Processing of Thin Films Based on Cellulose Nanocrystals and Biodegradable Polymers by Space-Confined Solvent Vapor Annealing and Morphological Characteristics.

L-poly(lactic acid), poly(3-hydroxybutyrate), and poly-hydroxybutyrate-co-hydroxyvalerate are biodegradable polymers that can be obtained from renewable biomass sources. The aim of this study was to develop three types of environmentally friendly film biocomposites of altered microstructure by combining each of the above-mentioned polymers with cellulose nanocrystal fillers and further processing the resulting materials via space-confined solvent vapor annealing. Cellulose was previously obtained from renewable biomass and further converted to cellulose nanocrystals by hydrolysis with the lactic acid. The solutions of biodegradable polymers were spin-coated onto solid substrates before and after the addition of cellulose nanocrystals. The obtained thin film composites were further processed via space-confined solvent vapor annealing to eventually favor their crystallization and, thus, to alter the final microstructure. Indeed, atomic force microscopy studies have revealed that the presence of cellulose nanocrystals within a biodegradable polymer matrix promoted the formation of large crystalline structures exhibiting fractal-, spherulitic- or needle-like morphologies.

Potential Role of GGBS and ACBFS Blast Furnace Slag at 90 Days for Application in Rigid Concrete Pavements.

Incorporating blast furnace slag into the composition of paving concrete can be one of the cost-effective ways to completely eliminate by-products from the pig iron production process (approximately 70% granulated slag and 30% air-cooled slag). The possibility to reintroduce blast furnace slag back into the life cycle will provide significant support to current environmental concerns and the clearance of tailings landfills. Especially in recent years, granulated and ground blast furnace slag (GGBS) as a substitute for cement and air-cooled blast furnace slag (ACBFS) aggregates as a substitute for natural aggregates in the composition of concretes have been studied by many researchers. But concrete compositions with large amounts of incorporated blast furnace slag affect the mechanical and durability properties through the interaction between the slag, cement and water depending on the curing times. This study focuses on identifying the optimal proportions of GGBS as a supplementary cementitious material (SCM) and ACBFS aggregates as a substitute to natural sand such that the performance at 90 days of curing the concrete is similar to that of the control concrete. In addition, to minimize the costs associated with grinding GGBS, the hydration activity index (HAI) of the GGBS, the surface morphology, and the mineral components were analyzed via X-ray diffraction, scanning electron microscopy (SEM), energy dispersive spectrometry (EDX), and nuclear magnetic resonance relaxometry (NMR). The flexural strength, the basic mechanical property of road concretes, increased from 28 to 90 days by 20.72% and 20.26% for the slag concrete but by 18.58% for the reference concrete. The composite with 15% GGBS and 25% ACBFS achieved results similar to the reference concrete at 90 days; therefore, they are considered optimal percentages to replace cement and natural sand in ecological pavement concretes. The HAI of the slag powder with a specific surface area equivalent to that of Portland cement fell into strength class 80 at the age of 28 days, but at the age of 90 days, the strength class was 100. The results of this research present three important benefits: the first is the protection of the environment through the recycling of two steel industry wastes that complies with European circular economy regulations, and the second is linked to the consequent savings in the disposal costs associated with wastefully occupied warehouses and the savings in slag grinding.

Developing Innovative Cement Composites Containing Vine Shoot Waste and Superplasticizers.

The expansion of the construction industry requires large quantities of construction materials; therefore, the utilization of alternative raw materials that reduce the environmental impact and enhance the quality of the construction materials has received increasing interest. The comparative performance of 1% Dynamon SR3 or Dynamon SR41 superplasticizers on the properties of cement paste with 1 wt.% vine shoot waste addition (VSW) was investigated after 28 days using Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and solid-state 27Al and 29Si nuclear magnetic resonance (NMR) spectroscopy. VSW does not delay the formation of calcium hydroxide and C-S-H and a slight decrease of the -OH band in samples containing superplasticizers, suggesting that free lime is converted to carbonates. The highest degree of crystallinity was remarked for the samples with superplasticizers. The structure of the cement paste with VSW and superplasticizers was corroborated with mechanical properties, showing increased strength in using VSW and superplasticizers. The results showed that adding 1% VSW and superplasticizers does not change the performance of the cement paste but reduces the water-cement ratio. The combination of VSW and superplasticizers led to cement composite with improved structural and mechanical properties suitable for construction.

