Study on cellulose nanofibrils/copolymacrolactone based nano-composites with hydrophobic behaviour, self-healing ability and antioxidant activity.

The multiple uses of cellulose nanofibrils (CNFs) originate from their availability from renewable resources, and are due to their physico-chemical properties, biodegradability and biocompatibility. At the same time, reducing sensitivity to humidity, increasing interfacial adhesion and hydrophobic modification of the CNF surface to diversify applications and improve operation, are current targets pursued. This study focuses on the preparation of a novel gel structure using cellulose nanofibrils (CNFs) and poly(ethylene brassylate-co-squaric acid) (PEBSA50/50), a bio-based copolymacrolactone. The primary goal is to achieve the gel with reduced sensitivity to humidity and enhanced hydrophobic behaviour. The new system was characterized in comparison to its constituent components using various techniques, such as Fourier transform infrared spectroscopy, thermal analysis, X-ray diffraction, and NIR - chemical imaging. Rheological tests demonstrated the formation of the CNF_PEBSA50/50 gel as a result of physical interactions between the two polymeric partners and revealed self-healing abilities for the prepared gels. Determination of the contact angle, surface free energy, as well as dynamic measurements of the vapour sorption of the CNF_PEBSA50/50 system, confirmed the achievement of the study's aim. Furthermore, the CNF_PEBSA50/50 network was utilized to encapsulate citric acid, resulting in the creation of a new bioactive composite with both antioxidant and antimicrobial activity.

Wittig and Wittig-Horner Reactions under Sonication Conditions.

Carbonyl olefinations are among the most important organic syntheses that form C=C bonds, as they usually have high yields and in addition offer excellent stereoselectivity. Due to these advantages, carbonyl olefinations have important pharmaceutical and industrial applications. These reactions contain an additional step of an α-functionalized carbanion to an aldehyde or ketone to produce alkenes, but syntheses performed using metal carbene complexes are also known. The Wittig reaction is an example of carbonyl olefination, one of the best ways to synthesize alkenes. This involves the chemical reaction between an aldehyde or ketone with a so-called Wittig reagent, for instance phosphonium ylide. Triphenylphosphine-derived ylides and trialkylphosphine-derived ylides are the most common phosphorous compounds used as Wittig reagents. The Wittig reaction is commonly involved in the synthesis of novel anti-cancer and anti-viral compounds. In recent decades, the use of ultrasound on the Wittig reaction (and on different modified Wittig syntheses, such as the Wittig-Horner reaction or the aza-Wittig method) has been studied as a green synthesis. In addition to the advantage of green synthesis, the use of ultrasounds in general also improved the yield and reduced the reaction time. All of these chemical syntheses conducted under ultrasound will be described further in the present review.

Preparation of an Antioxidant Assembly Based on a Copolymacrolactone Structure and Erythritol following an Eco-Friendly Strategy.

The study presents the achievement of a new assembly with antioxidant behaviour based on a copolymacrolactone structure that encapsulates erythritol (Eryt). Poly(ethylene brassylate-co-squaric acid) (PEBSA) was synthesised in environmentally friendly conditions, respectively, through a process in suspension in water by opening the cycle of ethylene brassylate macrolactone, followed by condensation with squaric acid. The compound synthesised in suspension was characterised by comparison with the polymer obtained by polymerisation in solution. The investigations revealed that, with the exception of the molecular masses, the compounds generated by the two synthetic procedures present similar properties, including good thermal stability, with a Tpeak of 456 °C, and the capacity for network formation. In addition, the investigation by dynamic light scattering techniques evidenced a mean diameter for PEBSA particles of around 596 nm and a zeta potential of -25 mV, which attests to their stability. The bio-based copolymacrolactone was used as a matrix for erythritol encapsulation. The new PEBSA-Eryt compound presented an increased sorption/desorption process, compared with the PEBSA matrix, and a crystalline morphology confirmed by X-ray diffraction analysis. The bioactive compound was also characterised in terms of its biocompatibility and antioxidant behaviour.

The Influence of Boron on the Structure and Properties of Hybrid Compounds Containing Zirconium and Phosphorus.

In the present work, novel organic-inorganic hybrid materials containing boron, zirconium, and phosphorus were synthesized at different molar ratios, using the sol-gel method, starting from zirconyl chloride hexa-hydrate, triethyl borate, and phenyl phosphonic acid as the precursors. The sol-gel process is used for the first time in the present work in order to obtain organic-inorganic hybrids (or the so-called inorganic polymers) containing together boron, zirconium, and phosphorus. The sol-gel syntheses were performed at room temperature in ethanol. Zirconium containing compounds are already well known for their applications in medicine in restorative or prosthetic devices, including dental implants, knee and hip replacements, middle-ear ossicular chain reconstruction, and so on. Zirconium is a strong transition metal, which started to replace hafnium and titanium in the last decade in important applications. On the other hand, boron has the capability (similar to carbon) to form stable covalently bonded molecular networks. In addition to this capability, boron also offers mixed metallic and nonmetallic properties, because of its place on the periodic table, at the border between metals and nonmetals. Boron is responsible for the higher thermal stability of synthesized hybrid compounds. In the structure of those hybrid compounds, zirconium, boron, and phosphorus atoms are always connected via an oxygen atom, by P-O-Zr, Zr-O-Zr, or Zr-O-B bridges.

