K) was evaluated. It was shown that CS modification with different vinyl monomers led to a difference in physical and transport properties. The composite membrane with the thin selective layer based on CS-PAN copolymer demonstrated optimal transport properties and exhibited the highest water content in the permeate with a reasonably high permeation flux.

As a rule, the polymeric membranes have low permeability in separation of low molecular weight components. In spite of this fact, the membrane processes have significant advantages compare with conventional technologies, in particular, low energy consumption and environmental friendliness. To improve transport properties of the polymer membrane their modification should be carried out. In the present work, the development of highly methanol-permeable pervaporation membranes based on poly-m-phenylene isophthalamide (PA) is achieved by two strategies: (i) modification of PA by novel synthesized and characterized highly stable metal–organic framework UiO-66(NH2)-EDTA particles and (ii) development of supported membranes with thin selective layer on the regenerated cellulose substrate. First time the composite structure has been simulated: atomistic molecular dynamics simulations demonstrate the partial penetration of polymer inside the modifier and confirms the nature of the interaction between polymer and modifier assessed by spectroscopic methods. The optimal characteristics in respect of industrial use are obtained for supported PA/UiO-66(NH2)-EDTA (15%) membrane: 1.55 kg/(m2h) permeation flux and 93.1 wt% methanol in the permeate for the separation of azeotropic methanol/toluene mixture.

Novel dense and supported (polyacrylonitrile substrate) mixed matrix membranes based on biopolymer sodium alginate (SA), modified by Zr-MOFs were developed to improve pervaporation dehydration properties of a parent SA membrane. The following Zr-MOFs were synthesized and tested as modifiers: unmodified UiO-66 and modified UiO-66(NH2)-AcOH and UiO-66(NH2)-EDTA. Two kinds of mixed matrix membranes were developed: without additional treatment and cross-linked with calcium chloride. The synthesized Zr-MOFs nanoparticles and developed SA and SA-Zr-MOFs membranes were studied using Fourier-transform infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy, surface area measurement, atomic force microscopy, X-ray diffraction analysis, thermogravimetric analysis, and swelling experiments. Dense and supported membranes were tested for their transport properties in the pervaporation dehydration of isopropanol (12, 30 wt% water for the untreated membranes and 12–100 wt% water for the cross-linked membranes). The best transport properties (dehydration of water/isopropanol mixtures at 22 °C) were demonstrated by a supported cross-linked membrane, containing 15 wt% of UiO-66: permeation flux 0.47–3.38 kg/(m2h), water content in permeate 99.9-97.5 wt%.

Membrane methods, especially pervaporation, are quickly growing up. In line with that, effective membrane materials based on biopolymers are required for the industrially significant mixtures separation. To essentially improve membrane transport characteristics, the application of the surface or/and bulk modifications can be carried out. In the present study, novel dense and supported membranes based on hydroxyethyl cellulose (HEC)/sodium alginate (SA) were developed for pervaporation dehydration of isopropanol using several approaches: (1) the selection of the optimal ratio of polymers, (2) the introduction of fullerenol in blend polymer matrix, (3) the selection of the optimal cross-linking agent for the membranes, (4) the application of layer-by-layer deposition of polyelectrolytes on supported membrane surface (poly(sodium 4-styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) and PSS/SA). Structural and physicochemical characteristics of the membranes were analyzed by different methods. A cross-linked supported membrane based on HEC/SA/fullerenol (5%) composite possessed the following transport characteristics in pervaporation dehydration of isopropanol (12–50 wt.% water): 0.42–1.72 kg/(m2h) permeation flux, and 77.8–99.99 wt.% water content in the permeate. The surface modification of this membrane with 5 bilayers of PSS/PAH and PSS/SA resulted in the increase of permeation flux up to 0.47–3.0 and 0.46–1.9 kg/(m2h), respectively, with lower selectivity.

We have simulated the melt of poly(carbosilane) dendrimers using atomistic models and have reproduced the effect predicted by the analytical theory; i.e., orientational autocorrelation functions of a segment from the same layer (numbered from periphery) are practically identical and do not depend on dendrimer size. The frequency dependences of the dielectric and NMR relaxation were obtained and studied in detail. The main contribution to the maxima of these dependences is given by the pulsation process. It leads to a shift of the maxima to low frequencies for the core segment in comparison with the maxima for peripheral segments. The contribution of local reorientation can also be significant, and in some cases this contribution manifests as an additional maximum. The nontrivial scaling laws in the frequency dependences of dielectric permittivity and NMR relaxation rate averaged over all layers of a dendrimer macromolecule are found. A similar scaling law is observed in the experiments on NMR relaxation b...

