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The paper focusses on the synthesis of novel hydrogels by joining natural biodegradable compounds with the aim to achieve biocompatible materials for bio related applications. The hydrogels were prepared from chitosan and citral by constitutional dynamic chemistry, incorporating both molecular and supramolecular dynamic features. The hydrophobic flexible citral has been reversible immobilized onto the hydrophilic chitosan backbone via imine bonds to form amphiphilic glycodynamers, which further self-ordered through supramolecular interactions into a 3D-network of biodynameric hydrogel. The synthetic pathway has been demonstrated by NMR and FTIR spectroscopy, X-ray diffraction and polarized light microscopy. Studies of the hydrogel morphology revealed a 3D porous microstructure, whose pores size correlated with the crosslinking degree. Rheological investigations evidenced high elasticity, thermo-responsiveness and thixotropic behavior. As a proof of the concept, the hydrogels proved in vivo biocompatibility on laboratory mice. The paper successfully implements the constitutional dynamic chemistry in generation of chitosan high performance hydrogels. [ABSTRACT FROM AUTHOR]

Chitosan based hydrogels are a class of cross-linked materials intensely studied for their biomedical, industrial and environmental application, but their biomedical use is limited because of the toxicity of different organic crosslinkers. To overcome this disadvantage, a new strategy to produce supramolecular chitosan hydrogels using low molecular weight compounds able to form covalent linkages and H-bonds to give a dual crosslinking is proposed. For this purpose we used 2-formylphenylboronic acid, which brings the advantage of imine stabilization via iminoboronate formation and potential antifungal activity due to the presence of boric acid residue. FTIR and NMR spectroscopy indicated that the gelling process took place by chemo-physical crosslinking forming a dual iminoboronate-chitosan network. Further, X-ray diffraction demonstrated a three-dimensional nanostructuring of the iminoboronate network with consequences on the micrometer-scale morphology and on the improvement of mechanical properties, as demonstrated by SEM and rheological investigation. The hydrogels proved strong antifungal activity against Candida planktonic yeasts and biofilms, promising to be a friendly treatment of the recurrent vulvovaginitis infections. [ABSTRACT FROM AUTHOR]

A smectogen liquid crystal based on benzoate units has been synthesized and structurally characterized by FTIR and 1 H NMR spectroscopy. Besides, its structure and supramolecular arrangement in the crystalline state was demonstrated by single crystal X-ray diffraction measurements. The thermotropic behaviour, monitored by differential scanning calorimetry and polarized light microscopy, consists in the formation of an enantiotropic smectic mesophase with a direct first order transition from the isotropic to smectic mesophase, and with its thermal stability range superposed on human body temperature. The smectogen liquid crystal has moderate wettability – suitable for biocompatible materials and presents good antipathogenic activity against gram positive and gram negative bacteria and fungus. All these properties recommend the understudied liquid crystal to be used in biochemical and biological applications. [ABSTRACT FROM AUTHOR]

The present paper focuses on the synthesis and characterization of new hydrogels and drug delivery systems, designed for local therapy. The hydrogels were obtained by reacting PEG-ylated chitosan derivatives with citral in different molar ratios of their functionalities. The drug delivery systems were obtained by the in situ hydrogelation of PEG-ylated chitosan derivatives with citral, in the presence of a hydrophilic anti-inflammatory drug, diclofenac sodium salt. The hydrogels and the drug delivery systems were characterized from the structural, supramolecular and morphological points of view by FTIR spectroscopy, wide angle X-ray diffraction, polarized optical microscopy and scanning electron microscopy. The in vitro release kinetics of the drug has been monitored in physiological conditions, while the in vivo release was evaluated by the somatic pain model on rats. The in vitro enzymatic degradability of the hydrogels was evaluated in the presence of lysozyme, leading to a significant mass loss of 47% in 21 days. All the findings, recommend the investigated materials as promising candidates for local drug delivery applications. Unlabelled Image [ABSTRACT FROM AUTHOR]

