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The initial goal of the project was to develop a more effective method for the purifications of oligonucleotides. This was achieved by developing a method of ion-exchange based on-column deprotection. The resulting method was compared to preestablished methods using LC-MS fraction analysis evaluated according to a purityscore with the acceptance criteria of ≥ 0.45. The on-column deprotection was shownto achieve a purity score > 0.6 for both of the fully thiolated and the partially thiolatedoligonucleotides while the other methods of regular ion-exchange chromatography,ion-pair chromatography and reversed phase chromatography only achieved a purityscore of ≥ 0.6 for only the fully thiolated oligonucleotides. The ion-exchange methodsbecame dependent on more chaotropic agents than expected, but the results gainedduring the resin screening portion of the project may provide a remedy. During theresin screening, the effects of two factors, pore size and ligand density, were investigated. Showing that the pore size did not affect the oligonucleotides to any extent,resulting in the ligand density being the major affecting factor. When studying thedifferent resins, a trend of lower retention with lower ligand density was observed.These results provide a foundation to use lower ligand density resins compatible withless harsh conditions when applying the on-column deprotection in future optimization for the purification of pharmaceutical oligonucleotides., Syftet med projektet var att utveckla en mer effektiv metod för upprening av oligonukleotider. Detta uppnåddes genom att utveckla en metod för direkt avlägsning av denskyddande gruppen direkt på kolonnen baserat på jonbytes kromatografi. Den resulterande metoden jämfördes med tidigare etablerade metoder genom LC-MS fraktionsanalys och utvärderades enligt ett renhetsbetyg med acceptanskriterier på ≥ 0,45.Metoden visade sig uppnå ett renhetsbetyg > 0,6 för både de fullständigt tiolieradeoch delvis tiolierade oligonukleotider, medan andra metoder som vanlig jonutbyteskromatografi, jonpars-kromatografi och reversed phase-kromatografi endast uppnådde ett renhetsbetyg ≤ 0,6 för fullständigt tiolierade oligonukleotider. Jonutbytesmetoderna blev beroende av fler kaotropiska kemikalier än förväntat, men resultatenfrån resin undersökningen under projektet kan ge en lösning på detta. Under resinundersökningen utreddes effekterna av två faktorer, porstorlek och liganddensitet. Detvisades att porstorleken inte påverkade oligonukleotiderna i någon större utsträckningoch att liganddensiteten var den avgörande faktorn. Vid studier av olika resiner observerades en trend mot lägre retention vid lägre liganddensitet. Dessa resultat ger engrund för att använda resiner med lägre liganddensitet i den utevecklade metoden.Vilket bör tillåta mindre hårda förhållanden vid fortsatt optimering av uppreningenför farmaceutiska oligonucleotider.

[Abstract] Introduction: Silver-releasing dressings are used in the treatment of infected wounds. Despite their widespread use, neither the amount of silver released nor the potential in vivo toxicity is known. The aim of this study was to evaluate the cytotoxic effects and the amount of silver released from commercially available dressings with infected wounds. Methods: The review was conducted according to the PRISMA statement. The Web of Science, PubMed, Embase, Scopus, and CINAHL databases were searched for studies from 2002 through December 2022. The criteria were as follows: population (human patients with infected wounds); intervention (commercial dressings with clinical silver authorized for use in humans); and outcomes (concentrations of silver ions released into tissues and plasma). Any study based on silver-free dressings, experimental dressings, or dressings not for clinical use in humans should be excluded. According to the type of study, systematic reviews, experimental, quasi-experimental, and observational studies in English, Spanish, or Portuguese were considered. The quality of the selected studies was assessed using the JBI critical appraisal tools. Studies that assessed at least 65% of the included items were included. Data were extracted independently by two reviewers. Results: 740 articles were found and five were finally selected (all of them quasi-experimental). Heterogeneity was found in terms of study design, application of silver dressings, and methods of assessment, which limited the comparability between studies. Conclusion: In vivo comparative studies of clinical dressings for control of infection lack a standardized methodology that allows observation of all the variables of silver performance at local and systemic levels, as well as evaluation of its cytotoxicity. It cannot be concluded whether the assessed concentrations of released silver in commercial dressings for the topical treatment of infected wounds are cytotoxic to skin cell

The initial goal of the project was to develop a more effective method for the purifications of oligonucleotides. This was achieved by developing a method of ion-exchange based on-column deprotection. The resulting method was compared to preestablished methods using LC-MS fraction analysis evaluated according to a purityscore with the acceptance criteria of ≥ 0.45. The on-column deprotection was shownto achieve a purity score > 0.6 for both of the fully thiolated and the partially thiolatedoligonucleotides while the other methods of regular ion-exchange chromatography,ion-pair chromatography and reversed phase chromatography only achieved a purityscore of ≥ 0.6 for only the fully thiolated oligonucleotides. The ion-exchange methodsbecame dependent on more chaotropic agents than expected, but the results gainedduring the resin screening portion of the project may provide a remedy. During theresin screening, the effects of two factors, pore size and ligand density, were investigated. Showing that the pore size did not affect the oligonucleotides to any extent,resulting in the ligand density being the major affecting factor. When studying thedifferent resins, a trend of lower retention with lower ligand density was observed.These results provide a foundation to use lower ligand density resins compatible withless harsh conditions when applying the on-column deprotection in future optimization for the purification of pharmaceutical oligonucleotides., Syftet med projektet var att utveckla en mer effektiv metod för upprening av oligonukleotider. Detta uppnåddes genom att utveckla en metod för direkt avlägsning av denskyddande gruppen direkt på kolonnen baserat på jonbytes kromatografi. Den resulterande metoden jämfördes med tidigare etablerade metoder genom LC-MS fraktionsanalys och utvärderades enligt ett renhetsbetyg med acceptanskriterier på ≥ 0,45.Metoden visade sig uppnå ett renhetsbetyg > 0,6 för både de fullständigt tiolieradeoch delvis tiolierade oligonukleotider, medan andra metoder som vanlig jonutbyteskromatografi, jonpars-kromatografi och reversed phase-kromatografi endast uppnådde ett renhetsbetyg ≤ 0,6 för fullständigt tiolierade oligonukleotider. Jonutbytesmetoderna blev beroende av fler kaotropiska kemikalier än förväntat, men resultatenfrån resin undersökningen under projektet kan ge en lösning på detta. Under resinundersökningen utreddes effekterna av två faktorer, porstorlek och liganddensitet. Detvisades att porstorleken inte påverkade oligonukleotiderna i någon större utsträckningoch att liganddensiteten var den avgörande faktorn. Vid studier av olika resiner observerades en trend mot lägre retention vid lägre liganddensitet. Dessa resultat ger engrund för att använda resiner med lägre liganddensitet i den utevecklade metoden.Vilket bör tillåta mindre hårda förhållanden vid fortsatt optimering av uppreningenför farmaceutiska oligonucleotider.

© 2013 Elsevier B.V. All rights reserved. This research was funded by the Robert A. Welch foundation under Grant E-1264 and the National Science Foundation (NSF) Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET-1133965). The authors also acknowledge Tecnológico de Monterrey Research chair (Grant CAT161) and CONACyT for fellowship #295368 to FRR., We previously showed that the affinity and capacity of ion exchange adsorbents of a given total charge density are improved by immobilization of the charges in pre-ordered clusters, rather than individually in random locations. This previous work used pentalysinamide and pentaargininamide as clustered ligands. This approach allows close control of cluster size, but is uneconomically expensive for some research and most practical applications. In this work, we demonstrate that the inexpensive synthetic analog of the natural polyamine spermine (H2N-CH2-CH2-CH2-NH-CH2-CH2-CH2-CH2-NH-CH2-CH2-CH2 NH2) also can serve as the basis of effective clustered adsorbents. The calcium-depleted form of the protein a lactalbumin, and RNA from baker's yeast, were adsorbed on a spermine Sepharose adsorbent. This adsorbent exhibited enhanced alpha lactalbumin binding capacity (Q(max) >1.6 and 1.3-fold higher than those for Qiagen DEAE and GE DEAE Sepharose adsorbents of much greater charge density) and higher initial binding affinity (Q(max)/K-D 2.4 and 2.1 fold higher, respectively). The new spermine-based matrix exhibited a higher value of the Z parameter, suggesting an increased number of apparent interaction sites between the protein and the resin, and functioned well in column mode. (C) 2013 Elsevier B.V. All rights reserved., Robert A. Welch foundation, National Science Foundation (NSF), CONACyT, Tecnológico de Monterrey, Depto. de Física Teórica, Fac. de Ciencias Físicas, TRUE, pub

Carbon materials constitute a broad family of solids that encompass a high variety of physical and chemical properties, including morphology. These materials have shown to be very useful as catalysts supports and, in this context, also for the heterogenization of metal complexes owing catalytic properties. This work is mainly, the summary of the results obtained in several research projects focused on developing heterogenized molecular catalysts by exploiting the properties of a plethora of carbon materials to address several immobilization procedures.

Modified or low-salinity waterflooding of carbonate oil reservoirs is of considerable economic interest because of potentially inexpensive incremental oil production. The injected modified brine changes the surface chemistry of the carbonate rock and crude oil interfaces and detaches some of adhered crude oil. Composition design of brine modified to enhance oil recovery is determined by labor-intensive trial-and-error laboratory corefloods. Unfortunately, limestone, which predominantly consists of aqueous-reactive calcium carbonate, alters injected brine composition by mineral dissolution/precipitation. Accordingly, the rock reactivity hinders rational design of brines tailored to improve oil recovery. Previously, we presented a theoretical analysis of 1D, single-phase brine injection into calcium carbonate-rock that accounts for mineral dissolution, ion exchange, and dispersion (Yutkin et al. in SPE J 23(01):084–101, 2018. https://doi.org/10.2118/182829-PA). Here, we present the results of single-phase waterflood-brine experiments that verify the theoretical framework. We show that concentration histories eluted from Indiana limestone cores possess features characteristic of fast calcium carbonate dissolution, 2:1 ion exchange, and high dispersion. The injected brine reaches chemical equilibrium inside the porous rock even at injection rates higher than 3.5 × 10- 3 m s- 1 (1000 ft/day). Ion exchange results in salinity waves observed experimentally, while high dispersion is responsible for long concentration history tails. Using the verified theoretical framework, we briefly explore how these processes modify aqueous-phase composition during the injection of designer brines into a calcium-carbonate reservoir. Because of high salinity of the initial and injected brines, ion exchange affects injected concentrations only in high surface area carbonates/limestones, such as chalks. Calcium-carbonate dissolution only affects aqueous solution pH. The rock surfac

