Institutul de Chimie Macromoleculară Petru Poni

Ionic liquids (ILs) and deep eutectic solvents (DESs) have been suggested as eco-friendly alternatives to organic solvents. A trace amount of water is often unavoidable as impurity, and water is also added on purpose to reduce their problematically high viscosity and lower their high price. Understanding the distinct effects of water on the properties of ILs/DESs is highly important. In this review, we collect published experimental and theoretical results for IL/DES-H2O systems at varied water concentrations and analyze them. Results from mechanistic studies, thermodynamic modelling and advanced experiments are collected and critically discussed. Six commonly studied IL/DES-H2O systems were selected to map experimental observations onto microscopic results obtained in mechanistic studies. A great variety of distinct contours of the excess properties can be observed over the entire compositional range, indicating that the properties of IL/DES-H2O systems are highly unpredictable. Mechanistic studies clearly demonstrate that the added H2O rapidly changes the heterogeneous 3D structures of pure ILs/DESs, leading to very different properties and behaviour. There are similarities between aqueous electrolytes and IL/DES solutions but the bulky and asymmetric organic cations in ILs/DESs do not conform to the standard salt dissolution and hydration concepts. Thermodynamic modelling previously assumes ILs/DESs to be either a neutral ion-pair or completely dissociated ions, neglecting specific ion hydration effects. A new conceptual framework is suggested for thermodynamic modelling of IL/DES-H2O binary systems to enable new technologies for their practical applications.

Ionic liquids (ILs) are a special category of molten salts solely composed of ions with varied molecular symmetry and charge delocalization. The versatility in combining varied cation-anion moieties and in functionalizing ions with different atoms and molecular groups contributes to their peculiar interactions ranging from weak isotropic associations to strong, specific, and anisotropic forces. A delicate interplay among intra- and intermolecular interactions facilitates the formation of heterogeneous microstructures and liquid morphologies, which further contributes to their striking dynamical properties. Microstructural and dynamical heterogeneities of ILs lead to their multifaceted properties described by an inherent designer feature, which makes ILs important candidates for novel solvents, electrolytes, and functional materials in academia and industrial applications. Due to a massive number of combinations of ion pairs with ion species having distinct molecular structures and IL mixtures containing varied molecular solvents, a comprehensive understanding of their hierarchical structural and dynamical quantities is of great significance for a rational selection of ILs with appropriate properties and thereafter advancing their macroscopic functionalities in applications. In this review, we comprehensively trace recent advances in understanding delicate interplay of strong and weak interactions that underpin their complex phase behaviors with a particular emphasis on understanding heterogeneous microstructures and dynamics of ILs in bulk liquids, in mixtures with cosolvents, and in interfacial regions.

Special properties of the polymeric nanomaterials (nanoscale size, large surface area to mass ratio and high reactivity individualize them in food packaging materials. They can be processed in precisely engineered materials with multifunctional and bioactive activity. This review offers a general view on polymeric nanocomposites and nanocoatings including classification, preparation methods, properties and short methodology of characterization, applications, selected types of them used in food packaging field and their antimicrobial, antioxidant, biological, biocatalyst and so forth, functions.

Abstract The oral delivery of drugs is regarded as the optimal means for achieving therapeutic effects owing to increased patient compliance. Unfortunately, the oral delivery route is beset with problems such as gastrointestinal (GI) destruction of labile molecules, low levels of macromolecular absorption, etc. To reduce the impact of digestive enzymes and to ensure the absorption of bioactive agents in an unaltered form, molecules may be incorporated into microparticulate carriers. Many approaches to achieve the oral absorption of a wide variety of drugs are currently under investigation. Among the different polymer-based drug delivery systems, polymeric micelles represent a promising delivery vehicle especially intended for poorly water-soluble pharmaceutical active ingredients in order to improve their oral bioavailability. Recent findings of a dextran-based polymeric micelle study for solubilization of a highly lipophilic drug, cyclosporin A (CsA), will be discussed.

