Photochemical stability of chitosan films doped with cannabis oil.

The effect of UV radiation from three different sources on chitosan (CS) films containing the addition of 10% by weight of cannabis oil was investigated. Cannabis oil (CBD) alone exposed to UV is unstable, but its photostability significantly increases in the chitosan matrix. The course of photochemical reactions, studied by FTIR spectroscopy, is slow and inefficient in chitosan with CBD, even under high-energy UV sources. The research also included chitosan films with CBD cross-linked with dialdehyde starch (DAS). Using AFM microscopy and contact angle measurements, the morphology and surface properties of prepared chitosan films with CBD were investigated, respectively. It was found that CBD embedded in CS is characterized by the best photostability under the influence of an LED emitting long-wave radiation. Using a monochromatic and polychromatic UV lamp (HPK and UV-C) emitting high-energy radiation, gradual degradation accompanied by oxidation was observed, both in the CS chains and in the CBD additive. Additionally, changes in surface properties are observed during UV irradiation. It was concluded that CS protects CBD against photodegradation, and a further improvement in photochemical stability is achieved after system cross-linking with DAS.

Chitosan Composites Containing Boron-Dipyrromethene Derivatives for Biomedical Applications.

The work is devoted to preparing and characterizing the properties of photosensitive composites, based on chitosan proposed for photodynamic therapy. Chitosan films with a 5% addition of two BODIPY dyes were prepared by solution casting. These dyes are dipyrromethene boron derivatives with N-alkyl phthalimide substituent, differing in the presence of iodine atoms in positions 2 and 6 of the BODIPY core. The spectral properties of the obtained materials have been studied by infrared and UV-vis absorption spectroscopy and fluorescence, both in solutions and in a solid state. Surface properties were investigated using the contact angle measurement. The morphology of the sample has been characterized by Scanning Electron and Atomic Force Microscopy. Particular attention was paid to studying the protein absorption and kinetics of the dye release from the chitosan. Adding BODIPY to the chitosan matrix leads to a slight increase in hydrophilicity, higher structure heterogeneity, and roughness, than pure chitosan. The presence of iodine atoms in the BODIPY structure caused the bathochromic effect, but the emission quantum yield decreased in the composites. It has been found that BODIPY-doped chitosan interacts better with human serum albumin and acidic α-glycoprotein than unmodified chitosan. The release rate of dyes from films immersed in methanol depends on the iodine present in the structure.

Photochemical and Thermal Stability of Bionanocellulose/Poly(Vinyl Alcohol) Blends.

This research focuses on novel ecological materials for biomedical and cosmetic applications. The cellulose of bacterial origin is well suited for such purposes, but its functional properties must be modified. In this work, the blends of bionanocellulose and poly(vinyl alcohol), BNC/PVA, were prepared based on in situ and ex situ methodology combined with impregnation and sterilization, using different concentrations of PVA. The main purpose of this work was to check the influence of UV radiation and high temperature, which can be sterilizing factors, on the properties of these mixtures. It was found that the crystallinity degree increases in UV-irradiated samples due to the photodegradation of the amorphous phase. This changes the mechanical properties: the breaking stress and Young's modulus decreased, while the strain at break increased in most UV-irradiated samples. The surface morphology, which we observed by using AFM, did not change significantly after exposure, but the roughness and surface free energy changed irregularly in samples obtained by different methods. However, the effects induced by UV-irradiation were not so crucial as to deteriorate the materials' properties designed for medical applications. Thermogravimetric analysis exhibited good thermal stability for all samples up to at least 200 °C, which allows for the prediction of these systems also in industrial sectors.

Chitosan-Gelatin Films Cross-Linked with Dialdehyde Cellulose Nanocrystals as Potential Materials for Wound Dressings.

