A review on the hydration properties of dietary fibers derived from food waste and their interactions with other ingredients: opportunities and challenges for their application in the food industry.

Dietary fiber (DF) significantly affects the quality attributes of food matrices. Depending on its chemical composition, molecular structure, and degree of hydration, the behavior of DF may differ. Numerous reports confirm that incorporating DF derived from food waste into food products has significant effects on textural, sensory, rheological, and antimicrobial properties. Additionally, the characteristics of DF, modification techniques (chemical, enzymatic, mechanical, thermal), and processing conditions (temperature, pH, ionic strength), as well as the presence of other components, can profoundly affect the functionalities of DF. This review aims to describe the interactions between DF and water, focusing on the effects of free water, freezing-bound water, and unfreezing-bound water on the hydration capacity of both soluble and insoluble DF. The review also explores how the structural, functional, and environmental properties of DF contribute to its hydration capacity. It becomes evident that the interactions between DF and water, and their effects on the rheological properties of food matrices, are complex and multifaceted subjects, offering both opportunities and challenges for further exploration. Utilizing DF extracted from food waste exhibits promise as a sustainable and viable strategy for the food industry to create nutritious and high-value-added products, while concurrently reducing reliance on primary virgin resources.

Comparison and assessment of methods for cellulose crystallinity determination.

The degree of crystallinity in cellulose significantly affects the physical, mechanical, and chemical properties of cellulosic materials, their processing, and their final application. Measuring the crystalline structures of cellulose is a challenging task due to inadequate consistency among the variety of analytical techniques available and the lack of absolute crystalline and amorphous standards. Our article reviews the primary methods for estimating the crystallinity of cellulose, namely, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman and Fourier-transform infrared (FTIR) spectroscopy, sum-frequency generation vibrational spectroscopy (SFG), as well as differential scanning calorimetry (DSC), and evolving biochemical methods using cellulose binding molecules (CBMs). The techniques are compared to better interrogate not only the requirements of each method, but also their differences, synergies, and limitations. The article highlights fundamental principles to guide the general community to initiate studies of the crystallinity of cellulosic materials.

Effect of the structural features of biobased linear polyester plasticizers on the crystallization of polylactides.

This work presents, for the first time, a detailed report on how the nucleation and crystallization of polylactide (PLLA) are affected by biobased aliphatic polyesters plasticizers. Three biobased polyesters were synthesized via solvent-free two-stage melt polycondensation of adipic acid (AdA) with three different biobased aliphatic diols and used as plasticizers for poly (L-lactic acid) (PLLA). The molecular structure of the synthesized polyesters was proved using 1H NMR, 13C NMR and Fourier transform infrared (FTIR) spectroscopy. PLLA/AdA-based blends containing 10 wt% of the polyester plasticizers were studied by tensile tests, dynamic mechanical analysis (DMA), wide-angle x-ray scattering (WAXS), differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM). Adding the plasticizers to PLLA decreased Tg by up to 11 °C and significantly increased the elongation at break by about 8 times compared with neat PLLA. The addition of 10 wt% of any AdA-based plasticizer to PLLA increases the nucleation rate from the glassy state by around 50-110 % depending on the plasticizer. The overall crystallization rate from the glassy state was 2-3 times faster for the plasticized PLLAs than neat PLLA. These results are a consequence of the lower energy barrier for both nucleation and growth processes. The incorporation of AdA-based linear polyesters had an incremental impact on the crystal growth rate (or secondary nucleation) of PLLA spherulites from the melt and glassy states. In conclusion, the AdA-based aliphatic polyesters allowed to enhance PLLA crystallization rates and showed interesting potential for the formulation of fully biobased PLLA blends.

UV-Light Curing of 3D Printing Inks from Vegetable Oils for Stereolithography.

