Evaluation of Poly(vinyl alcohol)-Xanthan Gum Hydrogels Loaded with Neomycin Sulfate as Systems for Drug Delivery.

In recent years, multidrug-resistant bacteria have developed the ability to resist multiple antibiotics, limiting the available options for effective treatment. Raising awareness and providing education on the appropriate use of antibiotics, as well as improving infection control measures in healthcare facilities, are crucial steps to address the healthcare crisis. Further, innovative approaches must be adopted to develop novel drug delivery systems using polymeric matrices as carriers and support to efficiently combat such multidrug-resistant bacteria and thus promote wound healing. In this context, the current work describes the use of two biocompatible and non-toxic polymers, poly(vinyl alcohol) (PVA) and xanthan gum (XG), to achieve hydrogel networks through cross-linking by oxalic acid following the freezing/thawing procedure. PVA/XG-80/20 hydrogels were loaded with different quantities of neomycin sulfate to create promising low-class topical antibacterial formulations with enhanced antimicrobial effects. The inclusion of neomycin sulfate in the hydrogels is intended to impart them with powerful antimicrobial properties, thereby facilitating the development of exceptionally efficient topical antibacterial formulations. Thus, incorporating higher quantities of neomycin sulfate in the PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations yielded promising cycling characteristics. These formulations exhibited outstanding removal efficiency, exceeding 80% even after five cycles, indicating remarkable and consistent adsorption performance with repeated use. Furthermore, both PVA/XG-80/20-2 and PVA/XG-80/20-3 formulations outperformed the drug-free sample, PVA/XG-80/20, demonstrating a significant enhancement in maximum compressive stress.

Optimization of Alkaline Extraction of Xylan-Based Hemicelluloses from Wheat Straws: Effects of Microwave, Ultrasound, and Freeze-Thaw Cycles.

The alkaline extraction of hemicelluloses from a mixture of three varieties of wheat straw (containing 40.1% cellulose, 20.23% xylan, and 26.2% hemicellulose) was analyzed considering the following complementary pre-treatments: freeze-thaw cycles, microwaves, and ultrasounds. The two cycles freeze-thaw approach was selected based on simplicity and energy savings for further analysis and optimization. Experiments planned with Design Expert were performed. The regression model determined through the response surface methodology based on the severity factor (defined as a function of time and temperature) and alkali concentration as variables was then used to optimize the process in a multi-objective case considering the possibility of further use for pulping. To show the properties and chemical structure of the separated hemicelluloses, several analytical methods were used: high-performance chromatography (HPLC), Fourier-transformed infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H-NMR), thermogravimetry and derivative thermogravimetry analysis (TG, DTG), and scanning electron microscopy (SEM). The verified experimental optimization result indicated the possibility of obtaining hemicelluloses material containing 3.40% glucan, 85.51% xylan, and 7.89% arabinan. The association of hot alkaline extraction with two freeze-thaw cycles allows the partial preservation of the hemicellulose polymeric structure.

New Quaternary Ammonium Derivatives Based on Citrus Pectin.

New citrus pectin derivatives carrying pendant N,N-dimethyl-N-alkyl-N-(2-hydroxy propyl) ammonium chloride groups were achieved via polysaccharide derivatization with a mixture of N,N-dimethyl-N-alkyl amine (alkyl = ethyl, butyl, benzyl, octyl, dodecyl) and epichlorohydrin in aqueous solution. The structural characteristics of the polymers were examined via elemental analysis, conductometric titration, Fourier Transform Infrared spectroscopy (FTIR) and 1D (1H and 13C) nuclear magnetic resonance (NMR). Capillary viscosity measurements allowed for the study of viscometric behavior as well as the determination of viscosity-average molar mass for pristine polysaccharide and intrinsic viscosity ([η]) values for pectin and its derivatives. Dynamic light scattering measurements (DLS) showed that pectin-based polymers formed aggregates in aqueous solution with a unimodal distribution. Critical aggregation concentration (cac) for the hydrophobic pectin derivatives were determined using fluorescence spectroscopy. Atom force microscopy (AFM) images allowed for the investigation of the morphology of polymeric populations obtained in aqueous solution, consisting of flocs and aggregates for crude pectin and its hydrophilic derivatives and well-organized aggregates for lipophilic pectin derivatives. Antimicrobial activity, examined using the disc diffusion method, proved that all polymers were active against Staphylococcus aureus bacterium and Candida albicans yeast.

Integrated Hemicellulose Extraction and Papermaking Fiber Production from Agro-Waste Biomass.