Novel mixed-matrix membranes based on polysulfone (PS) and fullerene C60 (up to 5 wt%) have been developed. Two membrane types formed from PS and PS-C60, a dense (diffusive) membrane and a supported membrane, consisted of a thin PS or PS-C60 selective layer (≈5 μm) on the surface of hydrophobic fluorocarbon polymer porous support (MFFC) were studied. The effect of fullerene incorporation on the structure and physical and chemical properties of PS membranes were investigated by scanning electron microscopy, nuclear magnetic resonance, contact angle measurements, sorption experiments, and wide-angle X-ray diffraction. The transport properties of the mixed matrix membranes containing up to 0.5 wt% fullerene were studied for the pervaporation of ethyl acetate–water mixture. The new mixed-matrix membranes, developed in this study, were selective to water, whereas the PS-0.5 % C60/MFFC composite membrane was found to have the best performance.

This work focuses on the incorporation of fullerenol nanoparticles to get PVA-fullerenol mixed matrix membranes for alcohol dehydration by pervaporation. Cross-linked hybrid membranes based on composites of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C60(OH)12 have been prepared by two different procedures. To improve the dispersion of the functionalized fullerene in the PVA network, the hydrodynamic properties of PVA, fullerenol and PVA/fullerenol composites in dilute solutions were studied by viscometry and dynamic light scattering. It was shown that the aggregate sizes increased with the increase of fullerenol content in the PVA/fullerenol composite solutions. The effect of low-hydroxylated fullerenol on the structure and morphology of PVA membranes was investigated by small-angle X-ray scattering and atomic force microscopy. It was observed that the incorporation of 5 wt.% fullerenol and cross-linking with maleic acid led to a more uniform distribution of the amorphous PVA phase. As a result, membrane transport characteristics were improved for the dehydration of n-butanol–water mixtures by pervaporation. The PVA membranes containing 35 wt.% maleic acid and 5 wt.% fullerenol exhibited the best transport properties. Keywords: Polyvinyl alcohol, Fullerenol, Composite, n-Butanol, Pervaporation

A novel vapor permeation-stepwise injection (VP-SWI) method for the determination of methanol and ethanol in biodiesel samples is discussed. In the current study, stepwise injection analysis was successfully combined with voltammetric detection and vapor permeation. This method is based on the separation of methanol and ethanol from a sample using a vapor permeation module (VPM) with a selective polymer membrane based on poly(phenylene isophtalamide) (PA) containing high amounts of a residual solvent. After the evaporation into the headspace of the VPM, methanol and ethanol were transported, by gas bubbling, through a PA membrane to a mixing chamber equipped with a voltammetric detector. Ethanol was selectively detected at +0.19 V, and both compounds were detected at +1.20 V. Current subtractions (using a correction factor) were used for the selective determination of methanol. A linear range between 0.05 and 0.5% (m/m) was established for each analyte. The limits of detection were estimated at 0.02% (m/m) for ethanol and methanol. The sample throughput was 5 samples h(-1). The method was successfully applied to the analysis of biodiesel samples.

Surface modification of polysulfone ultrafiltration membranes was performed via addition of an anionic polymer flocculant based on acrylamide and sodium acrylate (PASA) to the coagulation bath upon membrane preparation by non-solvent induced phase separation (NIPS). The effect of PASA concentration in the coagulant at different coagulation bath temperatures on membrane formation time, membrane structure, surface roughness, hydrophilic-hydrophobic balance of the skin layer, surface charge, as well as separation and antifouling performance was studied. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, contact angle and zeta potential measurements were utilized for membrane characterization. Membrane barrier and antifouling properties were evaluated in ultrafiltration of model solutions containing human serum albumin and humic acids as well as with real surface water. PASA addition was found to affect the kinetics of phase separation leading to delayed demixing mechanism of phase separation due to the substantial increase of coagulant viscosity, which is proved by a large increase of membrane formation time. Denser and thicker skin layer is formed and formation of macrovoids in membrane matrix is suppressed. FTIR analysis confirms the immobilization of PASA macromolecules into the membrane skin layer, which yields improvement of hydrophilicity and change of zeta potential. Modified membrane demonstrated better separation and antifouling performance in the ultrafiltration of humic acid solution and surface water compared to the reference membrane.

