State-of-the-Art Macromolecules in Portugal.

This Special Issue presents five contributions covering various topics, as it would be expected for an area as comprehensive and multidisciplinary as Macromolecules [...].

Transport Properties in Multicomponent Systems Containing Cyclodextrins and Nickel Ions.

In this work, we propose a comprehensive experimental study of the diffusion of nickel ions in combination with different cyclodextrins as carrier molecules for enhanced solubility and facilitated transport. For this, ternary mutual diffusion coefficients measured by Taylor dispersion method are reported for aqueous solutions containing nickel salts and different cyclodextrins (that is, α-CD, ß-CD, and γ-CD) at 298.15 K. A combination of Taylor dispersion and other methods, such as UV-vis spectroscopy, will be used to obtain complementary information on these systems. The determination of the physicochemical properties of these salts with CDs in aqueous solution provides information that allows us to understand solute-solvent interactions, and gives a significant contribution to understanding the mechanisms underlying diffusional transport in aqueous solutions, and, consequently, to mitigating the potential toxicity associated with these metal ions. For example, using mutual diffusion data, it is possible to estimate the number of moles of each ion transported per mole of the cyclodextrin driven by its own concentration gradient.

Chitosan-Based Beads Incorporating Inorganic-Organic Composites for Copper Ion Retention in Aqueous Solutions.

In recent years, there has been a challenging interest in developing low-cost biopolymeric materials for wastewater treatment. In the present work, new adsorbents, based on different types of chitosan (commercial, commercial chitin-derived chitosan and chitosan synthesized from shrimp shell waste) and inorganic-organic composites have been evaluated for copper ions removal. The efficacy of the synthesis of chitosan-based composite beads has been determined by studying various characteristics using several techniques, including FTIR spectroscopy, X-ray diffraction, porosimetry (N2 adsorption), and scanning electron microscopy (SEM). Adsorption kinetics was performed using different adsorption models to determine the adsorption behavior of the materials in the aqueous media. For all composite beads, regardless of the type of chitosan used, good capacity to remove copper ions from simulated waters was observed (up to 17 mg/g), which proves that the new materials hold potential for heavy metal retention. However, the adsorption efficiency was influenced by the type of chitosan used. Thus, for the series where commercial chitosan (CC) was used, the removal efficiency was approximately 29%; for the series with chitosan obtained from commercial chitin (SC), the removal efficiency was approximately 34%; for the series with chitosan enriched with CaCO3 (SH), the removal efficiency was approximately 52%.

Levulinic Acid-Based "Green" Solvents for Lignocellulose Fractionation: On the Superior Extraction Yield and Selectivity toward Lignin.

The high potential use of lignin in novel biomaterials and chemicals represents an important opportunity for the valorization of the most abundant natural resource of aromatic molecules. From an environmental perspective, it is highly desirable replacing the hazardous methods currently used to extract lignin from lignocellulosic biomass and develop more sustainable and environmentally friendly approaches. Therefore, in this work, levulinic acid (a "green" solvent obtained from biomass) was successfully used, for the first time, to selectively extract high-quality lignin from pine wood sawdust residues at 200 °C for 6 h (at atmospheric pressure). Moreover, the addition of catalytic concentrations of inorganic acids (i.e., H2SO4 or HCl) was found to substantially reduce the temperature and reaction times needed (i.e., 140 °C, 2 h) for complete lignin extraction without compromising its purity. NMR data suggests that condensed OH structures and acidic groups are present in the lignin following extraction. Levulinic acid can be easily recycled and efficiently reused several times without affecting its performance. Furthermore, excellent solvent reusability and performance of extraction of other wood residues has been successfully demonstrated, thus making the developed levulinic acid-based procedure highly appealing and promising to replace the traditional less sustainable methodologies.

Interactions between Sodium Hyaluronate and ß-Cyclodextrin as Seen by Transport Properties.

