A promising synthetic citric crosslinked ß-cyclodextrin derivative for antifungal drugs: Solubilization, cytotoxicity, and antifungal activity.

Effective antifungal therapy for the treatment of fungal keratitis requires a high drug concentration at the corneal surface. However, the use of natural ß-cyclodextrin (ßCD) in the preparation of aqueous eye drop formulations for treating fungal keratitis is limited by its low aqueous solubility. Here, we synthesized water-soluble anionic ßCD derivatives capable of forming water-soluble complexes and evaluated the solubility, cytotoxicity, and antifungal efficacy of drug prepared using the ßCD derivative. To achieve this, a citric acid crosslinked ßCD (polyCTR-ßCD) was successfully synthesized, and the aqueous solubilities of selected antifungal drugs, including voriconazole, miconazole (MCZ), itraconazole, and amphotericin B, in polyCTR-ßCD and analogous ßCD solutions were evaluated. Among the drugs tested, complexation of MCZ with polyCTR-ßCD (MCZ/polyCTR-ßCD) increased MCZ aqueous solubility by 95-fold compared with that of MCZ/ßCD. The inclusion complex formation of MCZ/ßCD and MCZ/polyCTR-ßCD was confirmed by spectroscopic techniques. Additionally, the nanoaggregates of saturated MCZ/polyCTR-ßCD and MCZ/ßCD solutions were observed using dynamic light scattering and transmission electron microscopy. Moreover, MCZ/polyCTR-ßCD solution exhibited good mucoadhesion, sustained drug release, and high drug permeation of porcine cornea ex vivo. Hen's Egg test-chorioallantoic membrane assay and cell viability study using Statens Seruminstitut Rabbit Cornea cell line showed that both MCZ/polyCTR-ßCD and MCZ/ßCD exhibited no sign of irritation and non-toxic to cell line. Additionally, antifungal activity evaluation demonstrated that all isolated fungi, including Candida albicans, Aspergillus flavus, and Fusarium solani, were susceptible to MCZ/polyCTR-ßCD. Overall, the results showed that polyCTR-ßCD could be a promising nanocarrier for the ocular delivery of MCZ.

The Use of New Waste-Based Plasticizer Made from Modified Used Palm Oil for Non-Glutinous Thermoplastic Starch Foam.

A novel waste-based plasticizer derived from modified used palm oil (mUPO) was successfully developed and has been used as a new plasticizer to non-glutinous thermoplastic starch foam to improve their properties. The molecular weight and hydroxyl number of the mUPO was 3150 g/mol and 192.19 mgOH/g, respectively. The effects of mUPO content ranging from 0 to 9 phr were investigated. The results revealed that the optimal mUPO content as an additive was 6 wt%. The addition of mUPO had a direct effect on the mechanical properties and thermal properties. The impact strength increased from 1.30 to 4.55 J/m, while the glass transition temperature (Tg) decreased from 70.83 to 66.50 °C by increasing mUPO from 0 phr to 6 phr in the thermoplastic starch foam. The mUPO, on the other hand, has also the potential to reduce shrinkage from 33.91 to 21.77% and moisture absorption from 5.93 to 1.73% by increasing the content from 0 phr to 6 phr in starch foam. Furthermore, the mUPO helps the forming of the foam structure as measured by SEM, and the mUPO utilization of waste-based material could be a promising green alternative plasticizer for starch components, especially starch foam applications.

Cotton Cord Coated with Cyclodextrin Polymers for Paraquat Removal from Water.

The contamination of hazardous agrochemical substances in water caused essential trouble for humans and the environment. The functional textile was used as an effective adsorbent for paraquat removal from an aqueous solution. The coating of anionic cyclodextrin polymer, issued from the cross-linking between 1,2,3,4-butanetetracarboxylic acid and ß-cyclodextrin in the presence of poly (vinyl alcohol), on the cotton cord, was firstly investigated. Their physicochemical characteristics were also characterized by gravimetry, acid-base titration, ATR-FTIR, 13C NMR, TGA, and stereo-microscopy. The BDP5 system revealed 107.3% coating yield, 1.13 mmol/g COOH groups, and 95.1% paraquat removal for 25 mg/L of initial concentration. The pseudo-second-order model was appropriate for kinetics using 6 h of contact time. Langmuir isotherm was suitable with the maximum adsorption of 30.3 mg/g for paraquat adsorption. The weight loss was 10.7% and 7.8%, respectively, for water and 5% v/v of HCI in ethanol after 120 h of contact time. Finally, the reusability efficiency stayed at 88.9% after five regeneration.

