Aging of a Poly(vinyl acetate)-Based White Glue and Its Durability in Contemporary Artworks.

While extensive research has focused on understanding the degradation mechanisms of Poly(vinyl acetate) (PVAC) paint under different environmental conditions, limited attention has been paid to the long-term stability of PVAC-based white glues, especially when used in artworks. This study investigates the accelerated degradation, under simulated photoaging, and isothermal treatment of a commercial PVAC-based white glue considered representative of this class of materials used in contemporary artworks to predict its durability and assess its behavior in art objects. Through accelerated aging experiments and comparison with natural aging observed in artworks, the study reveals the formation of chromophores and the release of plasticizers as key processes; in particular, the progressive darkening was considered an early indicator of degradation processes, before structural changes could be detected by FTIR or NMR spectroscopies. The plasticizer loss induces an increase in glass transition temperature, from 7 °C to temperatures higher than room temperature, affecting the adhesive's cohesive strength and contributing to the detachment of materials in artworks. The findings underscore the importance of preventive conservation measures to mitigate degradation issues in PVAC-based artworks.

S/N/O-Enriched Carbons from Polyacrylonitrile-Based Block Copolymers for Selective Separation of Gas Streams.

A series of polyacrylonitrile (PAN)-based block copolymers with poly(methyl methacrylate) (PMMA) as sacrificial bock were synthesized by atom transfer radical polymerization and used as precursors for the synthesis of porous carbons. The carbons enriched with O- and S-containing groups, introduced by controlled oxidation and sulfuration, respectively, were characterized by Raman spectroscopy, scanning electron microscopy, and X-ray photoelectron spectrometry, and their surface textural properties were measured by a volumetric analyzer. We observed that the presence of sulfur tends to modify the structure of the carbons, from microporous to mesoporous, while the use of copolymers with a range of molar composition PAN/PMMA between 10/90 and 47/53 allows the obtainment of carbons with different degrees of porosity. The amount of sacrificial block only affects the morphology of carbons stabilized in oxygen, inducing their nanostructuration, but has no effect on their chemical composition. We also demonstrated their suitability for separating a typical N2/CO2 post-combustion stream.

Thermal annealing as an easy tool for the controlled arrangement of gold nanoparticles in block-copolymer thin films.

Thermal annealing was used for the bottom-up fabrication of morphologically controlled gold-block-copolymer (Au-BC) nanocomposites. Three different blends formed by polystyrene (PS) homopolymer and PS-coated gold nanoparticles (PSSH@Au) were used as modifiers of asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA): PS26/PS26SH@Au, PS75/PS75SH@Au and PS167/PS167SH@Au (where the subscripts refer to the number of styrene monomeric units).The results indicated that all three blends used as modifiers (PSn/PSnSH@Au) were successfully located in the PS phase during thermally induced BC self-assembly for a composition range from 5 to 43 wt% without macro-phase separation. The PSnSH@Au moiety experienced molecular desorption, nanocrystal core coalescence and partial molecular re-encapsulation processes during thermal annealing, leading to sphere-like gold NPs with a larger average size (without exceeding an interdomain distance). Ligand chain length regulated the degree of coalescence and re-encapsulation, defining ultimate core size. Furthermore, proper combination of chain length and composition enabled tuning of NP partitioning and arrangement on different length scales through thermally activated cooperative assembly processes. These results have not only significant impact for establishing thermal processing as a useful tool for the precise control of NP size and distribution, but also much broader implications for many nanoparticle-based technologies.

Sensing soluble molecules through SERS substrates in one-step procedure: Unrevealing the Meiji woodblock printing materials.

Ultrasensitive SERS substrates allowed us to detect complex mixtures of coloring components from Meiji Japanese woodblock prints (1868-1912). In museum settings, compositional analyses have limitations due to restrictions to sampling advised by conservators and curators for the adequate preservation of the objects. An additional layer of complexity is brought by the high heterogeneity of heritage materials, usually not resolved with commercial portable instruments. High-performance instruments for in situ analyses are seldom available in museums. Furthermore, the chambers of most instruments for morphological or chemical characterization accommodate small samples rather than large or medium-sized objects. The innovative sampling strategy herein proposed comprises the gentle touch-dry removal of small coloring molecules weakly bound to the surface of heritage objects, transferred through a silicone sampler to planar SERS substrates with selected solvents in a one-step procedure. The analytical protocol reduces the amount of sample necessary for reliable identification of color components down to nanograms. The selectivity of the solvents combined with the geometry of the planar SERS sensing devices produces reliable signals for molecular identification, with no need for incision or wetting of the printed material. Further, 3D Raman imaging allowed us to reach an unprecedented degree of molecular discrimination, advancing previously available minimally-invasive instrumental methods used in heritage science research. The validation with historical inks from Meiji woodblock prints led to the identification of soluble synthetic azo ß-naphthols, barium sulfonic lakes, purple anilines, Prussian blue, glass arsenic sulfides and other traditional coloring media.