In this study, thin chitosan-gelatin biofilms cross-linked with dialdehyde cellulose nanocrystals for dressing materials were received. Two types of dialdehyde cellulose nanocrystals from fiber (DNCL) and microcrystalline cellulose (DAMC) were obtained by periodate oxidation. An ATR-FTIR analysis confirmed the selective oxidation of cellulose nanocrystals with the creation of a carbonyl group at 1724 cm-1. A higher degree of cross-linking was obtained in chitosan-gelatin biofilms with DNCL than with DAMC. An increasing amount of added cross-linkers resulted in a decrease in the apparent density value. The chitosan-gelatin biofilms cross-linked with DNCL exhibited a higher value of roughness parameters and antioxidant activity compared with materials cross-linked with DAMC. The cross-linking process improved the oxygen permeability and anti-inflammatory properties of both measurement series. Two samples cross-linked with DNCL achieved an ideal water vapor transition rate for wound dressings, CS-Gel with 10% and 15% addition of DNCL-8.60 and 9.60 mg/cm2/h, respectively. The swelling ability and interaction with human serum albumin (HSA) were improved for biofilms cross-linked with DAMC and DNCL. Significantly, the films cross-linked with DAMC were characterized by lower toxicity. These results confirmed that chitosan-gelatin biofilms cross-linked with DNCL and DAMC had improved properties for possible use in wound dressings.

Dialdehyde Starch Nanocrystals as a Novel Cross-Linker for Biomaterials Able to Interact with Human Serum Proteins.

In recent years, new cross-linkers from renewable resources have been sought to replace toxic synthetic compounds of this type. One of the most popular synthetic cross-linking agents used for biomedical applications is glutaraldehyde. However, the unreacted cross-linker can be released from the materials and cause cytotoxic effects. In the present work, dialdehyde starch nanocrystals (NDASs) were obtained from this polysaccharide nanocrystal form as an alternative to commonly used cross-linking agents. Then, 5-15% NDASs were used for chemical cross-linking of native chitosan (CS), gelatin (Gel), and a mixture of these two biopolymers (CS-Gel) via Schiff base reaction. The obtained materials, forming thin films, were characterized by ATR-FTIR, SEM, and XRD analysis. Thermal and mechanical properties were determined by TGA analysis and tensile testing. Moreover, all cross-linked biopolymers were also characterized by hydrophilic character, swelling ability, and protein absorption. The toxicity of obtained materials was tested using the Microtox test. Dialdehyde starch nanocrystals appear as a beneficial plant-derived cross-linking agent that allows obtaining cross-linked biopolymer materials with properties desirable for biomedical applications.

Thermal Stability of Fluorescent Chitosan Modified with Heterocyclic Aromatic Dyes.

Fluorescent biopolymer derivatives are increasingly used in biology and medicine, but their resistance to heat and UV radiation, which are sterilizing agents, is relatively unknown. In this work, chitosan (CS) modified by three different heterocyclic aromatic dyes based on benzimidazole, benzothiazole, and benzoxazole (assigned as IBm, BTh, and BOx) has been studied. The thermal properties of these CS derivatives have been determined using the Thermogravimetric Analysis coupled with the Fourier Transform Infrared spectroscopy of volatile degradation products. The influence of UV radiation on the thermal resistance of modified, fluorescent chitosan samples was also investigated. Based on the temperature onset as well as the decomposition temperatures at a maximal rate, IBm was found to be more thermally stable than BOx and BTh. However, this dye gave off the most volatile products (mainly water, ammonia, carbon oxides, and carbonyl/ether compounds). The substitution of dyes for chitosan changes its thermal stability slightly. Characteristic decomposition temperatures in modified CS vary by a few degrees (<10 °C) from the virgin sample. Considering the temperatures of the main decomposition stage, CS-BOx turned out to be the most stable. The UV irradiation of chitosan derivatives leads to minor changes in the thermal parameters and a decrease in the number of volatile degradation products. It was concluded that the obtained CS derivatives are characterized by good resistance to heat and UV irradiation, which extends the possibilities of using these innovative materials.

The Use of Chitosan and Starch-Based Flocculants for Filter Backwash Water Treatment.

Inorganic aluminum or iron salts supported with synthetic polymers are commonly used to eradicate colloidal particles from water in coagulation and flocculation processes. Nevertheless, these agents have several disadvantages, such as large volumes of sludge produced or environmental toxicity. Recently biodegradable polymers have been suggested as eco-friendly flocculants for water treatment. This study aimed to investigate the possibilities of using starch and chitosan and their oxidized derivatives as flocculants for filter backwash water treatment. Dialdehyde starch (DST) and dialdehyde chitosan (DCT) were synthesized by periodate oxidization of natural starch from corn and low molecular weight chitosan. The obtained materials have been characterized with scanning electron microscopy (SEM), ATR-FTIR spectroscopy, and thermogravimetric analysis (TGA). Furthermore, we studied the flocculation properties of polysaccharide flocculants in a series of jar tests. The effectiveness of chitosan and starched-based flocculants was compared to synthetic polymers commonly used to treat iron ions-rich filter backwash water. The environmental aspects of these chemicals, particularly the biodegradability of post-flocculation residues, were also addressed. It was found that oxidized starch and chitosan derivatives can be used as ecological flocculating materials to treat potable water or sludge.

