Mechanism of PVDF Membrane Formation by NIPS Revisited: Effect of Precipitation Bath Nature and Polymer-Solvent Affinity.

A new interpretation of the mechanism of the polyvinylidene fluoride (PVDF) membrane formation using the nonsolvent-induced phase separation (NIPS) method based on an analysis of the complete experimental phase diagram for the three-component mixture PVDF-dimethyl acetamide (DMAc)-water is proposed. The effects of the precipitation bath's harshness and thermodynamic affinity of the polymer's solvent on the morphology, crystalline structure, transport and physical-mechanical properties of the membranes are investigated. These characteristics were studied via scanning electron microscopy, wide-angle X-ray scattering, liquid-liquid porosimetry and standard methods of physico-mechanical analysis. It is established that an increase in DMAc concentration in the precipitation bath results in the growth of mean pore size from ~60 to ~150 nm and an increase in permeance from ~2.8 to ~8 L m-2 h-1 bar-1. It was observed that pore size transformations are accompanied by changes in the tensile strength of membranes from ~9 to ~11 and to 6 MPa, which were explained by the degeneration of finger-like pores and appearance of spherulitic structures in the samples. The addition of water to the dope solution decreased both the transport (mean pore size changed from ~55 to ~25 nm and permeance reduced from ~2.8 to ~0.5 L m-2 h-1 bar-1) and mechanical properties of the membranes (tensile strength decreased from ~9 to ~6 MPa). It is possible to conclude that the best membrane quality may be reached using pure DMAc as a solvent and a precipitation bath containing 10-30% wt. of DMAc, in addition to water.

Controlled Swelling of Monolithic Films as a Facile Approach to the Synthesis of UHMWPE Membranes.

A new method of fabricating porous membranes based on ultra-high molecular weight polyethylene (UHMWPE) by controlled swelling of the dense film was proposed and successfully utilized. The principle of this method is based on the swelling of non-porous UHMWPE film in organic solvent at elevated temperatures, followed by its cooling and further extraction of organic solvent, resulting in the formation of the porous membrane. In this work, we used commercial UHMWPE film (thickness 155 µm) and o-xylene as a solvent. Either homogeneous mixtures of the polymer melt and solvent or thermoreversible gels with crystallites acting as crosslinks of the inter-macromolecular network (swollen semicrystalline polymer) can be obtained at different soaking times. It was shown that the porous structure and filtration performance of the membranes depended on the swelling degree of the polymer, which can be controlled by the time of polymer soaking in organic solvent at elevated temperature (106 °C was found to be the optimal temperature for UHMWPE). In the case of homogeneous mixtures, the resulting membranes possessed both large and small pores. They were characterized by quite high porosity (45-65% vol.), liquid permeance of 46-134 L m-2 h-1 bar-1, a mean flow pore size of 30-75 nm, and a very high crystallinity degree of 86-89% at a decent tensile strength of 3-9 MPa. For these membranes, rejection of blue dextran dye with a molecular weight of 70 kg/mol was 22-76%. In the case of thermoreversible gels, the resulting membranes had only small pores located in the interlamellar spaces. They were characterized by a lower crystallinity degree of 70-74%, a moderate porosity of 12-28%, liquid permeability of up to 12-26 L m-2 h-1 bar-1, a mean flow pore size of up to 12-17 nm, and a higher tensile strength of 11-20 MPa. These membranes demonstrated blue dextran retention of nearly 100%.

Phase Equilibria and Structure Formation in the Polylactic-co-Glycolic Acid/Tetraglycol/Water Ternary System.

This paper concerns a detailed study of the phase separation and structure formation processes that occur in solutions of highly hydrophobic polylactic-co-glycolic acid (PLGA) in highly hydrophilic tetraglycol (TG) upon their contact with aqueous media. In the present work, cloud point methodology, high-speed video recording, differential scanning calorimetry, and both optical and scanning electron microscopy were used to analyze the behavior of PLGA/TG mixtures differing in composition when they are immersed in water (the so-called "harsh" antisolvent) or in a nonsolvent consisting of equal amounts of water and TG (a "soft" antisolvent). The phase diagram of the ternary PLGA/TG/water system was designed and constructed for the first time. The PLGA/TG mixture composition with which the polymer undergoes glass transition at room temperature was determined. Our data enabled us to analyze in detail the structure evolution process taking place in various mixtures upon their immersion in "harsh" and "soft" antisolvent baths and gain an insight into the peculiarities of the structure formation mechanism active in the course of antisolvent-induced phase separation in PLGA/TG/water mixtures. This provides intriguing opportunities for the controlled fabrication of a wide variety of bioresorbable structures-from polyester microparticles, fibers, and membranes to scaffolds for tissue engineering.

A New Look at the Structure and Thermal Behavior of Polyvinylidene Fluoride-Camphor Mixtures.

An experimental quasi-equilibrium phase diagram of the polyvinylidene fluoride (PVDF)-camphor mixture is constructed using an original optical method. For the first time, it contains a boundary curve that describes the dependence of camphor solubility in the amorphous regions of PVDF on temperature. It is argued that this diagram cannot be considered a full analogue of the eutectic phase diagrams of two low-molar-mass crystalline substances. The phase diagram is used to interpret the polarized light hot-stage microscopy data on cooling the above mixtures from a homogeneous state to room temperature and scanning electron microscopy data on the morphology of capillary-porous bodies formed upon camphor removal. Based on our calorimetry and X-ray studies, we put in doubt the possibility of incongruent crystalline complex formation between PVDF and camphor previously suggested by Dasgupta et al. (Macromolecules 2005, 38, 5602-5608). We also describe and discuss the high-temperature crystalline structure of racemic camphor, which is not available in the modern literature.

