Modulation of [CuOH/O]+ Properties in [2,2'-Bipyridine]2 Homoleptic Complexes through Substitution at the 6,6' Position by Methyl Groups.

In this paper, data from a DFT-based computational study on the reactivity of [Cu(2,2'-S-bpy)2]+PF6- (S indicating substitution by methyl groups at the 6 and/or 6' position and ranging from 0 to 100% through 50%) homoleptic complexes based toward tButOOH were presented. Computational results, supported by cyclic voltammetry analysis, prove the feasibility of finely tuning the chemical properties of the complexes and their reactivity by means of insertion of methyl moieties in selected positions within the bipyridine scaffold.

Quinoid-Thiophene-Based Covalent Organic Polymers for High Iodine Uptake: When Rational Chemical Design Counterbalances the Low Surface Area and Pore Volume.

A novel 2D covalent organic polymer (COP), based on conjugated quinoid-oligothiophene (QOT) and tris(aminophenyl) benzene (TAPB) moieties, is designed and synthesized (TAPB-QOT COP). Some DFT calculations are made to clarify the equilibrium between different QOT isomers and how they could affect the COP formation. Once synthetized, the polymer has been thoroughly characterized by spectroscopic (i.e., Raman, UV-vis), SSNMR and surface (e.g., SEM, BET) techniques, showing a modest surface area (113 m2 g-1) and micropore volume (0.014 cm3 g-1 with an averaged pore size of 5.6-8 Å). Notwithstanding this, TAPB-QOT COP shows a remarkably high iodine (I2) uptake capacity (464 %wt) comparable to or even higher than state-of-the-art porous organic polymers (POPs). These auspicious values are due to the thoughtful design of the polymer with embedded sulfur sites and a conjugated scaffold with the ability to counterbalance the relatively low pore volumes. Indeed, both morphological and Raman data, supported by computational analyses, prove the very high affinity between the S atom in our COP and the I2. As a result, TAPB-QOT COP shows the highest volumetric I2 uptake (i.e., the amount of I2 uptaken per volume unit) up to 331 g cm-3 coupled with a remarkably high reversibility (>80% after five cycles).

An Integrated Characterization Strategy on Board for Recycling of poly(vinyl butyral) (PVB) from Laminated Glass Wastes.

Polyvinyl butyral (PVB) is widely used as an interlayer material in laminated glass applications, mainly in the automotive industry, but also for construction and photovoltaic applications. Post-consumed laminated glass is a waste that is mainly landfilled; nevertheless, it can be revalorized upon efficient separation and removal of adhered glass. PVB interlayers in laminated glass are always plasticized with a significant fraction in the 20-40% w/w range of plasticizer, and they are protected from the environment by two sheets of glass. In this work, the aim is to develop a thorough characterization strategy for PVB films. Neat reference PVB grades intended for interlayer use are compared with properly processed (delaminated) post-consumed PVB grades from the automotive and construction sectors. Methods are developed to open opportunities for recycling and reuse of the latter. The plasticizer content and chemical nature are determined by applying well-known analytical techniques, namely, FT-IR, TGA, NMR. The issue of potential aging during the life cycle of the original laminated material is also addressed through NMR. Based on the findings, a sensor capable of directly sorting PVB post-consumer materials will be developed and calibrated at a later stage.

Design of a New Chiral Deep Eutectic Solvent Based on 3-Amino-1,2-propanediol and Its Application in Organolithium Chemistry.

A chiral glycerol derivative, namely 3-amino-1,2-propanediol, was employed for as the hydrogen bond donor (HBD) in the design of a new deep eutectic solvent (DES) with choline chloride acting as the hydrogen bond acceptor (HBA). The novel mixture was characterized and unambiguously classified as a DES. Furthermore, its synthetic usefulness was demonstrated in the room-temperature n-butyllithium-addition under air to carbonyl compounds and benzyl chloride. In some cases, pure products (100% conversion) were obtained by a simple extractive work-up in up to 72% isolated yield, thus suggesting the potential practical usefulness of this procedure as a green alternative to the classical Schenk procedure in volatile organic solvents for the synthesis of tertiary alcohols. The chirality of the HBD, bearing an interesting basic primary amino group, is an intriguing feature currently under investigation for further exploitation.