Abstract Natural fiber composites have experienced a renaissance in the last two decades as a response to societal demands for developing eco‐friendly, biodegradable and recyclable materials. They are now being extensively used in everyday products as well as in automotive, packaging, sports and construction industries. Hemp fiber is being used in most of these products because of its superior mechanical properties. Like other natural fibers, hemp fibers require modifications in order to improve their properties and interfacial bonding with polymer matrices, and to reduce their hydrophilic character. These modification methods can be grouped into three major categories: chemical, physical and biological. Chemical methods use chemical reagents to reduce fibers' hydrophilic tendency and thus improve compatibility with the matrix. They also expose more reactive groups on the fiber surface to facilitate efficient coupling with the matrix. Physical methods change structural and surface properties of the fiber and thereby influence the interfacial bonding with matrices, without extensively changing the chemical composition of the fibers. They are cleaner and simpler than the chemical methods. Biological methods use biological agents like fungi, enzymes and bacteria to modify the fiber surface properties. These methods are not toxic like chemical methods and are not energy‐intensive like physical methods. This paper presents an overview of recent developments in these methods. It is concluded that these methods almost invariably result in improvement in fiber/matrix interfacial bonding, resulting in increase in mechanical properties of the composites.

SUMMARY Wood and wood‐based products are widely used for structural building elements, but due to their composition, they are susceptible of combusting if exposed to fire. Fire safety is an important issue of building safety, especially when the building's fire load contents enhance the risks of fire spread. Therefore, the involved materials are very important to address the fire safety requirements. When existing timber structures are involved, the most usual way to improve its reaction to fire is to treat wood with fire retardant materials. The idea of this paper is to give an overall overview, on the existing fire‐retardant and intumescent coating materials, modification, and treatments that can be applied to wood and wood‐based products in order to improve their reaction to fire.

In the present comprehensive review we have specifically focused on polymer nanocomposites used as photocatalytic materials in fine organic reactions or in organic pollutants degradation. The selection of the polymer substrates for the immobilization of the active catalyst particles is motivated by several advantages displayed by them, such as: Environmental stability, chemical inertness and resistance to ultraviolet radiations, mechanical stability, low prices and ease availability. Additionally, the use of polymer nanocomposites as photocatalysts offers the possibility of a facile separation and reuse of the materials, eliminating thus the post-treatment separation processes and implicitly reducing the costs of the procedure. This review covers the polymer-based photocatalytic materials containing the most popular inorganic nanoparticles with good catalytic performance under UV or visible light, namely TiO2, ZnO, CeO2, or plasmonic (Ag, Au, Pt, Pd) NPs. The study is mainly targeted on the preparation, photocatalytic activity, strategies directed toward the increase of photocatalytic efficiency under visible light and reuse of the hybrid polymer catalysts.

Recent advances in nanotechnology have forced the obtaining of new materials with multiple functionalities. Due to their reduced dimensions, nanomaterials exhibit outstanding physio-chemical functionalities: increased absorption and reactivity, higher surface area, molar extinction coefficients, tunable plasmonic properties, quantum effects, and magnetic and photo properties. However, in the biomedical field, it is still difficult to use tools made of nanomaterials for better therapeutics due to their limitations (including non-biocompatible, poor photostabilities, low targeting capacity, rapid renal clearance, side effects on other organs, insufficient cellular uptake, and small blood retention), so other types with controlled abilities must be developed, called "smart" nanomaterials. In this context, the modern scientific community developed a kind of nanomaterial which undergoes large reversible changes in its physical, chemical, or biological properties as a consequence of small environmental variations. This systematic mini-review is intended to provide an overview of the newest research on nanosized materials responding to various stimuli, including their up-to-date application in the biomedical field.

