Highly Compressible, Superabsorbent, and Biocompatible Hybrid Cryogel Constructs Comprising Functionalized Chitosan and St. John's Wort Extract.

Biobased porous hydrogels enriched with phytocompounds-rich herbal extracts have aroused great interest in recent years, especially in healthcare. In this study, new macroporous hybrid cryogel constructs comprising thiourea-containing chitosan (CSTU) derivative and a Hypericum perforatum L. extract (HYPE), commonly known as St John's wort, were prepared by a facile one-pot ice-templating strategy. Benefiting from the strong interactions between the functional groups of the CSTU matrix and those of polyphenols in HYPE, the hybrid cryogels possess excellent liquid absorption capacity, mechanical resilience, antioxidant performance, and a broad spectrum of antibacterial activity simultaneously. Thus, owing to their design, the hybrid constructs exhibit an interconnected porous architecture with the ability to absorb over 33 and 136 times their dry weight, respectively, when contacted with a phosphate buffer solution (pH 7.4) and an acidic aqueous solution (pH 2). These cryogel constructs have extremely high compressive strengths ranging from 839 to 1045 kPa and withstand elevated strains of over 70% without developing fractures. Moreover, the water-swollen hybrid cryogels with the highest HYPE content revealed a complete and instant shape recovery after uniaxial compression. The incorporation of HYPE into CSTU cryogels enabled substantial improvement in scavenging reactive oxygen species and an expanded antibacterial spectrum toward multiple pathogens, including Gram-positive bacteria (Staphylococcus aureus and Staphylococcus epidermidis), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), and fungi (Candida albicans). Cell viability experiments demonstrated the cytocompatibility of the 3D cryogel constructs, which did not induce changes in the fibroblast morphology. This work showcases a simple and effective strategy to immobilize HYPE extracts on CSTU 3D networks, allowing the development of novel multifunctional platforms with promising potential in hemostasis, wound dressing, and dermal regeneration scaffolds.

Chitosan Sponges with Instantaneous Shape Recovery and Multistrain Antibacterial Activity for Controlled Release of Plant-Derived Polyphenols.

Biomass-derived materials with multiple features are seldom reported so far. Herein, new chitosan (CS) sponges with complementary functions for point-of-use healthcare applications were prepared by glutaraldehyde (GA) cross-linking and tested for antibacterial activity, antioxidant properties, and controlled delivery of plant-derived polyphenols. Their structural, morphological, and mechanical properties were thoroughly assessed by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and uniaxial compression measurements, respectively. The main features of sponges were modulated by varying the CS concentration, cross-linking ratio, and gelation conditions (either cryogelation or room-temperature gelation). They exhibited complete water-triggered shape recovery after compression, remarkable antibacterial properties against Gram-positive (Staphylococcus aureus (S. aureus), Listeria monocytogenes (L. monocytogenes)) and Gram-negative (Escherichia coli (E. coli), Salmonella typhimurium (S. typhimurium)) strains, as well as good radical scavenging activity. The release profile of a plant-derived polyphenol, namely curcumin (CCM), was investigated at 37 °C in simulated gastrointestinal media. It was found that CCM release was dependent on the composition and the preparation strategy of sponges. By linearly fitting the CCM kinetic release data from the CS sponges with the Korsmeyer-Peppas kinetic models, a pseudo-Fickian diffusion release mechanism was predicted.

Ion-Imprinted Polymeric Materials for Selective Adsorption of Heavy Metal Ions from Aqueous Solution.