Study of the Long-Term Aging of Polypropylene-Made Disposable Surgical Masks and Filtering Facepiece Respirators.

The main purpose of this work is to contribute to understanding the mechanism of oxidation of the polymeric components of common disposable masks used during the COVID-19 pandemic to offer the chemical basis to understand their long-term behavior under typical environmental conditions. Artificial aging of representative mask layers under isothermal conditions (110 °C) or accelerated photoaging showed that all the PP-made components underwent a fast oxidation process, following the typical hydrocarbon oxidation mechanism. In particular, yellowing and the melting temperature drop are early indicators of their diffusion-limited oxidation. Morphology changes also induced a loss of mechanical properties, observable as embrittlement of the fabric fibers. Results were validated through preliminary outdoor aging of masks, which allows us to predict they will suffer fast and extensive oxidation only in the case of contemporary exposure to sunlight and relatively high environmental temperature, leading to their extensive breakdown in the form of microfiber fragments, i.e., microplastics.

Ag5 nanoclusters with dual catalytic antiradical activities.

Silver nanoclusters of five atoms (Ag5) display outstanding catalytic activities for the deactivation of radicals. Using 2,2-diphenyl-1­picrylhydrazyl (DPPH) radical as a model system, we observed a fast radical reduction to DPPH anions using only [Ag5] 3 to 4 orders of magnitude less than [DPPH]. Moreover, nanoclusters remain stable at the end of the reaction, and can deactivate again DPPH radicals at the same rate, indicating that they act as anti-radical catalysts. The radical scavenger catalytic activity of Ag5 proceeds selectively through the oxidation of methanol (used to dissolve the radical) to formaldehyde, which is supported by DFT calculations. The obtained catalytic rate constants are almost 2 orders of magnitude higher than oxidases, and more than 4 orders of magnitude larger than graphene quantum dots. We also show that Ag5 not only catalyze the reduction of radicals but also their oxidation, promoting the inhibition of the autoxidation mechanisms of hydrocarbon polymers, which are very sensitive to the presence of radicals. For this purpose, thin films of two industrially relevant polymers (polyisoprene and acrylonitrile-butadienestyrene copolymer), were exposed to standard simulated photo-ageing conditions in the presence of Ag5. Using Attenuated Total Reflection-FTIR and DFT modeling we observed that, although Ag5 nanoclusters, with ≈ 15% surface coverage, do not totally inhibit the oxidation, they favour a decomposition that yields inactive products, in contrast with the more detrimental ketone formation pathway. These results not only open new possibilities for developing a post-process inhibition of polymer degradation, for which nowadays there are no efficient procedures, but also, they could be used as very efficient dual-redox catalytic radical scavengers for different industrial or biomedical purposes.

Plastic matters: an analytical procedure to evaluate the degradability of contemporary works of art.

The most significant results concerning a chemical study to evaluate the degradability of polymeric components in four contemporary works of art, partially or completely realized in plastics, are presented and discussed in this paper. The procedure applied is mainly based on the use of Fourier transform IR and UV-vis spectroscopies and pyrolysis-gas chromatography/mass spectrometry, and consists of the following steps: (1) compositional analysis of the artworks, with particular attention to components which may have a negative effect on the overall ageing; (2) evaluation of the actual state of conservation; (3) investigation of the accelerated ageing of reference polymer samples; and (4) monitoring of the natural ageing of the artworks. On such a basis, the following could be concluded. Stage Evidence by Loris Cecchini is made of poly(ether urethane) elastomer which contains a high amount of phthalates. Their exudation gives a sticky appearance to the artwork and their removal during ageing is the main cause of the loss of flexibility. The latex used by Andrés Pinal for tailoring Traxe de Home is a natural polyisoprene, whose oxidative degradation accounts for the extensive deterioration and yellowing of the artwork. The plaster sculptures of 3D Bodyscans 1:9 by Karin Sander are coated with an aliphatic epoxy resin. Its oxidation with formation of amides is the cause of the surface yellowing. The adhesive used by Dario Villalba for Tierra, Ladrillo y Agua is a commercial poly(vinyl acetate). Simulated photoageing suggests a fast deterioration due to deacetylation and cross-linking, which possibly is the main reason for the actual detachment of debris from the support.