In this paper, we perform computer simulation of two lysine-based dendrimers with Lys-2Lys and Lys-2Gly repeating units. These dendrimers were recently studied experimentally by NMR (Sci. Reports, 2018, 8, 8916) and tested as carriers for gene delivery (Bioorg. Chem., 2020, 95, 103504). Simulation was performed by molecular dynamics method in a wide range of temperatures. We have shown that the Lys-2Lys dendrimer has a larger size but smaller fluctuations as well as lower internal density in comparison with the Lys-2Gly dendrimer. The Lys-2Lys dendrimer has larger charge but counterions form more ion pairs with its NH 3 + groups and reduce the bare charge and zeta potential of the first dendrimer more strongly. It was demonstrated that these differences between dendrimers are due to the lower flexibility and the larger charge (+2) of each 2Lys spacers in comparison with 2Gly ones. The terminal CH 2 groups in both dendrimers move faster than the inner CH 2 groups. The calculated temperature dependencies of the spin-lattice relaxation times of these groups for both dendrimers are in a good agreement with the experimental results obtained by NMR.

Novel mixed matrix dense and supported membranes based on biopolymer sodium alginate (SA) modified by fullerenol were developed. Two kinds of SA&ndash, fullerenol membranes were investigated: untreated and cross-linked by immersing the dry membranes in 1.25 wt % calcium chloride (CaCl2) in water for 10 min. The structural and physicochemical characteristics features of the SA&ndash, fullerenol composite were investigated by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopic methods, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), and swelling experiments. Transport properties were evaluated in pervaporation dehydration of isopropanol in a wide concentration range. It was found that the developed supported cross-linked SA-5/PANCaCl2 membrane (modified by 5 wt % fullerenol) possessed the best transport properties (the highest permeation fluxes 0.64&ndash, 2.9 kg/(m2 h) and separation factors 26&ndash, 73,326) for the pervaporation separation of the water&ndash, isopropanol mixture in the wide concentration range (12&ndash, 90 wt % water) at 22 &deg, C and is suitable for the promising application in industry.

Fullerene derivatives with amino acids, peptides and proteins have wide perspectives in biomedical applications. Thus, development and up-scaling of synthesis procedures, as well as investigation of the physico-chemical and biological properties of these derivatives, are extremely important. The present paper systematizes the current literature data on synthesis, physico-chemical properties and application of fullerene derivatives with amino acids, peptides and proteins in biomedicine. Experimental and theoretical data presented in the review give a comprehensive overview of these substances and can be valuable for specialists in the fields of nanotechnology, nanomaterials and bionanomedicine.

In the present work, the novel dense and supported membranes based on polyvinyl alcohol (PVA) with improved transport properties were developed by bulk and surface modifications. Bulk modification included the blending of PVA with chitosan (CS) and the creation of a mixed-matrix membrane by introduction of fullerenol. This significantly altered the internal structure of PVA membrane, which led to an increase in permeability with high selectivity to water. Surface modification of the developed modified dense membranes, based on composites PVA-CS and PVA-fullerenol-CS, was performed through (i) making of a supported membrane with a thin selective composite layer and (ii) applying of the layer-by-layer assembly (LbL) method for coating of nano-sized polyelectrolyte (PEL) layers to increase the membrane productivity. The nature of polyelectrolyte type—(poly(allylamine hydrochloride) (PAH), poly(sodium 4-styrenesulfonate) (PSS), poly(acrylic acid) (PAA), CS), and number of PEL bilayers (2–10)—were studied. The structure of the composite membranes was investigated by FTIR, X-ray diffraction, and SEM. Transport properties were studied during the pervaporation separation of 80% isopropanol–20% water mixture. It was shown that supported membrane consisting of hybrid layer of PVA-fullerenol (5%)–chitosan (20%) with five polyelectrolyte bilayers (PSS, CS) deposited on it had the best transport properties.

In present work the nonequilibrium thermodynamic advantages for pervaporation process approximation are discussed. The calculation model, which aligns nonequilibrium thermodynamic, pervaporation data and vapor–liquid equilibrium data, is presented. The approximation of vapor–liquid equilibrium data for feed mixtures was performed by Wilson and NRTL equations. Approbation of proposed approach with the use of different membranes was carried out for six binary systems: methanol–water, ethanol–water, propanol-1–water, propanol-2–water, butanol-1–water and acetone–water. The compatibility between the experimental pervaporation data and the results of estimation are discussed.