Simulated Gastrointestinal Digestion of Nutritive Raw Bars: Assessment of Nutrient Bioavailability.

Raw bars have become popular among health-conscious consumers due to their nutrient-dense ingredients and lack of additives and preservatives. However, the effect of simulated gastrointestinal digestion on the nutrient content of these bars has yet to be extensively studied. In this study, four different raw bar recipes were subjected to simulated gastrointestinal digestion to evaluate the impact on their nutrient content. The recipes have dates and almond flour as base ingredients and specific ingredients such as Maca root powder, Ginger powder, Aronia powder, Pollen, Propolis extract, Astragalus powder, and Cacao powder. These variations were intended to provide diverse flavors and potential health benefits to cater to different preferences and needs. The in vitro digestion model was designed to mimic the conditions of the human gastrointestinal tract, including the mouth, stomach, and small intestine. The results showed that the simulated gastrointestinal digestion significantly impacted the nutrient content of the bars, with varying degrees of nutrient loss observed depending on the recipe. The highest phenolic content and antioxidant activity were observed in the salivary phase for all samples. Vitamin B content generally decreases from the salivary to the intestinal stage. After digestion, the recovery rates of total phenols, antioxidant capacity, and vitamins B1, B3, and B6 varied across the recipes. The recovery rates of vitamins B1, B3, and B6 were generally high across all recipes, indicating their stability and retention during digestion. The findings suggest that simulated GI digestion provides insights into the nutrient bioavailability of raw bars. These results can inform the formulation and optimization of raw bars to enhance nutrient absorption and nutritional value. Further research is warranted to investigate the effects of different processing techniques and ingredient combinations on nutrient bioavailability.

L-Poly(lactic acid) Production by Microwave Irradiation of Lactic Acid Obtained from Lignocellulosic Wastes.

L-polylactic acid (PLA), a semi-crystalline aliphatic polyester, is one of the most manufactured biodegradable plastics worldwide. The objective of the study was to obtain L-polylactic acid (PLA) from lignocellulosic plum biomass. Initially, the biomass was processed via pressurized hot water pretreatment at a temperature of 180 °C for 30 min at 10 MPa for carbohydrate separation. Cellulase and the beta-glucosidase enzymes were then added, and the mixture was fermented with Lacticaseibacillus rhamnosus ATCC 7469. The resulting lactic acid was concentrated and purified after ammonium sulphate and n-butanol extraction. The productivity of L-lactic acid was 2.04 ± 0.18 g/L/h. Then, the PLA was synthesized in two stages. Firstly, lactic acid was subjected to azeotropic dehydration at 140 °C for 24 h in the presence of xylene, using SnCl2 (0.4 wt.%) as a catalyst, resulting in lactide (CPLA). Secondly, microwave-assisted polymerization was carried out at 140 °C for 30 min with 0.4 wt.% SnCl2. The resulting powder was purified with methanol to produce PLA with 92.1% yield. The obtained PLA was confirmed using electrospray ionization mass spectrometry, nuclear magnetic resonance, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. Overall, the resulting PLA can successfully replace the traditional synthetic polymers used in the packaging industry.

Structural Characterization of Several Cement-Based Materials Containing Chemical Additives with Potential Application in Additive Manufacturing.

The rapid increase in additive manufacturing applications in all industries has highlighted the lack of innovative technologies and processes in the construction industry. Several European and international policies are in place to guide the development of the technological processes involved in the construction industry toward a sustainable future. Considering the global concerns regarding this industry, the purpose of this study was to develop new cement-based materials that are capable of accelerated hydration and early strength development for use in additive manufacturing. Ca(NO3)2·4H2O, Al2(SO4)3·18H2O and Na2S2O3·5H2O were used to obtain the accelerating effect in the hydration of Portland cement. Based on results obtained from X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM/EDX) techniques, as well as low-field nuclear magnetic resonance relaxometry (LF-NMR) techniques, it was demonstrated that all accelerators used have a quickening effect on cement hydration. The addition of Na2S2O3·5H2O or combined Na2S2O3·5H2O and Ca(NO3)2·4H2O led to obtaining new cement-based materials with early strength development and fast hydration of microorganized internal structures, critical characteristics for 3D printing.

