Effects of Structurally Different Tertiary Amines on the Properties of Quaternized Anionic Exchange Membranes Potentially Applicable for Water Electrolysis.

In this work, two structurally different monoamines (trimethylamine [TMA] and N-methylpiperidine [N-MPip]) are used for the amination of a g-VBC-15 graft copolymer, obtained by the functionalization of a mechanically robust, commercially available styrene-butadiene block copolymer (SB) with vinylbenzyl chloride (VBC) via solution free-radical polymerization. Results demonstrate that g-VBC-15-based membranes quaternized with TMA have superior electrochemical performance than N-MPip counterparts; while, the mechanical properties are good and only slightly inferior to those of N-MPip. Therefore, TMA is the selected monoamine to be alternatively mixed with two polyamines (tetramethyl-1,3-propanediamine [TMPDA] and N,N,N',N'',N''-pentamethyldiethylenetriamine [PMDETA]) into different proportions, in order to modulate the average functionality of the amination mixture in terms of number of amine functional groups available for the quaternization reaction of the membranes. g-VBC-15-based membranes derived therefrom are extensively characterized to assess their thermal, mechanical, and ex situ electrochemical properties. Results indicate that membranes quaternized with a TMA/PMDETA mixture (90:10 in mole) display the highest conductivity among all the investigated membranes aminated with polyamine-based mixtures. Moreover, they have comparable mechanical and electrochemical properties to those quaternized with TMA, while exhibiting a reduced water uptake.

Poly(ethylene glycol)-graft-poly(vinyl acetate) single-chain nanoparticles for the encapsulation of small molecules.

Amphiphilic poly(ethylene glycol)-graft-poly(vinyl acetate) copolymers with a low degree of grafting undergo self-folding in water driven by hydrophobic interactions, resulting in single-chain nanoparticles (SCNPs) possessing a hydrodynamic radius of about 10 nm. A temperature scan revealed a lower critical solution temperature (LCST)-type phase behavior. In addition, SAXS data collected close to the LCST showed that these SCNPs aggregate into one-dimensional elongated objects, preferentially. With respect to the typical linear complex-structured polymer chains, this material is ideally suited for industrial and/or biomedical applications because of its simple molecular architecture and persistence of SCNPs up to 100 mg mL-1. The so-obtained single-chain globular particles are able to swell upon loading with small hydrophobic molecules therefore promoting solubilization of flavors or drugs, which could be of interest in the food and pharmaceutical industry.

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen-Type Lanthanide (III) Complexes.

The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides stable and inert complexes KLnL2 upon simple reaction with lanthanide halides or pseudohalides LnX3 (Ln = Tb(3+) -Lu(3+) ; X = Cl(-) or TfO(-) ) of its potassium salt. All the complexes were completely characterized through nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) in the UV and some (Er(3+) , Tm(3+) , Yb(3+) ) also with Near-IR ECD (NIR-ECD) and luminescence (Tb(3+) , Tm(3+) ). Careful analysis of the NMR shifts demonstrated that the complexes are isostructural in solution and afforded an accurate geometry. This was further confirmed by means of Density Functional Theory (DFT) optimization of the Lu(3+) complex, and by comparing the ligand-centered experimental and time-dependent TD-DFT computed UV-ECD spectra. As final validation, we used the NIR-ECD spectrum of the Yb(3+) derivative calculated by means of Richardson's equations. The excellent match between calculated and experimental ECD spectra confirm the quality of the NMR structure.

Sponge-like Cryogels from Liquid-Liquid Phase Separation: Structure, Porosity, and Diffusional Gel Properties.

Macroporous gels find application in several scientific fields, ranging from art restoration to wastewater filtration or cell entrapment. In this work, two-component sponge-like cryogels are challenged to assess their cleaning performances and to investigate how pores size and connectivity affect physico-chemical properties. The gels were obtained through a freeze-thaw process, exploiting a spontaneous polymer-polymer phase-separation occurring in the pre-gel solution. During the freezing step, a highly hydrolyzed polyvinyl alcohol (H-PVA) forms the hydrogel walls. The secondary components, namely a partially hydrolyzed polyvinyl alcohol (L-PVA) or polyvinyl pyrrolidone (PVP), act as modular porogens, being partially extracted during gel washing. H-PVA/L-PVA and H-PVA/PVP mixtures were studied by confocal laser scanning microscopy to unveil sols and gels morphology at the micron-scale, while small angle X-ray scattering was used to get insights about characteristic dimensions at the nanoscale. The gelation mechanism was investigated through rheology measurements, and the characteristic exponents were compared to De Gennes' scaling laws gathered from percolation. In the field of art conservation, these sponge-like gels are ideal systems for the cleaning of artistic painted surfaces. Their interconnected pores allow the diffusion of cleaning fluids at the painted interface, facilitating dirt uptake and/or detachment. This study uncovered a direct relationship linking a gel's cleaning performance to its apparent tortuosity. These findings can pave the way to fine-tuning systems with enhanced cleaning abilities, not restricted to the restoration of irreplaceable priceless works of art, but with possible application in diverse research fields.