The present study deals with the valorization of corn stalks in an integrated processing strategy targeting two products: extracted hemicelluloses (HC) and papermaking fibers. Preliminary trials were conducted to assess the individual or the combined effects of biomass treatment on the quality of the obtained hemicelluloses and papermaking fibers. Depending on the hot alkaline extraction (HAE) conditions, the extracted HC had a xylan content between 44-63%. The xylan removal yield ranged between 19-35%. The recovery of HC from the extraction liquor and final black liquor was significantly affected by process conditions. The experimental approach continued with the study of HAE conditions on the obtained paper's mechanical properties. The optimization approach considered conserving paper strength properties while achieving an equilibrium with the highest possible HC extraction yield. The optimal values are sodium hydroxide concentration (1%), process time (33 min), and temperature (100 °C). The xylan content in the separated HC sample was ~55%. An extended extraction of HC from the resulting pulp under hot alkaline conditions with 5% NaOH was performed to prove the HC influence on paper strength. The xylan content in HC samples was 65%. The consequence of xylan content reduction in pulp leads to 30-50% mechanical strength loss.

Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications.

Because the combination of π-conjugated polymers with biocompatible synthetic counterparts leads to the development of bio-relevant functional materials, this paper reports a new oligo(2-methyl-2-oxazoline) (OMeOx)-containing thiophene macromonomer, denoted Th-OMeOx. It can be used as a reactive precursor for synthesis of a polymerizable 2,2'-3-OMeOx-substituted bithiophene by Suzuki coupling. Also a grafted polythiophene amphiphile with OMeOx side chains was synthesized by its self-acid-assisted polymerization (SAAP) in bulk. The results showed that Th-OMeOx is not only a reactive intermediate but also a versatile functional material in itself. This is due to the presence of 2-bromo-substituted thiophene and ω-hydroxyl functional end-groups, and due to the multiple functionalities encoded in its structure (photosensitivity, water self-dispersibility, self-assembling capacity). Thus, analysis of its behavior in solvents of different selectivities revealed that Th-OMeOx forms self-assembled structures (micelles or vesicles) by "direct dissolution".Unexpectedly, by exciting the Th-OMeOx micelles formed in water with λabs of the OMeOx repeating units, the intensity of fluorescence emission varied in a concentration-dependent manner.These self-assembled structures showed excitation-dependent luminescence as well. Attributed to the clusteroluminescence phenomenon due to the aggregation and through space interactions of electron-rich groups in non-conjugated, non-aromatic OMeOx, this behavior certifies that polypeptides mimic the character of Th-OMeOx as a non-conventional intrinsic luminescent material.

An Experimental Study on the Hot Alkali Extraction of Xylan-Based Hemicelluloses from Wheat Straw and Corn Stalks and Optimization Methods.

In this paper, we describe an experimental study on the hot alkali extraction of hemicelluloses from wheat straw and corn stalks, two of the most common lignocellulosic biomass constituents in Romania. The chemical compositions of the raw materials were determined analytically, and the relevant chemical components were cellulose, hemicelluloses, lignin, and ash. Using the response surface methodology, the optimum values of the hot alkaline extraction parameters, i.e., time, temperature, and NaOH concentration, were identified and experimentally validated. The physicochemical characterization of the isolated hemicelluloses was performed using HPLC, FTIR, TG, DTG, and 1H-NMR spectroscopy. The main hemicellulose components identified experimentally were xylan, arabinan, and glucan. The study emphasizes that both corn stalks and wheat straw are suitable as raw materials for hemicellulose extraction, highlighting the advantages of alkaline pretreatments and showing that optimization methods can further improve the process efficiency.

Synthesis of Bioactive Materials by In Situ One-Step Direct Loading of Syzygium aromaticum Essential Oil into Chitosan-Based Hydrogels.

Hydrogel conjugates based on chitosan and an essential oil were synthetized by an ultrasound-assisted emulsification approach. Rheology studies revealed a gel-type structure with pronounced compactness and flexibility while SEM showed the formation of a two-level ordered network with highly interconnected pores. The swelling studies indicated a pH-dependent behavior with a significant overshooting effect. The synergistic effects of the components in clove essential oil led to a strong antioxidant character and an enhanced antimicrobial activity of the conjugate hydrogels. The bioactivity was maintained for 6 months, despite a slight decrease in the antimicrobial effect. Hydrogel conjugates were found to be very stable even after two months immersed in acidic solutions that would otherwise dissolve the chitosan matrix. Ultrasound emulsification was proved as an efficient one-step loading method of hydrophobic clove essential oil into hydrophilic chitosan matrix. It was found that clove oil and its components have a double role. Besides providing bioactivity, they also behave as gelation-inducing agents, acting as an alternative to the classical chemical cross-linkers to ensure the good physical and chemical stabilization of chitosan.

A Real-Life Reproducibility Assessment for NMR Metabolomics.