Typical resins for UV-assisted additive manufacturing (AM) are prepared from petroleum-based materials and therefore do not contribute to the growing AM industry trend of converting to sustainable bio-based materials. To satisfy society and industry's demand for sustainability, renewable feedstocks must be explored; unfortunately, there are not many options that are applicable to photopolymerization. Nevertheless, some vegetable oils can be modified to be suitable for UV-assisted AM technologies. In this work, extended study, through FTIR and photorheology measurements, of the UV-curing of epoxidized acrylate from soybean oil (AESO)-based formulations has been performed to better understand the photopolymerization process. The study demonstrates that the addition of appropriate functional comonomers like trimethylolpropane triacrylate (TMPTA) and the adjusting of the concentration of photoinitiator from 1% to 7% decrease the needed UV-irradiation time by up to 25%. Under optimized conditions, the optimal curing time was about 4 s, leading to a double bond conversion rate (DBC%) up to 80% and higher crosslinking density determined by the Flory-Rehner empirical approach. Thermal and mechanical properties were also investigated via TGA and DMA measurements that showed significant improvements of mechanical performances for all formulations. The properties were improved further upon the addition of the reactive diluents. After the thorough investigations, the prepared vegetable oil-based resin ink formulations containing reactive diluents were deemed suitable inks for UV-assisted AM, giving their appropriate viscosity. The validation was done by printing different objects with complex structures using a laser based stereolithography apparatus (SLA) printer.

Microfibrillated cellulose from Argania spinosa shells as sustainable solid particles for O/W Pickering emulsions.

Microfibrillated cellulose (MFC) from Argan (Argania spinosa) shells was prepared by chemical purification of cellulose, then mechanical disintegration via high pressure homogenization was performed to isolate fibrils of cellulose. Chemical characterization of raw argan shell (AS-R), purified cellulose (AS-C), and argan shell MFC (AS-MFC) included FT-IR, XRD and NMR. Morphological characterization of AS-MFC was assessed using TEM. Next, the use of AS-MFC as oil-in-water (O/W) emulsions stabilizer was investigated. The particle concentration was observed to affect the long-term stability of the emulsions; high concentrations (0.5-1 % w/w) of AS-MFC resulted in emulsions that were thermodynamically stable during 15 days of storage, which was demonstrated by the droplet's size evolution. The suitable oil concentration for a maximum volume of emulsion using 1 % w/w AS-MFC was demonstrated. The results show that AS-MFC is able to stabilize 70 % w/w MCT oil without visual phase separation. Finally, CLSM shows the adsorption of AS-MFC at the oil-water interface and the formation of a 3D network surrounding oil droplets, confirming Pickering emulsion formation and stabilization.

Isocyanate-Free Fully Biobased Star Polyester-Urethanes: Synthesis and Thermal Properties.

A green strategy for the synthesis of nonisocyanate polyester-urethanes (NIPHEUs) was developed. These NIPHEUs were synthesized by step growth polymerization combining sugar-derived dimethyl-2,5-furan dicarboxylate (DMFD) with polyhydroxylurethanes (PHUs) adducts bearing four hydroxyl groups. The later hydroxyl urethane tetraols (HU-tetraols) building blocks were prepared by aminolysis of glycerol carbonate with two different aliphatic diamines having different chain lengths, 8 and 12 carbons. Qualitative and quantitative NMR analyses of the HU-tetraols showed the presence of primary and secondary hydroxyl moieties at different ratios. Hence, in the polycondensation stage, the stoichiometry of the diester was varied from 1 to 6 equiv in order to tailor the structural features of the prepared NIPHEUs. The success of the chain extension through polycondensation was confirmed by FTIR and NMR analyses. Thermal analyses of these new polymers demonstrated satisfactory thermal stability, with onset degradation temperatures ranging from 170 to 220 °C where the main first degradation stage occurs. Their melting temperatures ranged between 93 and 110 °C and seem to be driven by the thermal behavior of HU-tetraol monomers. Surprisingly, preliminary results from thermal analyses revealed the occurrence of a striking thermal change in the NIPHEUs upon repetitive heating cycles. This behavior may be related to a thermal-induced bond exchange probably driven by transcarbamoylation reaction. Such interesting vitrimer-like behavior for this new type of NIPHEUs would be unique and should be confirmed by a deeper study before leading to a new range of functional green materials.

Chemical Modification and Processing of Chitin for Sustainable Production of Biobased Electrolytes.