Solute carrier (SLC) transporters are membrane transport proteins, which catalyse the movement of nutrients, ions, and drugs across cell membranes. Here, I will present our contribution to understanding the mechanism of the sodium/proton exchangers (NHE), belonging to the SLC9 family of membrane transporters. NHEs exchange sodium ions for protons across biological membranes, which is a critical reaction for the fine-tuning of cytoplasmic and organelle pH, sodium levels and volume homeostasis. Dysfunction of NHE members has been linked to a number of diseases and disorders, such as hypertension, heart failure, autism spectrum disorder, epilepsy and the susceptibility of long COVID. Protein structures are important for developing mechanistic models, but due to technical challenges only bacterial homologue structures of NHE proteins were previously available. Accumulating many years of effort, we were able to determine the first structure of a mammalian Na+/H+ exchanger, the endosomal isoform NHE9 by single-particle cryo-EM. The structure of NHE9 demonstrated that NHE proteins are architecturally most similar to bacterial homologues with 13-TM segments and likely operated by a similar elevator mechanism (I). Interestingly, native MS and thermal-shift assays indicted that the NHE9 homodimer is stabilized by the binding of a rare lipid only found in late endosomes, which implies the cell may use this lipid as means to switch-on NHE9 activity once it reaches its correct functional localization. We further provided evidence that the large cytoplasmic tail in NHE proteins likely acts in an auto-inhibitory manner. It is only removed upon the binding of extrinsic proteins (II). Indeed, the first structure of a potassium specific K+/H+ exchanger KefC reveals how its cytoplasmic tail restricts movement of the ion-transporting domain to directly inhibit transport. The structure of KefC is also the first ion-bound state seen for this family and, unlike to the modeled Na+/H+ excha

Solute carrier (SLC) transporters are membrane transport proteins, which catalyse the movement of nutrients, ions, and drugs across cell membranes. Here, I will present our contribution to understanding the mechanism of the sodium/proton exchangers (NHE), belonging to the SLC9 family of membrane transporters. NHEs exchange sodium ions for protons across biological membranes, which is a critical reaction for the fine-tuning of cytoplasmic and organelle pH, sodium levels and volume homeostasis. Dysfunction of NHE members has been linked to a number of diseases and disorders, such as hypertension, heart failure, autism spectrum disorder, epilepsy and the susceptibility of long COVID. Protein structures are important for developing mechanistic models, but due to technical challenges only bacterial homologue structures of NHE proteins were previously available. Accumulating many years of effort, we were able to determine the first structure of a mammalian Na+/H+ exchanger, the endosomal isoform NHE9 by single-particle cryo-EM. The structure of NHE9 demonstrated that NHE proteins are architecturally most similar to bacterial homologues with 13-TM segments and likely operated by a similar elevator mechanism (I). Interestingly, native MS and thermal-shift assays indicted that the NHE9 homodimer is stabilized by the binding of a rare lipid only found in late endosomes, which implies the cell may use this lipid as means to switch-on NHE9 activity once it reaches its correct functional localization. We further provided evidence that the large cytoplasmic tail in NHE proteins likely acts in an auto-inhibitory manner. It is only removed upon the binding of extrinsic proteins (II). Indeed, the first structure of a potassium specific K+/H+ exchanger KefC reveals how its cytoplasmic tail restricts movement of the ion-transporting domain to directly inhibit transport. The structure of KefC is also the first ion-bound state seen for this family and, unlike to the modeled Na+/H+ excha

Modified or low-salinity waterflooding of carbonate oil reservoirs is of considerable economic interest because of potentially inexpensive incremental oil production. The injected modified brine changes the surface chemistry of the carbonate rock and crude oil interfaces and detaches some of adhered crude oil. Composition design of brine modified to enhance oil recovery is determined by labor-intensive trial-and-error laboratory corefloods. Unfortunately, limestone, which predominantly consists of aqueous-reactive calcium carbonate, alters injected brine composition by mineral dissolution/precipitation. Accordingly, the rock reactivity hinders rational design of brines tailored to improve oil recovery. Previously, we presented a theoretical analysis of 1D, single-phase brine injection into calcium carbonate-rock that accounts for mineral dissolution, ion exchange, and dispersion (Yutkin et al. in SPE J 23(01):084–101, 2018. https://doi.org/10.2118/182829-PA). Here, we present the results of single-phase waterflood-brine experiments that verify the theoretical framework. We show that concentration histories eluted from Indiana limestone cores possess features characteristic of fast calcium carbonate dissolution, 2:1 ion exchange, and high dispersion. The injected brine reaches chemical equilibrium inside the porous rock even at injection rates higher than 3.5 × 10- 3 m s- 1 (1000 ft/day). Ion exchange results in salinity waves observed experimentally, while high dispersion is responsible for long concentration history tails. Using the verified theoretical framework, we briefly explore how these processes modify aqueous-phase composition during the injection of designer brines into a calcium-carbonate reservoir. Because of high salinity of the initial and injected brines, ion exchange affects injected concentrations only in high surface area carbonates/limestones, such as chalks. Calcium-carbonate dissolution only affects aqueous solution pH. The rock surfac

Ion-exchange reactions are commonly used to develop novel metastable electrode materials for alkali-ion batteries that cannot be synthesized using direct chemical reactions. In this study, the electrochemical K to Na ion-exchange reaction mechanisms in a layered KxCoO2 cathode as a model system were investigated using operando and ex situ structure characterization techniques. Some level of K ions was observed to remain in the layered structure during the electrochemical ion-exchange reactions. Interestingly, the K ions are well separated from the Na-rich phases in the discharged state, and they form an intermediate phase in which K and Na ions are mixed at the top of charge. We discovered that such residual K ions prevent the collapse of the layered structure in the high-voltage regime, thereby improving the cycling stability in a Na-battery system.

Geopolymers are a class of alkaline-activated materials that have been considered as promising materials for radioactive waste disposal. Currently, metakaolin-based geopolymers (MK-GPs) are attracting interest for the immobilisation of radionuclides in contaminated water from the Fukushima Daiichi Nuclear Power Station. However, the associated chemical interaction mechanisms and the theoretical prediction of the adsorption behaviour of MK-GP in response to cationic radionuclides have not been thoroughly studied or fully understood. In addition, there is a lack of studies on the adsorption capacity of MK-GP for anionic radionuclides. In this study, two types of metakaolin-based (Metastar501 and Sobueclay) geopolymers were synthesised at a K2O:SiO2:H2O ratio of 1:1:13. The binding capacity and interaction mechanism of MK-GP with Cs+, Sr2+, Co2+, I-, IO3-, SeO32-, and SeO42- were evaluated based on the zeta potential, radionuclide binding, and alkali leaching. The results showed that MK-GP does not have the ability to incorporate anionic radionuclides irrespective of the metakaolin source used, but both types of geopolymers have a high capacity to immobilise cationic radionuclides. The uptake of Cs+ was observed as a one-to-one exchange between Cs+ and K+ whereas both one-two and one-one ion exchanges are possible in the case of Sr2+ and Co2+ with K+. The formation of cobalt blue (CoAl2O4) also contributed to the binding of Co2+. Thermodynamic modelling was conducted according to the ion exchange mechanism which predicts the binding of Cs+ and Sr2+ at low concentrations.

Alkali-activated (or geopolymer) membranes have emerged recently as an alternative for conventional ceramic membranes. Their main benefit is the simple and low-energy manufacturing not requiring sintering, and thus potential for clearly lower costs, while having largely similar performance as conventional ceramic materials. In this work, metakaolin, blast furnace slag, and their mixture (representing typical low, high, and medium Ca-content raw materials, respectively) were compared as aluminosilicate precursors for the preparation of self-supporting membrane disks (diameter 75 mm, height 3 mm). A thorough material characterization was performed to evaluate mechanical strength, shrinkage, microstructure, chemical composition, pore size distribution, specific surface area, zeta potential, and water flux at different temperatures (20–60 °C) and pressures (200–1000 kPa). Based on this screening, metakaolin-based membrane (i.e., the low-calcium system) indicated overall better performance than the two others based on blast furnace slag or their mixture. As a final part of the study, ammonium-containing model effluent ([NH4+] = 50 mg L⁻¹) was distributed through the membrane (using 200 kPa pressure at 25 °C) to evaluate the potential for nitrogen removal and recovery. The mass balance examination indicated that ammonium was retained in the membrane matrix (i.e., not concentrated in the retentate fraction), and thus the likely removal mechanism was via ion-exchange. The obtained results provide interesting insights for the further development of alkali-activated membranes for applications requiring ammonium nitrogen removal, such as membrane bioreactors in municipal wastewater treatment.

Geopolymers are a class of alkaline-activated materials that have been considered as promising materials for radioactive waste disposal. Currently, metakaolin-based geopolymers (MK-GPs) are attracting interest for the immobilisation of radionuclides in contaminated water from the Fukushima Daiichi Nuclear Power Station. However, the associated chemical interaction mechanisms and the theoretical prediction of the adsorption behaviour of MK-GP in response to cationic radionuclides have not been thoroughly studied or fully understood. In addition, there is a lack of studies on the adsorption capacity of MK-GP for anionic radionuclides. In this study, two types of metakaolin-based (Metastar501 and Sobueclay) geopolymers were synthesised at a K2O:SiO2:H2O ratio of 1:1:13. The binding capacity and interaction mechanism of MK-GP with Cs+, Sr2+, Co2+, I-, IO3-, SeO32-, and SeO42- were evaluated based on the zeta potential, radionuclide binding, and alkali leaching. The results showed that MK-GP does not have the ability to incorporate anionic radionuclides irrespective of the metakaolin source used, but both types of geopolymers have a high capacity to immobilise cationic radionuclides. The uptake of Cs+ was observed as a one-to-one exchange between Cs+ and K+ whereas both one-two and one-one ion exchanges are possible in the case of Sr2+ and Co2+ with K+. The formation of cobalt blue (CoAl2O4) also contributed to the binding of Co2+. Thermodynamic modelling was conducted according to the ion exchange mechanism which predicts the binding of Cs+ and Sr2+ at low concentrations.