The introduction of selective recognition sites toward certain heavy metal ions (HMIs) is a great challenge, which has a major role when the separation of species with similar physicochemical features is considered. In this context, ion-imprinted polymers (IIPs) developed based on the principle of molecular imprinting methodology, have emerged as an innovative solution. Recent advances in IIPs have shown that they exhibit higher selectivity coefficients than non-imprinted ones, which could support a large range of environmental applications starting from extraction and monitoring of HMIs to their detection and quantification. This review will emphasize the application of IIPs for selective removal of transition metal ions (including HMIs, precious metal ions, radionuclides, and rare earth metal ions) from aqueous solution by critically analyzing the most relevant literature studies from the last decade. In the first part of this review, the chemical components of IIPs, the main ion-imprinting technologies as well as the characterization methods used to evaluate the binding properties are briefly presented. In the second part, synthesis parameters, adsorption performance, and a descriptive analysis of solid phase extraction of heavy metal ions by various IIPs are provided.

Polysaccharide-Based Composite Hydrogels as Sustainable Materials for Removal of Pollutants from Wastewater.

Nowadays, pollution has become the main bottleneck towards sustainable technological development due to its detrimental implications in human and ecosystem health. Removal of pollutants from the surrounding environment is a hot research area worldwide; diverse technologies and materials are being continuously developed. To this end, bio-based composite hydrogels as sorbents have received extensive attention in recent years because of advantages such as high adsorptive capacity, controllable mechanical properties, cost effectiveness, and potential for upscaling in continuous flow installations. In this review, we aim to provide an up-to-date analysis of the literature on recent accomplishments in the design of polysaccharide-based composite hydrogels for removal of heavy metal ions, dyes, and oxyanions from wastewater. The correlation between the constituent polysaccharides (chitosan, cellulose, alginate, starch, pectin, pullulan, xanthan, salecan, etc.), engineered composition (presence of other organic and/or inorganic components), and sorption conditions on the removal performance of addressed pollutants will be carefully scrutinized. Particular attention will be paid to the sustainability aspects in the selected studies, particularly to composite selectivity and reusability, as well as to their use in fixed-bed columns and real wastewater applications.

National level adjustments to the challenges of the SARS-CoV2 pandemic on blood banking operations.

BACKGROUND: SARS-CoV2 causing coronavirus disease (COVID-19) is responsible for an unprecedented worldwide pandemic severely affecting all activities of societies including blood banking. We aimed to systematically collect key indicators in a nationally centralized blood banking system and to perform comparisons between 2020 and 2019. METHODS: Count data for January-December 2020 and 2019 were extracted from the integrated informatics system of Hungarian National Blood Transfusion Service and analyzed by simple graphics, tabulations, and statistics. RESULTS: Whole blood donation activity showed a highly significant decline due to a sharp decrease in field donations by an average fall of 24% (range:17%-28%) during March-May 2020 compared to identical period of 2019. A second, more moderate decline accompanied the second wave in late fall. The simultaneous increase in institutional donations did not counterbalance this decline. Donor exclusion rates fell significantly by an average of 1,1% (range:0.9%-1.6%) in the three spring lockdown-affected months. First-time and repeat donors showed decreased turn-out in larger proportions compared to highly repeat donors. Interestingly, among repeat and highly repeat donors, females showed less-pronounced declines compared to males while this was not observed among first-time donors. In June-September, a remarkable swing-back was observed among highly repeat female donors. Product utilization fell most notably for RBC (mean:26.2%) but also for PLT (mean:19.8%) and FFP (mean:24.3%) and showed a full recovery in June-September followed by a second decline. CONCLUSION: Trends and reaction patterns of blood banking reported by our study may be useful in future planning and adjustments of blood banking activities.

Preparation and Characterization of Semi-IPN Cryogels Based on Polyacrylamide and Poly(N,N-dimethylaminoethyl methacrylate); Functionalization of Carrier with Monochlorotriazinyl-ß-cyclodextrin and Release Kinetics of Curcumin.

