Systematic hydrolysis of PIM-1 and electrospinning of hydrolyzed PIM-1 ultrafine fibers for an efficient removal of dye from water

In this study, the Polymer of Intrinsic Microporosity (PIM-1) was systematically hydrolyzed in the presence of sodium hydroxide by varying the concentration of base, washing procedure and the time of the reaction. The chemical structure analyses confirmed that PIM-1 could be hydrolyzed by 65% up to 99% conversion depending on the synthesis procedure. The hydrolyzed PIM-1 samples have shown improved solubility which facilitates the fabrication of hydrolyzed PIM-1 ultrafine fibers by electrospinning technique. Extensive optimization studies were performed for the electrospinning of uniform and bead-free fibers from hydrolyzed PIM-1 with different degree of hydrolysis (65%, 86%, 94% and 99%). The electrospun hydrolysed PIM-1 fibrous samples have average fiber diameters (AFD) ranging from 0.58 ± 0.15 μm to 1.21 ± 0.15 μm, depending on the polymer concentration and applied electrospinning parameters. After electrospinning, self-standing hydrolyzed PIM-1 fibrous membranes were obtained which is useful as a filtering material for the adsorption of organic dyes from wastewater. Here, the capability of hydrolyzed PIM-1 electrospun fibrous membranes for the removal of dyes from aqueous solutions was investigated by using a batch adsorption process. The maximum adsorption capacity of fully hydrolyzed PIM-1 fibers was found 157 ± 16 mg g− 1 for Methylene Blue and 4 mg g− 1 for Congo red when the adsorption was conducted by 20 mg L− 1 dye solution without using any dilution. Moreover, maximum dye adsorption was also studied by using concentrated Methylene Blue solutions showing up to 272 mg g− 1 adsorption maximum. In addition, the self-standing fibrous hydrolyzed PIM-1 membrane was employed to separate Methylene Blue from an aqueous system by filtration without the necessity of additional driving force. The results indicate that hydrolyzed PIM-1 electrospun nanofibrous membranes can be a promising filtering material for wastewater treatment © 2017 Elsevier B.V

Comparison of pure and mixed gas permeation of the highly fluorinated polymer of intrinsic microporosity PIM-2 under dry and humid conditions: Experiment and modelling

This manuscript describes the gas separation performance of PIM-2, a partially fluorinated linear copolymer synthesized from 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethylspirobisindane (TTSBI) and decafluorobiphenyl (DFBP). As one of the early members of the family of polymers of intrinsic microporosity, it had never been tested as a gas separation membrane because of insufficient mechanical resistance. This has been solved only recently, allowing the preparation of robust self-standing films. Molecular modelling studies demonstrated a high fractional free volume (34%) and an elevated surface area (642 m2 g-1), and the latter is in good agreement with experimental BET results. Pure gas permeabilities measured on a fixed-volume time-lag instrument at 1 bar compare well with the results of mixed separation tests on a variable volume setup from 1-6 bar(a). Molecular modelling and independent sorption measurements on a gravimetric sorption balance both show strong dual-mode sorption behaviour, especially for CO2 and to a lesser extent for CH4. Temperature-dependent pure gas permeation measurements show typical Arrhenius behaviour, with a clear increase in the activation energy for diffusion with the increasing molecular size of the gas, indicating high size-selectivity. This is in agreement with the highly rigid PIM structure, determined by AFM force spectroscopy measurements. The dual-mode behaviour results in a moderate pressure dependence of the CO2 permeability and the CO2/N2 and CO2/CH4 selectivity, all slightly decreasing with increasing pressure. The presence of humidity in the gas stream has a remarkable small effect on the membrane performance, which is probably due to the high fluorine content and the consequently low water vapour solubility in the polymer, as confirmed by gravimetric sorption measurements. The manuscript describes an extensive study on the structure-property relationships in PIM-2. © 2019 Elsevier B.V.European Commission, EC Grantová Agentura Ceské Republiky, GA Ä?R: 18-05484S --Research on biogas upgrading presented in this work was supported by EU structural funding in the frame of Operational Programme Research, Development and Education, project No. CZ.02.1.01./0.0/0.0/17_049/0008419 “COOPERATION”. This work was further supported by the CNR-CAS bilateral agreement 2016–2018 “Innovative polymeric membranes for pervaporation and advanced gas and vapour separations” and by the Czech Science Foundation (grant no. 18-05484S ). Appendix A -

Spawning of bluefin tuna in the black sea: historical evidence, environmental constraints and population plasticity