Solute carrier (SLC) transporters are membrane transport proteins, which catalyse the movement of nutrients, ions, and drugs across cell membranes. Here, I will present our contribution to understanding the mechanism of the sodium/proton exchangers (NHE), belonging to the SLC9 family of membrane transporters. NHEs exchange sodium ions for protons across biological membranes, which is a critical reaction for the fine-tuning of cytoplasmic and organelle pH, sodium levels and volume homeostasis. Dysfunction of NHE members has been linked to a number of diseases and disorders, such as hypertension, heart failure, autism spectrum disorder, epilepsy and the susceptibility of long COVID. Protein structures are important for developing mechanistic models, but due to technical challenges only bacterial homologue structures of NHE proteins were previously available. Accumulating many years of effort, we were able to determine the first structure of a mammalian Na+/H+ exchanger, the endosomal isoform NHE9 by single-particle cryo-EM. The structure of NHE9 demonstrated that NHE proteins are architecturally most similar to bacterial homologues with 13-TM segments and likely operated by a similar elevator mechanism (I). Interestingly, native MS and thermal-shift assays indicted that the NHE9 homodimer is stabilized by the binding of a rare lipid only found in late endosomes, which implies the cell may use this lipid as means to switch-on NHE9 activity once it reaches its correct functional localization. We further provided evidence that the large cytoplasmic tail in NHE proteins likely acts in an auto-inhibitory manner. It is only removed upon the binding of extrinsic proteins (II). Indeed, the first structure of a potassium specific K+/H+ exchanger KefC reveals how its cytoplasmic tail restricts movement of the ion-transporting domain to directly inhibit transport. The structure of KefC is also the first ion-bound state seen for this family and, unlike to the modeled Na+/H+ excha

V této disertační práci byly studovány nekonvenční techniky odstraňování persistentních polutantů z vodných roztoků. Tyto kontaminanty jsou biologicky obtížně odbouratelné halogenované aromatické deriváty zastoupené vybranými sloučeninami ze skupiny léčiv, barviv a pesticidů. V rámci řešení této disertační práce byla testována separace kontaminantů (léčiv Diklofenak a Flufenamová kyselina, barviva Mordant Blue 9) z vod adsorpcí na uhlíkatých sorbentech jako je aktivní uhlí a alternativní sorbent biochar. Byla ověřována i možnost využití komerčně dostupných iontových kapalin pro navýšení sorpčních kapacit biocharu. Další část práce se zabývá metodami chemické degradace koncentrovaných vodných roztoků vybraných halogenovaných polutantů s využitím reduktivní hydrodehalogenace. Bylo ověřeno, že hydrodehalogenace pomocí Raneyovy (Al-Ni) nebo Devardovy slitiny (Al-Cu-Zn) v prostředí zředěného vodného hydroxidu sodného nebo draselného je velmi efektivní metodou degradace testovaných halogenderivátů. Poslední část výzkumu této disertační práce byla zaměřena na regeneraci a recyklaci iontových párů vznikajících působením zmíněných iontových kapalin na halogenované organické kyseliny, respektive jejich soli. Bylo zjištěno, že chemickou redukcí iontových párů pomocí NaBH4/NiSO4 a/nebo Raneyovy slitiny Al-Ni je možné regenerovat použité iontové kapaliny a využít je v dalším procesu iontové výměny, a to až v několika cyklech. Tato disertační práce prezentuje komplexní výzkum na sebe navazujících kroků odstraňování halogenovaných organických kontaminantů z vodných roztoků. Výsledky zmíněného výzkumu byly publikovány v sedmi impaktovaných zahraničních časopisech, byly prezentovány na třinácti národních a šesti mezinárodních konferencích formou přednášek a plakátových sdělení a jsou součástí kapitoly v knize a národního patentu., This dissertation thesis studied non-conventional techniques of removal of persistent pollutants such as halogenated aromatic compounds (represented by selected drugs, dyes and pesticides) from aqueous solutions. Separation of contaminants (drugs - diclofenac and flufenamic acid and dyes - Mordant Blue 9) was tested using adsorption on carbonaceous sorbents such as activated carbon and biochar as an alternative sorbent. The possibility of using commercial ionic liquids to increase biochar sorption capacity was also tested. The next part of this thesis studies the methods of chemical degradation of concentrated aqueous solutions of tested halogenated pollutants using reductive hydrodehalogenation. Hydrodehalogenation using the Raney (Al-Ni) alloy or Devarda's (Al-Cu-Zn) alloy in diluted aqueous sodium or potassium hydroxide was verified to be a very effective degradation method of the tested halogen derivatives. The last research part of this thesis focused on regeneration and recycling of ion pairs produced upon action of the above-mentioned ionic liquids on halogenated organic acids or their salts, respectively. Chemical reduction of the ion pairs using NaBH4/NiSO4 and/or the Raney Al-Ni alloy in NaOH was found to be capable of regenerating the used ionic liquids which can be applied in a subsequent process of ion exchange, even in several cycles. The thesis presents complex research focused on subsequently steps of halogenated organic contaminants removal from aqueous solutions. The results have been published in several journals and presented at national as well as international conferences in lectures and as posters; additionally, results constitute a chapter in a book and are included in a national patent., Fakulta chemicko-technologická, Dokončená práce s úspěšnou obhajobou

Solute carrier (SLC) transporters are membrane transport proteins, which catalyse the movement of nutrients, ions, and drugs across cell membranes. Here, I will present our contribution to understanding the mechanism of the sodium/proton exchangers (NHE), belonging to the SLC9 family of membrane transporters. NHEs exchange sodium ions for protons across biological membranes, which is a critical reaction for the fine-tuning of cytoplasmic and organelle pH, sodium levels and volume homeostasis. Dysfunction of NHE members has been linked to a number of diseases and disorders, such as hypertension, heart failure, autism spectrum disorder, epilepsy and the susceptibility of long COVID. Protein structures are important for developing mechanistic models, but due to technical challenges only bacterial homologue structures of NHE proteins were previously available. Accumulating many years of effort, we were able to determine the first structure of a mammalian Na+/H+ exchanger, the endosomal isoform NHE9 by single-particle cryo-EM. The structure of NHE9 demonstrated that NHE proteins are architecturally most similar to bacterial homologues with 13-TM segments and likely operated by a similar elevator mechanism (I). Interestingly, native MS and thermal-shift assays indicted that the NHE9 homodimer is stabilized by the binding of a rare lipid only found in late endosomes, which implies the cell may use this lipid as means to switch-on NHE9 activity once it reaches its correct functional localization. We further provided evidence that the large cytoplasmic tail in NHE proteins likely acts in an auto-inhibitory manner. It is only removed upon the binding of extrinsic proteins (II). Indeed, the first structure of a potassium specific K+/H+ exchanger KefC reveals how its cytoplasmic tail restricts movement of the ion-transporting domain to directly inhibit transport. The structure of KefC is also the first ion-bound state seen for this family and, unlike to the modeled Na+/H+ excha

Manganese is naturally present in water, but its increased concentration in potable water is undesirable for multiple reasons. This study investigates an alternative method of demanganization by a newly synthesized TiO2-based adsorbent prepared through the transformation of titanyl sulphate monohydrate to amorphous sodium titanate. Its adsorption capacity for Mn2+ was determined, while a range of influential factors, such as the effect of contact time, adsorbent dosage, pH value, and added ions was evaluated. The adsorbent appeared highly effective for Mn2+ removal owing to its unique characteristics. Besides adsorption via electrostatic interactions, ion-exchange was also involved in the Mn2+ removal. Although the Mn2+ removal occurred within the whole investigated pH range of 4–8, the maximum was achieved at pH 7, with qe = 73.83 mg g-1. Equilibrium data revealed a good correlation with Langmuir isotherm in the absence of any ions or in the presence of monovalent co-existing ions, while the results in the presence of divalent co-existing ions showed a better fit to Freundlich isotherm. Additionally, the presence of monovalent cations (Na+ , K+ ) only slightly decreased the Mn2+ removal efficiency as compared to divalent cations (Ca2+, Mg2+) that caused a greater decrease; however, the effect of anions (Cl- , SO4 2-) was insignificant. To provide insight into the adsorbent safety, the toxicity assessment was performed and showed no harmful effect on cell activity. Furthermore, the residual concentration of titanium after adsorption was always below the detection limit. The results imply that the synthesized TiO2-based adsorbent is a safe promising alternative method for demanganization., Mangan se přirozeně vyskytuje ve vodě, ale jeho zvýšená koncentrace v pitné vodě je nežádoucí z mnoha důvodů. Tato studie zkoumá alternativní metodu demanganizace nově syntetizovaným adsorbentem na bázi TiO2 připraveným přeměnou monohydrátu titanylsulfátu na amorfní titaničitan sodný. Jeho adsorpční kapacita byla stanovena pro Mn2+, přičemž byla hodnocena řada vlivných faktorů, jako je vliv doby kontaktu, dávka adsorbentu, hodnota pH a přidané ionty. Adsorbent se jevil jako vysoce účinný pro odstranění Mn2+ díky svým jedinečným vlastnostem. Kromě adsorpce prostřednictvím elektrostatických interakcí se na odstraňování Mn2+ podílela také iontová výměna. Přestože k odstranění Mn2+ došlo v celém zkoumaném rozmezí pH 4–8, maxima bylo dosaženo při pH 7, s qe = 73,83 mg g-1. Údaje o rovnováze odhalily dobrou korelaci s Langmuirovou izotermou v nepřítomnosti jakýchkoli iontů nebo v přítomnosti monovalentních koexistujících iontů, zatímco výsledky v přítomnosti divalentních koexistujících iontů ukázaly lepší shodu s Freundlichovou izotermou. Navíc přítomnost jednomocných kationtů (Na+, K+) snížila jen mírně účinnost odstraňování Mn2+ ve srovnání s dvojmocnými kationty (Ca2+, Mg2+), které způsobily větší pokles; vliv aniontů (Cl-, SO42-) byl nevýznamný. Aby bylo možné zhodnotit bezpečnost adsorbentu, bylo provedeno testování toxicity a nebyl prokázán žádný škodlivý účinek na buněčnou aktivitu. Navíc zbytková koncentrace titanu po adsorpci byla vždy pod detekčním limitem. Výsledky naznačují, že syntetizovaný adsorbent na bázi TiO2 je bezpečnou slibnou alternativní metodou pro demanganizaci

Solute carrier (SLC) transporters are membrane transport proteins, which catalyse the movement of nutrients, ions, and drugs across cell membranes. Here, I will present our contribution to understanding the mechanism of the sodium/proton exchangers (NHE), belonging to the SLC9 family of membrane transporters. NHEs exchange sodium ions for protons across biological membranes, which is a critical reaction for the fine-tuning of cytoplasmic and organelle pH, sodium levels and volume homeostasis. Dysfunction of NHE members has been linked to a number of diseases and disorders, such as hypertension, heart failure, autism spectrum disorder, epilepsy and the susceptibility of long COVID. Protein structures are important for developing mechanistic models, but due to technical challenges only bacterial homologue structures of NHE proteins were previously available. Accumulating many years of effort, we were able to determine the first structure of a mammalian Na+/H+ exchanger, the endosomal isoform NHE9 by single-particle cryo-EM. The structure of NHE9 demonstrated that NHE proteins are architecturally most similar to bacterial homologues with 13-TM segments and likely operated by a similar elevator mechanism (I). Interestingly, native MS and thermal-shift assays indicted that the NHE9 homodimer is stabilized by the binding of a rare lipid only found in late endosomes, which implies the cell may use this lipid as means to switch-on NHE9 activity once it reaches its correct functional localization. We further provided evidence that the large cytoplasmic tail in NHE proteins likely acts in an auto-inhibitory manner. It is only removed upon the binding of extrinsic proteins (II). Indeed, the first structure of a potassium specific K+/H+ exchanger KefC reveals how its cytoplasmic tail restricts movement of the ion-transporting domain to directly inhibit transport. The structure of KefC is also the first ion-bound state seen for this family and, unlike to the modeled Na+/H+ excha