Hybrid membranes based on composites of polyvinyl alcohol (PVA) and low-hydroxylated fullerenol C 60 (OH) 12 have been assembled. In this study, two different procedures for PVA membrane cross-linking were applied including a thermal treatment, with elevated temperatures (140 °C 100 min) and chemical treatment with the addition of 35% maleic acid to the polymer matrix and thermal treatment (110 °C 120 min). The structure of the membranes was examined by wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM). Thermal properties and stability were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It was found that fullerenol, being an effective cross-linker for PVA, prevented the crystallization of the polymer during annealing, resulting in the increase of membrane permeability for chemically cross-linked membranes. Transport properties of hybrid membranes containing up to 5 wt% fullerenol were studied by the pervaporation of (1) chemical-equilibrium quaternary mixtures of n -propyl acetate, acetic acid, n -propanol and water in order to identify the properties of the membranes used in the hybrid process of esterification+pervaporation, and (2) ternary azeotropic n -propyl acetate– n -propanol–water mixtures. All the membranes were selective with respect to water and the optimal transport properties were obtained for the PVA-5% fullerenol membranes containing maleic acid.

This paper continues research on the physicochemical features of nanocomposites of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and fullerene C 60 with the purpose of using them as a selective layer of composite membranes in pervaporation coupling esterification of acetic acid with ethanol to produce ethyl acetate. The C 60 –PPO/MFFC composite membranes containing up to 3 wt%C 60 were prepared in this work. SEM was employed in visualizing the internal morphology of the membranes. The nature of the interaction between PPO and C 60 molecules in composite was studied by NMR. TG analysis reveals the fact of increasing thermal destruction point of the membrane due to certain structural changes of the PPO matrix upon incorporation of the C 60 molecules. Transport properties of composite membranes with a selective layer containing up to 3 wt%C 60 were studied in the pervaporation of the quaternary mixture: ethanol, acetic acid, ethyl acetate, and water in order to identify the availability of their use in the hybrid process “esterification + pervaporation”. The strong permeability enhancement due to the introduction of C60 particles in the PPO network was observed whereas the selectivity was almost steady. The best complex of transport properties was obtained from the 2%C 60 –PPO/MFFC membrane.

Polyhydroxy fullerenes such as fullerenol C60(OH)22–24 have helped to bridge the gap between fullerenes and their innate solubility issues, where fullerenol solubility in water is 50 mg/ml whereas C60 solubility is 1.3 × 10−11 mg/ml. The improved solubility of these fullerene derivatives allows them to be better integrated into composite materials. Here we investigated the transport properties of cross-linked fullerenol–polyvinyl alcohol membranes with the addition of maleic acid for increased stability. High humidity causes the mechanical properties of polyvinyl alcohol to decrease. Using fullerenol as a cross-linker, we were able to decrease the sorption of water with these PVA membranes.

We have studied copolymer dendrimer structure: carbosilane dendrimers with terminal phenylbenzoate mesogenic groups attached by poly(ethylene) glycol (PEG) spacers. In this system PEG spacers are additional tuning to usual copolymer structure: dendrimer with terminal mesogenic groups. The dendrimer macromolecules were investigated in a dilute chloroform solution by 1H NMR methods (spectra and relaxations). It was found that the PEG layer in G = 5 generations dendrimer is “frozen” at high temperatures (above 260 K), but it unexpectedly becomes “unfrozen” at temperatures below 250 K (i.e., melting when cooling). The transition between these two states occurs within a small temperature range (~10 K). Such a behavior is not observed for smaller dendrimer generations (G = 1 and 3). This effect is likely related to the low critical solution temperature (LCST) of PEG and is caused by dendrimer conformations, in which the PEG group concentration in the layer increases with growing G. We suppose that the unusual behavior of PEG fragments in dendrimers will be interesting for practical applications such as nanocontainers or nanoreactors.

Poly(phenylene isophtalamide) (PA) was modified by fullerene C60 using solid-phase method. Novel ultrafiltra- tion membranes based on nanocomposites containing up to 10 wt% of fullerene and carbon black were prepared. Properties of PA/C60 composites in solutions were studied by light scattering and rheological methods. The relationship between char- acteristics of casting solutions and properties of nanocomposite membranes was studied. Scanning electron microscopy was used for structural characterization of the membranes. It was found that increase in fullerene content in nanocomposite enhances the membrane rigidity. All nanocomposite membranes were tested in dynamic (ultrafiltration) and static sorption experiments using a solution of protein mixture, with the purpose of studying protein sorption. The membranes modified by fullerene demonstrate the best values of flux reduced recovery after contact with protein solution. It was found that addition of fullerene C60 to the polymer improves technological parameters of the obtained composite membranes.