Knowledge of mass transport parameters, diffusion, and viscosity of hyaluronic acid (HA) in the presence of cyclodextrins is of considerable importance for areas such as food packaging and drug delivery, among others. Despite a number of studies investigating the functionalization of HA or the corresponding sodium salt by cyclodextrins, only a few studies have reported the effect of cyclodextrins on the mass transport of HA in the presence of these oligosaccharides. Here, we report the tracer binary and ternary interdiffusion coefficients of sodium hyaluronate (NaHy) in water and aqueous ß-cyclodextrin solutions. The diffusion behavior of sodium hyaluronate was dependent on the reduced viscosity of NaHy, which, in turn, presented a concave dependence on concentration, with a minimum at approximately 2.5 g dm-3. The significant decrease in the limiting diffusion coefficient of NaHy (at most 45%) at NaHy concentrations below 1 g dm-3 in the presence of ß-cyclodextrin, taking water as the reference, allowed us to conclude that NaHy strongly interacted with the cyclodextrin.

Interactions of Sodium Salicylate with ß-Cyclodextrin and an Anionic Resorcin[4]arene: Mutual Diffusion Coefficients and Computational Study.

The interaction between sodium salicylate (NaSal) and the two macrocycles 5,11,17,23-tetrakissulfonatomethylene-2,8,14,20-tetra(ethyl)resorcinarene (Na4EtRA) and ß-cyclodextrin (ß-CD) has been studied by the determination of ternary mutual diffusion coefficients, and spectroscopic and computational techniques. The results obtained by the Job method suggest that the complex formation is given in a 1:1 ratio for all systems. The mutual diffusion coefficients and the computational experiments have shown that the ß-CD-NaSal system presents an inclusion process, whereas the Na4EtRA-NaSal system forms an outer-side complex. This fact is also in line with the results obtained from the computational experiments, where the calculated solvation free energy has been found to be more negative for the Na4EtRA-NaSal complex because of the partial entry of the drug inside the Na4EtRA cavity.

Luminescent Papers with Asymmetric Complexes of Eu(III) and Tb(III) in Polymeric Matrices and Suggested Combinations for Color Tuning.

Complexes of lanthanide ions, such as Eu(III) (red light emission) and Tb(III) (green light emission), with proper ligands can be highly luminescent and color-tunable, also attaining yellow and orange emission under UV radiation. The ligands employed in this work were poly(sodium acrylate), working as polymeric matrix, and 1,10-phenanthroline, taking advantage of its antenna effect. Possibilities of color display were further enhanced by incorporating a cationic polyfluorene with blue emission. This strategy allowed for obtaining cyan and magenta, besides the aforementioned colors. Uncoated cellulose paper was impregnated with the resulting luminescent inks, observing a strong hypsochromic shift in excitation wavelength upon drying. Hence, while a cheap UV-A lamp sufficed to reveal the polyfluorene's blue emission, shorter wavelengths were necessary to visualize the emission due to lanthanide ions as well. The capacity to reveal, with UV-C radiation, a full-color image that remains invisible under natural light is undoubtedly useful for anti-counterfeiting applications. Furthermore, both lanthanide ion complexes and polyfluorenes were shown to have their luminescence quenched by Cu(II) ions and nitroarenes, respectively.

Reduced Chitosan as a Strategy for Removing Copper Ions from Water.

Toxic heavy metals are priority pollutants in wastewater, commonly present in dangerous concentrations in many places across the globe. Although in trace quantities copper is a heavy metal essential to human life, in excess it causes various diseases, whereby its removal from wastewater is a necessity. Among several reported materials, chitosan is a highly abundant, non-toxic, low-cost, biodegradable polymer, comprising free hydroxyl and amino groups, that has been directly applied as an adsorbent or chemically modified to increase its performance. Taking this into account, reduced chitosan derivatives (RCDs 1-4) were synthesised by chitosan modification with salicylaldehyde, followed by imine reduction, characterised by RMN, FTIR-ATR, TGA and SEM, and used to adsorb Cu(II) from water. A reduced chitosan (RCD3), with a moderate modification percentage (43%) and a high imine reduction percentage (98%), proved to be more efficient than the remainder RCDs and even chitosan, especially at low concentrations under the best adsorption conditions (pH 4, RS/L = 2.5 mg mL-1). RCD3 adsorption data were better described by the Langmuir-Freundlich isotherm and the pseudo-second-order kinetic models. The interaction mechanism was assessed by molecular dynamics simulations, showing that RCDs favour Cu(II) capture from water compared to chitosan, due to a greater Cu(II) interaction with the oxygen of the glucosamine ring and the neighbouring hydroxyl groups.