The majority of the nutrients in household wastewater are found in the urine and in order to facilitate the use the nutrients in the urine as fertilizer, the urine can be can be concentrated. To extract the nutrients from the urine, various technologies for urine concentration are being developed today. As the technologies are relatively new, urine concentration systems have not been installed on a larger scale. In this study, sustainability of three different urine concentration technologies was evaluated through a fictional case study for 2100 people that took inspiration from a planned residential area in Malmö, Sweden, where technology for urine concentration will be implemented in at least one of the buildings. The technologies were evaluated through a multi-criteria assessment (MCA), where different criteria within sustainability categories environment, technical, economic and health were determined based on the Sustainable Development Goals (SDGs). The technologies examined were alkaline dehydration, nitrification-distillation and ion-exchange using a pre-step of struvite precipitation. For the alkaline dehydration technology, fresh urine is added to an alkaline medium, in order to prevent nitrogen losses, and then dried. In the nitrification-distillation technology, stored urine is treated by first being stabilized by a partial nitrification and then distilled in order to reduce the volume. For the ion-exchange and struvite precipitation system, phosphorus is first precipitated from stored urine and nitrogen is then extracted through ion-exchange. The urine concentration technologies were assumed to be installed in semi-centralized treatment plants in basements in the residential area. The other household wastewater was assumed to be treated in the local wastewater treatment plant (WWTP). The results showed that all three urine concentration technologies may contribute to a significant increase in nitrogen recovery from the household sewer. However, this may, Majoriteten av näringen i hushållsavloppsvattnet finns i urinen och för att underlätta användningen av växtnäringsämnena i urinen som gödningsmedel kan den koncentreras. För att utvinna näringen ur urinen utvecklas idag olika tekniker för urinkoncentrering. Då teknikerna är relativt nya har system för urinkoncentrering inte installerats i en större skala. Därför utvärderades hållbarheten för tre olika urinkoncentreringsmetoder genom en fiktiv fallstudie som innefattade 2100 personer. Fallstudien fick inspiration från ett planerat bostadsområde i Malmö, Sverige, där teknik för urinkoncentrering ska implementeras i minst en av byggnaderna. Teknikerna utvärderades genom en multikriterieanalys (MKA), där kriterier inom hållbarhetskategorierna miljö, teknik, ekonomi och hälsa valdes utifrån de Globala målen. De tekniker som utvärderades var alkalisk urintorkning, nitrifikations-destillering och jonbyte där struvitutfällning tillämpades som förbehandling. För den alkaliska urintorkningen tillförs färsk urin till ett alkaliskt medium, för att förhindra kväveförluster, och torkas sedan. I nitrifikations-destillerings tekniken behandlas lagrat urin genom att det först stabiliseras genom en partiell nitrifikation för att sedan destilleras för att reducera volymen. För systemet med jonbyte och struvitfällning, fälls först fosfor från lagrat urin ut och sedan utvinns kvävet genom jonbyte. Urinkoncentreringsteknikerna antogs anläggas i semi-centraliserade reningsverk i källare i bostadsområdet. Övrigt hushållsvatten antogs renas i det lokala avloppsreningsverket. Resultatet visade att samtliga av de tre teknikerna för urinkoncentrering kan bidra till en betydande ökning kväveåtervinning från hushållsavloppet. Dock kan detta komma på bekostnad av ökade årliga kostnader för de boende i området. Innan det är möjligt att avgöra om urinkoncentrering kan vara ett alternativ som ett komplement till den befintliga avloppsreningen i Sege Park krävs vidare studier av urinkoncentreringstek

The present thesis is dedicated to the preparation and characterization of a series of supported nanoporous membranes, featuring various materials (metal-organic frameworks (MOFs), zeolites and polymers) and designs (single-component, multilayer and mixed matrix membranes (MMMs)), as well as the subsequent evaluation of their gas separation capabilities (Wicke-Kallenbach), using the binary gas mixtures propylene/propane and H2/CO2 as model systems. In the case of MOF-74, the right orientation of its 1D channels (perpendicular to the corundum support surface in the best case) inside the dense layers is of utter importance and was eventually achieved to some extent, for the first time ever, by further developing known synthesis procedures. Unfortunately, all resulting Mg-MOF-74 membranes were only able to separate H2 and CO2 due to a previously unknown adsorption-founded blockage/self-hindrance in the case of propylene/propane. Neat zeolite type X (NaX) membranes, on the other hand, oftentimes suffer from severe structural issues which could be avoided by pre-synthetically modifying the supports with either PDA (polydopamine) or APTES (3-amino-propyltriethoxysilane), thus simultaneously improving their separation efficiency for both gas mixtures. In order to investigate the possible benefits of using multilayered instead of monolayered systems for separating hydrogen from carbon dioxide, some of the PDA/NaX membranes were subsequently coated with a Matrimid top layer to create a novel kind of sandwich membrane. The same polyimide was also used to fabricate MMMs with good H2/CO2 separation capabilities, where it serves as flexible and protective matrix for the embedded separation-active zeolite X particles (inorganic filler phase). Furthermore, it could be shown that using post-synthetic pore optimizations like ion-exchanged faujasite particles (PbX, CuX, NiX and CoX) instead of NaX in the Matrimid-based MMMs as well as modifying the open Mg sites inside MOF-74’s 1D ch

The majority of the nutrients in household wastewater are found in the urine and in order to facilitate the use the nutrients in the urine as fertilizer, the urine can be can be concentrated. To extract the nutrients from the urine, various technologies for urine concentration are being developed today. As the technologies are relatively new, urine concentration systems have not been installed on a larger scale. In this study, sustainability of three different urine concentration technologies was evaluated through a fictional case study for 2100 people that took inspiration from a planned residential area in Malmö, Sweden, where technology for urine concentration will be implemented in at least one of the buildings. The technologies were evaluated through a multi-criteria assessment (MCA), where different criteria within sustainability categories environment, technical, economic and health were determined based on the Sustainable Development Goals (SDGs). The technologies examined were alkaline dehydration, nitrification-distillation and ion-exchange using a pre-step of struvite precipitation. For the alkaline dehydration technology, fresh urine is added to an alkaline medium, in order to prevent nitrogen losses, and then dried. In the nitrification-distillation technology, stored urine is treated by first being stabilized by a partial nitrification and then distilled in order to reduce the volume. For the ion-exchange and struvite precipitation system, phosphorus is first precipitated from stored urine and nitrogen is then extracted through ion-exchange. The urine concentration technologies were assumed to be installed in semi-centralized treatment plants in basements in the residential area. The other household wastewater was assumed to be treated in the local wastewater treatment plant (WWTP). The results showed that all three urine concentration technologies may contribute to a significant increase in nitrogen recovery from the household sewer. However, this may, Majoriteten av näringen i hushållsavloppsvattnet finns i urinen och för att underlätta användningen av växtnäringsämnena i urinen som gödningsmedel kan den koncentreras. För att utvinna näringen ur urinen utvecklas idag olika tekniker för urinkoncentrering. Då teknikerna är relativt nya har system för urinkoncentrering inte installerats i en större skala. Därför utvärderades hållbarheten för tre olika urinkoncentreringsmetoder genom en fiktiv fallstudie som innefattade 2100 personer. Fallstudien fick inspiration från ett planerat bostadsområde i Malmö, Sverige, där teknik för urinkoncentrering ska implementeras i minst en av byggnaderna. Teknikerna utvärderades genom en multikriterieanalys (MKA), där kriterier inom hållbarhetskategorierna miljö, teknik, ekonomi och hälsa valdes utifrån de Globala målen. De tekniker som utvärderades var alkalisk urintorkning, nitrifikations-destillering och jonbyte där struvitutfällning tillämpades som förbehandling. För den alkaliska urintorkningen tillförs färsk urin till ett alkaliskt medium, för att förhindra kväveförluster, och torkas sedan. I nitrifikations-destillerings tekniken behandlas lagrat urin genom att det först stabiliseras genom en partiell nitrifikation för att sedan destilleras för att reducera volymen. För systemet med jonbyte och struvitfällning, fälls först fosfor från lagrat urin ut och sedan utvinns kvävet genom jonbyte. Urinkoncentreringsteknikerna antogs anläggas i semi-centraliserade reningsverk i källare i bostadsområdet. Övrigt hushållsvatten antogs renas i det lokala avloppsreningsverket. Resultatet visade att samtliga av de tre teknikerna för urinkoncentrering kan bidra till en betydande ökning kväveåtervinning från hushållsavloppet. Dock kan detta komma på bekostnad av ökade årliga kostnader för de boende i området. Innan det är möjligt att avgöra om urinkoncentrering kan vara ett alternativ som ett komplement till den befintliga avloppsreningen i Sege Park krävs vidare studier av urinkoncentreringstek

We propose a simple polygonal model to describe the phase profile of ion-exchanged gratings. This model enables the design of these gratings, as well as the characterization of the ion-exchange process itself. Several ion-exchanged gratings were fabricated to validate the model and to characterize the process involved in their fabrication. From this characterization, we show the practical utility of the model by designing and fabricating both a grating that removes the zero order and a three splitter. The performance of these two elements was good, although the first one stood out especially because only 0.5% of the power remained in the zero order after diffraction. This polygonal model could be useful to design more complex diffractive elements

Novel composites of BEA zeolite and silver tungstophosphate were prepared by different procedures: two-step impregnation, ion-exchange, and as physical mixtures with varying component mass ratios. Composites were characterized using Atomic force microscopy, Infrared, Raman and Atomic absorption spectroscopy, and results were related to adsorption properties and antimicrobial efficiencies of the composites. Prepared samples were tested as antimicrobial agents for fungal and different bacterial strains, as well as for adsorbents for pesticide nicosulfuron in aqueous solutions by using High-performance liquid chromatography. Experimental conditions for batch adsorption testing were optimized in order to efficiently eliminate nicosulfuron from aqueous solutions, while enabling antimicrobial activity of these advanced materials. Antimicrobial efficiency of composites was verified, and indicated that silver ion persistence in the solid phase is of utmost significance for the antimicrobial activity. Spectroscopic investigation revealed interaction of the silver tungstophosphate active phase and the zeolite framework, giving evidence of uniform distribution of active sites in the synthesized materials that proved to be essential for adsorption application. The best obtained adsorption capacity, as well as highest antimicrobial efficiency, is found for composite samples prepared by two-step impregnation with (BEA: silver tungstophosphate) mass ratio 2:1. The amount of nicosulfuron removed from water suspension was 38.2 mg per gram of composite, and the minimum inhibitory concentration determined for all investigated gram-negative bacteria was 125 μg mL−1.

[EN] In the presented studies an influence of different parameters, such as zeolite sample porosity, form of used iron source ([Fe-3(OAc)(6)O(H2O)(3)](+)oligocations or FeSO4 solutions) and method of iron species deposition (ion-exchange, impregnation), on the catalytic activity in the process of the selective catalytic oxidation of ammonia (NH3-SCO) was studied. Conventional and mesoporous ZSM-5 zeolites, obtained by desilication and modified with iron species, were analysed with respect to their textural, surface and crystalline properties (N-2-sorption, HRTEM, SEM, XRD) as well as the form of introduced Fe species (UV-vis-DRS). Ion-exchange with [Fe-3(OAc)(6)O (H2O)(3)](+) oligocations and impregnation with these oligocations and FeSO4 solutions were found as the most effective methods of the zeolite samples activation for NH3-SCO.