Construction and demolition wastes (C&DW) are usually recognized as not dangerous, but their accumulation can generate serious environmental problems. In spite of C&DW high potential to be reused/recycled, the practical procedures need to be assessed in terms of environmental consequences. The objective of this study is to quantify the environmental impacts of C&DW recycling/reuse, specifically in the production of aggregate 0/30 mm, comparative to those generated during the natural inert processing, in terms of global impacts addressing the whole process and for each technological phase. The analysis was carried out using Life Cycle Assessment methodology, assisted by SimaPro software, and based on primary data collected directly from the Italian Emilia Romagna region. Three methods were used for impact quantification: Eco-Indicator 99, EDIP/UMIP and Cumulative Energy Demand. The analysis revealed that the environmental impacts generated by C&DW recycling/reuse accounting for about 40% of the impacts induced by natural inert processing.

H NMR), ESI mass spectrometry, X-ray crystallography and cyclic voltammetry. The proligands and their copper(ii) complexes exhibit moderate water solubility and good stability in aqueous environment, determined by investigating their proton dissociation and complex formation equilibria. The copper(ii) complexes showed moderate anticancer activity in established human cancer cell lines, while the proligands were devoid of cytotoxicity. The anticancer activity of the copper(ii) complexes correlates with their ability to induce ROS accumulation in cells, consistent with their redox potentials within the biological window, triggering the activation of antioxidation defense mechanisms in response to the ROS insult. These studies pave the way for the investigation of ROS-inducing copper(ii) complexes as prospective antiproliferative agents in cancer chemotherapy.

Stable chitosan/PVA-based hydrogels were obtained by combining covalent and physical cross-linking methods. As covalent cross-linkers, epoxy agents with different chain lengths were used, while freeze–thaw cycles were applied for additional physical cross-linking. The chemical structure of the hydrogel was examined by FTIR spectroscopy whereas the morphology was analyzed by SEM, showing well-defined pores with dimensions of around 50 μm in diameter. It was proved that gel fraction and the network morphology were deeply influenced by the synthesis conditions. Chitosan/PVA hydrogel showed a relative high swelling rate, reaching equilibrium in the first hour. The values obtained for the elastic modulus were relatively low (3–30 kPa); as a result, these hydrogels are soft and very flexible, and are ideal candidates for medical applications as wound or oral dressings. In addition, the natural antimicrobial activity of chitosan was enhanced by in situ generation of silver nanoparticles (AgNPs) under UV irradiation. The total amount of Ag from hydrogel was determined by elemental analyses and its crystalline state was confirmed by XRD. The CS/PVA hydrogels entrapped with AgNPs exhibited high inhibitory activity against S. aureus and K. pneumonia. The vitality tests confirmed the lack of cytotoxicity of CS/PVA hydrogels without and with AgNPs.

Every year about 7 million people die from of various types of cancer, making this disease responsible for 12.5% of deaths worldwide. Consequently, there is an overwhelming demand to develop new, more potent and effective, anticancer drugs. Natural products represent the most valuable source with inexhaustible reserves, in which the researchers work could identify novel active agents that may serve as the leads and scaffolds for transformation into desperately needed efficacious drugs. This paper is devoted to reviewing some of the most outstanding achievements in the application of natural products as models and precursors for anticancer agents published in the post 2000 literature. Particular emphasis is placed on the chemical modification of active principles isolated from natural products, in hope of obtaining the desirable derivatives for the treatment of different types of cancer, including pancreatic, gastric, breast, colon cancers and leukemia.

The bacterial KcsA channel conducts K(+) cations at high rates while excluding Na(+) cations. Herein, we report an artificial ion-channel formed by H-bonded stacks of crown-ethers, where K(+) cation conduction is highly preferred to Na(+) cations. The macrocycles aligned along the central pore surround the K(+) cations in a similar manner to the water around the hydrated cation, compensating for the energetic cost of their dehydration. In contrast, the Na(+) cation does not fit the macrocyclic binding sites, so its dehydration is not completely compensated. The present highly K(+)-selective macrocyclic channel may be regarded as a biomimetic of the KcsA channel.