Hybrid Coordination Networks for Removal of Pollutants from Wastewater.

The adsorption properties of two coordination polymers, resulting from the reaction of divalent metal (Ca2+ or Co2+) salts with (2-carboxyethyl)(phenyl)phosphinic acid, are presented in this paper. The structural and textural characterization before and after adsorption experiments is presented. The adsorbent materials were prepared using the hydrothermal procedure. The compound Ca[O2P(CH2CH2COOH)(C6H5)]2 (CaCEPPA) has a layered topology, with the phenyl groups oriented into the interlayer space and crystallizes in the monoclinic system. Compound Co2[(O2P(CH2CH2COO)(C6H5)(H2O)]2·2H2O (CoCEPPA) has a 1D structure composed of zig-zag chains. The adsorption performances of CaCEPPA and CoCEPPA materials were tested in the removal of cadmium and lead from aqueous solutions. The optimum pH of ions adsorption was found to be five for both adsorbent materials. Pseudo-first and second-order kinetic models were used for fitting kinetic experimental data, and Langmuir and Freundlich isotherms were used for modeling the equilibrium experimental data. The pseudo-second-order kinetic model and Langmuir isotherm best described the adsorption of Cd and Pb ions onto the studied materials, judging from the results of the error function (correlation coefficient, sum of square error, chi-square test, and average relative error) analysis. The studied materials present a higher affinity for Cd ions compared with the adsorption capacity developed for the removal of Pb ions from aqueous solutions. CoCEPPA showed the highest adsorption performance in the removal process of metal ions from aqueous solutions compared with CaCEPPA (qm = 54.9 mg Cd2+/g of CoCEPPA, qm = 36.5 mg Cd2+/g of CaCEPPA).

Polymeric Carriers Designed for Encapsulation of Essential Oils with Biological Activity.

The article reviews the possibilities of encapsulating essential oils EOs, due to their multiple benefits, controlled release, and in order to protect them from environmental conditions. Thus, we present the natural polymers and the synthetic macromolecular chains that are commonly used as networks for embedding EOs, owing to their biodegradability and biocompatibility, interdependent encapsulation methods, and potential applicability of bioactive blend structures. The possibilities of using artificial intelligence to evaluate the bioactivity of EOs-in direct correlation with their chemical constitutions and structures, in order to avoid complex laboratory analyses, to save money and time, and to enhance the final consistency of the products-are also presented.

Advancement in the Biomedical Applications of the (Nano)gel Structures Based on Particular Polysaccharides.

(Nano)gels from macromolecular compounds-natural, synthetic, or a combination thereof, suitable crosslinkers-and conferred characteristics-such as degradability, size, charge, amphiphilicity, responsiveness, and softness-are capable of responding to the challenges imposed by bioengineering applications. Polysaccharide-based gels have received particular attention in this field. This review addresses recent advancement in the use of (nano)gel structures prepared only from compounds based on gellan gum, heparin, chondroitin sulfate, carrageenan, guar gum, galactose, or agarose, which represent an important part of the special class of natural polymers, the polysaccharides. Also, future trends are taken into discussion regarding the (nano)gels' use in biomedical applications such as biomimetics, biosensors, artificial muscles, and chemical separations in relation with their ability to be used as a vehicle for various biomolecules due to their physicochemical properties, biocompatibility, and biodegradability.

Potentiometric detection and removal of copper using porphyrins.

BACKGROUND: Copper is an essential trace element with a great importance in industry, environment and biological systems. The great advantage of ion-selective sensors in comparison with other proposed techniques is that they are measuring the free metal ion activity which is responsible for their toxicity. Porphyrins are known to be among the best ionophores in formulation of ion-selective sensors. RESULTS: A symmetrically substituted meso-porphyrin, namely: 5,10,15,20-tetrakis(4-allyloxyphenyl)porphyrin (TAPP) was used in the construction of a new copper selective-sensor and was also tested for the removal of copper from waste waters. The potentiometric response characteristics (slope and selectivity) of copper-selective electrodes based on TAPP in o-nitrophenyloctylether (o-NPOE), dioctyl phtalate (DOP) and dioctyl sebacate (DOS) plasticized with poly(vinyl chloride) membranes are compared. CONCLUSIONS: The best results were obtained for the membrane plasticized with DOP. The sensor has linear response in the range 1x10-7 - 1x10-1 M with 28.4 ± 0.4 mV/decade near-Nernstian slope towards copper ions and presents good selectivity. Due to its chelating nature, the same porphyrin was also tested for the retention of copper from synthetic copper samples, showing a maximum adsorption capacity of 280 mg/g.

A novel sensor for monitoring of iron(III) ions based on porphyrins.

Three A(3)B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10(-7)-1 × 10(-1) M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples.

Manganese(III) porphyrin-based potentiometric sensors for diclofenac assay in pharmaceutical preparations.

Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac-selective electrodes. The electroactive material was incorporated either in PVC or a sol-gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 × 10(-6) - 1 × 10(-2) M with a slope of -59.7 mV/dec diclofenac, a detection limit of 1.5 × 10(-6) M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods.