A Comprehensive Strategy for Stepwise Design of a Lab PROTOTYPE for the Removal of Emerging Contaminants in Water Using Cyclodextrin Polymers as Adsorbent Material.

The significant environmental issue of water pollution caused by emerging contaminants underscores the imperative for developing novel cleanup methods that are efficient, economically viable, and that are intended to operate at high capacity and under continuous flows at the industrial scale. This study shows the results of the operational design to build a prototype for the retention at lab scale of pollutant residues in water by using as adsorbent material, insoluble polymers prepared by ß-cyclodextrin and epichlorohydrin as a cross-linking agent. Laboratory in-batch tests were run to find out the adsorbent performances against furosemide and hydrochlorothiazide as pollutant models. The initial evaluation concerning the dosage of adsorbent, pH levels, agitation, and concentration of pharmaceutical pollutants enabled us to identify the optimal conditions for conducting the subsequent experiments. The adsorption kinetic and the mechanisms involved were evaluated revealing that the experimental data perfectly fit the pseudo second-order model, with the adsorption process being mainly governed by chemisorption. With KF constant values of 0.044 (L/g) and 0.029 (L/g) for furosemide and hydrochlorothiazide, respectively, and the determination coefficient (R2) being higher than 0.9 for both compounds, Freundlich yielded the most favorable outcomes, suggesting that the adsorption process occurs on heterogeneous surfaces involving both chemisorption and physisorption processes. The maximum monolayer adsorption capacity (qmax) obtained by the Langmuir isotherm revealed a saturation of the ß-CDs-EPI polymer surface 1.45 times higher for furosemide (qmax = 1.282 mg/g) than hydrochlorothiazide (qmax = 0.844 mg/g). Based on these results, the sizing design and building of a lab-scale model were carried out, which in turn will be used later to evaluate its performance working in continuous flow in a real scenario.

Evaluation of the In Vitro Antimicrobial Efficacy against Staphylococcus aureus and epidermidis of a Novel 3D-Printed Degradable Drug Delivery System Based on Polycaprolactone/Chitosan/Vancomycin-Preclinical Study.

Acute and chronic bone infections, especially those caused by methicillin-resistant Staphylococcus aureus (MRSA), remains a major complication and therapeutic challenge. It is documented that local administration of vancomycin offers better results than the usual routes of administration (e.g., intravenous) when ischemic areas are present. In this work, we evaluate the antimicrobial efficacy against S. aureus and S. epidermidis of a novel hybrid 3D-printed scaffold based on polycaprolactone (PCL) and a chitosan (CS) hydrogel loaded with different vancomycin (Van) concentrations (1, 5, 10, 20%). Two cold plasma treatments were used to improve the adhesion of CS hydrogels to the PCL scaffolds by decreasing PCL hydrophobicity. Vancomycin release was measured by means of HPLC, and the biological response of ah-BM-MSCs growing in the presence of the scaffolds was evaluated in terms of cytotoxicity, proliferation, and osteogenic differentiation. The PCL/CS/Van scaffolds tested were found to be biocompatible, bioactive, and bactericide, as demonstrated by no cytotoxicity (LDH activity) or functional alteration (ALP activity, alizarin red staining) of the cultured cells and by bacterial inhibition. Our results suggest that the scaffolds developed would be excellent candidates for use in a wide range of biomedical fields such as drug delivery systems or tissue engineering applications.

Carvacrol and HP-ß-Cyclodextrin Complexes: Extensive Characterization and Potential Cytotoxic Effect in Human Colorectal Carcinoma Cells.

