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1.
Slot‑die coating of cellulose nanocrystals and chitosan for improved barrier properties of paper
Ylenia Ruberto, Vera Vivod, Janja Juhant Grkman, Gregor Lavrič, Claudia Graiff, Vanja Kokol, 2024, original scientific article

Abstract: Cellulose nanocrystals (CNCs) and chitosan (Cht) have been studied extensively for oxygen and water vapour barrier coatings in biodegradable, compostable or recyclable paper packaging. However, rare studies have been performed by using scalable, inexpensive, and fast continuous slot-die coating processes, and none yet in combination with fast' and high-throughput near-infrared (NIR) light energy drying. In this frame, we studied the feasibility of a moderately concentrated (11 wt%) anionic CNC and (2 wt%) cationic Cht coating (both containing 20 wt% sorbitol related to the weight of CNC/Cht), by using plain and pigment pre-treated papers. The effect of coating parameters (injection speed, dry thickness settings) were investigated on coating quantity (dry weight, thickness) and homogeneity (coverage), papers' structure (thickness, grammage, density), whiteness, surface wettability, barrier (air, oxygen and water vapour) properties and adhesion (surface strength). The coating homogeneity was dependent primarily on the suspensions' viscosity, and secondarily on the applied coating parameters, whereby CNCs could be applied at 1–2 times higher injection speeds (up to 80 mL/min) and versatile coating weights, but required a relatively longer time to dry. The CNCs thus exhibited outstanding air (4.2–1.5 nm/Pa s) and oxygen (2.7–1.1 cm3 mm/m2 d kPa) barrier performance at 50% RH and 22–33 g/m2 deposition, whereas on top deposited Cht (3–4 g/m2) reduced its wetting time and improved the water vapour barrier (0.23–0.28 g mm/m2 d Pa). The balanced barrier properties were achieved due to the polar characteristic of CNCs, the hydrophobic nature of Cht and the quantity of the applied bilayer coating that can provide sustainable paper-based packaging.
Keywords: paper, nanocellulose, chitosan, slot‑die coating, near-infrared (NIR) drying, barrier properties
Published in DKUM: 06.05.2024; Views: 70; Downloads: 4
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Cationised fibre-based cellulose multi-layer membranes for sterile and high-flow bacteria retention and inactivation
Vanja Kokol, Monika Kos, Vera Vivod, Nina Gunde-Cimerman, 2023, original scientific article

Abstract: Low-cost, readily available, or even disposable membranes in water purification or downstream biopharma processes are becoming attractive alternatives to expensive polymeric columns or filters. In this article, the potential of microfiltration membranes prepared from differently orientated viscose fibre slivers, infused with ultrafine quaternised (qCNF) and amino-hydrophobised (aCNF) cellulose nanofibrils, were investigated for capturing and deactivating the bacteria from water during vacuum filtration. The morphology and capturing mechanism of the single- and multi-layer structured membranes were evaluated using microscopic imaging and colloidal particles. They were assessed for antibacterial efficacy and the retention of selected bacterial species (Escherichia coli, Staphylococcus aureus, Micrococcus luteus), differing in the cell envelope structure, hydrodynamic biovolume (shape and size) and their clustering. The aCNF increased biocidal efficacy significantly when compared to qCNF-integrated membrane, although the latter retained bacteria equally effectively by a thicker multi-layer structured membrane. The retention of bacterial cells occurred through electrostatic and hydrophobic interactions, as well as via interfibrous pore diffusion, depending on their physicochemical properties. For all bacterial strains, the highest retention (up to 100% or log 6 reduction) at >50 L/h∗bar∗m2 flow rate was achieved with a 4-layer gradient-structured membrane containing different aCNF content, thereby matching the performance of industrial polymeric filters used for removing bacteria.
Keywords: fibrous membrane, cationised cellulose nanofibrils, amino-hydrophobised cellulose nanofibrils, antibacterial activity, multi-layer structure, flux, bacteria retention
Published in DKUM: 28.03.2024; Views: 102; Downloads: 0
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Phosphonate-modified cellulose nanocrystals potentiate the Th1 polarising capacity of monocyte-derived dendritic cells via GABA-B receptor
Marina Bekić, Miloš Vasiljević, Dušica Stojanović, Vanja Kokol, Dušan Mihajlović, Dragana Vučević, Petar S. Uskoković, Miodrag Čolić, Sergej Tomić, 2022, original scientific article