Adsorption of Cationic Pollutants from Water by Cotton Rope Coated with Cyclodextrin Polymers.

The contamination from perilous organic compounds (pesticide and dyes) in water generates a significant problem for the environment and humans. A modified textile was prepared by a coating of anionic cyclodextrin polymer, obtained from the cross-linking between citric acid and ß-cyclodextrin in the presence of poly (vinyl alcohol), on the cotton cord for cationic pollutant removal from an aqueous solution. Its physicochemical properties were also characterized by gravimetry, titration, stereomicroscopy, SEM, TGA, 13C NMR, and ATR-FTIR. The CC2 system exhibited 79.2% coating yield, 1.12 mmol/g COOH groups, 91.3% paraquat (PQ) removal, 97.0% methylene blue (MB) removal, and 98.3% crystal violet (CV) removal for 25 mg/L of initial concentration. The kinetics was fitted to the pseudo-second-order model using 6 h of contact time. The isotherm was suitable for the Langmuir isotherm with a maximum adsorption of 26.9 mg/g (PQ), 23.7 mg/g (MB), and 30.3 mg/g (CV). After 120 h of contact time in water and 5% v/v of HCI in ethanol, the weight loss was 7.5% and 5.6%, respectively. Finally, the recyclability performance reached 84.8% (PQ), 95.2% (MB), and 96.9% (CV) after five reuses.

Performance Evaluation of Combined Hydrothermal-Mechanical Pretreatment of Lignocellulosic Biomass for Enzymatic Enhancement.

Pretreatment is a crucial process in a lignocellulosic biorefinery. Corncob is typically considered as a natural renewable carbon source to produce various bio-based products. This study aimed to evaluate the performance of the hydrothermal-mechanical pretreatment of corncob for biofuels and biochemical production. Corncob was first pretreated by liquid hot water (LHW) at different temperatures (140-180 °C) and duration (30, 60 min) and then subjected to centrifugal milling to produce bio-powders. To evaluate the performance of this combined pretreatment, the energy efficiency and waste generation were investigated. The results indicated that the maximum fermentable sugars (FS) were 0.488 g/g biomass obtained by LHW at 180 °C, 30 min. In order to evaluate the performance of this combined pretreatment, the energy efficiency and waste generation were 28.3 g of FS/kWh and 7.21 kg of waste/kg FS, respectively. These obtained results indicate that the combined hydrothermal-mechanical pretreatment was an effective pretreatment process to provide high energy efficiency and low waste generation to produce biofuels. In addition, the energy efficiency and waste generation will be useful indicators for process scaling-up into the industrial scale. This combined pretreatment could be a promising pretreatment technology for the production of biofuels and biochemicals from lignocellulosic valorization.

Adsorption of Cationic Contaminants by Cyclodextrin Nanosponges Cross-Linked with 1,2,3,4-Butanetetracarboxylic Acid and Poly(vinyl alcohol).

Cationic organic pollutants (dyes and pesticides) are mainly hydrosoluble and easily contaminate water and create a serious problem for biotic and abiotic species. The elimination of these dangerous contaminants from water was accomplished by adsorption using cyclodextrin nanosponges. These nanosponges were elaborated by the cross-linking between 1,2,3,4-butanetetracarboxylic acid and ß-cyclodextrin in the presence of poly(vinyl alcohol). Their physicochemical characteristics were characterized by gravimetry, acid-base titration, TGA, 13C NMR, ATR-FTIR, Raman, X-ray diffraction, and Stereomicroscopy. The BP5 nanosponges displayed 68.4% yield, 3.31 mmol/g COOH groups, 0.16 mmol/g ß-CD content, 54.2% swelling, 97.0% PQ removal, 96.7% SO removal, and 98.3% MG removal for 25 mg/L of initial concentration. The pseudo-second-order model was suitable for kinetics using 180 min of contact time. Langmuir isotherm was suitable for isotherm with the maximum adsorption of 120.5, 92.6, and 64.9 mg/g for paraquat (PQ), safranin (SO), and malachite green (MG) adsorption, respectively. Finally, the reusability performance after five regeneration times reached 94.1%, 91.6%, and 94.6% for PQ, SO, and MG adsorption, respectively.

Sustainable Rigid Polyurethane Foam from Wasted Palm Oil and Water Hyacinth Fiber Composite-A Green Sound-Absorbing Material.