The aim of this study was to obtain solid carvacrol-cyclodextrin (CD) complexes for use in the pharmaceutical industry. To this end, the complexation of carvacrol at different pH values was studied in detail, to determine the type of CD and the reaction environment that supported the highest amount of encapsulated carvacrol. Evidence of the capability of hydroxypropyl-ß-cyclodextrins (HP-ß-CD) to form inclusion complexes with carvacrol (KC = 5042 ± 176 L mol-1) and more high complexation efficiency (2.824) was demonstrated for HP-ß-CDs using two different energy sources, ultrasound (US) (KC = 8129 ± 194 L mol-1 24 h) and microwave irradiation (MWI) (KC = 6909 ± 161 L mol-1), followed by spraying the resulting solution in a spray dryer. To confirm complex formation, the complexes were characterized using various instrumental methods to corroborate the carvacrol incorporation into the hydrophobic cavity of HP-ß-CD. The obtained carvacrol solid complexes were analyzed by 1H nuclear magnetic resonance (1H-NMR) and 2D nuclear magnetic resonance (ROSEY), differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and Fourier transform infrared spectroscopy (FTIR) characterization. The structures of the resulting complexes were also characterized by molecular modeling. Furthermore, 1 mM HP-ß-CD-carvacrol complex has been shown to reduce cell proliferation in HCT-116 colorectal cancer cells by 43%, much more than in a healthy lung fibroblast MRC-5 cell line (11%).

Removal of an Azo Dye from Wastewater through the Use of Two Technologies: Magnetic Cyclodextrin Polymers and Pulsed Light.

Water pollution by dyes is a huge environmental problem; there is a necessity to produce new decolorization methods that are effective, cost-attractive, and acceptable in industrial use. Magnetic cyclodextrin polymers offer the advantage of easy separation from the dye solution. In this work, the ß-CD-EPI-magnetic (ß-cyclodextrin-epichlorohydrin) polymer was synthesized, characterized, and tested for removal of the azo dye Direct Red 83:1 from water, and the fraction of non-adsorbed dye was degraded by an advanced oxidation process. The polymer was characterized in terms of the particle size distribution and surface morphology (FE-SEM), elemental analysis (EA), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), infrared spectrophotometry (IR), and X-ray powder diffraction (XRD). The reported results hint that 0.5 g and pH 5.0 were the best conditions to carry out both kinetic and isotherm models. A 30 min contact time was needed to reach equilibrium with a qmax of 32.0 mg/g. The results indicated that the pseudo-second-order and intraparticle diffusion models were involved in the assembly of Direct Red 83:1 onto the magnetic adsorbent. Regarding the isotherms discussed, the Freundlich model correctly reproduced the experimental data so that adsorption was confirmed to take place onto heterogeneous surfaces. The calculation of the thermodynamic parameters further demonstrates the spontaneous character of the adsorption phenomena (ΔG° = −27,556.9 J/mol) and endothermic phenomena (ΔH° = 8757.1 J/mol) at 25 °C. Furthermore, a good reusability of the polymer was evidenced after six cycles of regeneration, with a negligible decline in the adsorption extent (10%) regarding its initial capacity. Finally, the residual dye in solution after treatment with magnetic adsorbents was degraded by using an advanced oxidation process (AOP) with pulsed light and hydrogen peroxide (343 mg/L); >90% of the dye was degraded after receiving a fluence of 118 J/cm2; the discoloration followed a pseudo first-order kinetics where the degradation rate was 0.0196 cm2/J. The newly synthesized ß-CD-EPI-magnetic polymer exhibited good adsorption properties and separability from water which, when complemented with a pulsed light-AOP, may offer a good alternative to remove dyes such as Direct Red 83:1 from water. It allows for the reuse of both the polymer and the dye in the dyeing process.

Inactivation of Foodborne Viruses by UV Light: A Review.