The Influence of Blast Furnace Slag on Cement Concrete Road by Microstructure Characterization and Assessment of Physical-Mechanical Resistances at 150/480 Days.

The results presented in this paper on the appropriateness of using of blast furnace slag (BFS) in the composition of roads make an original contribution to the development of sustainable materials with the aim to reduce the carbon footprint and the consumption of natural resources. The novelty of this work consists of determining the optimal percentage of BSF in road concrete, in order to: increase mechanical resistances, reduce contractions in the hardening process, and ensure increased corrosion resistances, even superior to classic cement-based mixtures. Thus, the physical-mechanical characteristics and the microstructure of some road concretes were studied in the laboratory for three different recipes. We kept the same amount of ground granulated blast furnace slag (GGBS) as a substitute for Portland cement, respectively three percentages of 20%, 40%, 60% air-cooled blast furnace slag (ACBFS) and crushed as sand substitute from now on called S54/20, S54/40, S54/60. Drying shrinkage, mechanical resistances, carbonation-induced corrosion, microstructure characterization of hardened concretes, and degree of crystallinity by SEM and XRD measurements were analyzed after a longer curing period of 150/480 days. The obtained results on the three BSF mixtures indicated a reduction of drying shrinkage and implicitly increased the tensile resistance by bending to 150 days well above the level of the blank composition. The degree of crystallinity and the content of the majority phases of the mineralogical compounds, albites, quartz, and tobermorite out of the three BSF samples justifies the increase in the compressive strengths at the age of 480 days in comparison with the test samples. Scanning electron microscope (SEM) and X-ray diffraction measurements showed the highest compactness and lowest portlandite crystal content for the S54/20 slag composite. Future research concerns are the realization of experimental sections in situ, the study of the influence of BFS on the elasticity module of road concrete, and the opportunity to use other green materials that can contribute to the reduction of the carbon footprint, keeping the physical and mechanical properties of road concrete at a high level.

In Vitro Studies Demonstrate Antitumor Activity of Vanadium Ions from a CaO-P2O5-CaF2:V2O5 Glass System in Human Cancer Cell Lines A375, A2780, and Caco-2.

In this research, we investigated the structural and biological properties of phosphate glasses (PGs) after the addition of V2O5. A xV2O5∙(100 − x)[CaF2∙3P2O5∙CaO] glass system with 0 ≤ x ≤ 16 mol% was synthesized via a conventional melt-quenching technique. Several analysis techniques (dissolution tests, pH, SEM-EDS, FT-IR, and EPR) were used to obtain new experimental data regarding the structural behavior of the system. In vitro tests were conducted to assess the antitumor character of V2O5-doped glass (x = 16 mol%) compared to the matrix (x = 0 mol%) and control (CTRL-) using several tumoral cell lines (A375, A2780, and Caco-2). The characterization of PGs showed an overall dissolution rate of over 90% for all vitreous samples (M and V1−V7) and the high reactivity of this system. EPR revealed a well-resolved hyperfine structure (hfs) typical of vanadyl ions in a C4v symmetry. FT-IR spectra showed the presence of all structural units expected for P2O5, as well as very clear depolymerization of the vitreous network induced by V2O5. The MTT assay indicated that the viability of tumor cells treated with V7-glass extract was reduced to 50% when the highest concentration was used (10 µg/mL) compared to the matrix treatment (which showed no cytotoxic effect at any concentration). Moreover, the matrix treatment (without V2O5) provided an optimal environment for tumor cell attachment and proliferation. In conclusion, the two types of treatment investigated herein were proven to be very different from a statistical point of view (p < 0.01), and the in vitro studies clearly underline the cytotoxic potential of vanadium ions from phosphate glass (V7) as an antitumor agent.

The Potential Application of Natural Clinoptilolite-Rich Zeolite as Support for Bacterial Community Formation for Wastewater Treatment.