Ullmann homocoupling of arenediazonium salts in a deep eutectic solvent. Synthetic and mechanistic aspects.

A deep eutectic solvent (DES) based on glycerol and KF is successfully exploited as a solvent medium in Ullmann homocoupling of arenediazonium salts. The reactions were carried out in mild conditions and target products were obtained in fairly good yields. A computational study is presented aiming to understand the reaction mechanism and Raman spectroscopy is employed as an experimental tool to support it.

The Effectiveness of Superbolus on Postprandial Blood Glucose Management of Pregnant Women With Type 1 Diabetes.

AIM: Pregnancies of women with pregestational diabetes are at risk of after-meal glucose peaks and late after-meal hypoglycemia, particularly at breakfast. We aimed to explore the effectiveness of a specific feature of insulin pump therapy called superbolus in preventing these glucose swings. METHODS: In this retrospective observational study, we analyzed continuous glucose monitoring data of patients with type 1 diabetes in pregnancy who were advised to use superbolus to manage their breakfast. Some of the postprandial basal insulin delivery was partially reduced and delivered instead as additional insulin bolus on top of a normal bolus. Outcomes of interest were one hour after breakfast glucose levels, the time in glucose range for after breakfast period, the number of late hypoglycemic episodes. RESULTS: Overall, 21 consecutive pregnant women with type 1 diabetes (mean age 34.3 ± 5.5 years, mean pregestational body mass index 23.7 ± 4.7 kg/m2, HbA1c levels during pregnancy 6.1 ± 0.6%) were studied. Superbolus reduced after breakfast glucose peaks (one hour after breakfast glucose levels 130 ± 17 mg/dL vs 123 ± 10 mg/dL before and after superbolus use, respectively, P = .01), improved the time in glucose range for after breakfast period (70.4% vs 50.8%, P = .001), and reduced the number of late hypoglycemic episodes (3 [1-5] vs 1 [0-2], P< .0001). CONCLUSION: Superbolus was effective in avoiding after-meal glucose peaks, increased postprandial glucose time in target, without late hypoglycemia occurrence. It represents a valid option for the treatment of pregnant women with type 1 diabetes using insulin pump.

A multi-technique approach to unveil the redox behaviour and potentiality of homoleptic CuI complexes based on substituted bipyridine ligands in oxygenation reactions.

The effect of differently substituted 2,2'-bipyridine ligands (i.e. 6,6'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethoxy-2,2'-bipyridine and 2,2'-bipyridine) on the reversible oxidation of the resulting CuI homoleptic complexes is investigated by means of a multi-technique approach (electronic and vibrational spectroscopies, DFT, electrochemistry). Among the four tested complexes, [CuI(6,6'-dimethyl-2,2'-bipyridine)2] (PF6) shows a peculiar behavior when oxidized with an organic peroxide (i.e. tert-butyl hydroperoxide, tBuOOH). The simultaneous use of UV-Vis-NIR and Raman spectroscopy methods and cyclovoltammetry, supported by DFT based calculations, allowed identifying (i) the change in the oxidation state of the copper ion and (ii) some peculiar modification in the local structure of the metal leading to the formation of a [CuIIOH]+ species. The latter, being able to oxidize a model molecule (i.e. cyclohexene) and showing the restoration of the original CuI complex and the formation of cyclohexanone, confirms the potential of these simple homoleptic CuI complexes as model catalysts for partial oxygenation reactions.

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media.