Homogeneous membranes based on poly (phenylene isophtalamide) (PA) modified by multi-walled carbon nanotubes (MWCNT) Taunit® were prepared and studied in separation of methanol/MTBE mixture by pervaporation. It was shown that the membranes were selective with respect to methanol. The highest values of separation factor and permeability were obtained for membrane containing 2wt% MWCNT in comparison with PA and PA/MWCNT (5wt%) membranes. Study of membrane swelling in methanol made it possible to determine sorption degree, Flory-Huggins parameters of polymer-solvent interaction and coefficients of methanol diffusion in membrane. Sorption and diffusion characteristics were involved in the analysis of transport properties in the pervaporation process. It was established that PA/MWCNT nanocomposite membranes are effective in purification of MTBE from methanol impurities.

Modification of polymer properties by incorporation of nanoparticles is a way for the development of advanced membrane materials. New materials based on the compositions polymer - fullerene were developed for the use in pervaporation. Two polymers polyphenylene oxide (PPO) and polyphenylene isophtalamide (PA) were modified by fullerene C60. Their transport properties were studied in pervaporation of two systems: the reacting mixture ethanol - acetic acid - water - ethyl acetate by fullerene-containing PPO membranes and the methanol/cyclohexane mixture with azeotropic point by fullerene-containing PA membranes. The experimental study of sorption-diffusion parameters were carried out in sorption tests to analyze transport properties of the modified membranes as a function of the fullerene content in membranes.

New polymer nanocomposites consist of poly(phenylene isophtalamide) (PA) modified by carbon nanotubes (CNT) were obtained by the solid state interaction method to prepare dense membranes. The investigation of the PA/CNT nanocomposites was made by Raman spectroscopy. The morphology of the dense membrane was analyzed by SEM. The transport properties of the dense polyamide membranes modified by 2 and 5 wt% CNT were studied in pervaporation of methanol/ methyl tert-butyl ether mixture. It was shown that the selectivity with respect to methanol and permeability were the highest for membranes containing 2 wt% CNT as compared to membranes of pure PA and containing 5 wt% CNT. To analyze transport properties the sorption tests and contact angle measurements were employed.

Homogeneous membranes based on PA/C 60 composites were obtained and their internal morphology was visualized using SEM. The interaction between PA and C 60 was studied by spectroscopic methods. The effect of C 60 inclusion in the PA matrix on physical properties was characterized by measurement of the intrinsic viscosity, density, and glass transition temperature. Transport properties of pure PA and composite membranes were studied in pervaporation of the methanol/cyclohexane mixture. It was found that all membranes were essentially permeable for methanol. The permeability and so-called inverse selective separation properties were improving for membranes containing 2 and 5 wt.-% C 60 , whereas they decreased for higher C 60 content.

Possibility of modification of polyphenyleneisophthalamide with 5 wt % nanocarbon additive (fullerene, astralene, or graphite soot) was studied. The resulting composites were used to prepare asymmetric membranes, and the effect of carbon additives on the performance of these membranes was examined. Finally, the membranes were tested using a mixture of proteins of various molecular weights.

Homogeneous membranes based on fullerene‐polyphenylene oxide compositions containing up to 2 wt% fullerene C60 were prepared. The effect of fullerene addition on PPO transport properties was studied in gas separation and pervaporation processes. Permeability coefficients of H2, O2, N2, CH4, and CO2 were measured; a correlation between gas transport properties and membrane free volume was established. Pervaporation properties were studied for the system with ethyl acetate synthesis reaction: quaternary system ethanol—acetic acid—water—ethyl acetate and some constituent binary and ternary mixtures. Pervaporation in binary systems, ethanol–water and ethyl acetate–water was considered with the use of the data on sorption capacities and interaction parameters. In pervaporation of a quaternary reacting mixture, the permeate containing essentially ethyl acetate was obtained. Results show that membranes with fullerene additives exhibit improved transport properties.

Homogeneous fullerene-polyphenylene oxide membranes containing up to 2 wt % C60 are synthesized and characterized by the density, electrical resistivity, and contact angle with water and ethanol. The effect of fullerene additive on the transport characteristics of the membranes in pervaporation of water mixtures with ethanol and ethyl acetate is studied.

Mass-exchange characteristics of cellulose myristate or acetomyristate membranes in separating aqueous-organic, organic, or gas mixtures, particularly, in recovering aromatic hydrocarbons from binary mixtures with aliphatic alcohols, and also ethyl acetate from a mixture of esterification products, are studied.

This study focuses on the development of novel dense and supported mixed-matrix membranes based on chitosan and poly(2,6-dimethyl-1,4-phenylenoxide) (PPO) with low-hydroxylated fullerenol C60(OH)12. These novel membranes containing nano-carbon particles were prepared to reach high membrane performances for further integration in a dehydration process like distillation coupled with pervaporation. SEM microscopy was used to visualize the internal morphology of the membrane. It was found that all membranes were well stable and highly water-selective in spite of the different nature of polymers.