A novel rigid sound-absorbing material made from used palm oil-based polyurethane foam (PUF) and water hyacinth fiber (WHF) composite was developed in this research. The NCO index was set at 100, while the WHF content was set at 1%wt with mesh sizes ranging from 80 to 20. The mechanical properties, the morphology, the flammability, and the sound absorption coefficient (SAC) of the PUF composite were all investigated. When the WHF size was reduced from 80 to 20, the compression strength of the PUF increased from 0.33 to 0.47 N/mm2. Furthermore, the use of small fiber size resulted in a smaller pore size of the PUF composite and improved the sound absorption and flammability. A feasible sound-absorbing material was a PUF composite with a WHF mesh size of 80 and an SAC value of 0.92. As a result, PUF derived from both water hyacinth and used palm oil could be a promising green alternative material for sound-absorbing applications.

Adsorption of Paraquat by Poly(Vinyl Alcohol)-Cyclodextrin Nanosponges.

The contamination of hydrosoluble pesticides in water could generate a serious problem for biotic and abiotic components. The removal of a hazardous agrochemical (paraquat) from water was achieved by adsorption processes using poly(vinyl alcohol)-cyclodextrin nanosponges, which were prepared with various formulations via the crosslinking between citric acid and ß-cyclodextrin in the presence of poly(vinyl alcohol). The physicochemical properties of nanosponges were also characterized by different techniques, such as gravimetry, thermogravimetry, microscopy (SEM and Stereo), spectroscopy (UV-visible, NMR, ATR-FTIR, and Raman), acid-base titration, BET surface area analysis, X-ray diffraction, and ion exchange capacity. The C10D-P2 nanosponges displayed 60.2% yield, 3.14 mmol/g COOH groups, 0.335 mmol/g ß-CD content, 96.4% swelling, 94.5% paraquat removal, 0.1766 m2 g-1 specific surface area, and 5.2 × 10-4 cm3 g-1 pore volume. The presence of particular peaks referring to specific functional groups on spectroscopic spectra confirmed the successful polycondensation on the reticulated nanosponges. The pseudo second-order model (with R2 = 0.9998) and Langmuir isotherm (with R2 = 0.9979) was suitable for kinetics and isotherm using 180 min of contact time and a pH of 6.5. The maximum adsorption capacity was calculated at 112.2 mg/g. Finally, the recyclability of these nanosponges was 90.3% of paraquat removal after five regeneration times.

Release-killing properties of a textile modified by a layer-by-layer coating based on two oppositely charged cyclodextrin polyelectrolytes.

Infections represent a major medical concern and have severe impact on the public health economy. Antimicrobial coatings represent one major solution and are the subject of many investigations in academic and industrial research. Polyelectrolyte multilayers (PEMs) consist in the step-by-step deposition of polyanions and polycations films on surfaces. The wide range of disposable polyelectrolytes makes this approach among the most versatile methods as it allows to design surfaces that prevent bacterial adhesion, and kill bacteria by contact or by releasing antibacterial agents. The present work focused on the release-killing effect of an active PEM coating of a polyethylene terephthalate (PET) textile support. This activity was obtained thanks to the PEM film build up using cationic and anionic polyelectrolytes both based on cyclodextrins (PCD- and PCD+) that provided a reservoir property and prolonged release of triclosan (TCS). To this effect, a PET non-woven preliminarily modified with carboxylate groups by applying a thermofixation process was then treated by dip-coating, alternating soaking cycles in cationic PCD+ and in anionic PCD- solutions. Samples coated with such PEM film were then loaded with TCS whose release was assessed in dynamic mode in a phosphate buffered saline solution (PBS) at 37 °C. In parallel, TCS/PCD+ and TCS/PCD- interactions were investigated by Nuclear Magnetic Resonance (NMR) and phase solubility study, and the biocide activity was assessed against S. aureus and E. coli. Finally, the present study has demonstrated that our PCD+/PCD- PEM system presented release-killing properties that supplement the contact-killing effect of this system that was reported in a previous paper.

Layer-by-layer coating of textile with two oppositely charged cyclodextrin polyelectrolytes for extended drug delivery.

The coating of a nonwoven textile by polyelectrolyte multilayer film (PEM) issued from cationic and anionic ß-cyclodextrin (ßCD) polyelectrolytes according to the layer-by-layer (LbL) technique was successfully attempted. The tert-butyl benzoic acid (TBBA) was used as drug model to evaluate the loading capacity and sustained release properties of this PEM system. The build-up of the multilayer assembly was monitored in situ by optical waveguide lightmode spectroscopy (OWLS) on the one hand, and was assessed by gravimetry on the other hand when applied onto the textile substrate. In parallel, the complexation study of TBBA with both CD polyelectrolytes was also investigated by nuclear magnetic resonance (NMR) and isothermal titration calorimetry (ITC). The influence of thermal crosslinking of the multilayered coating on its stability and on TBBA release kinetics in phosphate buffered saline (PBS) at 37°C was studied. Finally, biological and microbiological tests were performed to investigate the cytocompatibility and the intrisic antibacterial activity of multilayer assemblies. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1408-1424, 2016.