Deep Eutectic Solvents have gained a lot of attention in the last few years because of their vast applicability in a large number of technological processes, the simplicity of their preparation and their high biocompatibility and harmlessness. One of the fields where DES prove to be particularly valuable is the synthesis and modification of inorganic materials-in particular, nanoparticles. In this field, the inherent structural inhomogeneity of DES results in a marked templating effect, which has led to an increasing number of studies focusing on exploiting these new reaction media to prepare nanomaterials. This review aims to provide a summary of the numerous and most recent achievements made in this area, reporting several examples of the newest mixtures obtained by mixing molecules originating from natural feedstocks, as well as linking them to the more consolidated methods that use "classical" DES, such as reline.

Copper-Free Halodediazoniation of Arenediazonium Tetrafluoroborates in Deep Eutectic Solvents-like Mixtures.

Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism.

Novel Thienyl DPP derivatives Functionalized with Terminal Electron-Acceptor Groups: Synthesis, Optical Properties and OFET Performance.

Three novel diketopyrrolopyrrole (DPP) based small molecules have been synthesized and characterized in terms of their chemical-physical, electrochemical and electrical properties. All the molecules consist of a central DPP electron acceptor core symmetrically functionalized with donor bi-thienyl moieties and flanked in the terminal positions by three different auxiliary electron-acceptor groups. This kind of molecular structure, characterized by an alternation of electron acceptor and donor groups, was purposely designed to provide a significant absorption at the longer wavelengths of the visible spectrum: when analysed as thin films, in fact, the dyes absorb well over 800 nm and exhibit a narrow optical bandgap down to 1.28 eV. A detailed DFT analysis provides useful information on the electronic structure of the dyes and on the features of the main optical transitions. Organic field-effect transistors (OFETs) have been fabricated by depositing the DPP dyes as active layers from solution: the different end-functionalization of the dyes had an effect on the charge-transport properties with two of the dyes acting as n-type semiconductors (electron mobility up to 4.4 ⋅ 10-2  cm2 /V ⋅ s) and the third one as a p-type semiconductor (hole mobility up to 2.3 ⋅ 10-3  cm2 /V ⋅ s). Interestingly, well-balanced ambipolar transistors were achieved by blending the most performant n-type and p-type dyes with hole and electron mobility in the order of 10-3  cm2 /V ⋅ s.

Critical Assessment of the Sustainability of Deep Eutectic Solvents: A Case Study on Six Choline Chloride-Based Mixtures.

An outline of the advantages, in terms of sustainability, of Deep Eutectic Solvents (DESs) is provided, by analyzing some of the most popular DESs, obtained by the combination of choline chloride, as a hydrogen bond acceptor, and six hydrogen bond donors. The analysis is articulated into four main issues related to sustainability, which are recurrently mentioned in the literature, but are often taken for granted without any further critical elaboration, as the prominent green features of DESs: their low toxicity, good biodegradability, renewable sourcing, and low cost. This contribution is intended to provide a more tangible, evidence-based evaluation of the actual green credentials of the considered DESs, to reinforce or question their supposed sustainability, also in mutual comparison with one another.

Lignin-Based Polymer Electrolyte Membranes for Sustainable Aqueous Dye-Sensitized Solar Cells.

In the quest for sustainable materials for quasi-solid-state (QS) electrolytes in aqueous dye-sensitized solar cells (DSSCs), novel bioderived polymeric membranes were prepared in this work by reaction of preoxidized kraft lignin with poly(ethylene glycol)diglycidylether (PEGDGE). The effect of the PEGDGE/lignin relative proportions on the characteristics of the obtained membranes was thoroughly investigated, and clear structure-property correlations were highlighted. In particular, the glass transition temperature of the materials was found to decrease by increasing the amount of PEGDGE in the formulation, indicating that polyethylene glycol chains act as flexible segments that increase the molecular mobility of the three-dimensional polymeric network. Concurrently, their swelling ability in liquid electrolyte was found to increase with the concentration of PEGDGE, which was also shown to influence the ionic transport efficiency within the membrane. The incorporation of these lignin-based cross-linked systems as QS electrolyte frameworks in aqueous DSSCs allowed the preparation of devices with excellent long-term stability under UV-vis light, which were found to be superior to benchmark QS-DSSCs incorporating state-of-the-art carboxymethylcellulose membranes. This study provides the first demonstration of lignin-based QS electrolytes for stable aqueous DSSCs, establishing a straightforward strategy to exploit the potential of lignin as a functional polymer precursor for the field of sustainable photovoltaic devices.

