Facile and Bioinspired Approach from Gallic Acid for the Synthesis of Biobased Flame Retardant Coatings of Basalt Fibers.

A sustainable, bioinspired approach to functionalize basalt fibers with an innovative gallic acid (GA)-iron phenyl phosphonate complex (BF-GA-FeP), for the purpose of improving the flame retardancy in composite materials, is developed. BFs were at first pretreated with O3, obtaining surface free hydroxyl groups that allowed the subsequent covalent immobilization of biosourced GA units on the fiber through ester linkages. Phenolic -OH groups of the GA units were then exploited for the complexation of iron phenyl phosphonate, resulting in the target-complex-coated BF fiber (BF-GA-FeP). Microwave plasma atomic emission spectroscopy and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analyses of BF-GA-FeP highlighted an increase in iron content, modification of fiber morphology, and occurrence of phosphorus, respectively. BFs, modified with a low amount of the developed complex, were used to reinforce a poly(lactic acid) (PLA) matrix in the production of a biocomposite (PLA/BF-FeP). PLA/BF-FeP showed a higher thermal stability than neat PLA and PLA reinforced with untreated BFs (PLA/BF), as confirmed by thermogravimetric analysis. The cone calorimeter test highlighted several advantages for PLA/BF-FeP, including a prolonged time to ignition, a reduced time to flame out, an 8% decrease in the peak heat release rate, and a 15% reduced fire propagating index compared to PLA/BF.

Biological Effects of Small Sized Graphene Oxide Nanosheets on Human Leukocytes.

Since the discovery of graphene, there has been a wide range of the literature dealing with its versatile structure and easy binding of biomolecules as well as its large loading capacity. In the emerging field of immunotherapy, graphene and its derivatives have potential uses as drug delivery platforms directly into tumour sites or as adjuvants in cancer vaccines, as they are internalized by monocytes which in turn may activate adaptive anti-tumoral immune responses. In this study, we expose cells of the innate immune system and a human acute monocytic leukemia cell line (THP-1) to low doses of small-sized GO nanosheets functionalized with bovine serum albumin (BSA) and fluorescein isothiocyanate (FITC), to study their acute response after internalization. We show by flow cytometry, uptake in cells of GO-BSA-FITC reaches 80% and cell viability and ROS production are both unaffected by exposure to nanoparticles. On the contrary, GO-BSA nanosheets seem to have an inhibitory effect on ROS production, probably due to their antioxidant properties. We also provided results on chemotaxis of macrophages derived from peripheral blood monocytes treated with GO-BSA. In conclusion, we showed the size of nanosheets, the concentration used and the degree of functionalization were important factors for biocompatibility of GO in immune cells. Its low cytotoxicity and high adaptability to the cells of the innate immune system make it a good candidate for deployment in immunotherapy, in particular for delivering protein antigens to monocytes which activate adaptive immunity.

Efficient synthesis and investigation of waste-derived adsorbent for water purification. Exploring the impact of surface functionalization on methylene blue dye removal.

In pursuit of sustainable water management, the preparation of adsorbent materials via waste upcycling for water purification practices plays a decisive role. The sulphonated biochar, PiNe-SO3H, employed to target the methylene blue dye adsorption, was successfully synthesized via a mild, step-economical chemical carbonization-functionalization reaction. The presence of SO3H groups on the PiNe-SO3H surface played a critical role in significantly enhancing the adsorption capacity. The observed MB dye uptake was predominantly attributed to chemisorption processes as evidenced by the results from kinetics, thermodynamics, and isotherms. To further confirm the role of -SO3H in the adsorption mechanism, a comparison was made with other PiNe materials lacking sulphonic groups, highlighting the superior adsorption capacity of PiNe-SO3H. Additionally, a fast and efficient regeneration process was proposed to develop a truly waste minimized protocol, enabling the recovery of up to 94 % of the ethanolic mixture used during this step.

A General Enantioselective C-H Arylation Using an Immobilized Recoverable Palladium Catalyst.

We herein report a general and efficient enantioselective C-H arylation of aryl bromides based on the use of BozPhos as the bisphosphine ligand and SP-NHC-PdII as recoverable heterogeneous catalyst. By exploiting the "release and catch" mechanism of action of the catalytic system, we used BozPhos as a broadly applicable chiral ligand, furnishing high enantioselectivities across all types of examined substrates containing methyl, cyclopropyl and aryl C-H bonds. For each reaction, the reaction scope was investigated, giving rise to 30 enantioenriched products, obtained with high yields and enantioselectivities, and minimal palladium leaching. The developed catalytic system provides a more sustainable solution compared to homogeneous systems for the synthesis of high added-value chiral products through recycling of the precious metal.