This article presents current possibilities of using polyester-based materials in hard and soft tissue engineering, wound dressings, surgical implants, vascular reconstructive surgery, ophthalmology, and other medical applications. The review summarizes the recent literature on the key features of processing methods and potential suitable combinations of polyester-based materials with improved physicochemical and biological properties that meet the specific requirements for selected medical fields. The polyester materials used in multiresistant infection prevention, including during the COVID-19 pandemic, as well as aspects covering environmental concerns, current risks and limitations, and potential future directions are also addressed. Depending on the different features of polyester types, as well as their specific medical applications, it can be generally estimated that 25-50% polyesters are used in the medical field, while an increase of at least 20% has been achieved since the COVID-19 pandemic started. The remaining percentage is provided by other types of natural or synthetic polymers; i.e., 25% polyolefins in personal protection equipment (PPE).

The aim of this study was to evaluate the antibacterial activity of coriander essential oil and its major constituent, linalool, in combination with antibiotics against Gram-positive (methicillin-susceptible and methicillin-resistant Staphylococcus aureus, S. epidermidis) and Gram-negative bacteria (Pseudomonas aeruginosa, Escherichia coli). The chemical composition of coriander essential oil was analyzed by gas chromatography with flame ionization and mass spectrometry detection. The antibacterial activity of coriander essential oil, linalool and their combinations with antibiotics were assessed by the broth microdilution and checkerboard assays respectively. Thirty-four compounds were identified in coriander essential oil, linalool (70·11%) being predominant. Coriander essential oil and linalool showed synergistic interactions with antibiotics (oxacillin, amoxicillin, gentamicin, ciprofloxacin, tetracycline) against both Gram-positive and Gram-negative bacteria. In these synergistic combinations, minimum inhibitory concentrations of antibiotics were markedly reduced; even antibiotic resistance reversal activity was recorded. These findings are very promising for the development of new therapeutic options for bacterial infections. SIGNIFICANCE AND IMPACT OF THE STUDY: Methicillin-resistant Staphylococcus aureus (MRSA) and Gram-negative bacteria are still major threats to human health and, therefore, identification of new antibacterial agents or combinations with high potency is needed. Our study found synergistic interactions between coriander essential oil/linalool and antibiotics against MRSA and other Gram-positive bacteria (methicillin-susceptible S. aureus, S. epidermidis), but also Gram-negative bacteria (Pseudomonas aeruginosa, Escherichia coli). Increase in antibiotic susceptibility and reversal of antibiotic resistance were also demonstrated. Combinations of coriander essential oil/linalool and antibiotics are thus very promising for the development of novel antibacterials.

Abstract Castor oil–polyurethane elastomers were prepared by reacting poly (1,4‐butane diol) (Terathane 1400) with aliphatic 1,6‐hexamethylene diisocyanate. The prepolymers were chain‐extended with bifunctional precursor chains and/or with castor oil as a trifunctional crosslinker at stoichiometric ratios. These resulted in a series of crosslinked polyurethane elastomers with different structures of the hard segment. The properties of the material were measured by differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, as well as tensile properties measurements. The effect of stoichiometric balance (i.e., OH/NCO molar ratio) on the final properties was evaluated. The formation of hydrogen bonds was observed by Fourier transform infrared.spectroscopy The measured properties were found to be strongly influenced by the molar ratio of chain extenders to the diisocyanate component. The glass transition temperatures ( T g ) for the polyurethanes with OH polyol /NCO/OH chain extender having molar ratios of 1:2:1 and 1:4:3 were found to be −70 and −57 °C, respectively. The polyurethanes networks with a OH/NCO molar ratio of 1:2:1 had excellent mechanical properties, indicating that this is the optimum ratio to be used in castor oil polyurethane elastomer formulations. The objective of this work was to study the effect of the castor oil crosslinker on the morphology of the resulting crosslinked polyurethanes and to correlate the morphology with the properties of these bio‐based crosslinked polyurethanes.