Abstract: Purpose: Phosphonates, like 3-AminoPropylphosphonic Acid (ApA), possess a great potential for the therapy of bone tumours, and their delivery via cellulose nanocrystals (CNCs) seems a promising approach for their increased efficacy in target tissues. However, the immunological effects of CNC-phosphonates have not been investigated thoroughly. The main aim was to examine how the modification of CNCs with phosphonate affects their immunomodulatory properties in human cells. Methods: Wood-based native (n) CNCs were modified via oxidation (ox-CNCs) and subsequent conjugation with ApA (ApA-CNCs). CNCs were characterised by atomic force microscopy (AFM) and nanoindentation. Cytotoxicity and immunomodulatory potential of CNCs were investigated in cultures of human peripheral blood mononuclear cells (PBMCs) and monocyte-derived dendritic cells (MoDCs)/T cells co-cultures by monitoring phenotype, cytokines production, allostimulatory and Th/Treg polarisation capacity. Results: AFM showed an increase in CNCs’ thickens, elasticity modulus and hardness during the modification with ApA. When applied at non-toxic doses, nCNCs showed a tolerogenic potential upon internalisation by MoDCs, as judged by their increased capacity to up-regulate tolerogenic markers and induce regulatory T cells (Treg), especially when present during the differentiation of MoDCs. In contrast, ox- and ApA-CNCs induced oxidative stress and autophagy in MoDCs, which correlated with their stimulatory effect on the maturation of MoDCs, but also inhibition of MoDCs differentiation. ApA-CNC-treated MoDCs displayed the highest allostimulatory and Th1/CTL polarising activity in co-cultures with T cells. These effects of ApA-CNCs were mediated via GABA-B receptor-induced lowering of cAMP levels in MoDCs, and they could be blocked by GABA-B receptor inhibitor. Moreover, the Th1 polarising and allostimulatory capacity of MoDCs differentiated with ApA-CNC were largely preserved upon the maturation of MoDCs, whereas nCNC- and ox-CNC-differentiated MoDCs displayed an increased tolerogenic potential. Conclusion: The delivery of ApA via CNCs induces potent DC-mediated Th1 polarisation, which could be beneficial in their potential application in tumour therapy.
Keywords: cellulose nanocrystals, phosphonates, dendritic cells, regulatory T-cell subsets, immunomodulation, GABA-B receptor
Published in DKUM: 17.08.2023; Views: 242; Downloads: 15
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Synergistic effect of screen-printed Al(OH)[sub]3 nanoparticles and phosphorylated cellulose nanofibrils on the thermophysiological comfort and high-intensive heat protection properties of flame-retardant fabric
Tjaša Kolar, Jelka Geršak, Nataša Knez, Vanja Kokol, 2022, original scientific article