Nanostructuring with Surfactants: The Self-Assembly of a New Poly(thiophene-phenylene) Conjugated Polymer Bearing Azacrown Ether Pendant Groups.

We report the synthesis of a new conjugated polymer bearing crown ether moieties, poly[(N(1-aza-[18]crown-6)carbamido)thiophene-2,5-diyl-alt-1,4-phenylene] (BG2). In water, BG2 forms a dispersion with a slightly cloudy appearance. We have studied the effect of adding surfactants, with different polar head groups, on these polymer-polymer aggregates. Special attention is given to the system with the anionic surfactant, sodium dodecyl sulfate (SDS). The combination of photophysical techniques with electrical conductivity, NMR (1H, 13C, and 27Na), DFT calculations, molecular dynamics simulations, and small-angle neutron scattering (SANS) provides a detailed picture on the behavior of the SDS/BG2 system in aqueous solution and in thin films. NMR, electric conductivity, and DFT results suggest that hydrophilic interactions occur between the polar headgroup of the surfactant (OSO3- Na+) and the aza-[18]-crown-6 moiety. DFT calculations confirmed the capability of BG2 to form stable complexes with the Na+ cations, where the cation can be either inside the azacrown cavity or sandwiched between the cavity and the polymer chain, which seem to determine the position of the surfactant hydrocarbon chain and, therefore, be responsible for the disruption of the BG2 aggregates and subsequent increase in the photoluminescence quantum yields. SANS measurements, made with hydrogenated and deuterated SDS in D2O, clearly show how micron-sized aggregates of BG2 are broken down by SDS and then how BG2 becomes preferentially incorporated within joint colloidal particles of BG2 and SDS with increasing [SDS]/[BG2] molar ratio.

Synthesis of ß-cyclodextrin-based nanosponges for remediation of 2,4-D polluted waters.

Two cyclodextrin-based nanosponges (CD-NSs) were synthesized using diamines with 6 and 12 methylene groups, CDHD6 and CDHD12, respectively, and used as adsorbents to remove 2,4-D from aqueous solutions. The physico-chemical characterization of the CD‒NSs demonstrated that, when using the linker with the longest chain length, the nanosponges show a more compact structure and higher thermal stability, probably due to hydrophobic interactions. SEM micrographs showed significant differences between the two nanosponges used. The adsorption of 2,4-D was assessed in terms of different parameters, including solid/liquid ratio, pH, kinetics and isotherms. Adsorption occurred preferentially at lower pH values and for short-chain crosslinked nanosponges; while the former is explained by the balance of acid-base characteristics of the adsorbent and adsorbate, the latter can be justified by the increase in the crosslinker-crosslinker interactions, predominantly hydrophobic, rather than adsorbent-adsorbate interactions. The maximum adsorption capacity at the equilibrium (qe) was 20,903 mmol/kg, obtained using CDHD12 with an initial 2,4-D concentration of 2 mmol/L. An environmentally friendly strategy, based on alkali desorption, was developed to recycle and reuse the adsorbents. On the basis of the results obtained, cyclodextrin-based nanosponges appear promising materials for an economically feasible removal of phenoxy herbicides, to be used as potential adsorbents for the sustainable management of agricultural wastewaters.

Paper-Based Probes with Visual Response to Vapors from Nitroaromatic Explosives: Polyfluorenes and Tertiary Amines.