What Fate for Plastics in Artworks? An Overview of Their Identification and Degradative Behaviour.

This review is conceived as a guide for material science researchers and conservators aiming to face the problem of deterioration of contemporary artworks entirely or partially made of plastics. It initially illustrates the analytical approaches for identifying polymeric material components in 3D art objects, such as sculptures and installations, and provides a perspective of their limits and advantages. Subsequently, the methodologies used for studying the deterioration of contemporary art plastics are reviewed, emphasising the main effects of the different types of degradation (i.e., migration of additives, oxidation and hydrolysis) and suggesting the appropriate techniques for their detection. Finally, the application of artificial ageing tests is critically assessed. All the concepts are elaborated through case studies and examples.

Biochemical characterization of Nostoc sp. exopolysaccharides and evaluation of potential use in wound healing.

Exopolysaccharides (EPS) produced by cyanobacteria are complex biomolecules of anionic nature with potential biomedical applications. In this study, the EPS produced by the Nostoc sp. strains PCC7936 and PCC7413 were characterized and evaluated as a biomaterial for new wound dressings. The addition of acetate ions to the culture medium slightly stimulated EPS production, achieving 1463.1 ± 16.0 mgL-1 (PCC7413) and 1372.1 ± 29.0 mgL-1 (PCC7936). Both EPS presented nine monosaccharide residues and a MW > 1000 kDa. The acetate addition changed the monosaccharide molar percentages. FTIR and DLS results confirmed the anionic nature and the presence of sulfate groups in both EPS, which are determinant features for biomedical applications. Both EPS at 1%(w/v) formed gels in the presence of 0.4%(w/v) FeCl3. Results obtained for MTT assay and wound healing in vitro scratch assay revealed hydrogels biocompatibility and ability to promote fibroblast migration and proliferation that was greater in PCC7936. The Nostoc EPS hydrogels presented promising properties to be applied in the treatment of skin injuries.

A Global View on Block Copolymers.

In this systematic review, a total of 45,143 publications on block copolymers, issued between 1952 and 2019, are analyzed in terms of number, source, language, institution, country, keywords, and block copolymer type, to find out their evolution and predict research trends. The number of publications devoted to block copolymers has been growing for over six decades, maintaining a consistent level throughout the last few years. In their majority, documents came out of the United States, although more recently, Chinese institutions are those displaying the largest production. Keywords analysis indicated that one-third of the publications concerned synthesis, around 20% explored self-assembly and morphological aspects, and another 20% referred to block copolymer applications in solution. In particular, 2019 confirmed the expansion of studies related to drug delivery, and in minor extent, to a deeper view of self-assembling. Styrene-butadiene-styrene block copolymer was the most popular in studies covering both basic and industrially oriented aspects. Other highly investigated copolymers are PEO-b-PPO-b-PEO (Pluronic©) and amphiphilic block copolymers based on polycaprolactone or poly(lactic acid), which owed their success to their potential as delivery vehicles. Future trending topics will concern nanomedicine challenges and technology-related applications, with a special attention toward the orientation and ordering of mesophase-separated morphologies.

Dissolution of amorphous nifedipine from micelle-forming carboxymethylcellulose derivatives.

We show that a novel amphiphilic graft copolymer combining the biodegradability and biocompatibility of oxidized carboxymethylcellulose (CMC) with that of hydrophilic poly(ethylene glycol) (PEG), and hydrophobic dodecylamine (DDA), improves the solubility and dissolution performance of nifedipine (NIF), considered as a model hydrophobic drug. The hydrophobic components of the graft copolymer have the multiple effect of favouring micelle formation and loading. At the same time, the interaction between the hydrophobic core and NIF has the secondary effect to suppress drug crystallization, favouring its dissolution, and to increase photostability. Oxidized CMC-g-PEG-DDA micelles reached values of drug concentration, loading capacity and encapsulation efficiency as high as 340 µg mL-1, 6.4 % and 34.1 %, respectively. Loaded micelles showed a good stability with a limited release profile at pH 1.2, whereas at pH 7.4 the swollen cores enable much higher and progressive release, that reaches 3.4 and 6.6 % after 3 and 5 h, respectively, corresponding to very competitive concentration of 34 and 66 µg mL-1.