The Association between Dysnatraemia during Hospitalisation and Post-COVID-19 Mental Fatigue.

COVID-19 may induce short- and long-term cognitive failures after recovery, but the underlying risk factors are still controversial. Here, we investigated whether (i) the odds of experiencing persistent cognitive failures differ based on the patients' disease course severity and sex at birth; and (ii) the patients' electrolytic profile in the acute stage represents a risk factor for persistent cognitive failures. We analysed data from 204 patients suffering from COVID-19 and hospitalised during the first pandemic wave. According to the 7-point WHO-OS scale, their disease course was classified as severe or mild. We investigated the presence of persistent cognitive failures collected after hospital discharge, while electrolyte profiles were collected during hospitalisation. The results showed that females who suffered from a mild course compared to a severe course of COVID-19 had a higher risk of presenting with persistent mental fatigue after recovery. Furthermore, in females who suffered from a mild course of COVID-19, persistent mental fatigue was related to electrolyte imbalance, in terms of both hypo- and hypernatremia, during hospitalisation in the acute phase. These findings have important implications for the clinical management of hospitalised COVID-19 patients. Attention should be paid to potential electrolyte imbalances, mainly in females suffering from mild COVID-19.

POLITAG-M-F as Heterogeneous Organocatalyst for the Waste-Minimized Synthesis of ß-Azido Carbonyl Compounds in Batch and under Flow Conditions.

We herein report a waste minimization protocol for the ß-azidation of α,ß-unsaturated carbonyl compounds using TMSN3. The selection of the appropriate catalyst (POLITAG-M-F), in combination with the reaction medium, resulted in enhanced catalytic efficiency and a low environmental footprint. The thermal and mechanical stability of the polymeric support allowed us to recover the POLITAG-M-F catalyst for up to 10 consecutive runs. The CH3CN:H2O azeotrope has a 2-fold positive effect on the process, increasing the efficiency of the protocol and minimizing waste generation. Indeed, the azeotropic mixture, used as a reaction medium and for the workup procedure, was recovered by distillation, leading to an easy and environmentally friendly procedure for product isolation in high yield and with a low E-factor. A comprehensive evaluation of the environmental profile was performed by the calculation of different green metrics (AE, RME, MRP, 1/SF) and a comparison with other literature available protocols. A flow protocol was defined to scale-up the process, and up to 65 mmol of substrates were efficiently converted with a productivity of 0.3 mmol/min.

Neural underpinnings of the slowness of information processing in patients with traumatic brain injury: insights from tract-based spatial statistics.

Slowness of information processing (SIP) is frequently reported after traumatic brain injury (TBI). Previous studies point toward a pivotal role of white matter damage on speed of information processing. However, little is known about the more comprehensive and ecological assessment of SIP in TBI. Here, we combined an ecological assessment of SIP with the use of tract-based spatial statistics (TBSS) on individuals' fractional anisotropy (FA) maps. Twenty-six moderate-to-severe patients with TBI (21 males and 5 females) participated in this study: 10 individuals were classified as not having SIP (SIP-) and 16 were classified as having SIP (SIP +). SIP + showed lower FA in bilateral anterior thalamic radiation, corticospinal tract, cingulum, and forceps, as well as in bilateral inferior fronto-occipital, inferior and superior longitudinal fasciculi and uncinate fasciculus. Overall, this result is consistent with and expands previous reports on information processing speed to a more comprehensive and ecological perspective on SIP in TBI.

Two Ecological Tools for Testing Slowness of Information Processing in Italian Patients with Moderate-to-Severe Traumatic Brain Injury.