Curcumin (CCM) is a natural hydrophobic polyphenol known for its numerous applications in the food industry as a colorant or jelly stabilizer, and in the pharmaceutical industry due to its anti-inflammatory, antibacterial, antioxidant, anti-cancer, and anti-Alzheimer properties. However, the large application of CCM is limited by its poor solubility in water and low stability. To enhance the bioavailability of CCM, and to protect it against the external degradation agents, a novel strategy, which consists in the preparation of semi-interpenetrating polymer networks, (s-IPNs) based on poly(N,N-dimethylaminoethyl methacrylate) entrapped in poly(acrylamide) networks, by a cryogelation technique, was developed in this work. All s-IPN cryogels were characterized by SEM, EDX, FTIR, and swelling at equilibrium as a function of pH. Functionalization of semi-IPN cryogel with monochlorotriazinyl-ß-cyclodextrin (MCT-ß-CD) led to IPN cryogel. The release profile of CCM from the composite cryogels was investigated at 37 °C, in pH 3. It was found that the cumulative release increased with the increase of the carrier hydrophobicity, as a result of increasing the cross-linking degree, the content and the molar mass of PDMAEMA. Fitting Higuchi, Korsmeyer-Peppas, and first order kinetic models on the CCM release profiles indicated the diffusion as the main driving force of drug release from the composite cryogels.

Trends in polysaccharide-based hydrogels and their role in enhancing the bioavailability and bioactivity of phytocompounds.

Over the years, polysaccharides such as chitosan, alginate, hyaluronic acid, k-carrageenan, xanthan gum, carboxymethyl cellulose, pectin, and starch, alone or in combination with proteins and/or synthetic polymers, have been used to engineer an extensive portfolio of hydrogels with remarkable features. The application of polysaccharide-based hydrogels has the potential to alleviate challenges related to bioavailability, solubility, stability, and targeted delivery of phytocompounds, contributing to the development of innovative and efficient drug delivery systems and functional food formulations. This review highlights the current knowledge acquired on the preparation, features and applications of polysaccharide/phytocompounds hydrogel-based hybrid systems in wound management, drug delivery, functional foods, and food industry. The structural, functional, and biological requirements of polysaccharides and phytocompounds on the overall performance of such hybrid systems, and their impact on the application domains are also discussed.

Self-Assembled Chitosan/Dialdehyde Carboxymethyl Cellulose Hydrogels: Preparation and Application in the Removal of Complex Fungicide Formulations from Aqueous Media.

Environmental contamination with pesticides occurs at a global scale as a result of prolonged usage and, therefore, their removal by low-cost and environmentally friendly systems is actively demanded. In this context, our study was directed to investigate the feasibility of using some self-assembled hydrogels, comprising chitosan (CS) and carboxymethylcellulose (CMC) or dialdehyde (DA)-CMC, for the removal of four complex fungicide formulations, namely Melody Compact (MC), Dithane (Dt), Curzate Manox (CM), and Cabrio®Top (CT). Porous CS/CMC and CS/DA-CMC hydrogels were prepared as discs by combining the semi-dissolution acidification sol-gel transition method with a freeze-drying approach. The obtained CS/CMC and CS/DA-CMC hydrogels were characterized by gel fraction yield, FTIR, SEM, swelling kinetics, and uniaxial compression tests. The batch-sorption studies indicated that the fungicides' removal efficiency (RE%) by the CS/CMC hydrogels was increased significantly with increasing sorbent doses reaching 94%, 93%, 66% and 48% for MC, Dt, CM and CT, respectively, at 0.2 g sorbent dose. The RE values were higher for the hydrogels prepared using DA-CMC than for those prepared using non-oxidized CMC when initial fungicide concentrations of 300 mg/L or 400 mg/L were used. Our results indicated that CS/DA-CMC hydrogels could be promising biosorbents for mitigating pesticide contamination of aqueous environments.

Feather-weight cryostructured thiourea-chitosan aerogels for highly efficient removal of heavy metal ions and bacterial pathogens.