Cationic ß-cyclodextrin polymer applied to a dual cyclodextrin polyelectrolyte multilayer system.

A polyelectrolyte multilayer film (PEM) based on cationic and anionic ß-cyclodextrin polyelectrolytes was coated onto a textile substrate for future drug delivery purposes. We firstly synthesized a novel cationic ß-cyclodextrin polymer (polyEPG-CD) by crosslinking ß-cyclodextrin (ßCD) with epichlorohydrin (EP) under basic conditions, in the presence of glycidyltrimetrylammonium chloride (GTMAC) as cationizing group. The influence of preparation conditions has been investigated in order to preferably obtain a water soluble fraction whose charge density and molecular weights were optimal for the layer-by-layer (LbL) deposition process. The different cationic cyclodextrin polymers obtained were characterized by FTIR, NMR, colloidal titration, conductimetry, thermogravimetric analysis and size exclusion chromatography. Besides, the counterpart polyelectrolyte was a ß-cyclodextrin polymer crosslinked with citric acid, polyCTR-CD, whose synthesis and characterization have been previously reported. Finally we realized the Layer by Layer (LbL) build-up of the PEM coating onto the textile support, using the dip coating method, by alternatively soaking it in cationic polyEPG-CD and anionic polyCTR-CD solutions. This multilayer self-assembly was monitored by SEM, gravimetry and OWLS in function of both polyelectrolytes concentrations and ratios. Solutions parameters such as pH, ionic strenght were also discussed.

Build-up of an antimicrobial multilayer coating on a textile support based on a methylene blue-poly(cyclodextrin) complex.

The aim of this work was to develop an antibacterial multilayer coating activated with methylene blue (MB) and based on chitosan (CHT) and cyclodextrin polyelectrolyte (polyCD) onto a non-woven polyethylene terephthalate (PET) textile support. The MB-free and MB-loaded systems were built-up by applying the dip-coating technique, alternating soak cycles of the PET textile preliminarily modified with carboxylate groups in CHT and in polyCD or polyCD/MB complex solutions. The layer-by-layer assembly build-up was followed by optical waveguide lightmode spectroscopy on the one hand and by gravimetry once it was applied on the textile substrate on the other hand. Two chitosan grades were used, low molecular weight (CHT-L) and medium molecular weight (CHT-M). The influence of the molar ratio CD/MB in the polyCD solutions was varied and finally the system underwent a post reticulation with genipin. Such parameters influences were investigated with regard to the loading capacity in MB of the systems, the release kinetics profiles of MB in pure water, phosphate buffer and MEM media, and the degradation of the self-assembled coating in the same media. Finally, biological and microbiological tests were performed to demonstrate the cytocompatibility of the systems and their ability to display a sustained antibacterial effect of the device through the MB prolonged release.

Multilayered textile coating based on a ß-cyclodextrin polyelectrolyte for the controlled release of drugs.

The aim of this work was to develop the formation of multilayered coating incorporating a cyclodextrin polyelectrolyte onto a non-woven polyethylene terephthalate (PET) textile support in order to obtain reservoir and sustained release properties towards bioactive molecules. We optimized the multilayer assembly immobilization onto the PET surface according to the layer-by-layer (LbL) deposition process. After a pre-treatment of the textile support aiming to offer a sufficient ionic character to the surface, it was alternatively immersed into two polyelectrolytes aqueous solutions consisting of chitosan (CHT) as polycation on the one hand, and a ß-cyclodextrin polymer (polyCTR-ßCD) as polyanion on the other hand. In a second approach, a TBBA/polyCTR-ßCD complex (4-tert-butylbenzoic acid, TBBA) was used in order to load the system with a drug model whose kinetics of release was assessed. Gravimetry, microscopy, OWLS, colorimetric titration, infrared and zetametry were used as characterization techniques. An effective deposition on the textile surface due to ionic interactions with alternation of up to 10 layers of each of both polyelectrolytes was clearly evidenced. However, we observed that layer formation occurred to a lesser extent when TBBA/polyCTR-ßCD complex was applied instead of polyCTR-ßCD alone. The release study showed that drug reservoir properties and release kinetics could be controlled by the number of layers in the system and that TBBA release was faster than the multilayered coating degradation.