<div><p>The lucrative and highly migratory Atlantic bluefin tuna, <em>Thunnus thynnus</em> (Linnaeus 1758<em>;</em> Scombridae), used to be distributed widely throughout the north Atlantic Ocean, Mediterranean Sea and Black Sea. Its migrations have supported sustainable fisheries and impacted local cultures since antiquity, but its biogeographic range has contracted since the 1950s. Most recently, the species disappeared from the Black Sea in the late 1980s and has not yet recovered. Reasons for the Black Sea disappearance, and the species-wide range contraction, are unclear. However bluefin tuna formerly foraged and possibly spawned in the Black Sea. Loss of a locally-reproducing population would represent a decline in population richness, and an increase in species vulnerability to perturbations such as exploitation and environmental change. Here we identify the main genetic and phenotypic adaptations that the population must have (had) in order to reproduce successfully in the specific hydrographic (estuarine) conditions of the Black Sea. By comparing hydrographic conditions in spawning areas of the three species of bluefin tunas, and applying a mechanistic model of egg buoyancy and sinking rate, we show that reproduction in the Black Sea must have required specific adaptations of egg buoyancy, fertilisation and development for reproductive success. Such adaptations by local populations of marine fish species spawning in estuarine areas are common as is evident from a meta-analysis of egg buoyancy data from 16 species of fish. We conclude that these adaptations would have been necessary for successful local reproduction by bluefin tuna in the Black Sea, and that a locally-adapted reproducing population may have disappeared. Recovery of bluefin tuna in the Black Sea, either for spawning or foraging, will occur fastest if any remaining locally adapted individuals are allowed to survive, and by conservation and recovery of depleted Mediterranean populations which could through time re-establish local Black Sea spawning and foraging.</p> </div

Polymers of Intrinsic Microporosity (PIMs)

Based on cumulative research from the past two decades, this personal perspective defines the structurally unique features of Polymers of Intrinsic Microporosity (PIMs), which result in a distinct combination of properties, including solution-processability and microporosity, providing organic materials suitable for the fabrication of membranes that perform efficient molecular sieving.</p

Amidoxime functionalized Polymers of Intrinsic Microporosity (PIM-1) electrospun ultrafine fibers for rapid removal of uranyl ions from water

The Polymers of Intrinsic Microporosity (PIM-1) is considered as one of the most promising polymer candidates for adsorption applications owing to its high surface area and the ability to tailor the functionality for the targeted species. This study reports a facile method for the preparation of amidoxime functionalized PIM-1 fibrous membrane (AF-PIM-FM) by electrospinning technique and its practical use for the extraction of U(VI) ions from aqueous systems via column sorption under continuous flow. Fibrous membrane form of amidoxime functionalized PIM-1 (AF-PIM-FM) was prepared by electrospinning method owing to its excellent processability in dimethylformamide. Bead-free and uniform fibers were obtained as confirmed by SEM imaging and average fiber diameter was 1.69 ± 0.34 μm for AF-PIM-FM. In addition, electrospun PIM-1 fibrous membrane (PIM-FM) was prepared as a control group. Structural and thermal characterization of powder and membrane forms of the materials were performed using FT-IR, 1 H NMR, XPS, Elemental analyses, TGA, and DSC. The porosity of the samples was measured by N2 sorption isotherms confirming amidoxime PIM-1 still maintain their porosity after functionalization. Amidoxime functionality along with membrane structure makes AF-PIM-FM a promising material for uranyl adsorption. First, a comparison between powder and membrane form of amidoxime functionalized PIM-1 was investigated using batch adsorption process. Although membrane form has shown slightly lower adsorption performance in the batch adsorption process, the advantage of using the membrane in column adsorption processes makes membrane form more feasible for real applications. In addition, amidoxime modification enhanced the uranium adsorption ability of PIM-FM up to 20 times. The effect of initial concentration and pH were investigated along with regeneration of the adsorbents. AF-PIM-FM was successfully used for five adsorption-desorption cycles without having any damage on the fibrous structure

Detection of twin pregnancies in ewes by pregnancy-associated glycoprotein assay and transabdominal ultrasonography

The objectives of the present study were to evaluate and compare the accuracy of transabdominal ultrasonography and pregnancy-associated glycoprotein (PAG) assay in the diagnosis of twin pregnancies in ewes and to evaluate the utility of the PAG assay for predicting fetal gender in singleton pregnancies. The animals in the study consisted of 179 pregnant ewes. The number of fetuses in the ewe was determined using transabdominal ultrasonography between days 40 and 60 (on days 40, 45, 50, 55, and 60). Blood samples were collected from all the ewes on the same day to determine the PAG concentrations. The results found were highly sensitive for the detection of twin pregnancies by transabdominal ultrasonography. The accuracy of transabdominal ultrasonography in detecting twin pregnancies was found to be higher on day 60 than on other days (P < 0.05). The sensitivities of PAG assay in detecting twin pregnancies on days 40, 45, 50, 55, and 60 were 91.67%, 66.67%, 81.82%, 88.89%, and 33.33%, respectively. The accuracies of the PAG assay in detecting twin pregnancies on days 40, 45, and 50 were found to be statistically significant higher than other days (P < 0.05). The PAG assay had low sensitivity and specificity for predicting fetal gender. It was concluded that twin pregnancies in ewes can be diagnosed with high accuracy using transabdominal ultrasonography on day 60 of pregnancy and as well as using the PAG assay during the early days of pregnancy (on days 40, 45, and 50). The PAG assay is not useful for predicting fetal gender. (C) 2019 Elsevier Inc. All rights reserved