Slowness of Information Processing (SIP) is frequently experienced after traumatic brain injury (TBI); however, the impact of SIP on everyday functioning may be underestimated by standard neuropsychological tests. OBJECTIVE: we aimed to adapt two ecological instruments assessing SIP in Italian patients with moderate-to-severe TBI, as formerly proposed by Winkens and colleagues for persons with stroke, testing also its possible relation with other neuropsychological processes and functional outcomes. METHOD: we performed an observational study on 37 patients with moderate-to-severe TBI and 35 demographically matched healthy controls, who underwent the Mental Slowness Observation Test (MSOT) and the Mental Slowness Questionnaire (MSQ), which had been adapted through a pilot study on independent sample of participants; extensive neuropsychological and functional evaluations were performed as well. RESULTS: We found good clinical and psychometric properties of the Italian adaptation of the MSOT and MSQ; also, performance on MSOT significantly correlated with executive functions. Moreover, patients with TBI are significantly slower and less accurate than healthy controls on the MSOT, in particular in tasks with time limits. Even if the subjective feeling of SIP does not differ between patients and controls, we found a significant correlation between MSQ and MSOT. Finally, the performances on the MSOT correlated with measures of functional outcome and community integration. CONCLUSIONS: the results support the use of the MSOT and the MSQ to measure SIP in an ecological fashion in patients with TBI, so that specific treatments for persons with acquired brain injury can be prescribed.

A Waste-Minimized Approach to Cassar-Heck Reaction Based on POLITAG-Pd0 Heterogeneous Catalyst and Recoverable Acetonitrile Azeotrope.

Three different Pd0 -based heterogeneous catalysts were developed and tested in the Cassar-Heck reaction (i. e., copper-free Sonogashira reaction) aiming at the definition of a waste minimized protocol. The cross-linked polymeric supports used in this investigation were designed to be adequate for different reaction media and were decorated with different pincer-type ionic ligands having the role of stabilizing the formation and dimension of palladium nanoparticles. Among the ionic tags tested, bis-imidazolium showed the best performances in terms of efficiency and durability of the metal catalytic system. Eventually, aqueous acetonitrile azeotrope was selected as the reaction medium as it allowed the best catalytic efficiency combined with easy recovery and reuse. Finally, the synergy between the selected catalyst and reaction medium allowed to obtain highly satisfactory isolated yields of a variety of substrates while using a low amount of metal catalyst. The high performance of the designed POLymeric Ionic TAG (POLITAG)-Pd0 , along with its good selectivity achieved in a copper-free process, also led to a simplified purification procedure allowing the minimization of the waste generated as also proven by the very low E-factor values (1.4-5) associated.

Metal Nanoparticles as Sustainable Tools for C-N Bond Formation via C-H Activation.

The design of highly active metal nanoparticles to be employed as efficient heterogeneous catalysts is a key tool for the construction of complex organic molecules and the minimization of their environmental costs. The formation of novel C-N bonds via C-H activation is an effective atom-economical strategy to access high value materials in pharmaceuticals, polymers, and natural product production. In this contribution, the literature of the last ten years on the use of metal nanoparticles in the processes involving direct C-N bond formation will be discussed. Where possible, a discussion on the role and influence of the support used for the immobilization and/or the metal chosen is reported. Particular attention was given to the description of the experiments performed to elucidate the active mechanism.

Azeotropes as Powerful Tool for Waste Minimization in Industry and Chemical Processes.

Aiming for more sustainable chemical production requires an urgent shift towards synthetic approaches designed for waste minimization. In this context the use of azeotropes can be an effective tool for "recycling" and minimizing the large volumes of solvents, especially in aqueous mixtures, used. This review discusses the implementation of different kinds of azeotropic mixtures in relation to the environmental and economic benefits linked to their recovery and re-use. Examples of the use of azeotropes playing a role in the process performance and in the purification steps maximizing yields while minimizing waste. Where possible, the advantages reported have been highlighted by using E-factor calculations. Lastly azeotrope potentiality in waste valorization to afford value-added materials is given.

Cognitive Outcomes and Relationships with Phenylalanine in Phenylketonuria: A Comparison between Italian and English Adult Samples.

We aimed to assess if the same cognitive batteries can be used cross-nationally to monitor the effect of Phenylketonuria (PKU). We assessed whether a battery, previously used with English adults with PKU (AwPKU), was also sensitive to impairments in Italian AwPKU. From our original battery, we selected a number of tasks that comprehensively assessed visual attention, visuo-motor coordination, executive functions (particularly, reasoning, planning, and monitoring), sustained attention, and verbal and visual memory and learning. When verbal stimuli/or responses were involved, stimuli were closely matched between the two languages for psycholinguistic variables. We administered the tasks to 19 Italian AwPKU and 19 Italian matched controls and compared results from with 19 English AwPKU and 19 English matched controls selected from a previously tested cohort. Participant election was blind to cognitive performance and metabolic control, but participants were closely matched for age and education. The Italian AwPKU group had slightly worse metabolic control but showed levels of performance and patterns of impairment similar to the English AwPKU group. The Italian results also showed extensive correlations between adult cognitive measures and metabolic measures across the life span, both in terms of Phenylalanine (Phe) levels and Phe fluctuations, replicating previous results in English. These results suggest that batteries with the same and/or matched tasks can be used to assess cognitive outcomes across countries allowing results to be compared and accrued. Future studies should explore potential differences in metabolic control across countries to understand what variables make metabolic control easier to achieve.