Abstract Considerable confusion exists in the literature concerning the structure and properties of polyarylacetylenes. Taking into account the significant structural aspects from the literature data with our recent results on the polypentadeuterophenylacetylene isomers, we present our findings concerning this class of polymer.

The introduction of selective recognition sites toward certain heavy metal ions (HMIs) is a great challenge, which has a major role when the separation of species with similar physicochemical features is considered. In this context, ion-imprinted polymers (IIPs) developed based on the principle of molecular imprinting methodology, have emerged as an innovative solution. Recent advances in IIPs have shown that they exhibit higher selectivity coefficients than non-imprinted ones, which could support a large range of environmental applications starting from extraction and monitoring of HMIs to their detection and quantification. This review will emphasize the application of IIPs for selective removal of transition metal ions (including HMIs, precious metal ions, radionuclides, and rare earth metal ions) from aqueous solution by critically analyzing the most relevant literature studies from the last decade. In the first part of this review, the chemical components of IIPs, the main ion-imprinting technologies as well as the characterization methods used to evaluate the binding properties are briefly presented. In the second part, synthesis parameters, adsorption performance, and a descriptive analysis of solid phase extraction of heavy metal ions by various IIPs are provided.

Nanosized spinel ferrites MFe 2 O 4 (M = Ni, Co, and Zn) have been prepared by sol‐gel autocombustion method using citric acid as a fuel agent. The materials are characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). The spinel ferrites have been applied for Congo‐Red (CR) dye adsorption using batch technique. Different kinetic and equilibrium models have been fitted by nonlinear regression to analyze the adsorption data. In accordance with Langmuir isotherm, the maximum adsorption capacity at 293 K is 14.06 mg/g for CoFe 2 O 4 and 17.13 mg/g for NiFe 2 O 4 . The values of mean free energy determined from Dubinin‐Radushkevich isotherm are higher than 8 (kJ mol −1 ), indicating a chemisorption mechanism. Based on the calculated thermodynamic parameters (free energy, enthalpy, and entropy) the adsorption of CR onto ferrites is a spontaneous and endothermic process. Response surface methodology has been applied to construct the multiple regression models for prediction of the adsorption capacity and removal efficiency. The model‐based optimization has been performed using genetic algorithms and desirability function approach. The single‐objective optimization has yielded a maximum value of color removal efficiency of 98.995%, using NiFe 2 O 4 adsorbent. The multiobjective optimization has resulted in the improvement of both removal efficiency and adsorption capacity.

Vitamin B12 (VB12)-modified dextran-g-polyethyleneoxide cetyl ether (DEX-g-PEO-C16) was synthesized by linking VB12 residues to a DEX-g-PEO-C16 copolymer via a 2,2'-(ethylenedioxy)bis(ethylamine) spacer. The level of VB12 substitution on the DEX-g-PEO-C16 copolymer reached 1.68% (w/w). In aqueous solution, DEX-based copolymers form micelles that can entrap within their hydrophobic core up to 8.5% w/w of cyclosporin A (CsA), a poorly water soluble immunosuppressant. The permeability of Caco-2 cell membranes to CsA incorporated in VB12 modified and unmodified polymeric micelles was monitored in the presence and absence of intrinsic factor (IF). The apical (AP) to basolateral (BL) permeation of CsA through Caco-2 cell monolayers after 24 h of transport was significantly higher (1.8 and 2.3 times in absence and presence of IF, respectively) in the case of CsA loaded in VB12-modified polymeric micelles, compared to CsA in unmodified micelles. The results point to possible improvement in the application of polysaccharide-based polymeric micelles as targeted polymeric drug carriers for the oral delivery of poorly water soluble drugs.