In the present work we report on the development of a novel and sustainable electrolyte based on chitin. Chitin biopolymer was carboxymethylated in simple, mild, and green conditions in order to fine-tune the final properties of the electrolyte. To this end, chitin was modified for various reaction times, while the molar ratio of the reagents, e.g., sodium hydroxide and monochloroacetic acid, was maintained fixed. The resulting chitin derivatives were characterized using various techniques. Under optimized conditions, modified chitin derivatives exhibiting a distinct degree of carboxymethylation and acetylation were obtained. Structural features, morphology, and properties are discussed in relation to the chemical structure of the chitin derivatives. For electrolyte applications, the ionic conductivity increased by three magnitudes from 10-9 S·cm-1 for unmodified chitin to 10-6 S·cm-1 for modified chitin with the highest degree of acetylation. Interestingly, the chitin derivatives formed free-standing films with and without the addition of up to 60% of ionic liquid, the ionic conductivity of the obtained solid electrolyte system reaching the value of 10-3 S·cm-1.

Prickly pear peels as a valuable resource of added-value polysaccharide: Study of structural, functional and film forming properties.

Valorization of agricultural by-products constitutes a promising approach for sustainable development. Mucilage was extracted with a simple and safe method from Opuntia ficus-indica fruit peels which are considered as unexploited wastes resulting from the huge consumption of prickly pears. Structural and functional properties of the extracted polysaccharide were studied. Peels mucilage was composed of 97% carbohydrates, essentially galactose, arabinose, xylose and galacturonic acid. Specific signals of these sugars were observed in 13C and 1H NMR spectra and their chemical fingerprint was obtained by ATR-FTIR. Viscosity measurements of mucilage solution revealed a shear-thinning behavior. The extracted biopolymer exhibited good solubility in water, foaming and emulsifying capacities. Favorable thermal stability was manifested up to 250 °C. In order to conceive novel applications of this biopolymer as biodegradable packaging, its film-forming properties were studied. Red-colored films were obtained with high water contact angle (~91°), solubility (~42%) and grease proof character. Mechanical properties were comparable to those of other polysaccharides films with decent elongation at break reaching 66%.

Clicking Biobased Polyphenols: A Sustainable Platform for Aromatic Polymeric Materials.

Lignin, tannins, and cashew nut shell liquid are considered the main sources of aromatic-based macromolecules. They represent an abundant alternative feedstock for the elaboration of aromatic chemicals and polymers, with a view to replacing some fossil-based fractions. Located in different tissues of plants, these compounds, with a large diversity and structural complexity, have, to date, been considered as byproducts derived from fractionation-separation industrial processes with low added value. In the last decade, the use of click chemistry as a tool for the synthesis of controlled macromolecular architectures has seen much development in fundamental and applied research for a wide range of applications. It could represent a valid solution to overcome the main limitations encountered in the chemical modification of natural sources of chemicals, with an environmentally friendly approach to create new substrates for the development of innovative polymers and materials. After a brief description of the main aromatic biopolymers, including the main extraction techniques, along with their structure and their properties, this Review describes chemical modifications that have mainly been focused on natural polyphenols, with the aim of introducing clickable groups, and their further use for the synthesis of biobased materials and additives. Special emphasis is given to several as-yet unexplored chemical features that could contribute to further fundamental and applied materials science research.

Development of plasticized edible films from Opuntia ficus-indica mucilage: A comparative study of various polyol plasticizers.

Mucilage polysaccharide was extracted from Opuntia ficus-indica cladodes (Cactaceae) and its composition was determined by sugar analysis using HPLC-RID and its structural features were elucidated by FTIR and 1H and 13C NMR. Films from the extracted mucilage were loaded at 40% (w/w) with glycerol, sorbitol, PEG 200 or PEG 400. The physical, thermal, mechanical and barrier properties of the obtained films were investigated. The highest water vapor barrier properties of plasticized mucilage films were obtained with sorbitol reaching water vapor permeability (WVP) values up to 3 times lower than the other films. The tensile strength (TS) values of films plasticized with PEG 200 and sorbitol were about 2 times higher than those of glycerol-plasticized films. The significant effect of polyol type plasticizers on the different properties of mucilage edible films was related to their structural features that promote different interactions with mucilage polysaccharides as demonstrated by FTIR and thermal properties.