Polymeric Dopant-Free Hole Transporting Materials for Perovskite Solar Cells: Structures and Concepts towards Better Performances.

Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impressive efficiency (25.5%), but their long-term stability still needs to be addressed for industrial production. One of the most sizeable reasons for instability is the doping of the Hole Transporting Material (HTM), being the salt commonly employed as a vector bringing moisture in contact with perovskite film and destroying it. With this respect, the research focused on new and stable "dopant-free" HTMs, which are inherently conductive, being able to effectively work without any addition of dopants. Notwithstanding, they show impressive efficiency and stability results. The dopant-free polymers, often made of alternated donor and acceptor cores, have properties, namely the filming ability, the molecular weight tunability, the stacking and packing peculiarities, and high hole mobility in absence of any dopant, that make them very attractive and a real innovation in the field. In this review, we tried our best to collect all the dopant-free polymeric HTMs known so far in the perovskite solar cells field, providing a brief historical introduction, followed by the classification and analysis of the polymeric structures, based on their building blocks, trying to find structure-activity relationships whenever possible. The research is still increasing and a very simple polymer (PFDT-2F-COOH) approaches PCE = 22% while some more complex ones overcome 22%, up to 22.41% (PPY2).

Screening of postpartum diabetes in women with gestational diabetes: high-risk subgroups and areas for improvements-the STRONG observational study.

AIMS: To assess the proportion of women with gestational diabetes (GDM) by performing postpartum Oral Glucose Tolerance Test (OGTT) and to identify GDM phenotypes at high-risk of postpartum dysglycemia (PPD). METHODS: Observational, retrospective, multicenter study involving consecutive GDM women. Recursive partitioning (RECPAM) analysis was used to identify distinct and homogeneous subgroups of women at different PPD risk. RESULTS: From a sample of 2,736 women, OGTT was performed in 941 (34.4%) women, of whom 217 (23.0%) developed PPD. Insulin-treated women having family history of diabetes represented the subgroup with the highest PPD risk (OR 5.57, 95% CI 3.60-8.63) compared to the reference class (women on diet with pre-pregnancy BMI < = 28.1 kg/m2). Insulin-treated women without family diabetes history and women on diet with pre-pregnancy BMI > 28.1 kg/m2 showed a two-fold PPD risk. Previous GDM and socioeconomic status represent additional predictors. Fasting more than post-prandial glycemia plays a predictive role, with values of 81-87 mg/dl (4.5-4.8 mmol/l) (lower than the current diagnostic GDM threshold) being associated with PPD risk. CONCLUSIONS: Increasing compliance to postpartum OGTT to prevent/delay PPD is a priority. Easily available characteristics identify subgroups of women more likely to benefit from preventive strategies. Fasting BG values during pregnancy lower than those usually considered deserve attention.

Assessing the Structure of Protic Ionic Liquids Based on Triethylammonium and Organic Acid Anions.

We present a computational analysis of the short-range structure of three protic ionic liquids based on strong organic acids: trifluoracetate, methanesulfonate, and triflate of triethylammonium. Accurate ab initio computations carried out on the gas-phase dimers show that the protonation of triethylamine is spontaneous. We have identified the anion-cation binding motif that is due to the presence of a strong hydrogen bond and to electrostatic interactions. The strength of the hydrogen bond and the magnitude of the binding energy decrease in the order trifluoroacetate ≳ methanesulfonate > triflate. The corresponding simulations of the bulk phases, obtained using a semiempirical evaluation of the interatomic forces, reveal that on short timescales, the state of the three liquids remains highly ionized and that the gas-phase cation-/anion-binding motif is preserved while no other peculiar structural features seem to emerge.