Although it is well-known that nitroaromatic compounds quench the fluorescence of different conjugated polymers and form colored Meisenheimer complexes with proper nucleophiles, the potential of paper as a substrate for those macromolecules can be further developed. This work undertakes this task, impregnating paper strips with a fluorene-phenylene copolymer with quaternary ammonium groups, a bisfluorene-based cationic polyelectrolyte, and poly(2-(dimethylamino)ethyl methacrylate) (polyDMAEMA). Cationic groups make the aforementioned polyfluorenes attachable to paper, whose surface possesses a slightly negative charge and avoid interference from cationic quenchers. While conjugated polymers had their fluorescence quenched with nitroaromatic vapors in a non-selective way, polyDMAEMA-coated papers had a visual response that was selective to 2,4,6-trinitrotoluene (TNT), and that could be easily identified, and even quantified, under natural light. Far from implying that polyfluorenes should be ruled out, it must be taken into account that TNT-filled mines emit vapors from 2,4-dinitrotoluene (DNT) and dinitrobenzene isomers, which are more volatile than TNT itself. Atmospheres with only 790 ppbv TNT or 277 ppbv DNT were enough to trigger a distinguishable response, although the requirement for certain exposure times is an important limitation.

On the Development of Phenol-Formaldehyde Resins Using a New Type of Lignin Extracted from Pine Wood with a Levulinic-Acid Based Solvent.

Resole resins have many applications, especially for foam production. However, the use of phenol, a key ingredient in resoles, has serious environmental and economic disadvantages. In this work, lignin extracted from pine wood using a "green" solvent, levulinic acid, was used to partially replace the non-sustainable phenol. The physicochemical properties of this novel resin were compared with resins composed of different types of commercial lignins. All resins were optimized to keep their free formaldehyde content below 1 wt%, by carefully adjusting the pH of the mixture. Substitution of phenol with lignin generally increases the viscosity of the resins, which is further increased with the lignin mass fraction. The addition of lignin decreases the kinetics of gelification of the resin. The type and amount of lignin also affect the thermal stability of the resins. It was possible to obtain resins with higher thermal stability than the standard phenol-formaldehyde resins without lignin. This work provides new insights regarding the development of lignin-based resoles as a very promising sustainable alternative to petrol-based resins.

Enhanced water absorption of tissue paper by cross-linking cellulose with poly(vinyl alcohol).

Abstract: Tissue paper was the only paper grade whose consumption increased during 2020 in Europe. In a highly competitive context, this work explores a strategy based on bisacrylamide cross-linkers and poly(vinyl alcohol) (PVA), seeking to enhance the water uptake of pulps for tissue paper and the key properties of the resulting tissue sheets: water absorption capacity, capillarity, softness, porosity, and strength. For that, α-cellulose from cotton and a kraft hardwood pulp, in parallel, were reacted with N,N'-methylenebisacrylamide, both in the absence and in the presence of PVA. The water desorption rate of the modified polymers was monitored. Pulp blends were then mixed with a conventional softwood pulp (30%) to prepare laboratory tissue paper sheets (20 g m-2). For cotton cellulose, cross-linking with PVA more than doubled the water uptake, up to 7.3 g/g. A significant enhancement was also obtained in the case of pulps, up to 9.6 g/g, and in the case of paper, to 11.9 g/g. This improvement was consistent with a drastic increase in porosity, and it was not detrimental to paper strength.

Effect of Hofmeister Ions on Transport Properties of Aqueous Solutions of Sodium Hyaluronate.

Tracer diffusion coefficients obtained from the Taylor dispersion technique at 25.0 °C were measured to study the influence of sodium, ammonium and magnesium salts at 0.01 and 0.1 mol dm-3 on the transport behavior of sodium hyaluronate (NaHy, 0.1%). The selection of these salts was based on their position in Hofmeister series, which describe the specific influence of different ions (cations and anions) on some physicochemical properties of a system that can be interpreted as a salting-in or salting-out effect. In our case, in general, an increase in the ionic strength (i.e., concentrations at 0.01 mol dm-3) led to a significant decrease in the limiting diffusion coefficient of the NaHy 0.1%, indicating, in those circumstances, the presence of salting-in effects. However, the opposite effect (salting-out) was verified with the increase in concentration of some salts, mainly for NH4SCN at 0.1 mol dm-3. In this particular salt, the cation is weakly hydrated and, consequently, its presence does not favor interactions between NaHy and water molecules, promoting, in those circumstances, less resistance to the movement of NaHy and thus to the increase of its diffusion (19%). These data, complemented by viscosity measurements, permit us to have a better understanding about the effect of these salts on the transport behaviour of NaHy.