The aim of this study was to investigate the use of natural zeolite as support for microbial community formation during wastewater treatment. Scanning electron microscopy (SEM), thermal decomposition and differential thermogravimetric curves (TGA/DGT) techniques were used for the physicochemical and structural characterization of zeolites. The chemical characterization of wastewater was performed before and after treatment, after 30 days of using stationary zeolite as support. The chemical composition of wastewater was evaluated in terms of the products of nitrification/denitrification processes. The greatest ammonium (NH4+) adsorption was obtained for wastewater contaminated with different concentrations of ammonium, nitrate and nitrite. The wastewater quality index (WWQI) was determined to assess the effluent quality and the efficiency of the treatment plant used, showing a maximum of 71% quality improvement, thus suggesting that the treated wastewater could be discharged into aquatic environments. After 30 days, NH4+ demonstrated a high removal efficiency (higher than 98%), while NO3+ and NO2+ had a removal efficiency of 70% and 54%, respectively. The removal efficiency for metals was observed as follows (%): Mn > Cd > Cr > Zn > Fe > Ni > Co > Cu > Ba > Pb > Sr. Analysis of the microbial diversity in the zeolite samples indicated that the bacteria are formed due to the existence of nutrients in wastewater which favor their formation. In addition, the zeolite was characterized by SEM and the results indicated that the zeolite acts as an adsorbent for the pollutants and, moreover, as a support material for microbial community formation under optimal conditions. Comparing the two studied zeolites, NZ1 (particle size 1−3 mm) was found to be more suitable for wastewater treatment. Overall, the natural zeolite demonstrated high potential for pollutant removal and biomass support for bacteria community growth in wastewater treatment.

Freeze-Thaw Effect on Road Concrete Containing Blast Furnace Slag: NMR Relaxometry Investigations.

The present work investigates the effect of freeze-thaw cycles on the porosity of three mixtures of road concrete containing blast furnace slag in comparison with two mixtures made with conventional materials. The main technique used in our investigations is nuclear magnetic resonance (NMR) relaxometry. This permitted the extraction of information with respect to the freeze-thaw effect on pore-size distribution, which influences both the mechanical strength and the molecular transport through the material. Moreover, by using this technique, the structure of the air voids was analyzed for the entire pore system in the cement paste and the aggregate particles. The samples under study were first dried in a vacuum oven and then saturated with water or cyclohexane where the distribution of the transverse relaxation times of the protons was recorded. The NMR relaxation measurements were performed on samples extracted from specimens maintained at 300 freeze-thaw cycles and on control samples extracted from specimens kept in water during the freeze-thaw period. Scanning Electron Microscopy (SEM) was used to analyze the microstructure of concrete samples in order to obtain information about the pore sizes and the distance between them. The results from the NMR relaxation measurements were consistent with those obtained by using standard techniques for determining the porosity and the freeze-thaw resistances. The investigations made it possible to establish the optimal composition of blast furnace slag that can be incorporated into road concrete compositions. This non-invasive technique can also complete standard techniques for assessing the porosity and the progress of internal cracks during the freeze-thaw test.

Determination of Three Chromium Textile Azo Dyes in Wastewater by SPE-LC-ESI(-)-MS/MS.

In the present work, a procedure to determine three textile azo dyes, chromium-complexes [Nylosan Dark Brown (NDB), Lanasyn Dark Brown (LDB), and Lanasyn Red (LR)], from wastewater using solid-phase extraction (SPE) followed by LC-electrospray ionization negative mode tandem mass spectrometry (LC-ESI(-)-MS/MS) has been developed. The extraction/concentration and recovery degree of these dyes from liquid matrices were done on Strata WAX/NH2 cartridges. The chromatographic separation was performed using a Luna C18 (2) 100Å column by isocratic elution with a methanol-acetonitrile-water (0.2% formic acid and 2 mM ammonium formate) mixture. The linearity, the LOD, and the LOQ were determined for each textile dye. The accuracy, the precision (intra- and inter-day), and the matrix effect were also performed for the validation of the developed procedure. These chromium-complex azo dyes often used in the dyeing process by a textile factory in Romania were monitored in the influent and effluent wastewater from a treatment plant situated in its area. Applying the developed SPE-LC-ESI(-)-MS/MS procedure, the following textile dyes were detected (ng/L) in the collected wastewater samples during a 24-h period: NDB 150.1, LDB 200.6, and LR 89.0-244.0 in influents and NDB 22.8, LDB 78.6, and LR 74.0 in effluents.