GO Nanosheets: Promising Nano Carrier for the S29, 1-(2-Chloro-2-(4-chlorophenyl-ethyl)-N-(4-fluorobenzyl)-1H-pyrazolo[3,4-d] pyrimidin-4-amine, Therapeutic Agent in Neuroblastoma.

Graphene oxide (GO) derivatives are reported as a valid alternative to conventional carriers of therapeutic agents, because they have a large surface area, an excellent electrical and thermal conductivity and a great capacity for selective binding of drugs and therapeutics, due to the functionalization of their surfaces, edges and sides. In this work GO nanosheets, synthesized by electrochemical exfoliation of graphite (patent N 102015000023739, Tor Vergata University), were investigated as possible carriers of an anticancer drug, the S29, an inhibitor of a cytoplasmic tyrosine kinase (c-SRC) on a neuroblastoma cell line (SK N BE 2 cells). Neuroblastoma is a heterogenous tumor whose characteristics range from spontaneous regression to aggressive phenotypes that are due to different mutations that often occur in SRC family kinases. Inhibitors of tyrosine kinases are currently investigated for their anti-tumoral effects on aggressive neuroblastomas, but their uptake in cells and pharmacokinetics needs to be improved. In this work S29 was stably conjugated with highly water-dispersible GO nanoparticles. S29/GO complex formation was induced by 1h sonication and its stability was analyzed by chromatography coupled with spectrophotometry and mass spectrometry. The synthesized composite (GO-S29) was delivered into SK N BE 2 cells and its effects on cell viability, production of reactive oxygen species (ROS) and migration were studied. The results show that the compound GO-S29 exerts anti-tumoral effects on the neuroblastoma cell line, higher than both GO and S29 do alone and that GO has an additive effect on S29.

Innovative Technologies for Cultural Heritage. Tattoo Sensors and AI: The New Life of Cultural Assets.

Conservation and restoration of cultural heritage is something more than a simple process of maintaining the existing. It is an integral part of the improvement of the cultural asset. The social context around the restoration shapes the specific actions. Today, preservation, restoration, enhancement of cultural heritage are increasingly a multidisciplinary science, meeting point of researchers coming from heterogeneous study areas. Data scientists and Information technology (IT) specialists are increasingly important. In this context, networks of a new generation of smart sensors integrated with data mining and artificial intelligence play a crucial role and aim to become the new skin of cultural assets.

Correction: Smart Electrochemical Portable Tools for Cultural Heritage Analysis: A Review. Sensors, 2019, 19, 4303.

The authors wish to make the following corrections to this paper [...].

Adult cognitive outcomes in phenylketonuria: explaining causes of variability beyond average Phe levels.

OBJECTIVE: The objective was to deepen the understanding of the causes of individual variability in phenylketonuria (PKU) by investigating which metabolic variables are most important for predicting cognitive outcomes (Phe average vs Phe variation) and by assessing the risk of cognitive impairment associated with adopting a more relaxed approach to the diet than is currently recommended. METHOD: We analysed associations between metabolic and cognitive measures in a mixed sample of English and Italian early-treated adults with PKU (N = 56). Metabolic measures were collected through childhood, adolescence and adulthood; cognitive measures were collected in adulthood. Metabolic measures included average Phe levels (average of median values for each year in a given period) and average Phe variations (average yearly standard deviations). Cognition was measured with IQ and a battery of cognitive tasks. RESULTS: Phe variation was as important, if not more important, than Phe average in predicting adult outcomes and contributed independently. Phe variation was particularly detrimental in childhood. Together, childhood Phe variation and adult Phe average predicted around 40% of the variation in cognitive scores. Poor cognitive scores (> 1 SD from controls) occurred almost exclusively in individuals with poor metabolic control and the risk of poor scores was about 30% higher in individuals with Phe values exceeding recommended thresholds. CONCLUSIONS: Our results provide support for current European guidelines (average Phe value = < 360 µmol/l in childhood; = < 600 µmo/l from 12 years onwards), but they suggest an additional recommendation to maintain stable levels (possibly Phe SD = < 180 µmol/l throughout life). PUBLIC SIGNIFICANCE STATEMENTS: We investigated the relationship between how well people with phenylketonuria control blood Phe throughout their life and their ability to carry out cognitive tasks in adulthood. We found that avoiding blood Phe peaks was as important if not more important that maintaining average low Phe levels. This was particularly essential in childhood. We also found that blood Phe levels above recommended European guidelines was associated with around 30% increase in the risk of poor cognitive outcomes.