Bionanocellulose/Poly(Vinyl Alcohol) Composites Produced by In-Situ Method and Ex-Situ/Impregnation or Sterilization Methods.

The purpose of the work was to obtain composites based on bionanocellulose (BNC) and poly(vinyl alcohol) (PVA) for specific biomedical and cosmetic applications and to determine how the method and conditions of their preparation affect their utility properties. Three different ways of manufacturing these composites (in-situ method and ex-situ methods combined with sterilization or impregnation) were presented. The structure and morphology of BNC/PVA composites were studied by ATR-FTIR spectroscopy and scanning microscopy (SEM, AFM). Surface properties were tested by contact angle measurements. The degree of crystallinity of the BNC fibrils was determined by means of the XRD method. The mechanical properties of the BNC/PVA films were examined using tensile tests and via the determination of their bursting strength. The water uptake of the obtained materials was determined through the gravimetric method. The results showed that PVA added to the nutrient medium caused an increase in biosynthesis yield. Moreover, an increase in base weight was observed in composites of all types due to the presence of PVA. The ex-situ composites revealed excellent water absorption capacity. The in-situ composites appeared to be the most durable and elastic materials.

Fluorescent Chitosan Modified with Heterocyclic Aromatic Dyes.

Chitosan is a valuable, functional, and biodegradable polysaccharide that can be modified to expand its applications. This work aimed to obtain chitosan derivatives with fluorescent properties. Three heterocyclic aromatic dyes (based on benzimidazole, benzoxazole, and benzothiazole) were synthesized and used for the chemical modification of chitosan. Emission spectroscopy revealed the strong fluorescent properties of the obtained chitosan derivatives even at a low N-substitution degree of the dye. The effect of high-energy ultraviolet radiation (UV-C) on modified chitosan samples was studied in solution with UV-Vis spectroscopy and in the solid state with FTIR spectroscopy. Moreover, cytotoxicity towards three different cell types was evaluated to estimate the possibilities of biomedical applications of such fluorescent chitosan-based materials. It was found that the three new derivatives of chitosan were characterized by good resistance to UV-C, which suggests the possibility of using these materials in medicine and various industrial sectors.

Measured and predicted freeze-thaw days frequencies in climate change conditions in central Poland.

The rate of progression of geomorphological phenomena is greatly influenced by freeze-thaw processes. In the face of air temperature increasing over the past few decades, a question of the future impact of these processes arises, notably in the temperate and cold climate zones. Using the mean, maximum and minimum daily air temperature data in the period 1951-2018 obtained from three weather stations located in the vicinity of Jeziorsko reservoir (central Poland), we have determined the mathematical correlation, described with a polynomial function, between the mean monthly air temperature and the monthly number of freeze-thaw days (FTD). A freeze-thaw day is a day when the maximum air temperature is above 0 °C while the minimum air temperature equals or is below this threshold. The number of FTDs within the study area averaged 64-71 and demonstrated a downward trend of 2-4 FTDs/10 years. The study period (1951-2018), includes a clearly marked distinct sub-period (1991-2018), when the reservoir was in operation, which experienced 58-68 FTDs. Considering the assumed rise in temperature, one should expect a further, though slightly slower, decline in the future number of FTDs. Depending on the accepted model of the temperature increase, which for the area of Poland (Central Europe) in the perspective of 30 years oscillates between +1.1 to +1.3 °C, the number of FTDs within the study area is expected to decline by -4.5 to -5.3 FTD, i.e. 6-7% and 5.4-5.5 FTD i.e. 8-9% respectively.

Corona Charging of Isotactic-Polypropylene Composites.

A new approach to obtaining piezoelectric polymeric films based on the isotactic-polypropylene (i-PP) using corona discharge with the energy of 45 W·min/m2 was presented. Detailed analyses with Atomic Force Microscopy (AFM) led to the conclusion that the surface quality was the important factor influencing the possibility of charging the i-PP composites, which was necessary to induce the permanent piezoelectric effect. It has been found that the high surface smoothness of the polymer films contributed to improved piezoelectric properties without the need for an additional polymer modification such as orientation, foaming or doping with fillers. The values of the piezoelectric constant, d33, of the studied samples were compared to these values for the analogous systems polarized with a constant electric field of 100 V/µm. The milder conditions of the film polarization during the corona discharge process are sufficient to achieve the electrets in i-PP films. The simple and cheap method proposed can be profitable in obtaining flexible electrets in the form of thin films for the production of personal biomedical sensors.