[EN] In the presented studies an influence of different parameters, such as zeolite sample porosity, form of used iron source ([Fe-3(OAc)(6)O(H2O)(3)](+)oligocations or FeSO4 solutions) and method of iron species deposition (ion-exchange, impregnation), on the catalytic activity in the process of the selective catalytic oxidation of ammonia (NH3-SCO) was studied. Conventional and mesoporous ZSM-5 zeolites, obtained by desilication and modified with iron species, were analysed with respect to their textural, surface and crystalline properties (N-2-sorption, HRTEM, SEM, XRD) as well as the form of introduced Fe species (UV-vis-DRS). Ion-exchange with [Fe-3(OAc)(6)O (H2O)(3)](+) oligocations and impregnation with these oligocations and FeSO4 solutions were found as the most effective methods of the zeolite samples activation for NH3-SCO.

Natural zeolite and bentonite were utilized as mineral additives in the mix-design of environmentally safe cement-based building materials. The adsorptive abilities of these two clayey raw materials, i.e. their affinity to immobilize heavy metal ions Zn2+, Ni2+, Pb2+ and Cu2+ were investigated. Singleand multi-solutions of Zn2+, Ni2+, Pb2+ and Cu2+ were prepared for the experiment. The obtained results were submitted to analysis via pseudo-first and pseudo-second order kinetic models. Langmuir and Freundlich isotherms were analyzed. Bentonite exhibited better adsorption affinity than zeolite towards all four investigated cations. As a proof, a leaching test was conducted on seven different cement binders with different mineral additives (fly ash, zeolite, bentonite). The leachates obtained on the samples of cement with addition of fly ash and clay (either zeolite or bentonite) contained lower concentrations of Zn2+, Ni2+, Pb2+ and Cu2+ ions than leachates obtained on the samples of cement binder with fly ash solely as a result of adsorption and hydration mechanisms that immobilized heavy metals within cementitious composites., Prirodni zeolit i bentonit korišćeni su kao mineralni dodaci u mešavinskom dizajnu ekološki sigurnih građevinskih materijala na bazi cementa. Ispitane su adsorptivne sposobnosti ove dve glinene sirovine, tj. njihov afinitet da imobiliziraju jone teških metala Zn2+, Ni2+, Pb2+ i Cu2+. Za eksperiment su pripremljeni pojedinačni i multi-rastvori Zn2+, Ni2+, Pb2+ i Cu2+ . Dobijeni rezultati su analizirani pomoću kinetičkih modela pseudo prvog i pseudo drugog reda. Analizirane su izoterme Langmuira i Freundlicha. Bentonit je pokazao bolji adsorpcioni afinitet od zeolita prema sva četiri ispitivana katjona. Kao dokaz, ispitano je ispitivanje ispiranja na sedam različitih veziva za cement sa različitim mineralnim dodacima (leteći pepeo, zeolit, bentonit). Eluati dobijeni na uzorcima cementa sa dodatkom letećeg pepela i gline (bilo zeolita ili bentonita) sadržavale su niže koncentracije jona Zn2+, Ni2+, Pb2+ i Cu2+ u odnosu na eluat dobijen na uzorcima cementnog veziva sa letećim pepelom. Razlog za dobijanje ovakvih rezultata su adsorpcioni i hidratacioni mehanizmi koji imobiliziraju teške metale u cementnim kompozitima.

To utilize sugars as a feedstock for renewable industries, the feedstock often needs to be very pure. This is due to ionic species contaminating the sugar feedstock being potent catalyst poisons in many cases. To remove ionic species from the sugar feedstock, it is dissolved and purified using packed ion-exchange columns. In this report, a lab-scale setup of a large scale ion-exchange setup was constructed. The system was then modelled using Matlab. The goal was to produce a lab-scale setup that in theory operates similarly to the large setup and develop a model that can predict the behaviour of the system. The feed sugar content was varied using glucose, the range of glucose concentrations tested were 0, 10, 30, and 50 wt% glucose. The feed linear flow velocity was also varied, the flows studied were 0.65, 1.3 and 2.6 m/h respectively. To simulate the kinetics of adsorption of ionic species to the resin, the equilibrium adsorption isotherm was measured experimentally. Both the temperature effect and the effect of different glucose concentrations in the liquid was studied. It was found that lower temperatures favoured the resin performance at higher glucose temperatures and higher glucose concentration had a negative effect on the resin performance. As the isotherm had been determined for the different glucose concentrations, experimental data of the lab-scale setup was compared to model simulations. The model shows promise in emulating the experimental setup. The experimental setup does however need more work to raise reproducibility of the setup which has been a major issue throughout., Skalning och modellering av en kromatografikolonn för rening av sockerlösningar. För att uppnå klimatmålen behöver fossila råvaror inom kemiindustrin bytas ut mot förnybara råvaror. Socker är en råvara med stor potential inom industrin, men är ofta förorenat med salter. Därför utforskas rening av sockerlösningar här. För att använda socker som förnybar råvara för kemiindustri behöver sockret ofta vara mycket rent. Detta är på grund av att salter och andra orenheter i sockret ofta är mycket starka katalysatorgift. För mycket salt i inflödet till en process kan därför förstöra katalysatorn och därmed hela processen. För att rena sockret från salter löses det upp och renas med jonbytarkromatografi. Jonbytarkromatografi som process fungerar genom att pumpa en förorenad vätska genom en kolonn. Kolonnen innehåller en bädd av fast packningsmaterial med speciella platser där föroreningarna kan fästas på. Packningsmaterialet tar då upp föroreningarna ur vätskan, men låter resten av vätskan passera och på så sätt kan man få en mycket ren vätska som produkt. I denna rapport konstruerades en labbskalad variant av en existerande storskalig jonbytarkolon. Processen simulerades även med hjälp av datorverktyg. Målet var att producera en enhet på labbskala som i teorin producerar jämförbara resultat som den storskaliga enheten och sedan utveckla en modell som kan förutspå hur systemet beter sig. Frågeställningen var följande: Kan en labbskalad variant av reningsprocessen konstrueras och kunde den ge rimliga resultat? Kan processen modelleras med datorverktyg och vilka effekter har olika parametrar på processens beteende? Fördelar med att ha en labbskalad variant av en processenhet gentemot att endast ha en storskalig process är flera. Mängden tid, arbete och resurser som krävs för att utföra tester minskar drastiskt med storleken på uppsättningen. Om man sedan går ett steg längre och bygger en simuleringsmodell av uppsättningen, så kan försök utföras på mycket kortare tid än möjligt

Rare earth elements (REE) present multiple applications in technological devices but also drawbacks (scarcity and water contaminant). The current study aims to valorise the banana wastes - banana rachis (BR), banana pseudo-stem (BPS) and banana peel (BP) as sustainable adsorbent materials for the recovery of REE (Nd3+, Eu3+, Y3+, Dy3+ and Tb3+). The adsorbent materials were characterized using analytical techniques such as: Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, zeta potential and scanning electron microscopy with energy dispersive X-ray probe. The adsorption performance and mechanisms were studied by pH dependence, equilibrium isotherms, kinetics, thermodynamics, ion-exchange and desorption evaluation. The results show good adsorption capacities for the three materials, highlighting BR that presents ~100 mg/g for most of the REE. The adsorption process (100 mg REE/L) reaches the 60% uptake in 8 min and the equilibrium within 50 min. On the other hand, the thermodynamic study indicates that the adsorption is spontaneous and exothermic (¿H° < 40 kJ/mol). The adsorption mechanism is based on the presence of carboxylic groups that induce electrostatic interactions and facilitate the surface nucleation of REE microcrystals coupled to an ion exchange process as well as the presence of other oxygen containing groups that establish weak intermolecular forces. The recovery of REE from the adsorbent (~97%) is achieved using EDTA as desorbing solution. This research indicates that banana waste and particularly BR is a new and promising renewable bioresource to recover REE with high adsorption capacity and moderated processing cost., Peer Reviewed, Postprint (author's final draft)

There is a desire for a fully automated downstream process in pharmaceutical protein production. One part of the downstreaming process is preparative chromatography. A good separation between the product and other proteins, as well as good productivity, are desired. Due to the batch nature of chromatographic separation, an iterative learning controller (ILC) could be a suitable choice for achieving these goals. ILC based on time-varying perturbation models have been successfully applied to control batch reactors in the past. The purpose of this master thesis was to test the application of time-varying perturbation model-based ILC for automation of preparative chromatography. The application of an ILC was performed using simulations of an ion-exchange chromatographic purification process. Since protein purification by chromatography is commonly performed with gradient elution, the slope of the gradient was chosen as the input parameter for the controller. The slope was controlled via the gradient time, i.e. the time it takes for the elution buffer to go from its initial to its final concentration. First, the resolution between two peaks was used as the output parameter of the controller. The controller was able to successfully reach the desired resolution, however using only the gradient time resulted in a non-linear process trajectory, which resulted in difficulties in process control. Secondly, an objective function was constructed using the resolution and the productivity of the process. The objective function had a local extrema, which was considered the process optimum and thus the derivative of the objective function was used as output parameter. This configuration showed promise, although the estimation of the derivative during live runs was a limiting factor. ILC shows promise for use in preparative chromatography. Multiple-input-multiple-output configurations should be considered for future applications, as such configurations could circumvent the problems c, Det fins en önskan om fullständigt automatiserade nedströmsprocesser i framställandet av proteiner för läkemedelsbruk. En del av nedströmsprocessen är preparativ kromatografi. En god separation mellan produkt och andra proteiner, samt god produktivitet, är av intresse. På grund att kromatografisk separation ofta körs satsvis så skulle en iterative learning controller (ILC) vara ett bra val för att åstadkomma dessa mål. ILC baserad på tidsvarierande perturbationsmodeller har tidigare tillämpats för att reglera satsvisa reaktorer med goda resultat. Syftet med detta projekt var att testa tillämpningen av en sådan ILC för att automatisera preparativ kromatografi. Tillämpningen av en ILC utfördes genom simuleringar av en kromatografisk reningsprocess i en jonbytarkolonn. Eftersom proteinupprening med kromatografi ofta utförs med gradienteluering så valdes lutningen av gradienten som in-parameter för styrning. Lutningen kontrollerades via gradienttiden, dvs tiden det tar för elueringsbufferten att gå från sin start- till slutkoncentration. Först användes upplösningen mellan två toppar i kromatogrammet som ut-parameter. Regulatorn lyckades nå den önskade upplösningen, men att enbart använda gradientlutningen som in-parameter visade sig leda till en icke-linjär processbana, vilket ledde till svårigheter i regleringen. Därefter konstruerades en målfunktion med hjälp av upplösningen och processens produktivitet. Målfunktionen hade en lokal extrempunkt som ansågs vara processoptimat och därav valdes målfunktionens derivata som ut-parameter. Denna konfiguration var lovande, men begränsades av derivataberäkningen under körningens gång. ILC uppvisar potential för användning i preparativ kromatografi. Konfigurationer med flera in- och ut-parametrar bör övervägas för framtida tillämpning, då sådana konfigurationer skulle kunna kringgå problemen som orsakades av den icke-linjära processbanan. Alternativt så kan en annan objektivfunktion konstrueras. Ett naturligt nästa steg är att t, Proteins are molecules that can possess many different qualities, some of which are beneficial to humans. An example of such a protein is insulin, which is used to treat diabetes. Proteins for use in pharmaceuticals are produced in living organisms along with other, less beneficial or even harmful proteins, and thus need to be properly purified before use. One part of the purification process is called preparative chromatography. Ion-exchange chromatography is commonly used for protein purification, and involves the use of a column to which the different proteins stick, while other molecules flow through. Salt is then flushed through the column to remove the stuck proteins. The strength with which the proteins stick to the column varies from protein to protein, so higher concentrations of salt are needed for proteins that are more strongly stuck. Thus, it is possible to separate one protein from the other by gradually increasing the salt concentration while the column is being flushed. Choosing how this salt concentration should increase requires many experiments and work hours. In this master thesis, a method for making the separation of proteins as good as possible automatically is tested. The method used is called iterative learning control (ILC), which means that information from previous chromatography runs is used to predict how the salt concentration needs to change to give the desired separation. Several simulations of a chromatography process were run to develop the controller. In the end, the ILC was able to control the processes and thus shows promise for the automation of preparative chromatography processes, although more work needs to be performed before it can function optimally. In the future, an ILC for preparative chromatography could be combined with the other purification steps to create a fully automated protein purification process., Proteiner är molekyler som kan ha många olika egenskaper, varav vissa är förmånliga för människor. Ett exempel på ett sådant protein är insulin, som används för att behandla diabetes. Proteiner för läkemedelsbruk produceras ofta i levande organismer tillsammans med andra, mindre gynnsamma eller till och med skadliga proteiner, och behöver således renas ordentligt före användning. En del av reningsprocessen kallas för preparativ kromatografi. Jonbytarkromatografi är vanligt för upprening av proteiner, och involverar användandet av en kolonn som de olika proteinerna fastnar på, medan andra molekyler flödar igenom. Salt spolas sedan genom kolonnen för att ta bort proteinerna som fastnat. Proteiner binder olika hårt till kolonnen, vilket innebär att högre koncentrationer av salt krävs för proteinerna som sitter fast hårdare. Därför går det att separera ett protein från ett annat genom att gradvis öka koncentrationen salt medan kolonnen spolas. Att välja hur denna ökning av koncentration ska gå till kräver många experiment och arbetstimmar. I detta examensarbete har en metod för att göra separation av proteiner så bra som möjligt automatiskt testats. Metoden som använts kallas för reglering med iterativ inlärning (iterative learning controller, eller ILC), som innebär att information från tidigare kromatografikörningar används för att förutsäga hur saltkoncentrationen behöver ändras för att ge den önskade separationen. Flera simuleringar av en kromatografiprocess kördes för att utveckla regulatorn. I slutändan så var ILC:n kapabel till att reglera processerna och således visar metoden potential för automatisering av preparativ kromatografi, men mer arbete behöver utföras innan det fungerar optimalt. I framtiden kan ILC för preparativ kromatografi kombineras med andra reningssteg för att skapa en fullständigt automatisk proteinuppreningsprocess.