Smart Electrochemical Portable Tools for Cultural Heritage Analysis: A Review.

. Protecting Cultural Heritage (CH) from corrosion and other environmental damages, mainly involving metallic or organic layers contained in artwork, represents a major challenge for conservation scientists. Electrochemical techniques provide useful information about the deterioration effects of metallic coatings and organic layers. Recently, Electrochemical Impedance Spectroscopy (EIS) has been successfully applied in the study of metallic corrosion. However, EIS has not succeeded in becoming a routine technique, due to problems regarding both instrumental apparatus (which is not ideal for in situ analysis, especially with previous cell configurations), and the difficulty with data processing. At the same time, new portable electrochemical sensors, immunosensors, and biosensors have successfully made a scientific impact, mainly with in situ diagnosis of organic components contained in CH objects. For this purpose, this review presents two sections: the first describes the analytical optimization of impedance electrochemical cell geometries that are suitable for in situ metal-coating investigation; the second reports on the assembly of small electrochemical sensors, immunosensors, and biosensors, which useful for in situ organic layer characterization. This overview summarizes the state of the art regarding the application of electrochemical techniques and small electrochemical devices as alternative tools for the understanding of CH.

Polymer-Anchored Bifunctional Pincer Catalysts for Chemoselective Transfer Hydrogenation and Related Reactions.

A series of polymer-supported cooperative PC(sp3 )P pincer catalysts was synthesized and characterized. Their catalytic activity in the acceptorless dehydrogenative coupling of alcohols and the transfer hydrogenation of aldehydes with formic acid as a hydrogen source was investigated. This comparative study, examining homogeneous and polymer-tethered species, proved that carefully designing a link between the support and the catalytic moiety, which takes into consideration the mechanism underlying the target transformation, might lead to superior heterogeneous catalysis.

Graphene Oxide Oxygen Content Affects Physical and Biological Properties of Scaffolds Based on Chitosan/Graphene Oxide Conjugates.

Tissue engineering is a highly interdisciplinary field of medicine aiming at regenerating damaged tissues by combining cells with porous scaffolds materials. Scaffolds are templates for tissue regeneration and should ensure suitable cell adhesion and mechanical stability throughout the application period. Chitosan (CS) is a biocompatible polymer highly investigated for scaffold preparation but suffers from poor mechanical strength. In this study, graphene oxide (GO) was conjugated to chitosan at two weight ratios 0.3% and 1%, and the resulting conjugates were used to prepare composite scaffolds with improved mechanical strength. To study the effect of GO oxidation degree on scaffold mechanical and biological properties, GO samples at two different oxygen contents were employed. The obtained GO/CS scaffolds were highly porous and showed good swelling in water, though to a lesser extent than pure CS scaffold. In contrast, GO increased scaffold thermal stability and mechanical strength with respect to pure CS, especially when the GO at low oxygen content was used. The scaffold in vitro cytocompatibility using human primary dermal fibroblasts was also affected by the type of used GO. Specifically, the GO with less content of oxygen provided the scaffold with the best biocompatibility.

Smart Portable Devices Suitable for Cultural Heritage: A Review.

This article reviews recent portable sensor technologies to apply in the Cultural Heritage (CH) fields. The review has been prepared in the form of a retrospective description of the sensor's history and technological evolution, having: new nanomaterials for transducers, miniaturized, portable and integrated sensors, the wireless transmission of the analytical signals, ICT_Information Communication Technology and IoT_Internet of Things to apply to the cultural heritage field. In addition, a new trend of movable tattoo sensors devices is discussed, referred to in situ analysis, which is especially important when scientists are in the presence of un-movable and un-tangible Cultural Heritage and Art Work objects. The new proposed portable contact sensors (directly applied to art work objects and surfaces) are non-invasive and non-destructive to the different materials and surfaces of which cultural heritage is composed.