Chitosan as a Protective Matrix for the Squaraine Dye.

Chitosan was used as a protective matrix for the photosensitive dye-squaraine (2,4-bis[4-(dimethylamino)phenyl]cyclobutane-1,3-diol). The physicochemical properties of the obtained systems, both in solution and in a solid-state, were investigated. However, it was found that diluted chitosan solutions with a few percent additions of dye show an intense fluorescence, which is suppressed in the solid-state. This is related to the morphology of the heterogeneous modified chitosan films. The important advantage of using a biopolymer matrix is the prevention of dye degradation under the influence of high energy ultraviolet (UV) radiation while the dye presence improves the chitosan heat resistance. It is caused by mutual interactions between macromolecules and dye. Owing to the protective action of chitosan, the dye release in liquid medium is limited. Chitosan solutions with a few percent additions of squaraine can be used in biomedical imaging thanks to the ability to emit light, while chitosan films can be protective coatings resistant to high temperatures and UV radiation.

Cellular Polyolefin Composites as Piezoelectric Materials: Properties and Applications.

Piezoelectric polymers characterized by flexibility are sought for applications in microelectronics, medicine, telecommunications, and everyday devices. The objective of this work was to obtain piezoelectric polymeric composites with a cellular structure and to evaluate their usefulness in practice. Composites based on polyolefins (isotactic-polypropylene and polyethylene) with the addition of aluminosilicate fillers were manufactured by extrusion, and then polarized in a constant electric field at 100 V/µm. The content of mineral fillers up to 10 wt% in the polymer matrix enhances its electric stability and mechanical strength. The value of the piezoelectric coefficient d33 attained ~150 pC/N in the range of lower stresses and ~80 pC/N in the range of higher stresses, i.e., at ~120 kPa. The materials exhibited high durability in time, therefore, they can be used as transducers of mechanical energy of the human motion into electric energy. It was demonstrated that one shoe insert generates an energy of 1.1 mJ after a person walks for 300 s. The miniaturized integrated circuits based on polyolefin composites may be applied for the power supply of portable electronics. Due to their high sensitivity, they can be recommended for measuring the blood pulse.

Recent Achievements in Polymer Bio-Based Flocculants for Water Treatment.

Polymer flocculants are used to promote solid-liquid separation processes in potable water and wastewater treatment. Recently, bio-based flocculants have received a lot of attention due to their superior advantages over conventional synthetic polymers or inorganic agents. Among natural polymers, polysaccharides show many benefits such as biodegradability, non-toxicity, ability to undergo different chemical modifications, and wide accessibility from renewable sources. The following article provides an overview of bio-based flocculants and their potential application in water treatment, which may be an indication to look for safer alternatives compared to synthetic polymers. Based on the recent literature, a new approach in searching for biopolymer flocculants sources, flocculation mechanisms, test methods, and factors affecting this process are presented. Particular attention is paid to flocculants based on starch, cellulose, chitosan, and their derivatives because they are low-cost and ecological materials, accepted in industrial practice. New trends in water treatment technology, including biosynthetic polymers, nanobioflocculants, and stimulant-responsive flocculants are also considered.

N-Halamine Hydantoin-Containing Chitosan: Synthesis, Characterization, Thermal and Photolytic Stability Studies.

Current demand for new protective materials ensuring sterility is systematically growing. The purpose of this work was the synthesis of the biocidal N-halamine hydantoin-containing chitosan (CS-CMH-Cl) and characterization of its properties. The functionalization of the chitosan by 5-hydantoinacetic acid substitution leads to obtaining the CS-CMH polymer, which was chlorinated in next step to transform N-H into N-Cl bonds. In this study, the possibility of forming two biocidal N-Cl bonds in hydantoin ring, grafted onto chitosan chains, was proved. The structure and stability of the prepared material was confirmed by spectroscopic (FTIR, NMR, colorimetric test) and microscopic analyses (SEM, AFM). Surface properties were investigated based on contact-angle measurements. In addition, the thermal and photochemical stability of the obtained samples were determined as functional features, determining the range of potential use. It was found that both modified chitosan polymers (CS-CMH and CS-CMH-Cl) were characterized by the smaller thermal stability and more hydrophilic and rougher surface than unmodified CS. Photooxidative degradation of the obtained materials was observed mainly on the sample surface. After irradiation, the surfaces became more hydrophilic-especially in the case of the CS-CMH-Cl-which is advantageous from the point of view of the antibacterial properties. Antibacterial tests against S. aureus and E. coli confirmed the antibacterial activities of received CS-CMH-Cl material.