Prirodni zeolit i bentonit korišćeni su kao mineralni dodaci u mešavinskom dizajnu ekološki sigurnih građevinskih materijala na bazi cementa. Ispitane su adsorptivne sposobnosti ove dve glinene sirovine, tj. njihov afinitet da imobiliziraju jone teških metala Zn2+, Ni2+, Pb2+ i Cu2+. Za eksperiment su pripremljeni pojedinačni i multi-rastvori Zn2+, Ni2+, Pb2+ i Cu2+ . Dobijeni rezultati su analizirani pomoću kinetičkih modela pseudo prvog i pseudo drugog reda. Analizirane su izoterme Langmuira i Freundlicha. Bentonit je pokazao bolji adsorpcioni afinitet od zeolita prema sva četiri ispitivana katjona. Kao dokaz, ispitano je ispitivanje ispiranja na sedam različitih veziva za cement sa različitim mineralnim dodacima (leteći pepeo, zeolit, bentonit). Eluati dobijeni na uzorcima cementa sa dodatkom letećeg pepela i gline (bilo zeolita ili bentonita) sadržavale su niže koncentracije jona Zn2+, Ni2+, Pb2+ i Cu2+ u odnosu na eluat dobijen na uzorcima cementnog veziva sa letećim pepelom. Razlog za dobijanje ovakvih rezultata su adsorpcioni i hidratacioni mehanizmi koji imobiliziraju teške metale u cementnim kompozitima., Natural zeolite and bentonite were utilized as mineral additives in the mix-design of environmentally safe cement-based building materials. The adsorptive abilities of these two clayey raw materials, i.e. their affinity to immobilize heavy metal ions Zn2+, Ni2+, Pb2+ and Cu2+ were investigated. Singleand multi-solutions of Zn2+, Ni2+, Pb2+ and Cu2+ were prepared for the experiment. The obtained results were submitted to analysis via pseudo-first and pseudo-second order kinetic models. Langmuir and Freundlich isotherms were analyzed. Bentonite exhibited better adsorption affinity than zeolite towards all four investigated cations. As a proof, a leaching test was conducted on seven different cement binders with different mineral additives (fly ash, zeolite, bentonite). The leachates obtained on the samples of cement with addition of fly ash and clay (either zeolite or bentonite) contained lower concentrations of Zn2+, Ni2+, Pb2+ and Cu2+ ions than leachates obtained on the samples of cement binder with fly ash solely as a result of adsorption and hydration mechanisms that immobilized heavy metals within cementitious composites.

To utilize sugars as a feedstock for renewable industries, the feedstock often needs to be very pure. This is due to ionic species contaminating the sugar feedstock being potent catalyst poisons in many cases. To remove ionic species from the sugar feedstock, it is dissolved and purified using packed ion-exchange columns. In this report, a lab-scale setup of a large scale ion-exchange setup was constructed. The system was then modelled using Matlab. The goal was to produce a lab-scale setup that in theory operates similarly to the large setup and develop a model that can predict the behaviour of the system. The feed sugar content was varied using glucose, the range of glucose concentrations tested were 0, 10, 30, and 50 wt% glucose. The feed linear flow velocity was also varied, the flows studied were 0.65, 1.3 and 2.6 m/h respectively. To simulate the kinetics of adsorption of ionic species to the resin, the equilibrium adsorption isotherm was measured experimentally. Both the temperature effect and the effect of different glucose concentrations in the liquid was studied. It was found that lower temperatures favoured the resin performance at higher glucose temperatures and higher glucose concentration had a negative effect on the resin performance. As the isotherm had been determined for the different glucose concentrations, experimental data of the lab-scale setup was compared to model simulations. The model shows promise in emulating the experimental setup. The experimental setup does however need more work to raise reproducibility of the setup which has been a major issue throughout., Skalning och modellering av en kromatografikolonn för rening av sockerlösningar. För att uppnå klimatmålen behöver fossila råvaror inom kemiindustrin bytas ut mot förnybara råvaror. Socker är en råvara med stor potential inom industrin, men är ofta förorenat med salter. Därför utforskas rening av sockerlösningar här. För att använda socker som förnybar råvara för kemiindustri behöver sockret ofta vara mycket rent. Detta är på grund av att salter och andra orenheter i sockret ofta är mycket starka katalysatorgift. För mycket salt i inflödet till en process kan därför förstöra katalysatorn och därmed hela processen. För att rena sockret från salter löses det upp och renas med jonbytarkromatografi. Jonbytarkromatografi som process fungerar genom att pumpa en förorenad vätska genom en kolonn. Kolonnen innehåller en bädd av fast packningsmaterial med speciella platser där föroreningarna kan fästas på. Packningsmaterialet tar då upp föroreningarna ur vätskan, men låter resten av vätskan passera och på så sätt kan man få en mycket ren vätska som produkt. I denna rapport konstruerades en labbskalad variant av en existerande storskalig jonbytarkolon. Processen simulerades även med hjälp av datorverktyg. Målet var att producera en enhet på labbskala som i teorin producerar jämförbara resultat som den storskaliga enheten och sedan utveckla en modell som kan förutspå hur systemet beter sig. Frågeställningen var följande: Kan en labbskalad variant av reningsprocessen konstrueras och kunde den ge rimliga resultat? Kan processen modelleras med datorverktyg och vilka effekter har olika parametrar på processens beteende? Fördelar med att ha en labbskalad variant av en processenhet gentemot att endast ha en storskalig process är flera. Mängden tid, arbete och resurser som krävs för att utföra tester minskar drastiskt med storleken på uppsättningen. Om man sedan går ett steg längre och bygger en simuleringsmodell av uppsättningen, så kan försök utföras på mycket kortare tid än möjligt

Natural zeolite and bentonite were utilized as mineral additives in the mix-design of environmentally safe cement-based building materials. The adsorptive abilities of these two clayey raw materials, i.e. their affinity to immobilize heavy metal ions Zn2+, Ni2+, Pb2+ and Cu2+ were investigated. Singleand multi-solutions of Zn2+, Ni2+, Pb2+ and Cu2+ were prepared for the experiment. The obtained results were submitted to analysis via pseudo-first and pseudo-second order kinetic models. Langmuir and Freundlich isotherms were analyzed. Bentonite exhibited better adsorption affinity than zeolite towards all four investigated cations. As a proof, a leaching test was conducted on seven different cement binders with different mineral additives (fly ash, zeolite, bentonite). The leachates obtained on the samples of cement with addition of fly ash and clay (either zeolite or bentonite) contained lower concentrations of Zn2+, Ni2+, Pb2+ and Cu2+ ions than leachates obtained on the samples of cement binder with fly ash solely as a result of adsorption and hydration mechanisms that immobilized heavy metals within cementitious composites., Prirodni zeolit i bentonit korišćeni su kao mineralni dodaci u mešavinskom dizajnu ekološki sigurnih građevinskih materijala na bazi cementa. Ispitane su adsorptivne sposobnosti ove dve glinene sirovine, tj. njihov afinitet da imobiliziraju jone teških metala Zn2+, Ni2+, Pb2+ i Cu2+. Za eksperiment su pripremljeni pojedinačni i multi-rastvori Zn2+, Ni2+, Pb2+ i Cu2+ . Dobijeni rezultati su analizirani pomoću kinetičkih modela pseudo prvog i pseudo drugog reda. Analizirane su izoterme Langmuira i Freundlicha. Bentonit je pokazao bolji adsorpcioni afinitet od zeolita prema sva četiri ispitivana katjona. Kao dokaz, ispitano je ispitivanje ispiranja na sedam različitih veziva za cement sa različitim mineralnim dodacima (leteći pepeo, zeolit, bentonit). Eluati dobijeni na uzorcima cementa sa dodatkom letećeg pepela i gline (bilo zeolita ili bentonita) sadržavale su niže koncentracije jona Zn2+, Ni2+, Pb2+ i Cu2+ u odnosu na eluat dobijen na uzorcima cementnog veziva sa letećim pepelom. Razlog za dobijanje ovakvih rezultata su adsorpcioni i hidratacioni mehanizmi koji imobiliziraju teške metale u cementnim kompozitima.