Supramolecular Approach for Efficient Processing of Polylactide/Starch Nanocomposites.

All-biobased and biodegradable nanocomposites consisting of poly(l-lactide) (PLLA) and starch nanoplatelets (SNPs) were prepared via a new strategy involving supramolecular chemistry, i.e., stereocomplexation and hydrogen-bonding interactions. For this purpose, a poly(d-lactide)-b-poly(glycidyl methacrylate) block copolymer (PDLA-b-PGMA) was first synthesized via the combination of ring-opening polymerization and atom-transfer radical polymerization. NMR spectroscopy and size-exclusion chromatography analysis confirmed a complete control over the copolymer synthesis. The SNPs were then mixed up with the copolymer for producing a PDLA-b-PGMA/SNPs masterbatch. The masterbatch was processed by solvent casting for which a particular attention was given to the solvent selection to preserve SNPs morphology as evidenced by transmission electron microscopy. Near-infrared spectroscopy was used to highlight the copolymer-SNPs supramolecular interactions mostly via hydrogen bonding. The prepared masterbatch was melt-blended with virgin PLLA and then thin films of PLLA/PDLA-b-PGMA/SNPs nanocomposites (ca. 600 µm) were melt-processed by compression molding. The resulting nanocomposite films were deeply characterized by thermogravimetric analysis and differential scanning calorimetry. Our findings suggest that supramolecular interactions based on stereocomplexation between the PLLA matrix and the PDLA block of the copolymer had a synergetic effect allowing the preservation of SNPs nanoplatelets and their morphology during melt processing. Quartz crystal microbalance and dynamic mechanical thermal analysis suggested a promising potential of the stereocomplex supramolecular approach in tuning PLLA/SNPs water vapor uptake and mechanical properties together with avoiding PLLA/SNPs degradation during melt processing.

The Electrospun Ceramic Hollow Nanofibers.

Hollow nanofibers are largely gaining interest from the scientific community for diverse applications in the fields of sensing, energy, health, and environment. The main reasons are: their extensive surface area that increases the possibilities of engineering, their larger accessible active area, their porosity, and their sensitivity. In particular, semiconductor ceramic hollow nanofibers show greater space charge modulation depth, higher electronic transport properties, and shorter ion or electron diffusion length (e.g., for an enhanced charging-discharging rate). In this review, we discuss and introduce the latest developments of ceramic hollow nanofiber materials in terms of synthesis approaches. Particularly, electrospinning derivatives will be highlighted. The electrospun ceramic hollow nanofibers will be reviewed with respect to their most widely studied components, i.e., metal oxides. These nanostructures have been mainly suggested for energy and environmental remediation. Despite the various advantages of such one dimensional (1D) nanostructures, their fabrication strategies need to be improved to increase their practical use. The domain of nanofabrication is still advancing, and its predictable shortcomings and bottlenecks must be identified and addressed. Inconsistency of the hollow nanostructure with regard to their composition and dimensions could be one of such challenges. Moreover, their poor scalability hinders their wide applicability for commercialization and industrial use.

Lignin-Based Materials Through Thiol-Maleimide "Click" Polymerization.

In the present report an environmentally friendly approach to transforming renewable feedstocks into value-added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11-maleimidoundecylenic acid (11-MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11-maleimidoundecanoyl chloride (11-MUC). Different degrees of substitution were achieved by using various amounts of the 11-MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide-lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol-ene "click" polymerization with thiol-containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers.

Epoxy Monomers Cured by High Cellulosic Nanocrystal Loading.

The present study focuses on the use of cellulose nanocrystals (CNC) as the main constituent of a nanocomposite material and takes advantage of hydroxyl groups, characteristic of the CNC chemical structure, to thermally cross-link an epoxy resin. An original and simple approach is proposed, based on the collective sticking of CNC building blocks with the help of a DGEBA/TGPAP-based epoxy resin. Scientific findings suggest that hydroxyl groups act as a toxic-free cross-linking agent of the resin. The enhanced protection against water degradation as compared to neat CNC film and the improvement of mechanical properties of the synthesized films are attributed to a good compatibility between the CNC and the resin. Moreover, the preservation of CNC optical properties at high concentrations opens the way to applying these materials in photonic devices.