Vinylbenzyl Chloride/Styrene-Grafted SBS Copolymers via TEMPO-Mediated Polymerization for the Fabrication of Anion Exchange Membranes for Water Electrolysis.

In this work, a commercial SBS was functionalized with the 2,2,6,6-tetramethylpiperidin-N-oxyl stable radical (TEMPO) via free-radical activation initiated with benzoyl peroxide (BPO). The obtained macroinitiator was used to graft both vinylbenzyl chloride (VBC) and styrene/VBC random copolymer chains from SBS to create g-VBC-x and g-VBC-x-co-Sty-z graft copolymers, respectively. The controlled nature of the polymerization as well as the use of a solvent allowed us to reduce the extent of the formation of the unwanted, non-grafted (co)polymer, thereby facilitating the graft copolymer's purification. The obtained graft copolymers were used to prepare films via solution casting using chloroform. The -CH2Cl functional groups of the VBC grafts were then quantitatively converted to -CH2(CH3)3N+ quaternary ammonium groups via reaction with trimethylamine directly on the films, and the films, therefore, were investigated as anion exchange membranes (AEMs) for potential application in a water electrolyzer (WE). The membranes were extensively characterized to assess their thermal, mechanical, and ex situ electrochemical properties. They generally presented ionic conductivity comparable to or higher than that of a commercial benchmark as well as higher water uptake and hydrogen permeability. Interestingly, the styrene/VBC-grafted copolymer was found to be more mechanically resistant than the corresponding graft copolymer not containing the styrene component. For this reason, the copolymer g-VBC-5-co-Sty-16-Q with the best balance of mechanical, water uptake, and electrochemical properties was selected for a single-cell test in an AEM-WE.

Self-Assembly of Soluplus in Aqueous Solutions: Characterization and Prospectives on Perfume Encapsulation.

Soluplus is an amphiphilic graft copolymer intensively studied as a micellar solubilizer for drugs. An extensive characterization of the nanostructure of its colloidal aggregates is still lacking. Here, we provide insights into the polymer's self-assembly in water, and we assess its use as an encapsulating agent for fragrances. The self-assembly properties of Soluplus aqueous solutions were studied over a wide concentration range (1-70% w/w) by means of small-angle neutron scattering (SANS), differential scanning calorimetry, NMR, and rheometry. SANS analyses revealed the presence of polymeric micelles with a fuzzy surface interacting via a 2-Yukawa potential, up to 15% w/w polymer. Increasing the polymer concentration up to 55% w/w led to tightly packed micelles described according to the Teubner-Strey model. The ability of Soluplus to encapsulate seven perfume molecules, 2-phenyl ethanol, l-carvone, linalool, florhydral, ß-citronellol, α-pinene, and R-limonene, was then examined. We showed that the fragrance's octanol/water partition coefficient (log Kow), widely used to characterize the solubilization capacity, is not sufficient to characterize such systems and the presence of specific functional groups or molecular conformation needs to be considered. In fact, the combination of SANS, NMR, confocal laser scanning microscopy, and confocal Raman microscopy showed that the perfumes, interacting with different regions of the polymer aggregates, are able to tune the systems' structures resulting in micelles, matrix-type capsules, core-shell capsules, or oil-in-water emulsions.

Carbon dioxide hydrogenation to formic acid by using a heterogeneous gold catalyst.

AUROlite, consisting of gold supported on titania (picture shows extrudates in a steel net cage), is a robust catalyst for the production of catalyst-free HCOOH/NEt(3) adducts from H(2), CO(2), and neat NEt(3). Pure HCOOH is freed from the adducts by amine exchange.

Encapsulation of volatile compounds in liquid media: Fragrances, flavors, and essential oils in commercial formulations.

The first marketed example of the application of microcapsules dates back to 1957. Since then, microencapsulation techniques and knowledge have progressed in a plethora of technological fields, and efforts have been directed toward the design of progressively more efficient carriers. The protection of payloads from the exposure to unfavorable environments indeed grants enhanced efficacy, safety, and stability of encapsulated species while allowing for a fine tuning of their release profile and longer lasting beneficial effects. Perfumes or, more generally, active-loaded microcapsules are nowadays present in a very large number of consumer products. Commercial products currently make use of rigid, stable polymer-based microcapsules with excellent release properties. However, this type of microcapsules does not meet certain sustainability requirements such as biocompatibility and biodegradability: the leaking via wastewater contributes to the alarming phenomenon of microplastic pollution with about 4% of total microplastic in the environment. Therefore, there is a need to address new issues which have been emerging in relation to the poor environmental profile of such materials. The progresses in some of the main application fields of microencapsulation, such as household care, toiletries, cosmetics, food, and pesticides are reviewed herein. The main technologies employed in microcapsules production and the mechanisms underlying the release of actives are also discussed. Both the advantages and disadvantages of every technique have been considered to allow a careful choice of the most suitable technique for a specific target application and prepare the ground for novel ideas and approaches for encapsulation strategies that we expect to be proposed within the next years.