Viruses on some foods can be inactivated by exposure to ultraviolet (UV) light. This green technology has little impact on product quality and, thus, could be used to increase food safety. While its bactericidal effect has been studied extensively, little is known about the viricidal effect of UV on foods. The mechanism of viral inactivation by UV results mainly from an alteration of the genetic material (DNA or RNA) within the viral capsid and, to a lesser extent, by modifying major and minor viral proteins of the capsid. In this review, we examine the potential of UV treatment as a means of inactivating viruses on food processing surfaces and different foods. The most common foodborne viruses and their laboratory surrogates; further explanation on the inactivation mechanism and its efficacy in water, liquid foods, meat products, fruits, and vegetables; and the prospects for the commercial application of this technology are discussed. Lastly, we describe UV's limitations and legislation surrounding its use. Based on our review of the literature, viral inactivation in water seems to be particularly effective. While consistent inactivation through turbid liquid food or the entire surface of irregular food matrices is more challenging, some treatments on different food matrices seem promising.

Potential of pulsed light technology for control of SARS-CoV-2 in hospital environments.

The emergence of the SARS-CoV-2 infection and its potential transmission through touching surfaces in clinical environments have impelled the use of conventional and novel methods of disinfection to prevent its spreading. Among the latter, pulsed light may be an effective, non-chemical decontamination alternative. Pulsed light technology inactivates microorganisms and viruses by using high intensity polychromatic light pulses, which degrades nucleic acids and proteins. This review describes this technology, compiles and critically analyzes the evidence about the virucidal efficacy of pulsed light technology with view on its potential use against SARS-CoV-2 in touching surfaces in health-care facilities. The efficacy of pulsed light proved against many different kind of viruses allows to conclude that is a suitable candidate to inactivate SARS-CoV-2 as long as the required fluence is applied and the appropriated exposure to contaminated surfaces is guaranteed.

Comprehensive Characterization of Linalool-HP-ß-Cyclodextrin Inclusion Complexes.

The objective of the present study is to obtain linalool- cyclodextrin (CDs) solid complexes for possible applications in the food industry. For this purpose, a detailed study of linalool complexation was carried out at different pH values, to optimize the type of CDs and reaction medium that support the highest quantity of encapsulated linalool. Once demonstrated the ability of hydroxypropyl-ß-cyclodextrin (HP-ß-CDs), to form inclusion complexes with linalool (KC = 921 ± 21 L mol-1) and given their greater complexation efficacy (6.788) at neutral pH, HP-ß-CDs were selected to produce solid inclusion complexes by using two different energy sources, ultrasounds and microwave irradiation, subsequently spraying the solutions obtained in the Spray Dryer. To provide scientific solidity to the experimental results, the complexes obtained were characterized by using different instrumental techniques in order to confirm the inclusion of linalool in the HP-ß-CDs hydrophobic cavity. The linalool solid complexes obtained were characterized by using 1H nuclear magnetic resonance (1H-NMR) and 2D nuclear magnetic resonance (ROSEY), differential scanning calorimetry, thermogravimetry and Fourier transform infrared spectrometry. Moreover, the structure of the complex obtained were also characterized by molecular modeling.

Synthesis of New Cyclodextrin-Based Adsorbents to Remove Direct Red 83:1.

Two cyclodextrins (CDs), γ- and hydroxypropyl (HP)-γ-CDs were used to synthesize new adsorbents by using epichlorohydrin (EPI) as cross-linking agent in order to remove Direct Red 83:1 (DR) from water. Both polymers were characterized in terms of Fourier spectroscopy, nuclear magnetic resonance, particle size distribution and thermogravimetric analysis. Experimental data for both polymers were well fitted to the pseudo-second order and intraparticle diffusion model, indicating that in the adsorption both chemical and physical interactions are essential in the removal of DR. Three different isotherm models were analyzed, concluding that γ-CDs-EPI followed the Temkin isotherm and HP-γ-CDs-EPI the Freundlich isotherm, these results suggested that the adsorption was happening onto heterogeneous surfaces. The results of the Gibbs free energy showed that the adsorption was spontaneous at room temperature. In order to eliminate the remaining dye after the polymer treatment, and advanced oxidation process (AOP) was considered, achieving more than 90% of removal combining both mechanisms.