Abstract: Al(OH)3 nanoparticles (ATH NPs) and phosphorylated cellulose nanofibrils (PCNFs) were used as user-friendly and comfortable coating components on flame-retardant fabric to improve its thermophysiological comfort and high-intensive heat protection properties. The effect of the PCNF imprinting and its attachment after the post-printing of a hydrophobic polyacrylate (AP) on the same (back side) or the other (front) side of the fabric, with and without the addition of ATH NPs, was considered, to maintain the front side (facing the wearer) as hydrophilic while keeping the back side (facing the outside) hydrophobic. The amount of coatings applied and their patterning were studied, varied with the ATH NPs’ concentration (1.7, 3.3 and 6.7 wt%) and screen mesh size used (60 and 135), based on the coating’ mass, fabric’s air permeability, thickness and microstructure. The reduced moisture build-up (55%), increased the water vapour (13%) and heat (12%) transfer from the skin, were assessed by applying PCNF under the AP, being more pronounced in the case of using a 135 mesh-sized screen, given the smaller, more densely distributed, thinner and imprinted pattern coatings. These effects were further improved by the addition of nanoporous ATH NPs, which allowed more homogeneous spreading of the moisture and its faster transport. Such a treatment also shifted the fabric’s degradation temperature towards higher values (up to 15°C), retained up to 30% of high-heat flux (21 kW/m2), prolonged the time to ignition by 11 s and reduced the total heat released by up to 60%, thereby providing better protection when exposed to the heat, due to the presence of the phosphorous (PCNF) promoted generation of an Al2O3 char acting as a barrier layer, while also reducing the production of heat and generation of smoke by 75%.
Keywords: tekstilna tehnologija, ognjevaren tekstil, Al(OH)3 nanodelci, celulozni nanofibrili, tiskanje tekstilij, optične lastnosti, termofiziološko udobje, toplotna zaščita, flame-retardant textile, Al(OH)3 nanoparticles, phosphorylated cellulose nanofibrils, screen-printing, thermophysiological comfort, heat protection
Published in DKUM: 12.07.2023; Views: 344; Downloads: 11
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Using different surface energy models to assess the interactions between antiviral coating films and phi6 model virus
Zdenka Peršin Fratnik, Olivija Plohl, Vanja Kokol, Lidija Fras Zemljič, 2023, original scientific article

Abstract: High molecular weight chitosan (HMWCh), quaternised cellulose nanofibrils (qCNF), and their mixture showed antiviral potential in liquid phase, while this effect decreased when applied to facial masks, as studied in our recent work. To gain more insight into material antiviral activity, spin-coated thin films were prepared from each suspension (HMWCh, qCNF) and their mixture with a 1:1 ratio. To understand their mechanism of action, the interactions between these model films with various polar and nonpolar liquids and bacteriophage phi6 (in liquid phase) as a viral surrogate were studied. Surface free energy (SFE) estimates were used as a tool to evaluate the potential adhesion of different polar liquid phases to these films by contact angle measurements (CA) using the sessile drop method. The Fowkes, Owens–Wendt–Rabel–Kealble (OWRK), Wu, and van Oss–Chaudhury–Good (vOGC) mathematical models were used to estimate surface free energy and its polar and dispersive contributions, as well as the Lewis acid and Lewis base contributions. In addition, the surface tension SFT of liquids was also determined. The adhesion and cohesion forces in wetting processes were also observed. The estimated SFE of spin-coated films varied between mathematical models (26–31 mJ/m2) depending on the polarity of the solvents tested, but the correlation between models clearly indicated a significant dominance of the dispersion components that hinder wettability. The poor wettability was also supported by the fact that the cohesive forces in the liquid phase were stronger than the adhesion to the contact surface. In addition, the dispersive (hydrophobic) component dominated in the phi6 dispersion, and since this was also the case in the spin-coated films, it can be assumed that weak physical van der Waals forces (dispersion forces) and hydrophobic interactions occurred between phi6 and the polysaccharide films, resulting in the virus not being in sufficient contact with the tested material during antiviral testing of the material to be inactivated by the active coatings of the polysaccharides used. Regarding the contact killing mechanism, this is a disadvantage that can be overcome by changing the previous material surface (activation). In this way, HMWCh, qCNF, and their mixture can attach to the material surface with better adhesion, thickness, and different shape and orientation, resulting in a more dominant polar fraction of SFE and thus enabling the interactions within the polar part of phi6 dispersion.
Keywords: films, surface free energy, SFE mathematical models, phi6, wettability, spreading, interactions
Published in DKUM: 21.04.2023; Views: 461; Downloads: 28
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VPLIV TISKANJA NANOMATERIALOV NA TOPLOTNO-OGNJEVARNE IN TERMOFIZIOLOŠKE LASTNOSTI TKANINE : doktorska disertacija
Tjaša Kolar, 2022, doctoral dissertation