Použití popsaného způsobu vyhodnocení potenciometrických měření s pevnými stříbrnými amalgámovými elektrodami (AgSAE) umožnilo využít tyto elektrody i při nižších požadavcích na mechanické obnovení jejich povrchů. Opakovatelnost diagramů zobrazujících ustálené hodnoty potenciálů Ei vs. Vzi (označujících sledované vzorky vody odebrané z příslušných pěti kroků v pořadí od Vz1 do Vz5 její postupné technologické úpravy a po přídavku 0,9·10-3 M AgNO3) týkajících se AgSAE větších průměrů d než 1 mm byla lepší než u menších AgSAE. Výsledky potvrdily, že při d  1 mm byl charakter získaných diagramů Ei vs. Vzi v pořadí od i = 1 do i = 5 neměnný a potenciálně technologicky využitelný např. jako grafický ukazatel zmíněné nastavené sekvence technologických úprav., The use of the described evaluation of potentiometric measurements using silver solid amalgam electrodes (AgSAE) enabled to apply these electrodes even with lesser requirements on mechanical renewing of its surfaces. Diagrams Ei vs. Vzi based on steady values of electrochemical potentials Ei of AgSAE in the set of aqueous samples (containing added 0,9·10-3 M AgNo3) Vzi, i = 1 to 5 and corresponding to the adequate sequence of purification steps of the technical waters were registered. Repeatability of diagrams Ei vs. Vzi concerning AgSAE of diameters more than 1 mm was better than that of lower diameters. Certain influence of the selected sequences of tested aqueous solutions on the profile of Ei vs. Vzi diagrams has been observed, as well.

The main challenge for copper smelters is to ensure product quality under the constant increase in impurities (As, Se, Mo, Co, Zn, Sb, and Pb) in copper ores that has occurred over the years. The presence of toxic elements, such as As(V), in acidic streams rich Cu(II) and Zn(II) (pH 2.0–2.5) limits the valorisation of both metals. In this study, a novel combination of the following two ion-exchange-based processes were proposed: i) membrane selectrodialysis (SED) for the selective separation of Zn(II)/Cu(II) from As(V) and ii) solvent-impregnated ion-exchange (IX) resins for the selective separation of Zn(II) from Cu(II). The selective separation of As(V), which is present in solution as H3AsO4/H2AsO4–, is achieved using a combination of monocharge and non-monocharge selective cation-exchange membranes to avoid the co-precipitation of As(V) when IX resins are used for Cu(II)/Zn(II) recovery. This combination of processes represents the novelty of the present study since it could be used in hydrometallurgical industries to remove As(V) and, at the same time, to valorize two value-added metals [Cu(II) and Zn(II)]. At the moment, only single-stage processes have been proposed. Using SED, a Cu(II)/Zn(II)-rich stream [97¿±¿2% Cu(II) and 82¿±¿3% Zn(II)] was obtained, and 60¿±¿4% of As(V) was removed from the initial feed stream. Then, the separation of Zn(II) from Cu(II) was proposed using Lewatit VP OC 1026 resin at pH¿=¿2.2 and 4.3, respectively. In this IX resin process, it was possible to recover 70¿±¿3% of Zn(II) and 98¿±¿2% of Cu(II) and to concentrate Zn(II) and Cu(II) around 30- and 23-times, respectively., Postprint (author's final draft)

Lignosulfonate (LS) is a large-scale surplus product of the forest and paper industries, and has primarily been utilized as a low-cost plasticizer in making concrete for the construction industry. LS is an anionic redox-active polyelectrolyte and is a promising candidate to boost the charge capacity of the positive electrode (positrode) in redox-supercapacitors. Here, the physical-chemical investigation of how this biopolymer incorporates into the conducting polymer PEDOT matrix, of the positrode, by means of counter-ion exchange is reported. Upon successful incorporation, an optimal access to redox moieties is achieved, which provides a 63% increase of the resulting stored electrical charge by reversible redox interconversion. The effects of pH, ionic strength, and concentrations, of included components, on the polymer?polymer interactions are optimized to exploit the biopolymer-associated redox currents. Further, the explored LS-conducting polymer incorporation strategy, via aqueous synthesis, is evaluated in an up-scaling effort toward large-scale electrical energy storage technology. By using an up-scaled production protocol, integration of the biopolymer within the conducting polymer matrix by counter-ion exchange is confirmed and the PEDOT-LS synthesized through optimized strategy reaches an improved charge capacity of 44.6 mAh g?1.

Environmental and economic concerns over the last decades have introduced new research opportunities for the application of several techniques in order to improve the removal of contaminants, as well as to explore methods to recover added-value elements. One example could be the recovery of metals ions from mining activity wastewaters in an approach to circular economy scheme. Therefore, in this work the separation and recovery of Zn and Cu, from acidic mine waters, as valuable metals is proposed. For that, an ion-exchange process with resins using a fixed bed configuration is used at labscale. A solvent impregnated (e.g. Lewatit VP OC 1026) and a chelating (e.g. Lewatit TP 207) resins were used for the recovery of Zn and Cu, respectively. Results showed that it was possible to separate and concentrate both metals (Zn around 10 times and Cu about 40 times). For that, ion-exchange resins provide a circular economy approach for metallurgical processing plants, Postprint (author's final draft)

μ-XANES is used to study the modifications in the alkali and alkaline-earth environments induced by the Na+/K+ ion-exchange process in various Na –silicate glasses. The results indicate that the ion-exchange process induces a shortening of the Na–O, Ca–O and Mg–O bond distances. The contraction of the Na–O, Ca–O and Mg–O coordination shell allows a better accommodation of the K+ cations in the glass network and thereby leads to partial relaxation of the stress developed by the Na+/K+ ion-exchange. Nevertheless, despite the stress relaxation process, the K+ environment in the ion-exchanged glass is not equivalent to the one in Na,K–silicate as-melted glasses. Hence, this study clearly shows that the ion swapping forced K+ cations to occupy smaller sites which are not achievable via the melt quench route for glasses with the same K amount., SCOPUS: ar.j, info:eu-repo/semantics/published

It was intended for GLuc-C9D, a variant of the Gaussia Luciferase with a C-term Solubility Enhancing Peptide (SEP)-Tag to be expressed in E. Coli for structural characterization. Through SDS-PAGE under non-reducing conditions it was observed that GLuc-C9D aggregates into disulphide-linked polymers while staying in solution when expressed in standard BL21(DE3)-cells. Expression of GLuc-C9D as a monomeric protein was increased by co-expression of the sulfhydryl oxidase, Erv1p, and a human Protein Disulphide Isomerase. It was possible to separate monomeric from polymeric GLuc-C9D by gel-filtration and ammonium sulphate precipitation. Data obtained by Circular Dichroism indicated a mostly unstructured protein with ~20 % helical and sheet formation. At the time of writing, it was discovered that the gene for GLuc-TG, a E100A+G103 variant, had been supplied rather than GLuc-C9D. The findings are expected to remain unaffected by this discovery.

It was intended for GLuc-C9D, a variant of the Gaussia Luciferase with a C-term Solubility Enhancing Peptide (SEP)-Tag to be expressed in E. Coli for structural characterization. Through SDS-PAGE under non-reducing conditions it was observed that GLuc-C9D aggregates into disulphide-linked polymers while staying in solution when expressed in standard BL21(DE3)-cells. Expression of GLuc-C9D as a monomeric protein was increased by co-expression of the sulfhydryl oxidase, Erv1p, and a human Protein Disulphide Isomerase. It was possible to separate monomeric from polymeric GLuc-C9D by gel-filtration and ammonium sulphate precipitation. Data obtained by Circular Dichroism indicated a mostly unstructured protein with ~20 % helical and sheet formation. At the time of writing, it was discovered that the gene for GLuc-TG, a E100A+G103 variant, had been supplied rather than GLuc-C9D. The findings are expected to remain unaffected by this discovery.

Дисертація присвячена розробці комплексних методів знесолення високомінералізованих вод. Досліджено процеси натрій-катіонного пом’якшення морської води. Було встановлено, що високоосновний аніоніт ефективно розділяє нітрати, сульфати та хлориди з можливістю одночасного пом’якшення води. Вивчено процеси електрохімічної переробки концентратів баромембранного опріснення води з отриманням окислених сполук хлору. Досліджено процеси електрохімічного концентрування розчинів хлористого натрію та кальцію. Вперше в процесах електрохімічної переробки хлоридних розчинів був застосований високоосновний аніоніт АВ-17-8 для фіксації окислених сполук хлору. Вперше вивчено процеси електрохімічної переробки хлоридних регенераційних розчинів в алюмінієві коагулянти. Запропоновані технологічні схеми опріснення високомінералізованих вод, які дозволяють отримати очищену воду при повній переробці утворених концентратів у цільові продукти.

Дисертація присвячена розробці комплексних методів знесолення високомінералізованих вод. Досліджено процеси натрій-катіонного пом’якшення морської води. Було встановлено, що високоосновний аніоніт ефективно розділяє нітрати, сульфати та хлориди з можливістю одночасного пом’якшення води. Вивчено процеси електрохімічної переробки концентратів баромембранного опріснення води з отриманням окислених сполук хлору. Досліджено процеси електрохімічного концентрування розчинів хлористого натрію та кальцію. Вперше в процесах електрохімічної переробки хлоридних розчинів був застосований високоосновний аніоніт АВ-17-8 для фіксації окислених сполук хлору. Вперше вивчено процеси електрохімічної переробки хлоридних регенераційних розчинів в алюмінієві коагулянти. Запропоновані технологічні схеми опріснення високомінералізованих вод, які дозволяють отримати очищену воду при повній переробці утворених концентратів у цільові продукти., This dissertation is devoted to the developing of complex methods of highly mineralized water desalination. The processes of sodium-cationic softening and ion-exchange stabilization of water were studied. For the first time it was shown that water with high mineral content can be effectively softened on the strong-acid cation ion-exchanger with the following regeneration of ion-exchanger by solutions after baromembrane desalination of water. Using the concentrates with 4 % salt content provides complete desorption of hardness cations from ion-exchanger. According to the approach of complete factorial experiment а regression equation was obtained. It helps to establish a relationship between the concentrations of hardness ions in the filtrate water and a volume of passed solution and initial concentration of hardness ions. It was shown that the weak-acid cation ion-exchanger effectively sorbs the hardness ions from water solutions even at significant amount of sodium chloride. The results of ion-exchange separation of anions in sewage were described. It was shown that chlorides, nitrates and sulfates effectively separated on high-basic ion-exchanger AV-17-8. It was established that the efficiency of separation is reliant on initial concentration and ratio of these anions in a water solution. Generally, with the increasing of initial concentration of anions the efficiency of their separation is decreasing. Moreover, using AV-17-8 ion-exchanger in basic form provides simultaneously water softening. The processes of regeneration of high-basic anion ion-exchanger were studied. Using some reagents like ammonia, alkali, sodium carbonate, potassium carbonate or different chlorine salts helps in obtaining solutions, which are suitable for the future producing of mineral fertilizers. For example, the ion-exchanger in chloride, nitrate and sulfate form is regenerated by the subsequent exposure of ammonia sulfate and calcium chloride solutions. As the result, the solutions of m, Диссертация посвящена разработке комплексных методов обессоливания высокоминерализованных вод. Исследованы процессы натрий-катионного умягчения морской воды. Было установлено, что высокоосновный анионит эффективно разделяет нитраты, сульфаты и хлориды с возможностью одновременного умягчения воды. Изучены процессы электрохимической переработки концентратов баромембранного опреснения воды с получением окисленных соединений хлора. Исследованы процессы электрохимического концентрирования растворов хлористого натрия и кальция. Впервые в процессах электрохимической переработки хлоридных растворов был использован высокоосновный анионит АВ-17-8 для фиксации окисленных соединений хлора. Впервые изучены процессы электрохимической переработки хлоридных регенерационных растворов в алюминиевые коагулянты. Предложены технологические схемы опреснения высокоминерализованных вод, которые позволяют получить очищенную воду при полной переработке образованных концентратов в целевые продукты.