Modelling the Inactivation and Possible Regrowth of Salmonella enterica Treated with Chlorophyllin-Chitosan Complex and Visible Light.

The study focuses on predictive modelling of inactivation of Salmonella enterica after treatment with chlorophyllin-chitosan complex and visible light. Salmonella cells were incubated with chlorophyllin-chitosan complex (0.001% chlorophyllin and 0.1% chitosan) for different times (5-60 min) and then illuminated with visible light (λ=405 nm, H e=38 J/cm2). Inactivation curves and post-treatment regrowth curves were built based on microbiological viability tests and data were fitted to ten inactivation and two regrowth models. The photoactivated complex reduced Salmonella population, which were unable to regrow. Weibull and Baranyi models were the best to describe the inactivation and regrowth kinetics respectively. In conclusion, data from the kinetic analysis and predictive modelling confirmed that photoactivated chlorophyllin-chitosan complex is a promising non-thermal approach for inactivation of Gram-negative pathogens, since no bacterial regrowth after treatment has been predicted.

A Smart Strategy to Improve t-Resveratrol Production in Grapevine Cells Treated with Cyclodextrin Polymers Coated with Magnetic Nanoparticles.

One of the most successfully procedures used to increase the production of t-resveratrol in Vitis vinifera suspension-cultured cells is the application of cyclodextrins (CDs) and methyl jasmonate (MJ) as elicitors. In particular, ß-CDs are characterized by their chemical structure which makes them special, not only by acting as elicitors, but also because they are compounds capable of trapping high added-value hydrophobic molecules such as t-resveratrol. However, the use of ß-CDs as elicitors increases the production costs of this compound, making their industrial exploitation economically unfeasible. Therefore, the development of ß-CDs recovery strategies is necessary to provide a viable solution to their industrial use. In this work, carboxymethylated and hydroxypropylated ß-CDs have been used to form polymers using epichlorohydrin (EPI) as a cross-linking agent. The polymers were coated to Fe3O4 nanoparticles and were jointly used with MJ to elicit V. vinifera suspension-cultured cells. Once elicitation experiments were finished, a magnet easily allowed the recovery of polymers, and t-resveratrol was extracted from them by using ethyl acetate. The results indicated that the production of t-resveratrol in the presence of free carboxymethyl-ß-CDs was much lower than that found in the presence of carboxymethyl-ß-cyclodextrins-EPI polymer coated magnetic nanoparticles. In addition, the maximal levels of t-resveratrol were found at 168 h of elicitation in the presence of 15 g/L hydroxypropyl-ß-CDs polymer coated magnetic nanoparticles and MJ, and non-t-resveratrol was found in the extracellular medium, indicating that all the t-resveratrol produced by the cells and secreted into the culture medium was trapped by the polymer and extracted from it. This work also showed that polymers can be regenerated and reused during three cycles of continuous elicitation since the induction and adsorption capacity of hydroxypropyl-ß-CDs polymer-coated magnetic nanoparticles after these cycles of elicitation remained high, allowing high concentrations of t-resveratrol to be obtained.

Egg By-Products as a Tool to Remove Direct Blue 78 Dye from Wastewater: Kinetic, Equilibrium Modeling, Thermodynamics and Desorption Properties.