Abstract: Namen doktorske disertacije je bil preučiti učinek uporabe ekonomsko in ekološko sprejemljivejših nanodelcev Al-hidroksida (v primerjavi s SWCNT) kot zaviralcev gorenja in načina njihovega nanosa (v kombinaciji s hidrofilno PCNF ali hidrofobno AP) na izboljšanje termofizioloških, toplotnih in mehanskih lastnosti ognjevarno-zaščitne tkanine. Analizirana sta bila vpliva finosti šablone (60 in 135 mesh) in postopka tiskanja (enoslojno ali dvoslojno na hrbtni strani ali enoslojno na obeh straneh). V prvem delu disertacije je bil preučen vpliv različno velikih (20–50 nm) ATH/AMH ND na toplotno stabilnost filmov MFC. Toplotno najstabilnejši film z 0,15 ut% dodatkom 20 nm AMH ND in začetkom večstopenjske razgradnje pri 305 °C je v primerjavi s filmom iz čiste MFC imel 20 % višji ostanek pri 600 °C ter 42 % nižjo specifično toplotno kapaciteto. Prav tako je bil film prilagodljiv, optično transparenten (95 %), hidrofoben (68°), z natezno trdnostjo 69 MPa in elastičnim modulom 5,7 GPa ter nizko prepustnostjo kisika (2.192 cm3/m2/dan). V drugem delu disertacije je tkanina zaradi sinergističnih učinkov 1,5 ut% PCNF in 6,7 ut% ATH ND enostranskega dvoslojnega nanosa na hrbtni strani zadržala do 30 % visoko intenzivnega toplotnega toka (21 kW/m2), izkazala 15 °C boljšo temperaturno stabilnost, 11 s daljši čas do vžiga, zmanjšano količino sproščene toplote (za 60 %) in dima (za 75 %) ter izrazito asimetrično omočljivost (lice CA – 36°, hrbet CA – 121°) ob povečanem prenosu vodne pare (17 %) in toplote (22 %). Tkanina, tiskana z 0,4 ut% SWCNT v AP na hrbtni strani in 1,5 ut% PCNF na lični, je imela poleg izboljšane toplotne zaščite (18 °C boljša temperaturna stabilnost), termofiziološkega udobja (25 % povišan prenos toplote, 17 % vodne pare) in asimetrične omočljivosti (lice CA – 48°, hrbet CA – 129°) tudi visoko UV-zaščito (UPF 109), brez spremembe barve. Na strani z nanesenimi SWCNT je tkanina z električno prevodnostjo (4,9 · 10–4 S/cm) izkazala tudi potencial za antistatično zaščito ter zaščito pred elektromagnetnim sevanjem.
Keywords: toplotno-ognjevarna tkanina, termofiziološke lastnosti, fibrilirana nanoceluloza, nanodelci aluminijevega hidroksida, enoplastne ogljikove nanocevke, šablonsko tiskanje
Published in DKUM: 30.11.2022; Views: 781; Downloads: 73
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Odvzem premoženjske koristi, pridobljene s kaznivim dejanjem, kot zakonodajni, teoretični in praktični problem : doktorska disertacija
Vanja Verdel Kokol, 2020, doctoral dissertation

Abstract: Znaten delež kaznivih dejanj je izvršenih prav zaradi pridobivanja protipravne premoženjske koristi. Zato zahteva racionalna kriminalitetna politika v trajnostnem zoperstavljanju takšnim kaznivim dejanjem učinkovit, predvsem pa domišljen in ustrezno zasnovan sistem odvzema premoženjske koristi. Ob tem na račun učinkovitega odvzema koristi ne sme priti do posega v temeljne ustavne pravice. Problematika kazenskopravnega odvzema premoženjske koristi se tako osredotoča na tri ključne vidike, in sicer na interes države, da storilci ne obdržijo premoženjske koristi, ki jo pridobijo z izvrševanjem kaznivih dejanj, po drugi strani mora biti zadoščeno načelom zakonitosti, nujnosti in sorazmernosti, da se prekomerno ne posega v pravice obdolžencev, vse večji pomen pa pridobiva tudi ustrezno varstvo premoženjskih interesov oškodovancev.
Keywords: kazenskopravni odvzem premoženjske koristi, začasno zavarovanje, mednarodno sodelovanje, varstvo oškodovancev, primarni obligatorni odvzem koristi, metoda izračuna premoženjske koristi, institucionalna pristojnost
Published in DKUM: 17.06.2021; Views: 1451; Downloads: 389
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