Thermosetting Polyurethane Resins as Low-Cost, Easily Scalable, and Effective Oxygen and Moisture Barriers for Perovskite Solar Cells.

Long-term stability of perovskite solar cells (PSCs) is one of the main issues to be solved for forthcoming commercialization of this technology. In this work, thermosetting polyurethane (PU)-based resins are proposed as effective encapsulants for perovskite solar cells to prevent degradation caused by both moisture and oxygen. Application consists of drop-casting the precursor mixture directly over the devices followed by in situ polymerization, avoiding the use of other adhesives. PUs are cost-effective, lightweight, thermal, and light-stable materials whose mechanical, chemical, and physical properties can be easily tuned by thoughtful choice of their precursor. Encapsulated PSCs show extremely good stability when stored under ambient light (maximum, 1000 lux), controlled humidity (28-65%), and temperature (18-30 °C) by retaining 94% of the initial power conversion efficiency after 2500 h (4 months), whereas control devices lose 90% of their performance after 500 h (T80 = 37 h); once stored according to ISOS-D-1, PU-protected devices showed T80 > 1200 h. Encapsulated devices are stable even when immersed in pure water. The demonstration of PUs as promising solution-processed encapsulant materials for PSCs can pave the way for these to become a cost-effective encapsulation route alternative for future industrialization of this technology.

Photoanodes for Aqueous Solar Cells: Exploring Additives and Formulations Starting from a Commercial TiO2 Paste.

Whereas the commercialization of dye-sensitized solar cells (DSSCs) is finally proceeding taking advantage of their low cost and tunable optical features, such as colour and transparency for both indoor and building-integrated applications, the corresponding aqueous counterpart is still at its infancy. As the TiO2 electrode is a fundamental component for hybrid solar cells, this work investigates the effect of different molecular (α-terpineol, propylene carbonate) and polymeric (polyethylene oxide, polyethylene glycol, carboxymethyl cellulose and xanthan gum) additives that can be introduced into a commercial TiO2 paste for for screen-printing (or doctor blade). Among all, the addition of polyethylene glycol leads to the best cell performances, with markedly increased short-circuit current density (+18 %) and power conversion efficiency (+48 %) with respect to the pristine (commercial) counterpart. When further explored at different concentration levels, electrodes fabricated from polyethylene glycol-based pastes show different morphologies, thicknesses and performances, which are investigated through (photo)electrochemical, structural, physical-chemical and microscopic techniques.

Hydrogel Electrolytes Based on Xanthan Gum: Green Route towards Stable Dye-Sensitized Solar Cells.

The investigation of innovative electrolytes based on nontoxic and nonflammable solvents is an up-to-date, intriguing challenge to push forward the environmental sustainability of dye-sensitized solar cells (DSSCs). Water is one of the best choices, thus 100% aqueous electrolytes are proposed in this work, which are gelled with xanthan gum. This well-known biosourced polymer matrix is able to form stable and easily processable hydrogel electrolytes based on the iodide/triiodide redox couple. An experimental strategy, also supported by the multivariate chemometric approach, is used here to study the main factors influencing DSSCs efficiency and stability, leading to an optimized system able to improve its efficiency by 20% even after a 1200 h aging test, and reaching an overall performance superior to 2.7%. In-depth photoelectrochemical investigation demonstrates that DSSCs performance based on hydrogel electrolytes depends on many factors (e.g., dipping conditions, redox mediator concentrations, etc.), that must be carefully quantified and correlated in order to optimize these hydrogels. Photovoltaic performances are also extremely reproducible and stable in an open cell filled in air atmosphere, noticeably without any vacuum treatments.