Free-Radical-Induced Grafting from Plasma Polymer Surfaces.

With the advances in science and engineering in the second part of the 20th century, emerging plasma-based technologies continuously find increasing applications in the domain of polymer chemistry, among others. Plasma technologies are predominantly used in two different ways: for the treatment of polymer substrates by a reactive or inert gas aiming at a specific surface functionalization or for the synthesis of a plasma polymer with a unique set of properties from an organic or mixed organic-inorganic precursor. Plasma polymer films (PPFs), often deposited by plasma-enhanced chemical vapor deposition (PECVD), currently attract a great deal of attention. Such films are widely used in various fields for the coating of solid substrates, including membranes, semiconductors, metals, textiles, and polymers, because of a combination of interesting properties such as excellent adhesion, highly cross-linked structures, and the possibility of tuning properties by simply varying the precursor and/or the synthesis parameters. Among the many appealing features of plasma-synthesized and -treated polymers, a highly reactive surface, rich in free radicals arising from deposition/treatment specifics, offers a particular advantage. When handled carefully, these reactive free radicals open doors to the controllable surface functionalization of materials without affecting their bulk properties. The goal of this review is to illustrate the increasing application of plasma-based technologies for tuning the surface properties of polymers, principally through free-radical chemistry.

Polylactide/Poly(ω-hydroxytetradecanoic acid) Reactive Blending: A Green Renewable Approach to Improving Polylactide Properties.

A green manufacturing technique, reactive extrusion (REx), was employed to improve the mechanical properties of polylactide (PLA). To achieve this goal, a fully biosourced PLA based polymer blend was conceived by incorporating small quantities of poly(ω-hydroxytetradecanoic acid) (PC14). PLA/PC14 blends were compatibilized by transesterification reactions promoted by 200 ppm titanium tetrabutoxide (Ti(OBu)4) during REx. REx for 15 min at 150 rpm and 200 °C resulted in enhanced blend mechanical properties while minimizing losses in PLA molecular weight. SEM analysis of the resulting compatibilized phase-separated blends showed good adhesion between dispersed PC14 phases within the continuous PLA phase. Direct evidence for in situ synthesis of PLA-b-PC14 copolymers was obtained by HMBC and HSQC NMR experiments. The size of the dispersed phase was tuned by the screw speed to "tailor" the blend morphology. In the presence of 200 ppm Ti(OBu)4, inclusion of only 5% PC14 increased the elongation at break of PLA from 3 to 140% with only a slight decrease in the tensile modulus (3200 to 2900 MPa). Furthermore, PLA's impact strength was increased by 2.4× that of neat PLA for 20% PC14 blends prepared by REx. Blends of PLA and PC14 are expected to expand the potential uses of PLA-based materials.

Polymerization topochemistry of cellulose nanocrystals: a function of surface dehydration control.

The activation (dehydration) of cellulose nanocrystals (CNCs) toward surface "brush" polymerization is accomplished either by freeze drying or solvent exchange. However, the question of which one of these protocols to choose over the other is generally open-ended. The current study attempts to shed light on this question by installing a standard polymer, polycaprolactone (PCL), onto the surface of both freeze-dried and solvent-exchanged CNCs by ring-opening polymerization (ROP) and examining the differences in polymerization and final product properties. The work is the first to demonstrate that the efficiency of surface polymerization and final product properties are in fact influenced by the protocols. The differences between the two sample PCL-grafted CNCs were investigated by X-ray photoelectron spectroscopy (XPS), elemental analysis, gel permeation chromatography (GPC), and contact-angle measurements. The freeze-dried samples had a significantly reduced PCL surface density. The crystallinity of the solvent-exchanged PCL-grafted CNCs (SECNC-g-PCL), however, was lower than that of either pure CNCs or freeze-dried PCL-grafted CNCs (FDCNC-g-PCL). It was determined that solvent exchange sufficiently modified the CNC surface to provide enhanced reactivity, an effect that was not as apparent for FDCNC-g-PCL. The solvent-exchanged CNCs tended to have more porous, nanotextured surfaces that were tended to be more responsive toward brush polymerization. In addition to the physical dissimilarities in surface morphology and surface accessibility contributing to topochemical differences between the two species, it was also found that the dispersibility, aggregation, and thermal stability were different.