Betulin is a naturally originating terpenoid, which attracted the attention of researchers due to its bioactive properties, including antitumor activity. This paper reports new betulin-imine derivatives, their synthesis, structural characterization and investigation of their antioxidant and anticancer activities. To this aim, a betulin aldehyde has been firstly prepared via an oxidation reaction using a Tempo reagent, which was further reacted with a series of aliphatic amines via an acid condensation reaction. The proposed chemical structures were confirmed using 1H-NMR and FTIR spectroscopy and single crystal X-ray diffraction, and characterized by solubility tests, ultraviolet-visible (UV-Vis) and photoluminescence spectroscopy, thermogravimetric analysis and polarized light microscopy. All the compounds were easily soluble in common organic solvents, and showed good thermal stability. They showed strong birefringence under polarized light indicating their crystalline nature, which was attributed to single crystal diffraction and they belong to the Sohnke P212121 space groups. The investigation of optical properties using photoluminescence spectroscopy revealed that all the imines emitted blue light in solution and in the solid state. The DPPH radical scavenging test showed that the antioxidant activity of betulin was significantly improved by imination with the increase of the aliphatic chain length. The antitumor activity investigated in vitro using the MTS assay on human breast cancer cell line MCF-7 (adenocarcinoma) and on non-tumorigenic epithelial cell line MCF-10A showed that the betulin-imine derivatives have improved antitumor activity and selectivity compared to neat betulin, suggesting that a medium length of the alkyl chain is favorable for the antiproliferative activity. [ABSTRACT FROM AUTHOR]

This paper reports new formulations based on chitosan, citral, and diclofenac sodium salt (DCF). The central idea was to encapsulate an anionic drug into a polycationic hydrogel matrix in order to increase the intermolecular forces between them and thus to ensure slower drug release, while citral was used as a penetration enhancer to assure efficient delivery of the drug. Hydrogels without drug were also synthesized and used as a reference. The structure, morphology, and supramolecular architecture of the drug delivery systems were evaluated by FTIR spectroscopy, scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction. The drug release kinetics was monitored in vitro by UV-VIS spectroscopy, in physiological conditions, while the enzymatic and hydrolytic degradability of the hydrogels were evaluated in the presence of lysozyme and phosphate buffer saline (PBS), at 37 °C. All of the data revealed that the anionic DCF was strongly anchored into the polycationic matrix and the drug was slowly released over 7 days. Moreover, the release rate can be controlled by simple variation of the molar ratio between the polycationic chitosan and lipophilic citral. [ABSTRACT FROM AUTHOR]

The aim of the paper was to investigate the ability of an eco-friendly luminescent xerogel prepared by chitosan crosslinking with a phenothiazine luminogen to detect and remove heavy metals. Its ability to give a divergent morphological and optical response towards fifteen environmental relevant metals was investigated by naked eye and UV lamp, fluorescence spectroscopy and scanning electron microscopy. A distinct response was noted for mercury, consisting in the transformation of the xerogel into a rubber-like material accompanied by the red shifting of the color of emitted light from yellow-green to greenish-yellow domain. The particularities of the metals anchoring into the xerogel were analyzed by FTIR spectroscopy and X-ray diffraction. The morphological changes and the metal uptake were analyzed by SEM-EDAX, swelling and gravimetric methods. It was concluded that mercury has a superior affinity towards this heteroatoms rich system, leading to a secondary crosslinking. This directed a great absorption capacity of 1673 mg/g and a specific morphological response for mercury ion concentrations up to 0.001 ppm. • A luminescent organic xerogel was investigated for heavy metal detection and removal. • The xerogel showed a distinct morphological behavior towards mercury ions. • This was sensible and selective over a large series of environment relevant metals. • This was attributed to a secondary morphology due to a supplementary crosslinking. [ABSTRACT FROM AUTHOR]