Effect of Acetone as Co-Solvent on Fabrication of Polyacrylonitrile Ultrafiltration Membranes by Non-Solvent Induced Phase Separation.

For the first time, the presence of acetone in the casting solutions of polyacrylonitrile (PAN) in dimethylsulfoxide or N-methyl-2-pyrrolidone was studied with regards to thermodynamical aspects of phase separation of polymeric solutions induced by contact with non-solvent (water), formation and performance of porous membranes of ultrafiltration range. The positions of the liquid equilibrium binodals on the phase diagrams of these three-component and pseudo-three-component mixtures were determined. For PAN-N-methyl-2-pyrrolidone-water glass transition curve on a ternary phase diagram was plotted experimentally for the first time. The real-time evolution of the structure of mixtures of PAN with solvents (co-solvents) upon contact with a non-solvent (water) has been studied. The thermodynamic analysis of the phase diagrams of these mixtures, together with optical data, made it possible to propose a mechanism of structure formation during non-solvent induced phase separation of different mixtures. The addition of acetone promotes the formation of a spongy layer on the membrane surface, which decreases the probability of defect formation on the membrane surface and keeps finger-like macrovoids from the underlying layers of the membrane. It was shown that the molecular weight cut-off (MWCO) of the membranes can be improved from 58 down to 1.8 kg/mol by changing the acetone content, while polymer concentration remained the same.

Relationship between Phenolic Compounds and Antioxidant Activity in Berries and Leaves of Raspberry Genotypes and Their Genotyping by SSR Markers.

The red raspberry is one of the world's most popular berries. The main direction of its breeding has switched to nutritional quality, and the evaluation of raspberry germplasm for antioxidant content and activity is very important. As berries, raspberry leaves contain valuable bioactive compounds, but the optimal time for their collection is unknown. We evaluated 25 new breeding lines and standard raspberry cultivars for their polyphenolic content and antioxidant capacity. The antioxidant activity of berries correlated better with the content of total phenolics (0.88 and 0.92) and flavonoids (0.76 and 0.88) than with anthocyanins (0.37 and 0.66). Two breeding lines were significantly superior to the standard cultivars and can be used in further breeding. Leaves collected in three phenological phases of the raspberry contained more phenolics (5.4-fold) and flavonoids (4.1-fold) and showed higher antioxidant activities (2.4-fold in FRAP assay, 2.2-fold in ABTS) than berries. The optimal time for harvesting raspberry leaves is the fruit ripening stage, with exceptions for some cultivars. Genetic diversity analysis using microsatellite (SSR) markers from flavonoid biosynthesis genes divided the genotypes into five clusters, generally in agreement with their kinships. The relationship between genetic data based on metabolism-specific SSR markers and the chemical diversity of cultivars was first assessed. The biochemical and genetic results show a strong correlation (0.78). This study is useful for further the improvement of raspberry and other berry crops.

Assessing Impacts of Transgenic Plants on Soil Using Functional Indicators: Twenty Years of Research and Perspectives.

Assessment of the effects of transgenic plants on microbiota and soil fertility is an important part of the overall assessment of their biosafety. However, the environmental risk assessment of genetically modified plants has long been focused on the aboveground effects. In this review, we discuss the results of two decades of research on the impact of transgenic plants on the physicochemical properties of soil, its enzyme activities and microbial biomass. These indicators allow us to assess both the short-term effects and long-term effects of cultivating transgenic plants. Most studies have shown that the effect of transgenic plants on the soil is temporary and inconsistent. Moreover, many other factors, such as the site location, weather conditions, varietal differences and management system, have a greater impact on soil quality than the transgenic status of the plants. In addition to the effects of transgenic crop cultivation, the review also considers the effects of transgenic plant residues on soil processes, and discusses the future prospects for studying the impact of genetically modified plants on soil ecosystems.

Transferability and Polymorphism of SSR Markers Located in Flavonoid Pathway Genes in Fragaria and Rubus Species.

Strawberry (Fragaria) and raspberry (Rubus) are very popular crops, and improving their nutritional quality and disease resistance are important tasks in their breeding programs that are becoming increasingly based on use of functional DNA markers. We identified 118 microsatellite (simple sequence repeat-SSR) loci in the nucleotide sequences of flavonoid biosynthesis and pathogenesis-related genes and developed 24 SSR markers representing some of these structural and regulatory genes. These markers were used to assess the genetic diversity of 48 Fragaria and Rubus specimens, including wild species and rare cultivars, which differ in berry color, ploidy, and origin. We have demonstrated that a high proportion of the developed markers are transferable within and between Fragaria and Rubus genera and are polymorphic. Transferability and polymorphism of the SSR markers depended on location of their polymerase chain reaction (PCR) primer annealing sites and microsatellite loci in genes, respectively. High polymorphism of the SSR markers in regulatory flavonoid biosynthesis genes suggests their allelic variability that can be potentially associated with differences in flavonoid accumulation and composition. This set of SSR markers may be a useful molecular tool in strawberry and raspberry breeding programs for improvement anthocyanin related traits.