Photopolymerizable pullulan: Synthesis, self-assembly and inkjet printing.

HYPOTHESIS: Pullulan, an exopolysaccharide consisting of maltotriose repeating units, has recently found many applications in different fields, such as food, packaging, cosmetics and pharmaceuticals. The introduction of photo-crosslinkable methacrylic units potentially allows to use pullulan derivative in inkjet 3D printing. EXPERIMENTS: Pullulan was functionalized with methacrylic groups and the derivative was characterized by NMR, FT-IR and Raman spectroscopy. Water dispersions were thoroughly investigated by optical microscopy, SAXS and rheology to evaluate the self-assembly properties and they were used as photo-crosslinkable inks in a 3D printer, also in comparison with pristine pullulan. The structural and mechanical properties of the obtained films were studied by Atomic Force Microscopy and tensile strength tests. FINDINGS: The introduction of methacrylic groups moderately affects the self-assembly of the polymer in water, resulting in a slight increase of the gyration radius of the polymer coils and in a small decrease of the viscosity, retaining the typical shear-thinning behavior of concentrated polysaccharides in water. The structural and mechanical properties of the 3D printed films are much more affected, showing the presence of sub-micrometric phase segregated domains which are further separated by the cross-linking. As a result, the deformability of the materials is improved, with a lower tensile strength.

Tuning the Encapsulation of Simple Fragrances with an Amphiphilic Graft Copolymer.

The encapsulation of poorly water-soluble compounds such as perfumes, flavors, and bioactive molecules is a key step in the formulation of a large variety of consumer products in the fields of household care and personal care. We study the encapsulation ability of an amphiphilic poly(ethylene glycol)-graft-poly(vinyl acetate) (PEG-g-PVAc) graft copolymer, extending the focus to the entire phase diagram of polymer/perfume/water systems with three common natural fragrances. The three perfume molecules (2-phenyl ethanol, L-carvone, and α-pinene) possess different water affinities, as expressed by their octanol/water partition coefficients. The investigation of the polymorphism of PEG-g-PVAc in these systems is carried out by means of dynamic light scattering, small-angle X-ray scattering, NMR spectroscopy, and confocal laser scanning microscopy. The results presented here demonstrate that the choice of fragrance can dramatically affect the supramolecular structures formed by the polymer in aqueous solution, with important consequences on formulations of industrial interest such as the demixing of complex perfume blends when one or more of the components have no chemical affinity for any of the polymer blocks.

Interaction between a cationic bolaamphiphile and DNA: The route towards nanovectors for oligonucleotide antimicrobials.

Bacterial resistance to antimicrobials is a global threat that requires development of innovative therapeutics that circumvent its onset. The use of Transcription Factor Decoys (TFDs), DNA fragments that act by blocking essential transcription factors in microbes, represents a very promising approach. TFDs require appropriate carriers to protect them from degradation in biological fluids and transfect them through the bacterial cell wall into the cytoplasm, their site of action. Here we report on a bolaform cationic surfactant, [12-bis-THA]Cl2, with proven transfection activity in vivo. By studying the physical-chemical properties of its aqueous solutions with light scattering, cryo-TEM, ζ-potential, absorption and fluorescence spectroscopies, we prove that the bolaamphiphiles associate into transient vesicles which convert into one-dimensional elongated structures over time. These surfactant assemblies complex TFDs with extremely high efficiency, if compared to common cationic amphiphiles. At Z+/-=11, the nanoplexes are stable and have a size of 120nm, and they form independently of the original morphology of the [12-bis-THA]Cl2 aggregate. DNA is compacted in the nanoplexes, as shown through CD spectroscopy and fluorescence, but is readily released in its native form if sodium taurocholate is added.

Circularly polarized luminescence under near-UV excitation and structural elucidation of a Eu complex.

A new chiral diketonate ligand based on carvone binds early lanthanides. The Eu complex displays high circularly polarized (g(lum) = 0.82) red luminescence under near-UV excitation in the solid state. This is the first report on such CPL activity in the solid state with a rigorous protocol to exclude artifacts. Paramagnetic NMR spectroscopy revealed the nature and structure of the active species.