Designing of economically feasible and recyclable polysaccharide-based materials with thiourea functional groups for removal of specific metal ions such as Ag(I), Au(I), Pb(II) or Hg(II) remains a major challenge for environmental applications. Here, we introduce ultra-lightweight thiourea-chitosan (CSTU) aerogels engineered by combining successive freeze-thawing cycles with covalent formaldehyde-mediated cross-linking and lyophilization. All aerogels exhibited outstanding low densities (0.0021-0.0103 g/cm3) and remarkable high specific surface areas (416.64-447.26 m2/g), outperforming the common polysaccharide-based aerogels. Benefitting from their superior structural features (honeycomb interconnected pores and high porosity), CSTU aerogels demonstrate fast sorption rates and excellent performance in sorption of heavy metal ions from highly-concentrated single or binary-component mixtures (1.11 mmol Ag (I)/g and 0.48 mmol Pb(II)/g). A remarkable recycling stability was observed after five sorption-desorption-regeneration cycles when the removal efficiency was up to 80 %. These results support the high potential of CSTU aerogels in the treatment of metal-containing wastewater. Moreover, the Ag(I)-loaded CSTU aerogels exhibited excellent antimicrobial properties against Escherichia coli and Staphylococcus aureus bacterial strains, the killing rate being around 100 %. This data points towards the potential application of developed aerogels in circular economy, by employing the spent Ag(I)-loaded aerogels in the biological decontamination of waters.

Ice-Templated and Cross-Linked Xanthan-Based Hydrogels: Towards Tailor-Made Properties.

The use of polysaccharides with good film-forming properties in food packaging systems is a promising area of research. Xanthan gum (XG), an extracellular polysaccharide, has many industrial uses, including as a common food additive (E415). It is an effective thickening agent, emulsifier, and stabilizer that prevents ingredients from separating. Nevertheless, XG-based polymer films have some disadvantages, such as poor mechanical properties and high hydrophilic features, which reduce their stability when exposed to moisture and create difficulties in processing and handling. Thus, the objective of this work was to stabilize a XG matrix by cross-linking it with glycerol diglycidyl ether, 1,4-butanediol diglycidyl ether, or epichlorohydrin below the freezing point of the reaction mixture. Cryogelation is an ecological, friendly, and versatile method of preparing biomaterials with improved physicochemical properties. Using this technique, XG-based cryogels were successfully prepared in the form of microspheres, monoliths, and films. The XG-based cryogels were characterized by FTIR, SEM, AFM, swelling kinetics, and compressive tests. A heterogeneous morphology with interconnected pores, with an average pore size depending on both the nature of the cross-linker and the cross-linking ratio, was found. The use of a larger amount of cross-linker led to both a much more compact structure of the pore walls and to a significant decrease in the average pore size. The uniaxial compression tests indicated that the XG-based cryogels cross-linked with 1,4-butanediol diglycidyl ether exhibited the best elasticity, sustaining maximum deformations of 97.67%, 90.10%, and 81.80%, respectively.

Analysis of Copper(II), Cobalt(II) and Iron(III) Sorption in Binary and Ternary Systems by Chitosan-Based Composite Sponges Obtained by Ice-Segregation Approach.

With the intensive industrial activity worldwide, water pollution by heavy metal ions (HMIs) has become a serious issue that requires strict and careful monitoring, as they are extremely toxic and can cause serious hazards to the environment and human health. Thus, the effective and efficient removal of HMIs still remains a challenge that needs to be solved. In this context, copper(II), cobalt(II) and iron(III) sorption by chitosan (CS)-based composite sponges was systematically investigated in binary and ternary systems. The composites sponges, formed into beads, consisting of ethylenediaminetetraacetic acid (EDTA)- or diethylenetriaminepentaacetic acid (DTPA)-functionalized CS, entrapping a natural zeolite (Z), were prepared through an ice-segregation technique. The HMI sorption performance of these cryogenically structured composite materials was assessed through batch experiments. The HMI sorption capacities of CSZ-EDTA and CSZ-DTPA composite sponges were compared to those of unmodified sorbents. The Fe(III) ions were mainly taken up when they were in two-component mixtures with Co(II) ions at pH 4, whereas Cu(II) ions were preferred when they were in two-component mixtures with Co(II) ions at pH 6. The recycling studies indicated almost unchanged removal efficiency for all CS-based composite sorbents even after the fifth cycle of sorption/desorption, supporting their remarkable chemical stability and recommending them for the treatment of HMI-containing wastewaters.