Characterization of contemporary and historical acrylonitrile butadiene styrene (ABS)-based objects: Pilot study for handheld Raman analysis in collections.

Plastic materials are increasingly becoming part of private and public collections worldwide, either as design objects or artistic sculptures. The preservation of these highly degradable materials requires novel analytical approaches able to reveal their chemical composition to inform the tailoring of appropriate conservation procedures. In this work Raman spectroscopy and Surface-enhanced Raman Scattering (SERS) were proposed as methods for the characterization of ABS-based contemporary and historical LEGO® objects. Twenty-three objects of twelve different colors were analyzed by handheld and benchtop Raman instrumentation. In all cases clear identification of the constituent polymer matrices (ABS, polycarbonate, poly(methyl metacrylate)) was obtained. In addition, identification of major color components was achieved, such as copper phthalocyanines in green and blue objects. Low cost handheld instrumentation provided acceptable sensitivity towards polymers and coloring media, and was found suitable for initial screening of the objects. Benchtop Raman was used to confirm and further extend identification, as well as for building background information. Finally, SERS sensitivity was found comparable to the sensitivity achieved by benchtop Raman instrumentation. However, the associated minimally-invasive sampling method made SERS a valid alternative to direct Raman spectroscopy for the analysis of immovable and/or large-sized objects. Overall, this work represents the first systematic investigation on the potential of Raman and SERS spectroscopies as methods for minimal invasive and/or in situ analysis of historical and contemporary plastic objects.

Some Guidelines for the Synthesis and Melting Characterization of Azide Poly(ethylene glycol) Derivatives.

We provide fundamental guidelines in the form of a tutorial to be taken into account for the preparation and characterization of a specific class of poly(ethylene glycol) (PEG) derivatives, namely azide-terminated PEGs. Special attention is given to the effect of these chain end groups and their precursors on properties affecting the PEGylation of proteins, nanoparticles and nanostructured surfaces. Notwithstanding the presence of 13C satellite peaks, we show that 1H NMR enables not only the routine quantitative determination of chain-end substitution, but is also a unique method to calculate the absolute number average molecular weight of PEG derivatives. In the use of size exclusion chromatography to get molecular weight distributions, we highlight the importance of distinguishing between eventual secondary reactions involving molecular weight changes and the formation of PEG complexes due to residual amounts of metal cations from reactants. Finally, we show that azide end groups affect PEG melting behavior. In contrast to oxygen-containing end groups, azides do not interact with PEG segments, thus inducing defect formation in the crystal lattice and the reduction of crystal sizes. Melting temperature and degree of crystallinity decrease become especially relevant for PEGs with very low molecular weight, and its comprehension is particularly important for solid-state applications.

Micellization phenomena in semicrystalline block copolymers: reflexive and critical views on the formation of cylindrical micelles.

Investigations on the self-assembly of block copolymers in solution have in some way a less well-studied history than the study of their phase separation in the solid state, and many aspects are yet not completely understood. Here we focus on the behavior of a specific class of copolymers, namely semicrystalline block copolymers, capable of forming cylindrical aggregates in a solvent selective for the non-crystalline, complementary block. A common model of micellization is proposed, in principle applicable to most of these copolymeric systems.

Detection of degradation markers from polymer surfaces by a novel SERS-based strategy.

This paper provides new insights for the study of polymer degradation through the detection of markers released at the polymer surface using Al-coated SERS active substrates. Combining a nanodestructive sampling procedure with the SERS sensitivity allows achieving detection limits much lower than traditional polymer characterization techniques, opening the way to the use of SERS as part of an innovative strategy to diagnose surface degradation in polymeric museum artefacts. The method was applied to artificially photo-aged model polymers and to museum artworks.

Surface enhanced Raman scattering (SERS) in the visible range on scalable aluminum-coated platforms.