Effect of Cobalt and Chromium Ions on the Chlorhexidine Digluconate as Seen by Intermolecular Diffusion.

Metal ions such as cobalt (II) and chromium (III) might be present in the oral cavity, as a consequence of the corrosion of Co-Cr dental alloys. The diffusion of such metal ions into the organism, carried by saliva, can cause health problems as a consequence of their toxicity, enhanced by a cumulative effect in the body. The effect of the chlorhexidine digluconate, which is commonly used in mouthwash formulations, on the transport of these salts is evaluated in this paper by using the Taylor dispersion technique, which will allow an assessment of how the presence of chlorhexidine digluconate (either in aqueous solution or in a commercial formulation) may affect the diffusion of metal ions. The ternary mutual diffusion coefficients of metal ions (Co and Cr) in the presence of chlorhexidine digluconate, in an artificial saliva media, were measured. Significant coupled diffusion of CoCl2 (and CrCl3) and chlorhexidine digluconate is observed by analysis of the non-zero values of the cross-diffusion coefficients, D12 and D21. The observed interactions between metal ions and chlorhexidine digluconate suggest that the latter might be considered as an advantageous therapeutic agent, once they contribute to the reduction of the concentration of those ions inside the mouth.

Poly(ß-cyclodextrin)-Activated Carbon Gel Composites for Removal of Pesticides from Water.

Pesticides are widely used in agriculture to increase and protect crop production. A substantial percentage of the active substances applied is retained in the soil or flows into water courses, constituting a very relevant environmental problem. There are several methods for the removal of pesticides from soils and water; however, their efficiency is still a challenge. An alternative to current methods relies on the use of effective adsorbents in removing pesticides which are, simultaneously, capable of releasing pesticides into the soil when needed. This reduces costs related to their application and waste treatments and, thus, overall environmental costs. In this paper, we describe the synthesis and preparation of activated carbon-containing poly(ß-cyclodextrin) composites. The composites were characterized by different techniques and their ability to absorb pesticides was assessed by using two active substances: cymoxanil and imidacloprid. Composites with 5 and 10 wt% of activated carbon showed very good stability, high removal efficiencies (>75%) and pesticide sorption capacity up to ca. 50 mg g-1. The effect of additives (NaCl and urea) was also evaluated. The composites were able to release around 30% of the initial sorbed amount of pesticide without losing the capacity to keep the maximum removal efficiency in sorption/desorption cycles.

Thermo- and pH-Responsive Gelatin/Polyphenolic Tannin/Graphene Oxide Hydrogels for Efficient Methylene Blue Delivery.

Gelatin (GE), amino-functionalized polyphenolic tannin derivative (TN), and graphene oxide (GO) were associated to yield thermo- and pH-responsive hydrogels for the first time. Durable hydrogel assemblies for drug delivery purposes were developed using the photosensitizer methylene blue (MB) as a drug model. The cooling GE/TN blends provide brittle physical assemblies. To overcome this disadvantage, different GO contents (between 0.31% and 1.02% wt/wt) were added to the GE/TN blend at 89.7/10.3 wt/wt. FTIR and RAMAN spectroscopy analyses characterized the materials, indicating GO presence in the hydrogels. Incorporation studies revealed a total MB (0.50 mg/mL) incorporation into the GE/TN-GO hydrogel matrices. Additionally, the proposed systems present a mechanical behavior similar to gel. The GO presence in the hydrogel matrices increased the elastic modulus from 516 to 1650 Pa. SEM revealed that hydrogels containing MB present higher porosity with interconnected pores. Dissolution and swelling degree studies revealed less stability of the GE/TN-GO-MB hydrogels in SGF medium (pH 1.2) than SIF (pH 6.8). The degradation increased in SIF with the GO content, making the polymeric matrices more hydrophilic. MB release studies revealed a process controlled by Fickian diffusion. Our results point out the pH-responsible behavior of mechanically reinforced GE/TN-GO-MB hydrogels for drug delivery systems purposes.