The paper deals with the design and investigation of the morphology, in vitro drug release and biocompatibility of some new formulations based on polyvinyl alcohol boric acid (PVAB) and diclofenac sodium salt (DCF), with the aim to explore the ability of PVAB to act as a matrix for controlled drug delivery systems. A series of three formulations was obtained by mixing the drug and the polymeric matrix in different mass ratios, with high drug content from 10% w/w to 30% w/w. Their structural and supramolecular characterization, performed by FTIR spectroscopy and X-ray diffraction, revealed important physical interactions between the drug and the polymeric matrix. The morphological data, obtained by X-ray diffraction, polarized optical microscopy and scanning electron microscopy revealed the presence of the drug into the PVAB polymeric matrix, as micrometric polycrystals with a mean diameter in the range 10–15 μm, depending on the drug/polymer ratio. The investigation of their surface peculiarities indicated highly hydrophilic surfaces with a water to air contact angle between 29.9 and 41.4 deg and a surface free energy of 45.6–54.2 N/m2. The in vitro release kinetics was monitored by UV-VIS spectroscopy and the cytotoxic effect was investigated in vitro on fibroblasts and HeLa cells. The PVAB proved excellent cytocompatibility, a relative cell viability of the fibroblasts higher than 90% being recorded for concentrations of PVAB up to 7.5% w/v. The drug has been strongly anchored into the electron deficient PVAB matrix, fact which led to its prolonged release up to 5 days. These findings recommend PVAB as a versatile tool for the development of sustained release drug delivery systems with real chances to cross the gap from theory to applications. The biocompatible PVAB polymer led to sustained release drug delivery systems by anchoring the DCF drug into the polymeric matrix through strong physical interactions. Image 1 • Poly(vinyl alcohol boric acid) (PVAB) was used for the development of drug delivery systems. • Diclofenac (DCF) drug was anchored by electrostatic interactions in the polymeric matrix. • The drug delivery systems released the encapsulated drug in a sustained manner. • The evaluation of the PVAB cytotoxicity revealed high potential for bioapplications. [ABSTRACT FROM AUTHOR]

Microbial infections are a serious healthcare related problem, causing several complications and even death. That is why, the development of new drug delivery systems with prolonged effect represents an interesting research topic. This study presents the synthesis and characterization of new hydrogels based on chitosan and three halogenated monoaldehydes. Further, the hydrogels were used as excipients for the development of drug delivery systems (DDS) by the incorporation of fluconazole, an antifungal drug. The systems were structurally characterized by Fourier Transformed Infrared Spectroscopy and Nuclear Magnetic Resonance, both methods revealing the formation of the imine linkages between chitosan and the aldehydes. The samples presented a high degree of ordering at supramolecular level, as demonstrated by WXRD and POM and a good water-uptake, reaching a maximum of 1.6 g/g. The obtained systems were biodegradable, loosing between 38 and 49 % from their initial mass in the presence of lysozyme in 21 days. The ability to release the antifungal drug in a sustained manner for seven days, along with the high values of the inhibition zone diameter, reaching a maximum of 64 mm against Candida parapsilosis for the chlorine containing sample, recommend these systems as promising materials for bioapplications. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract The paper focuses on the synthesis and characterization of new drug delivery systems for local therapy. They were prepared by in situ hydrogelation of chitosan biopolymer with nitrosalicylaldehyde in the presence of a model drug, varying the crosslinking density. The structural, supramolecular and morphological characteristics of the systems were studied by FTIR spectroscopy, X-ray diffraction and, POM and SEM microscopy. In vitro release of the drug has been explored in simulated physiological conditions and in vivo release was investigated by the somatic pain model on rats. Information on the biodegradation of the systems was gain by simulating experiments of enzymatic degradation. The systems were biodegradable and showed a prolonged drug release, assuring an in vivo efficient therapeutic effect over 5 days, with no systemic toxicity. All these findings demonstrated that the new hydrogels based on nitrosalicyl-imine-chitosan provides a practical approach for sustained drug delivery for local chemotherapy. [ABSTRACT FROM AUTHOR]