Physically cross-linked chitosan/dextrin cryogels entrapping Thymus vulgaris essential oil with enhanced mechanical, antioxidant and antifungal properties.

Herein, we entrapped Thymus vulgaris essential oil (EO) within the physically cross-linked sponge-like architecture of cryogels by ice template-assisted freeze-drying. Their 3D cryogenically-structured network was built through hydrogen bonding formed by blending two naturally-derived polysaccharides, chitosan and dextrin. The embedment of EOs within the cryogel matrix generates porous films with an increased elasticity that allows their fast shape recovery after full compression. Thus, the swollen EOs-loaded cryogel films exhibited an elastic modulus of 3.00 MPa, which is more than 40 times higher than that of polysaccharide films without EOs (an elastic modulus of only 0.07 MPa). In addition, the encapsulation of bioactive compounds endows the bio-based films with both antioxidant and antifungal properties, showing a radical scavenging activity of 65% and a zone inhibition diameter of 40 mm for Candida parapsilosis fungi. Our results recommend the entrapment of EOs into bio-based cryogel carriers as a straightforward approach to provide 'green' polysaccharide-based films having both improved physicochemical properties and remarkable antifungal activity.

Composite cryo-beads of chitosan reinforced with natural zeolites with remarkable elasticity and switching on/off selectivity for heavy metal ions.

Combining ion-imprinting technology with pH-dependent adsorptive features of acid- or salt-activated zeolites brings up the opportunity to develop composite polymer materials with 'desired' sorption properties and performances. In this respect, we present here Co2+-imprinted composite cryo-beads with switching on/off selectivity towards the template ions, engineered by selecting the appropriate zeolite-treatment conditions and/or controlling the initial sorption pH values. Co2+ chelating efficiency of all cryo-beads was investigated either at pH 4 or 6 depending on zeolite conditioning strategy. The maximum sorption capacity values of ion-imprinted cryo-beads were from about 5 up to 7 times higher compared with those of non-imprinted ones. Under competitive conditions (Cu2+, Ni2+, Fe2+ and Cd2+ ions), the change of pH value from 4 to 6 resulted in a remarkable quenching of Co2+ selectivity generated by the zeolite shift from the H+-form to the Na+-form. The presence of zeolites within cryogel matrix generated composites with outstanding elasticity that allows the instant recovery of gels after full compression. These results indicate that the cryogel-type composites can be successfully re-used in separation processes for several times without losing their features.

Removal of heavy metal ions from multi-component aqueous solutions by eco-friendly and low-cost composite sorbents with anisotropic pores.

Copper, nickel, zinc, chromium, and iron ions are the prevailing contaminants in the aqueous effluents resulting from the photo-etching industry. In this context, we investigate here the metal ion sorption performance of an ion-imprinted cryogel (IIC), consisting of low-cost materials coming from renewable resources, towards multi-component metal ion solutions. The IIC sorbent, which is based on a chitosan matrix embedding a natural zeolite, was synthesized using a straightforward strategy by coupling copper-imprinting and unidirectional ice-templating methods. As consequence, the 1D-orientation and the interconnectivity of flow-channels sustain the fast metal ion diffusion within the IIC anisotropic structure. The removal efficiency of IIC sorbent reached 50% after 30 min, and the sorption equilibrium was attained within 150 min. For assessing the successful formation of imprinted cavities with well-defined sizes controlled by the radius of copper ions used as template, selectivity studies were performed on binary, ternary, and five-component synthetic mixtures. The efficiency of IIC as sorbent was further evaluated on real-life aqueous effluents discharged from photo-etching processes; thus, an IIC dosage of 6 g L-1 was found to remove 98.89% of Cu2+, 94.56% of Fe3+, 91.67% of Ni2+, 92.24% of Zn2+, and 82.76% of Cr3+ ions from this type of industrial wastewaters.