Free radical generation and concentration in a plasma polymer: the effect of aromaticity.

Plasma polymer films (PPF) have increasing applications in many fields due to the unique combination of properties of this class of materials. Among notable features arising from the specifics of plasma polymerization synthesis, a high surface reactivity can be advantageously used when exploited carefully. It is related to the presence of free radicals generated during the deposition process through manifold molecular bond scissions in the energetic plasma environment. In ambient atmosphere, these radicals undergo autoxidation reactions resulting in undesired polymer aging. However, when the reactivity of surface radicals is preserved and they are put in direct contact with a chemical group of interest, a specific surface functionalization or grafting of polymeric chains can be achieved. Therefore, the control of the surface free radical density of a plasma polymer is crucially important for a successful grafting. The present investigation focuses on the influence of the hydrocarbon precursor type, aromatic vs aliphatic, on the generation and concentration of free radicals on the surface of the PPF. Benzene and cyclohexane were chosen as model precursors. First, in situ FTIR analysis of the plasma phase supplemented by density functional theory calculations allowed the main fragmentation routes of precursor molecules in the discharge to be identified as a function of energy input. Using nitric oxide (NO) chemical labeling in combination with X-ray photoelectron spectroscopy analysis, a quantitative evaluation of concentration of surface free radicals as a function of input power has been assessed for both precursors. Different evolutions of the surface free radical density for the benzene- and cyclohexane-based PPF, namely, a continuous increase versus stabilization to a plateau, are attributed to different plasma polymerization mechanisms and resulting structures as illustrated by PPF characterization findings. The control of surface free radical density can be achieved through the stabilization of radicals due to the proximity of incorporated aromatic rings. Aging tests highlighted the inevitable random oxidation of plasma polymers upon exposure to air and the necessity of free radical preservation for a controlled surface functionalization.

Key advances in the chemical modification of nanocelluloses.

Nanocelluloses, including nanocrystalline cellulose, nanofibrillated cellulose and bacterial cellulose nanofibers, have become fascinating building blocks for the design of new biomaterials. Derived from the must abundant and renewable biopolymer, they are drawing a tremendous level of attention, which certainly will continue to grow in the future driven by the sustainability trend. This growing interest is related to their unsurpassed quintessential physical and chemical properties. Yet, owing to their hydrophilic nature, their utilization is restricted to applications involving hydrophilic or polar media, which limits their exploitation. With the presence of a large number of chemical functionalities within their structure, these building blocks provide a unique platform for significant surface modification through various chemistries. These chemical modifications are prerequisite, sometimes unavoidable, to adapt the interfacial properties of nanocellulose substrates or adjust their hydrophilic-hydrophobic balance. Therefore, various chemistries have been developed aiming to surface-modify these nano-sized substrates in order to confer to them specific properties, extending therefore their use to highly sophisticated applications. This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.

Use of free radicals on the surface of plasma polymer for the initiation of a polymerization reaction.

A novel approach to functionalize plasma polymer films (PPFs) through the grafting polymerization initiated from free radicals trapped in the film was developed in this work. 2-Ethylhexyl acrylate (EHA) was chosen as radically polymerizable monomer given the wide use of its corresponding polymer in coating and adhesive applications. The occurrence of the grafting was first confirmed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). Then grafted chains were studied in more detail. The thickness of grafted chains was quantitatively estimated by angle-resolved XPS (ARXPS), while their morphology and interfacial behavior were qualitatively investigated by atomic force microscopy (AFM), contact angle measurements, and quartz crystal microbalance (QCM). The latter technique provided additional insights regarding the swelling behavior of the grafted layer and its stability upon exposure to challenging environments. Reported scientific findings suggest to use this approach for the covalent binding of a very thin layer on the top surface of a PPF without affecting its bulk properties.