The present study reports the synthesis and characterization of 12 drug delivery systems (DDS) for the co-delivery of antifungal and antiviral agents. The systems were obtained by an in situ hydrogelation method of 6 chitosan oligomers with values of the polymerization degree between 14 and 51, with 2-formylphenylboronic acid, in the presence of tenofovir. The structural characterization by NMR and FTIR spectroscopy demonstrated the formation of imine linkages, while WXRD revealed the 3D layered architecture of the systems. SEM and POM images demonstrated the uniform distribution of tenofovir into the matrix, while the Zeta potential measurements revealed the strong interactions which develop between system components. The obtained DDSs presented biodegradability, hemocompatibility and in vivo biocompatibility, which along with their ability to release both the drug and the antifungal aldehyde make them promising materials for the treatment of HIV infection and its associated co-infections' symptoms. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: New Schiff base dimers based on phenothiazine heterocycle have been obtained with high yield and purity by condensation of 3-formyl-10-methyl-phenothiazine with various amines. The structural characterization was performed by elemental analysis, FTIR, 1D and 2D NMR spectroscopy and single crystal and powder wide angle X-ray diffraction. The obtained compounds have high thermal stability and some of them self-assemble into cubic mesophase and form stable molecular glass. The thermotropic study performed by polarized optical microscopy and differential scanning calorimetry revealed the possibility to control the compound morphology by thermal annealing and blending miscible components. The photophysical characterization indicates green light emission, with good absolute fluorescence quantum yield, large Stokes shift and high purity and fully saturated color. The special thermal behavior and photophysical properties appear to be significantly dependent on the special supramolecular architecture generated by the hockey-stick shape of the imino-phenothiazine mesogenic core. Collectively, the properties of these azomethines provide a starting point for new compounds with great advantages for optoelectronic applications. [Copyright &y& Elsevier]

The paper reports a series of three new PEGylated phenothiazine derivatives which keep the potential of valuable building blocks for preparing eco-materials addressed to a large realm of fields, from bio-medicine to opto-electronics. They were synthetized by connecting the hydrophilic poly(ethylene glycol) to the hydrophobic phenothiazine via an ether, ester, or amide linking group. The successful synthesis of the targeted polymers and their purity were demonstrated by NMR and FTIR spectroscopy methods. Their capacity to self-assembly in water was studied by DLS and UV–vis techniques and the particularities of the formed aggregates were investigated by fluorescence spectroscopy, SEM, AFM, POM and UV light microscopy. The biocompatibility was assessed on normal human dermal fibroblasts and human cervical cancer cells. The synthetized compounds showed the formation of luminescent aggregates and proved excellent biocompatibility on normal cells. In addition, a concentration dependent cytotoxicity against HeLa cancer cells was noticed for the PEGylated phenothiazine containing an ester unit. Unlabelled Image • PEG was successfully grafted on phenothiazine via ether, ester of amide linking unit. • The PEGylated phenothiazines were water soluble and formed stable luminescent aggregates. • They presented in vitro biocompatibility on normal cells. • The ester containing polymer presented concentration dependent cytotoxicity against HeLa cells. [ABSTRACT FROM AUTHOR]

• Urea controlled release systems based on chitosan and salicyladehyde were prepared. • They showed porous structure, good water absorbency and hydrolytic stability. • Urea has been anchored into the hydrogel walls as micrometric crystals by H-bonds. • The in vivo release study revealed a prolonged urea delivery during 35 days. • The new formulations are promising candidates as multifunctional soil conditioners. 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. [ABSTRACT FROM AUTHOR]

An alternant poly(dihexyl fluorene-co diphenyl oxadiazole) has been synthetized by microwave-assisted oxidative polymerization. The structure has been confirmed by 1H-NMR and FTIR spectroscopies. Gel permeation chromatography indicated high molecular weight and low polydispersity index. DFT calculations suggested a complete separation of HOMO and LUMO orbitals, which were located on fluorene and oxadiazole moiety, respectively. X-ray diffraction, polarized light microscopy, and atomic force microscopy indicated the polymer tendency to stack into a layered morphology with a more compact structure for the films prepared by spin coating. Furthermore, UV-vis and photoluminescence spectroscopies indicated the formation of H-aggregates which played a key role in photoluminescence quenching in solid state. Nevertheless, the good charge mobility gained due to the orbital overlapping in H-aggregates led to excellent electroluminescence, which enabled the development of white OLED devices with outstanding stability. [ABSTRACT FROM AUTHOR]