We demonstrate the potential of combining plasmonic Bragg grating structures, with the scattering effect of a rough Al layer to tune SERS enhancement in the visible region. Novel Al-based substrates with good analytical reproducibility and enhancement factors in the range of 107-109 are produced by a scalable procedure which meets the development of producing sustainable SERS platforms.

Relaxation Dynamics in Polyethylene Glycol/Modified Hydrotalcite Nanocomposites.

Polyethylene glycol-based nanocomposites containing an organo-modified hydrotalcite with loadings ranging from 0.5 to 5 wt.% were prepared by melt mixing performed just above the melting point of the polymer matrix. In these conditions, the dispersion of the nanofiller within the polymer matrix was quite homogeneous as revealed by TEM analyses. The effect of various thermal treatments and filler loadings was thoroughly investigated by means of rheological, morphological and gas chromatography-mass spectrometry, hyphenated to thermogravimetry analysis tests. Unfilled polyethylene glycol exhibited a continuous decrease in complex viscosity upon heating. In contrast, the complex viscosity of nanocomposites containing nanofiller loadings higher than 1 wt.% showed first a decrease, followed by an increase in the complex viscosity as the temperature increases, exhibiting a minimum between 130 and 140 °C. Annealing at 180 °C for different times further increased the viscosity of the system. This unusual behavior was explained by the occurrence of grafting reactions between the ⁻OH terminal groups of the polyethylene glycol chains and the hydroxyl groups of the organo-modified filler, thus remarkably affecting the relaxation dynamics of the system.

Self-assembly: a minimalist route to the fabrication of nanomaterials.

Self-assembly of molecular or nonmolecular components by non-covalent interactions offers an invaluable tool for the preparation of discrete nanostructures and extended 2D and 3D materials, which are often not accessible by any other fabrication process. In this article we summarize the most recent advances in the generation of nanomaterials such as self-assembled monolayers (SAMs) and structures formed from amphiphilic molecules, colloids, peptides, and polymers by nontemplated self-assembly either at the solid state or in solution. The current status of templated self-assembly and the use of self-assembled structures as template and for patterning other materials is also covered. A special emphasis is placed on strategies presenting either original and somehow exploratory approaches, eventually combining bottom-up and top-down methods, or that concern methods for the production of materials with potential application, e.g., in photonics, as sensors, for drug delivery and electric and magnetic devices. In all the sections, we outline self-organization and applications enabled with self-separated block copolymers.

Preparation and characterization of crosslinked chitosan/gelatin scaffolds by ice segregation induced self-assembly.

Chitosan and gelatin are biodegradable and biocompatible polymers which may be used in the preparation of 3D scaffolds with applications in biomedicine. Chitosan/gelatin scaffolds crosslinked with glutaraldehyde were prepared by ice segregation induced self-assembly (ISISA); a unidirectional freezing at -196°C followed freeze-drying to produce macroporous materials with a well-patterned structure. This process may be included within the green chemistry by the preparation of the porous structures without using organic solvents, moreover is a versatile, non-difficult and cheap process. The scaffolds prepared by ISISA were characterized by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, and their stability was evaluated by degree swelling and degradation tests. The scaffolds present properties as high porosity, high degree swelling and good stability which make them suitable of applications as biomaterials.

Tuning Ordered Pattern of Pd Species through Controlled Block Copolymer Self-Assembly.

We report a method for the preparation of ordered patterns of Pd species on a substrate based on the use of polystyrene-block-poly(ethylene oxide) copolymer (PS-b-PEO) templates and selective inclusion of palladium (Pd) species in the PEO domains. PS-b-PEO samples of different total molecular masses self-assemble in a cylindrical microphase-separated morphology, in which vertically aligned PEO cylinders, with different diameters depending on the molecular mass, are organized in a hexagonal array of different lateral spacings. The cylindrical nanostructure is maintained after the selective inclusion of Pd species (Pd acetate and Pd nanoparticles (NPs) after reduction of Pd ions of the salt) in the PEO cylinders so that the characteristic sizes (diameters and lateral spacings) of the included Pd species are tuned by the characteristic sizes of the block copolymer (BCP) template, which are regulated by molecular mass. Treatment of nanocomposites at elevated temperatures in air removes the polymer matrix and leads to the formation of arrays of palladium oxide (PdO) NPs covering a solid support. The patterns of PdO NPs are characterized by different particle diameters and gap distances, mirroring the patterns and characteristic nanodimensions of the parent BCPs used as templates.