Quench is a widely used technique in organic synthesis or inorganic material treatment but only limited studies have been performed on aluminosilicate. In this work, the quench effect on the textural properties and surface functional groups has been studied by the functionalization of a waste-derived aluminosilicate material. The porous structure has been changed in the presence of a quench reagent. We consider that this difference originated due to the prevention of replacement of potassium atoms in surface ion-exchange sites by hydrogen atoms. Surface characterization including SEM, XPS and FTIR further confirmed the preservation of Si[sbnd]O[sbnd]K functional groups. Meanwhile, due to the differences between the electronegativities of potassium atoms and hydrogen atoms the ion-exchange ability for heavy metals of the quenched samples was significantly enhanced and this has been validated by adsorption experiments with various kinds of metals. The mass balance for leaching calcium and potassium atoms also revealed that the enhanced ion-exchange capacity was caused by the improved liberation of potassium and calcium atoms from the aluminosilicate network. Moreover, the leaching test for metal doped material shows a limited amount of metal leaching under acidic conditions, indicating the potential application of this material in industrial wastewater treatment or catalysis applications. © 2016 Elsevier B.V.

Quench is a widely used technique in organic synthesis or inorganic material treatment but only limited studies have been performed on aluminosilicate. In this work, the quench effect on the textural properties and surface functional groups has been studied by the functionalization of a waste-derived aluminosilicate material. The porous structure has been changed in the presence of a quench reagent. We consider that this difference originated due to the prevention of replacement of potassium atoms in surface ion-exchange sites by hydrogen atoms. Surface characterization including SEM, XPS and FTIR further confirmed the preservation of Si[sbnd]O[sbnd]K functional groups. Meanwhile, due to the differences between the electronegativities of potassium atoms and hydrogen atoms the ion-exchange ability for heavy metals of the quenched samples was significantly enhanced and this has been validated by adsorption experiments with various kinds of metals. The mass balance for leaching calcium and potassium atoms also revealed that the enhanced ion-exchange capacity was caused by the improved liberation of potassium and calcium atoms from the aluminosilicate network. Moreover, the leaching test for metal doped material shows a limited amount of metal leaching under acidic conditions, indicating the potential application of this material in industrial wastewater treatment or catalysis applications. © 2016 Elsevier B.V.

Detailed knowledge of the processes that metals undergo during dry weather periods whilst deposited on urban surfaces and their environmental significance is essential to predict the potential influence of metals on stormwater quality and thereby to develop appropriate stormwater pollution mitigation measures. However, very limited research has been undertaken in this area. Accordingly, this study investigated the geochemical phase and particle size relationships of seven metals which are commonly associated with urban road dust, using sequential extraction in order to assess their mobility characteristics. Metals in the sequentially extracted fractions of exchangeable, reducible, oxidisable and residual were found to follow a similar trend for different land uses even though they had variable accumulation loads. The high affinity of Cd and Zn for exchangeable reactions in both, bulk and size-fractionated solid samples confirmed their high mobility, while the significant enrichment of Ni and Cr in the stable residual fraction indicated a low risk of mobility. The study results also confirmed the availability of Cu, Pb and Mn in both, stable and mobile fractions. The fine fraction of solids (<150 µm) and antecedent dry days can be highlighted as important parameters when determining the fate of metals associated with urban road dust. The outcomes from this study are expected to contribute to the development of effective stormwater pollution mitigation strategies by taking into consideration the metal-particulate relationships.

Quench is a widely used technique in organic synthesis or inorganic material treatment but only limited studies have been performed on aluminosilicate. In this work, the quench effect on the textural properties and surface functional groups has been studied by the functionalization of a waste-derived aluminosilicate material. The porous structure has been changed in the presence of a quench reagent. We consider that this difference originated due to the prevention of replacement of potassium atoms in surface ion-exchange sites by hydrogen atoms. Surface characterization including SEM, XPS and FTIR further confirmed the preservation of Si[sbnd]O[sbnd]K functional groups. Meanwhile, due to the differences between the electronegativities of potassium atoms and hydrogen atoms the ion-exchange ability for heavy metals of the quenched samples was significantly enhanced and this has been validated by adsorption experiments with various kinds of metals. The mass balance for leaching calcium and potassium atoms also revealed that the enhanced ion-exchange capacity was caused by the improved liberation of potassium and calcium atoms from the aluminosilicate network. Moreover, the leaching test for metal doped material shows a limited amount of metal leaching under acidic conditions, indicating the potential application of this material in industrial wastewater treatment or catalysis applications. © 2016 Elsevier B.V.

The integration of up-concentration processes to increase the efficiency of primary sedimentation, as a solution to achieve energy neutral wastewater treatment plants, requires further post-treatment due to the missing ammonium removal stage. This study evaluated the use of zeolites as a post-treatment step, an alternative to the biological removal process. A natural granular clinoptilolite zeolite was evaluated as a sorbent media to remove low levels (up to 100 mg-N/L) of ammonium from treated wastewater using batch and fixed bed columns. After being activated to the Na-form (Z-Na), the granular zeolite shown an ammonium exchange capacity of 29 ± 0.8 mg N-NH4+/g in single ammonium solutions and 23 ± 0.8 mg N-NH4+/g in treated wastewater simulating up-concentration effluent at pH = 8. The equilibrium removal data were well described by the Langmuir isotherm. The ammonium adsorption into zeolites is a very fast process when compared with polymeric materials (zeolite particle diffusion coefficient around 3 × 10- 12 m2/s). Column experiments with solutions containing 100 mg N-NH4+/L provide effective sorption and elution rates with concentration factors between 20 and 30 in consecutive operation cycles. The loaded zeolite was regenerated using 2 g NaOH/L solution and the rich ammonium/ammonia concentrates 2–3 g/L in NaOH were used in a liquid-liquid membrane contactor system in a closed-loop configuration with nitric and phosphoric acid as stripping solutions. The ammonia recovery ratio exceeded 98%. Ammonia nitrate and di-ammonium phosphate concentrated solutions reached up to 2–5% wt. of N., Peer Reviewed, Postprint (author's final draft)

Zagađenje prirodnih voda jonima teških metala predstavlja rastuću opasnost za čoveka i životnu sredinu. Postupci koji se koriste u tretmanima otpadnih voda praćeni su velikim investicionim i operativnim troškovima, kao i troškovima odlaganja iskorišćenog materijala nakon obrade. Jedno od rešenja predstavlja primenu adsorpcije uz korišćenje adsorbenata niske cene među kojima se izdvaja prirodni zeolit koji je mineralni resurs Srbije. Cilj istraživanja u ovoj doktorskoj disertaciji je bio razvoj procesa uklanjanja jona teških metala iz otpadnih voda korišćenjem zeolita. Izabrani su prirodni zeolitklinoptilolit iz ležišta Zlatokop u Vranjskoj Banji koje se smatra najvećim u Evropi, i zeolit A koji je komercijalno najdostupniji sintetički zeolit. U eksperimentima je ispitano uklanjanje dvovalentnih katjona Cu(II), Mn(II), Zn(II), Ni(II) i Pb(II) iz vodenih rastvora korišćenjem prirodnog zeolita u vidu praha i sintetičkog zeolita 4A u vidu kuglica. Eksperimentalna ispitivanja su obuhvatila određivanje adsorpcionih kapaciteta zeolita, ravnotežnih parametara, mehanizma i kinetike procesa, potrebnog vremena kontakta zeolita i rastvora za postizanje ravnoteže, kao i afiniteta prirodnog zeolita u pogledu uklanjanja različitih katjona. U cilju primene u pilot-postrojenju i industriji u procesima prečišćavanja otpadnih voda, u ovom radu je ispitana i mogućnost primene fluidizovanog sloja kuglica zeolita A za uklanjanje Cu(II) i Mn(II) iz vodenih rastvora.

Global demand for clean water is becoming a persistent concern and this has stimulated research into efficient and effective desalination and water treatment processes. Ion-exchange (IEX) resins have been used for water purification, but are limited by the continuous depletion of the resins and the need for large volumes of acid and base solutions for their regeneration. This Thesis presents a new chemical/thermal regeneration method and the novel use of mixed-bead and mixed-bed IEX resins for future desalination purposes.Mixed-bead resins composed of weak-acid and weak-base groups were synthesized and used for sorption studies with saline, followed by regeneration with ammonium bicarbonate (AB) and heating at 80°C. It was found that AB followed by heating provides 100% regeneration of these resins. Unfortunately, the low IEX capacities of polyampholytic resins restrict their commercial applications. However, a novel process was developed for increasing their IEX capacity by exposing Ni²⁺ and Ca²⁺ saturated resins to concentrated AB solutions, followed by heating. This was found to increase the IEX capacity by 4−5× with a corresponding increase in observable pore size and Brunauer-Emmett-Teller surface area.Although these mixed-bead resins could be completely regenerated using AB and heating, this also causes their thermal degradation, so the exhausted resins were also regenerated using AB washing but without heating. This was highly effective and showed an increased IEX capacity when in AB form, with higher selectivity for Na⁺ and HCO3‾ ions. It was also discovered that mixed-bed resin systems of strong-acid and strong-base resins, can be used to desalt 0.1M NaCl solution, producing about 6× the resin mass of drinking quality water, and this system can also be regenerated using concentrated AB in situ. In general, regeneration processes using AB could be applied for mixed-bead and mixed-bed systems in a continuous process, minimizing chemical waste, environmental i

A screening of Pd/zeolite-based catalysts in the PrOx-CO reaction in H2-rich streams was performed using zeolites with different cations (H+, Na+ and Cs+) prepared by ion exchange and framework type (MFI and FAU). The assessment of the catalytic performance displayed by these zeolite-based samples revealed that both parameters play an important role in the catalytic behaviour. The optimisation of both parameters led to the preparation of an optimum catalyst, which showed high CO conversion and CO selectivity during long-term stability tests.