Could the porous chitosan-based composite materials have a chance to a "NEW LIFE" after Cu(II) ion binding?

Currently, biosorption is considered a leading-edge environmentally-friendly method for the low-cost remediation of wastewaters contaminated with metal ions. However, the safe disposal of metal-loaded biosorbents is still a challenging issue. In this context, our major objective was to explore the possibility of "waste minimization" by reusing the metal-loaded biosorbents in further environmental applications, particularly into the oxidative catalysis of dyes. Thus, the decolourisation efficiency (DE) of Methyl Orange (MO) in aqueous solutions under ambient light using copper-imprinted chitosan-based composites in comparison to non-imprinted ones was investigated in this work. The MO degradation was established first in the absence of any co-catalyst, when a DE value of 95.3% was achieved by the ion-imprinted catalysts within 360 min of reaction, compared to only 67.4% attained by the non-imprinted ones. Under Fenton-like conditions, the apparent degradation rate constant was seventy times higher, the DE increasing within 40 min to about 98.6%, and 70.5% respectively, whereas the content of co-catalyst (H2O2) was significantly lowered compared to other reported studies. The straightforward preparation of copper-loaded composites, along with their excellent stability and high efficiency even after four consecutive reaction runs support our ion-imprinted systems as potential catalysts for dye removal by oxidative decolourisation treatments.

Chitosan-based ion-imprinted cryo-composites with excellent selectivity for copper ions.

An original strategy is proposed here to design chitosan-based ion-imprinted cryo-composites (II-CCs) with pre-organized recognition sites and tailored porous structure by combining ion-imprinting and ice-templating techniques. The cryo-composites showed a tube-like porous morphology with interconnected parallel micro-channels, the distance between the channel walls being around 15 µm. Both the entrapment of a natural zeolite and the presence of carboxylate groups, generated by partial hydrolysis of amide moieties, led to II-CCs with controlled swelling ratios (25-40 g/g, depending on pH) and enhanced overall chelating efficiency (260 mg Cu2+/g composite). To point out the importance of introducing Cu2+ recognition sites, sorption experiments using mixtures of Cu2+ and other competing ions (Co2+, Ni2+, Zn2+ or/and Pb2+) were also carried out. The higher values of selectivity coefficients obtained for the II-CCs compared to those of non-imprinted ones highlight the remarkable potential of our sorbents for decontamination of wastewaters and recycling of Cu2+ ions.

Analise da maturidade fetal no liquido amniotico e sua correlacao com as complicacoes perinatais nas formas graves das sindromes hipertensivas na gravidez / Correlation of fetal maturity analysis in the amniotic fluid and perinatal complications of severe hypertension in pregnancy

O objetivo deste estudo foi analise da maturidade fetal, atraves do estudo do liquido amniotico obtido pela amniocentese, e sua correlacao com as complicacoes neonatais nas formas graves das sindromes hipertensivas na gravidez. Foram estudadas, de forma retrospectiva, 91 amostras de liquido amniotico avaliando-se a maturidade fetal atraves do teste de Clements e contagem de celulas orangiofilas. Considerou-se maduro, quando teste de Clements foi positivo ate o terceiro tubo e/ou celulas orangiofilas maior ou igual a 10 por cento; intermediario, quando teste de Clements foi positivo ate o segundo tubo e contagem de celulas orangiofilas de 6 por cento a 9 por cento e imaturo quando teste de Clements foi positivo ate o primeiro tubo ou negativo e/ou positivo de celulas orangiofilas menor ou igual a 5 por cento...