Natural Deep Eutectic Solvents as Rust Removal Agents from Lithic and Cellulosic Substrates.

The peculiar physicochemical features of deep eutectic solvents (DESs), in particular their tunability, make them ideal media for various applications. Despite their ability to solubilize metal oxides, their use as rust removers from valuable substrates has not yet been thoroughly investigated. In this study, we chose three known DESs, consisting of choline chloride and acetic, oxalic or citric acid for evaluating their ability to remove corrosion products from a cellulose-based material as linen fabric and two different lithotypes, as travertine and granite. The artificial staining was achieved by placing a rusty iron grid on their surfaces. The DESs were applied by means of cellulose poultice on the linen fabrics, while on the rusted stone surfaces with a cotton swab. Macro- and microscopic observations, colorimetry and SEM/EDS analysis were employed to ascertain the cleaning effectiveness and the absence of side effects on the samples after treatment. Oxalic acid-based DES was capable of removing rust stains from both stone and cellulose-based samples, while choline chloride/citric acid DES was effective only on stone specimens. The results suggest a new practical application of DESs for the elimination of rust from lithic and cellulosic substrates of precious and artistic value.

Pyoderma gangrenosum in ulcerative colitis patient treated with vedolizumab: adsorptive granulocyte/monocyte apheresis as a new therapeutic option refractory cases - a case report and literature review.

Extraintestinal manifestations occur rather frequently in ulcerative colitis (UC) and Crohn's disease patients and are usually related to an exacerbation of the underlying intestinal bowel disease but sometimes may run a course independent of the inflammatory bowel diseases (IBD). About one-third of patients with IBD develop extraintestinal manifestations, such as pyoderma gangrenosum (PG). PG is an uncommon inflammatory skin disorder of unknown pathogenesis. There are no specific serological or histological markers, and diagnosis is predominantly clinical. Topical and systemic therapies are both vital aspects of treatment and immune modulators have been used with increasing success in recent years, although immunosuppressive drugs raise some concerns due to an increased risk of serious and opportunistic infections and cancer, particularly in elderly and comorbid patients, underlining the unmet need for safer alternative therapies. Thus, in this case report, we highlighted an adsorptive granulocyte/monocyte apheresis (GMA) as a new therapeutic possibility in IBD patients with extraintestinal manifestations. We report a case of a 60-year woman with a history of UC with a Mayo grade 3 score which was associated with a PG. Given that the patients maintained clinical remission with vedolizumab, we preferred not to perform a combined treatment with other antitumor necrosis factor-alpha or ciclosporin, thus avoiding an increased risk of serious infections in the patient. Therefore, we performed the extracorporeal leukocyte apheresis. The patient progressed favorably, with progressive improvement of skin and bowel disease. Therefore, adsorptive GMA has a very favorable safety profile and has been confirmed in numerous studies. In this study, we underlined that an intensive regimen of GMA paves the way to an ideal option for patients with severe and refractory PG complicated with UC.

Prevention of Swelling Phenomenon of Alginate Beads To Improve the Stability and Recyclability of Encapsulated Horse Liver Alcohol Dehydrogenase.

Horse Liver Alcohol Dehydrogenase (HLADH) has been immobilized on calcium-alginate beads and used for both oxidation and reduction reactions. To avoid swelling of the beads and their subsequent breakage, calcium ions were added to both reaction and storage solutions, allowing the beads to maintain the initial structural features. The techniques used for this purpose revealed that 2 mM Ca2+ is the optimal concentration, which does not significantly change the weight of the beads, the amount of water in them, and their external and internal structure. The optimized experimental procedure has been used to verify the properties of the enzyme in terms of reusability, storage, and thermal stability. The addition of calcium ions allows the enzyme to retain more than 80 % of its initial activity for fourteen cycles and approximately 50 % at the twentieth cycle. Moreover, when the biocatalyst has been stored in a buffer solution containing 2 mM Ca2+ , the retention of enzyme activity after 30 days was 100 %, compared to that measured before incubation. The encapsulated enzyme exhibits greater thermal stability than free HLADH up to at least 60 °C, preventing dimer dissociation into the two subunits.

Biodeterioration of stone monuments: Studies on the influence of bioreceptivity on cyanobacterial biofilm growth and on the biocidal efficacy of essential oils in natural hydrogel.

An important field of research is devoted to the development of innovative, sustainable, and safe methodologies to counteract biodeterioration of stone monuments due to the growth of microbial communities. However, besides the biocide's efficacy, it is crucial to consider the features of substrates on which biocides must be applied, to define the so-called bioreceptivity of the lithic faces. In this research five different lithotypes, namely Lecce stone, Travertine, Peperino, Serena stone, and Granite, have been used as substrates for the growth of cyanobacterial biofilms. Open porosity, hygroscopic properties, and roughness parameters have been investigated for each lithotype and correlated to the photosynthetic yields of the biofilms colonizing the different stones to propose an easy method to estimate stone bioreceptivity. Different levels of coverage of the stone surfaces have been accomplished in relation to the typology of lithotypes. To develop innovative restoration methodologies against biodeterioration of stone monuments, a hydrogel-biocide system has been optimized by using a polysaccharide dispersion as a matrix where to embed T. vulgaris essential oil (at 0.25 % or 0.1 %) or its main component thymol (at 0.18 % or 0.07 %). The efficacy and the effect of the innovative biocide have been evaluated combining microscopy, photosynthetic measurements, and colorimetric analyses and both the biocides (with T. vulgaris EO or thymol) showed to be highly effective against the cyanobacterial biofilms for at least six months from the treatment without inducing any significant alteration to the lithic surfaces. The efficacy of thymol alone allows to treat colonized surfaces with a single active ingredient, or at least a mixture thereof, much cheaper and reproducible. The results obtained in this work pave the way to develop a sustainable cleaning protocol to counteract the biodeterioration of stone monuments or historic buildings induced by the presence of phototrophic biofilms that endangered their conservation.