Crosslinking of Chitosan with Dialdehyde Chitosan as a New Approach for Biomedical Applications.

Materials based on natural high molecular compounds are particularly interesting for biomedical applications. It is known that the cross-linking agent used for preparation of biomacromolecule-based materials is as important as used biopolymer. Therefore, natural cross-linkers containing reactive carbonyl groups are of great interest especially for modifying properties of natural polysaccharides. One of the most popular cross-linking agents is glutaraldehyde. Nevertheless, the unreacted particles can be released from the cross-linked material and cause cytotoxic effects. This can be eliminated when using a cross-linker based e.g., on polysaccharides. This article describes quick and efficient synthesis of dialdehyde chitosan (DACS) and its application for the preparation of chitosan films. Materials obtained with different amount of DACS were fully characterized in terms of structure and surface morphology. Thermal and mechanical properties as well as hydrophilic character were also examined. The results obtained were compared with the materials obtained by cross-linking chitosan with low molecular weight glutaraldehyde and high molecular weight cross-linking agent based on polysaccharide-dialdehyde starch. Toxicity of all obtained materials was tested using the Microtox® test. It has been shown that due to better mechanical, thermal and surface properties as well as lower toxicity, dialdehyde chitosan is a very promising crosslinking agent.

Surface Studies of UV Irradiated Polypropylene Films Modified with Mineral Fillers Designed as Piezoelectric Materials.

Isotactic-polypropylene (i-PP) films with inorganic minerals such as Sillikolloid, perlite, or glass beads were prepared. The obtained polymeric films were subjected to an orientation process. Moreover, this paper includes results how the artificial accelerated weathering influences surface properties of the unoriented and oriented i-PP films with the mineral fillers. Changes in the ultraviolet (UV) treated polymeric films were studied with attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and by measuring contact angles. The results revealed that photooxidation of i-PP was more effective in the presence of the fillers and depended on the type of the filler but not on its amount. Moreover, the oriented samples experienced more effective photooxidation compared with the unoriented ones. In all studied samples the same photoproducts were detected, suggesting the same route of polymer photooxidation with and without the filler. These polymeric films were produced for potential applications in the devices in which piezoelectric effect can be used.

The role of freeze-thaw action in dam reservoir cliff degradation assessed by terrestrial laser scanning: A case study of Jeziorsko Reservoir (central Poland).

Cliff recession is a combined result of wave action in the shore zone and geomorphological processes in the transformed cliff. As several processes usually take place simultaneously or consecutively, so distinguishing between the impact of each one of them individually on cliff erosion is impossible. Jeziorsko Reservoir is characterized by large fluctuations of water level in the annual cycle (several metres), hence in winter, when the water level in the reservoir is the lowest, the exposed cliff is not directly influenced by wave erosion. Sediments resulting from freeze-thaw action are accumulated at the bluff toe. However, in early spring, when freeze-thaw processes are continued, the water level in the reservoir is elevated, reaching the bluff toe. Wave erosion in that period causes removal of the material accumulated at the bluff toe and, consequently, cliff degradation. These processes interact. In 2015, the normal water level in the reservoir was lowered by 0.5 m leaving the bluff toe unaffected by wave erosion also in spring and summer months. These conditions enabled us to distinguish between the effects inflicted by freeze-thaw action and other sub-aerial geomorphological processes and wave erosion on cliff recession. This paper summarizes a series of detailed terrestrial laser scanning (TLS) measurements of morphological changes in an active cliff developing in coherent deposits in the temperate zone, resulting from freeze-thaw processes. Field research was conducted in 2014-2015 and 2018. The results of this study indicate that in coherent deposits in the temperate zone freeze-thaw action plays an important role among sub-aerial geomorphological processes such as wetting and drying of the surface sediments, linear erosion or mass movements causing cliff recession.