Eggshell, a waste material from food manufacturing, can be used as a potential ecofriendly adsorbent for the elimination of textile dyes from water solutions. The adsorption process was evaluated varying factors such as initial dye load, contact time, pH, quantity of adsorbent, and temperature. The initial dye load (Direct Blue 78) was in the range of 25-300 mg/L. The kinetics of adsorption were analyzed using different models, such as pseudo-first-order, pseudo-second-order, and intraparticle diffusion model. Also, the experimental data at equilibrium were studied using Freundlich, Langmuir, and Temkin isotherms. The kinetics followed pseudo-second-order, then pseudo-first-order, and finally the model of intraparticle diffusion. The results obtained for data at equilibrium follow the order: Freundlich > Langmuir > Temkin. The adsorption equilibrium showed a maximum capacity of adsorption (qmax) of 13 mg/g at pH 5, and using 0.5 g of eggshell. Dye adsorption was enhanced with increasing temperatures. The thermodynamic study revealed the spontaneity and endothermic nature of the adsorption process. The desorption study shows that the eggshell could be reused in different adsorption/desorption cycles. A novel advanced oxidation process could degrade more than 95% of the dye. The results show that eggshell is a waste material useful to remove hazardous dyes from wastewater, which may alleviate the environmental impact of dyeing industries.

Effect of Thymol and Carvacrol Encapsulated in Hp-Β-Cyclodextrin by Two Inclusion Methods against Geotrichum citri-aurantii.

Geotrichum citri-aurantii causes sour rot in citrus fruits and is responsible for important economic losses during storage. However, the availability of chemical fungicides for the control of this pathogen is limited. Thus, the aim of this research was to evaluate the antifungal efficacy of thymol and carvacrol encapsulated in 2-hydroxylpropyl-beta-cyclodextrin (HP-ß-CD) (prepared by the microwave irradiation method [MW] and solubility method [S]) for inhibition of G. citri-aurantii using in vitro bioassays broth (micro and macrodilutions methods) and inoculated food testing. Both encapsulated thymol and carvacrol were shown to be effective for inhibiting G. citri-aurantii growth in in vitro assays. Thymol was more effective in inhibiting G. citri-aurantii, while better encapsulation was provided by MW. HP-ß-CD-thymol encapsulated by MW (HP-ß-CD-thymol-MW) showed the lowest 50% effective dose (ED50 = 1.16 mM), minimum inhibitory concentration (MIC = 5.06 mM), and minimum fungicide concentration (MFC = 52.6 mM). HP-ß-CD-thymol-MW was found highly effective in reducing the growth rate and mycelial growth inhibition. Finally, HP-ß-CD-thymol-MW and HP-ß-CD-carvacrol-MW showed a higher persistent effect than thymol and carvacrol in their natural form in inhibiting this fungus. Therefore, HP-ß-CD-thymol-MW could be a promising alternative to synthetic fungicides for controlling G. citri-aurantii, the causal agent of citrus sour rot. PRACTICAL APPLICATION: Encapsulated thymol and carvacrol in HP-ß-Cyclodextrins are effective for controlling G. citri-aurantii in in vitro experiments. Encapsulation of thymol and carvacrol by microwave irradiation method (MW) was more effective than the solubility (S) method. Thymol was more effective than carvacrol, and the best results on G. citri-auriantii inhibition were achieved using the HP-ß-CD-thymol-MW method (which gave the lowest ED50 , MIC, and MFC).

Thorough characterization and stability of HP-ß-cyclodextrin thymol inclusion complexes prepared by microwave technology: A required approach to a successful application in food industry.

BACKGROUND: The aims of the present study were to obtain a stable dry powder formulation of cyclodextrins (CDs) encapsulating thymol, for successful use as an ingredient on an industrial scale, and to characterize the thymol-CDs complexes using different techniques. RESULTS: Thymol was successfully solubilized in aqueous solutions and the Kc value increased with the pH of the media until the pH was neutral, giving the highest values (2583 ± 176 L mol-1 ) for HP-ß-cyclodextrins (HP-ß-CDs). The best encapsulation efficiency of thymol in solid complexes was obtained using the microwave (MWI) encapsulation method. The different characterization techniques have demonstrated the affinity of HP-ß-CDs for thymol molecules, forming stable complexes. CONCLUSIONS: The results support the use of the MWI method in the preparation of solid HP-ß-CD-thymol complexes, due to greater encapsulation efficiency and technological and economic advantages for industrial applications. © 2018 Society of Chemical Industry.