Nuclear magnetic resonance (NMR) metabolomics is currently popular enough to attract both specialized and non-specialized NMR groups involving both analytical trained personnel and newcomers, including undergraduate students. Recent interlaboratory studies performed by established NMR metabolomics groups demonstrated high reproducibility of the state-of-the-art NMR equipment and SOPs. There is, however, no assessment of NMR reproducibility when mixing both analytical experts and newcomers. An interlaboratory assessment of NMR quantitation reproducibility was performed using two NMR instruments belonging to different laboratories and involving several operators with different backgrounds and metabolomics expertise for the purpose of assessing the limiting factors for data reproducibility in a multipurpose NMR environment. The variability induced by the operator, automatic pipettes, NMR tubes and NMR instruments was evaluated in order to assess the limiting factors for quantitation reproducibility. The results estimated the expected reproducibility data in a real-life multipurpose NMR laboratory to a maximum 4% variability, demonstrating that the current NMR equipment and SOPs may compensate some of the operator-induced variability.

Thermosensitive Poloxamer-graft-Carboxymethyl Pullulan: A Potential Injectable Hydrogel for Drug Delivery.

A thermosensitive copolymer composed of amphiphilic triblock copolymer, poloxamer 407, grafted on hydrophilic pullulan with pendant carboxymethyl groups (CMP) was prepared and characterized. The structure of the new copolymer was assessed by Fourier transform infrared (FT-IR) and 1H nuclear magnetic resonance (1H NMR) spectroscopy. The content of the poloxamer in the grafted copolymer was 83.8% (w/w). The effect of the copolymer concentration on the gelation behavior was analyzed by the vertical method and rheological tests; the gel phase of the copolymer occurred at a lower concentration (11%, w/v) as compared with poloxamer (18%, w/v). The starting gelation time under the simulated physiological conditions (phosphate buffer with a pH of 7.4, at 37 °C) was sensitive on the rest temperature before the test, this being 990 s and 280 s after 24 h rest at 4 °C and 20 °C, respectively. The rheological tests evidenced a high elasticity and excellent ability of the copolymer to recover the initial structure after the removal of the applied force or external stimuli. Moreover, the hydrogel has proved a sustained release of amoxicillin (taken as a model drug) over 168 h. Taken together, the results clearly indicate that this copolymer can be used as an injectable hydrogel.

Bile salts adsorption on dextran-based hydrogels.

Dextran-based gels bearing two types of pendant N, N-dimethyl-N-alkyl-N-(2-hydroxypropyl) ammonium chloride groups with different alkyl chain length substituents (C2 and C12/C16, respectively) at the quaternary nitrogen were synthesized and structural characteristics of the compounds were studied by elemental analysis, potentiometric titration, FTIR and NMR spectroscopy. The morphology and size of polymeric microspheres were examined by SEM and their swelling behavior in water was also investigated. The hydrogels were evaluated as sorbents for sodium cholate (NaCA) and sodium deoxycholate (NaDCA) in water and 10 mM NaCl solutions. Different isotherm models (nearest-neighbor-interaction, Langmuir, Freundlich, Dubinin-Raduskevich, Sips and Hill) were used to elucidate the adsorption mechanism and established the characteristics of the most efficient polymeric sorbent. The maximum adsorption capacity of the gels was highly controlled by gel hydrophobicity which enhanced gel-bile salt affinity but decreased binding cooperativity. Swelling porosity, ionic strength and ligand lipophilicity were other factors that also affected the adsorption process. The hydrogel having 25 mol% pendant dodecyl groups retained the maximum amount of bile salts (1051 mg NaCA/g and 1138 mg NaDCA/g). All hydrophobically modified hydrogels revealed a better affinity and strength of binding compared to commercial Cholestyramine®.

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media.

End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional "hydrophobic amphiphile", was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a "block-molecule". According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL's propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

Designing chitosan based eco-friendly multifunctional soil conditioner systems with urea controlled release and water retention.

The paper reports new soil conditioner systems obtained by in situ hydrogelation of chitosan with salicylaldehyde in the presence of urea fertilizer, designed to address both fertilization and water retention of the soil. The new systems were structural, supramolecular and morphological characterized by FTIR spectroscopy, XRD diffraction, POM and SEM microscopy. The rate of urea release has been investigated by NMR analysis and the release mechanism has been assessed by fitting five mathematical models. The formulations showed high water absorbency of 68 g/g, and they induced water holding capacity in soil up to 154% and an increment of the nitrogen content in soil to almost double, leading to a growth of plants with almost 70% higher compared to the reference soil. All these data revealed the new systems as new multifunctional soil conditioner ecoproducts capable to address both fertilizing and water retention issues, with high potential of application for sustainable agriculture.

Triphenylamine-based rhombimine macrocycles with solution interconvertable conformation.

Three imine macrocycles having rhomboidal shape were synthesized in good yields by [2+2] cyclocondensation reaction between equimolar quantities of (R,R)-1,2-diaminocyclohexane and 4,4'-bisformyl triphenylamine derivatives. The macrocycles structure was assigned by electrospray ionization mass spectrometry (ESI-MS), (1)H-NMR, and elemental analysis. UV, FTIR spectroscopy, and TG measurements were also used to characterize and prove the structure of these compounds. A conformational modification arising out of the rotation of triphenylamine group around the flexible cyclohexane-N bonds was observed in solution by (1)H-NMR and UV spectroscopy for all three macrocycles.