Support-Activity Relationship in Heterogeneous Catalysis for Biomass Valorization and Fine-Chemicals Production.

Heterogeneous catalysts are progressively expanding their field of application, from high-throughput reactions for traditional industrial chemistry with production volumes reaching millions of tons per year, a sector in which they are key players, to more niche applications for the production of fine chemicals. These novel applications require a progressive utilization reduction of fossil feedstocks, in favor of renewable ones. Biomasses are the most accessible source of organic precursors, having as advantage their low cost and even distribution across the globe. Unfortunately, they are intrinsically inhomogeneous in nature and their efficient exploitation requires novel catalysts. In this process, an accurate design of the active phase performing the reaction is important; nevertheless, we are often neglecting the importance of the support in guaranteeing stable performances and improving catalytic activity. This review has the goal of gathering and highlighting the cases in which the supports (either derived or not from biomass wastes) share the worth of performing the catalysis with the active phase, for those reactions involving the synthesis of fine chemicals starting from biomasses as feedstocks.

Non-linear Terahertz driving of plasma waves in layered cuprates.

The hallmark of superconductivity is the rigidity of the quantum-mechanical phase of electrons, responsible for superfluid behavior and Meissner effect. The strength of the phase stiffness is set by the Josephson coupling, which is strongly anisotropic in layered cuprates. So far, THz light pulses have been used to achieve non-linear control of the out-of-plane Josephson plasma mode, whose frequency lies in the THz range. However, the high-energy in-plane plasma mode has been considered insensitive to THz pumping. Here, we show that THz driving of both low-frequency and high-frequency plasma waves is possible via a general two-plasmon excitation mechanism. The anisotropy of the Josephson couplings leads to markedly different thermal effects for the out-of-plane and in-plane response, linking in both cases the emergence of non-linear photonics across Tc to the superfluid stiffness. Our results show that THz light pulses represent a preferential knob to selectively drive phase excitations in unconventional superconductors.

Ionic and covalent crosslinking in chitosan-succinic acid membranes: Effect on physicochemical properties.

In this work, chitosan-succinic acid membranes were prepared by casting method and the physicochemical and mechanical properties of non-neutralized and neutralized with NaOH films were compared. Mechanical strength, flexibility, thermal stability and water-vapor permeability of chitosan membranes are significantly improved after neutralization. These improvements could be partly ascribed to the use of a dicarboxylic acid, which decreases the spacing between chitosan chains as a consequence of ionic crosslinking. Moreover, the addition of the strong base to the hydrogel promotes the formation of amide bonds, as suggested by FTIR analysis and demonstrated by acid-base titration. The favorable features of chitosan-succinic acid films as well as the possibility to easily incorporate drugs, enzymes, essential oils or other additives in the hydrogel, make such membranes suitable for many applications.

Table Olives Fermented in Iodized Sea Salt Brines: Nutraceutical/Sensory Properties and Microbial Biodiversity.

This research aimed to study the influence of different brining processes with iodized and noniodized salt on mineral content, microbial biodiversity, sensory evaluation and color change of natural fermented table olives. Fresh olives of Olea europaea Carolea and Leucocarpa cvs. were immersed in different brines prepared with two different types of salt: the PGI "Sale marino di Trapani", a typical sea salt, well known for its taste and specific microelement content, and the same salt enriched with 0.006% of KIO3. PGI sea salt significantly enriches the olive flesh in macroelements as Na, K and Mg, and microelements such as Fe, Mn, Cu and Zn. Instead, Ca decreases, P remains constant, while iodine is present in trace amounts. In the olives fermented in iodized-PGI sea salt brine, the iodine content reached values of 109 µg/100 g (Carolea cv.) and 38 µg/100 g (Leucocarpa cv.). The relationships between the two varieties and the mineral composition were explained by principal component analysis (PCA) and cluster analysis (CA). Furthermore, analyzing the fermenting brines, iodine significantly reduces the microbial load, represented only by yeasts, both in Carolea cv. and in Leucocarpa cv. Candida is the most representative genus. The sensory and color properties weren't significantly influenced by iodized brining. Only Carolea cv. showed significative difference for b* parameter and, consequently, for C value. Knowledge of the effects of iodized and noniodized brining on table olives will be useful for developing new functional foods, positively influencing the composition of food products.

Effect of Surfactant Structure on the Superactivity of Candida rugosa Lipase.

In this work, we present the effects of ionic and zwitterionic surfactants on the hydrolytic activity of Candida rugosa lipase (CRL), one of the most important and widely used microbial lipases. A series of amine N-oxide surfactants was studied to explore the relationship between their molecular structures and their effect on catalytic properties of CRL. These zwitterionic amphiphiles are known for their ability to form aggregates that can increase their size, thanks to a sphere-rod transition, without any additive. Enzyme activity seemed to be improved by morphological changes of micelles from spherical to rod-like, and the structure of the monomers played a crucial role in this transition. In fact, all the amine oxides investigated provoked superactivation, but the CRL activity increased by lengthening the alkyl chain of N-oxide surfactants, whereas it decreased in the presence of bulky head groups. Superactivity was mainly because of an increase in kcat (0.57 s-1 in buffer, 0.80-1.99 s-1 in surfactant solutions) and, in some cases, a decrease in KM (2 × 10-3 M in buffer, 1.08-4.28 × 10-3 M in surfactant solutions). Micelles seemed to play a dual role: superactivity occurred at surfactant concentrations higher than their critical micelle concentration, but, on the other hand, micelles subtracted the substrate from the bulk, making it unavailable for the catalysis.