Removal of Imidacloprid from Water by Microalgae Nannochloropsis sp. and Its Determination by a Validated RP-HPLC Method.

The large-scale use of pesticides is one of the main causes of the dramatic degradation of our environment. Pesticides such as imidacloprid (IMID) have been linked to declines in bee health and toxicity to other beneficial insects. They pose a threat to human health due to their persistence in the environment and accumulation in the food chain. Therefore, it is essential to test possible environmentally-friendly solutions for their elimination. The present study evaluates the efficiency of microalgae Nannochloropsis sp. for the removal of IMID from synthetic wastewater. The influence of aeration, light, and the presence of UV radiation on the degradation of IMID were factors considered in the study. A rapid RP-HPLC method was developed and validated for the analysis and quantification of IMID in the context of bioremediation with microalgae. Nannochloropsis sp. removed 4.39 µg mL-1 from an initial content of 9.59 µg mL-1 (reaching approximately 50%) of IMID in the first 20 h. This study demonstrated that the removal of IMID by the marine microalgae Nannochloropsis sp. is both effective and light-dependent.

Non-Newtonian Thermosensitive Nanofluid Based on Carbon Dots Functionalized with Ionic Liquids.

Non-Newtonian nanofluids present outstanding features in terms of energy transfer and conductivity with high application in numerous areas. In this work, non-Newtonian nanofluids based on carbon dots (Cdots) functionalized with ionic liquids (ILs) are developed. The nanofluids are produced using a simple, single-step method where the raw materials for the Cdots synthesis are glucose and waste biomass (chitin from crab shells). The use of ILs as both reaction media and functionalization molecules allows for the development of a new class of nanofluids, where the ILs on the Cdots surface represent the base-fluid. Here, the well-known benign IL 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) and a novel home-made IL (1-tosylate-3-methyl-imidazolium triflate) [Tmi][Trif] are used. The nanofluids obtained from both substrates show, apart from high conductivity and viscosity, light absorption, and good wettability, an appealing thermal sensitivity behavior. This thermal sensitivity is preserved even when applied as thin films on glass slides and can be boosted using the surface plasmon resonance effect. The results reported demonstrate that the new Cdots/IL-based nanofluids constitute a versatile and cost-effective route for achieving high-performance thermosensitive non-Newtonian sustainable nanofluids with tremendous potential for the energy coatings sector and heat transfer film systems.

Chitosan-Based Coacervate Polymers for Propolis Encapsulation: Release and Cytotoxicity Studies.

Chitosan-DNA (CS-DNA) and Chitosan-Pectin (CS-P) hydrogels were formulated as a sustained drug delivery carrier for drug delivery. For this, hydrogels were prepared by emulsion technique: mixing aqueous phase of the CS and DNA or P solution with benzyl alcohol using a high-performance dispersing instrument. Green Propolis (GP) was incorporated by imbibition: hydrogels were placed in GP aqueous solution (70 µg/mL) for 2 h. The specimens were freeze-dried and then characterized using different techniques. In vitro cell viability and morphology were also performed using the MG63 cell line. The presence of P was evidenced by the occurrence of a strong band at 1745 cm-1, also occurring in the blend. DNA and CS-DNA showed a strong band at 1650 cm-1, slightly shifted from the chitosan band. The sorption of GP induced a significant modification of the gel surface morphology and some phase separation occurs between chitosan and DNA. Drug release kinetics in water and in saliva follow a two-step mechanism. Significant biocompatibility revealed that these hydrogels were non-toxic and provided acceptable support for cell survival. Thus, the hydrogel complexation of chitosan with DNA and with Pectin provides favorable micro-environment for cell growth and is a viable alternative drug delivery system for Green Propolis.