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Nonisocyanate polyurethanes (NIPUs) and NIPU nanocomposites (NIPU-NCs) were developed from renewable sources. NIPUs were synthesized from a sustainable precursor, castor oil cyclic carbonate (CO-CC), via polyaddition with linalool diamine (LDA) at 110 °C. NIPU properties improved upon the incorporation of 0.5 wt% multiwalled carbon nanotubes (MWCNTs) via covalent (amine-functionalised MWCNTs) and non-covalent (pristine and oxidized MWCNTs) methods. These formulations resulted in the NIPU nanocomposites NIPU-MWCNT-NH2, NIPU-MWCNTs and NIPU-MWCNT-COOH. The physicochemical, thermal and morphological properties of NIPU and NIPU-NCs were studied via multiple techniques such as FTIR, NMR, XRD, TGA, DSC, SEM, water contact angle analysis, XPS and optical microscopy. These samples were applied for coating applications on a mild steel substrate (MST) and glass slides to study antifouling, anticorrosion and UV shielding. Thermal analyses of NIPUs and NIPU-NCs revealed good thermal stability with an appropriate glass transition (Tg) and onset degradation (Td) temperature. Indeed, water contact angle values showed hydrophilic properties, which prompt applications in marine coatings. Biodegradation studies implied that the structural network retained its stability even after immersion for 45 days in a PBS medium. Additionally, NIPUs and NIPU-MWCNT-NH2 demonstrated enhanced UV shielding capability. Finally, NIPU-MWCNT-NH2 exhibited anticorrosion with an impedance modulus ‖Z‖ of 7.43 × 102 (Ω cm2) and essential antifouling properties as well as significantly reduced algae adhesion to 3.143 million per mL. [ABSTRACT FROM AUTHOR]

The viability of modern horticulture heavily relies on adopting sustainable practices. Understanding soil spatial variability on heavy clay soils and its impact on young trees is crucial to design suitable soil and water management strategies that guarantee the sustainability of orchards. The objective of this study was to assess in an orchard with heavy clay soils of the Riverine Plain, NSW, the impact of soil spatial variability on the development of young almond (Prunus dulcis (Mill.) D. A. Webb) trees and evaluate the use of remote and proximal sensing tools for identifying threatening factors for the sustainability of the crop. Soil and aerial surveys were used to assess the soil and crop spatial variability in an 8.3‐ha irrigation block. The site was divided into five areas based on apparent electrical conductivity (ECa) measurements where soil samples were collected. Tree growth, soil, and plant water status were monitored in two contrasting areas in ECa. In the first year of study, a significant and positive correlation was found between ECa and percentage of ground canopy cover. Soil analysis and soil moisture monitoring revealed that high values of exchangeable sodium percentage, which are indicative of sodic soils prone to dispersion, and limited water infiltration were the cause of the reduced tree growth in areas with low ECa. The impact of soil spatial variability on tree growth decreased in the second growing season due to weather and water management factors that influenced soil water content. This study showcases the usefulness of remote and proximal sensing in assessing potential soil‐spatial‐related issues in newly established orchards as well as the impact soil spatial variability can have on tree development in the first years after planting. Core Ideas: Development of young almond trees was influenced by soil spatial variability.Apparent electrical conductivity (ECa) was positively correlated with canopy growth.Low ECa was associated with high exchangeable sodium percentage and low water infiltration.The degree of impact that soil variability had on tree growth was growing season dependent. [ABSTRACT FROM AUTHOR]

To date, the public health system has been impacted by the increasing costs of many diagnostic and therapeutic pathways due to limited resources. At the same time, we are constantly seeking to improve these paths through approaches aimed at personalized medicine. To achieve the required levels of diagnostic and therapeutic precision, it is necessary to integrate data from different sources and simulation platforms. Today, artificial intelligence (AI), machine learning (ML), and predictive computer models are more efficient at guiding decisions regarding better therapies and medical procedures. The evolution of these multiparametric and multimodal systems has led to the creation of digital twins (DTs). The goal of our review is to summarize AI applications in discovering new immunotherapies and developing predictive models for more precise immunotherapeutic decision-making. The findings from this literature review highlight that DTs, particularly predictive mathematical models, will be pivotal in advancing healthcare outcomes. Over time, DTs will indeed bring the benefits of diagnostic precision and personalized treatment to a broader spectrum of patients. [ABSTRACT FROM AUTHOR]

Research on personality in leadership indicates that self-selection to leadership careers and artistic careers correlates with diverging personality profiles. People in leadership careers traditionally display lower neuroticism and higher conscientiousness than artistic individuals. In between, there are individuals entering arts management careers. To study these individuals directly, we collected Norwegian data from 91 musical theater students and 102 arts management students and compared with 109 business management students. As expected, conscientiousness and neuroticism predicted artistic careers against business management careers, aligned with the "arts for arts' sake" myth of artists. Interestingly, arts management careers were not different from artistic careers. They weren't more motivated to take on leadership roles than performing artists either. However, the Highly Sensitive Person Scale indicated that narrower traits of sensitivity predicted higher levels of motivation to lead in many artists. Some arts and arts management students seem to bring unique talents into forms of leadership particularly useful for artistic organizations. Our findings are discussed in terms of how leadership characteristics operate in the field of art, and the effect of domain-specific characteristics in this setting. [ABSTRACT FROM AUTHOR]

Polyurethane (PU) foams are key players within the large foam market, with applications such as thermal insulating materials, cushioning, protective equipment, etc. With the current regulatory constraints on the use of toxic isocyanates and the ambitious goals to increase the renewable content of plastics while valorizing waste, isocyanate-free liquid formulations containing biofillers that are able to easily self-foam are needed for more sustainable PU foams in the future. Herein, we incorporate various abundant waste stream-sourced biofillers (proteins, lignin derivatives, and polysaccharides) into isocyanate-free PU formulations composed of CO2-based poly(cyclic carbonate)s, diamines and a catalyst. The formulations containing up to 30 wt% of biofillers are foamed at 100 °C without adding any external foaming agent. Moisture naturally present in the biofillers partially hydrolyses the cyclic carbonates, which generates the blowing agent (CO2). The biofiller, even at a low content (1 wt%), stabilizes the growing cells, providing homogeneous foams. Although the nature of the biofiller does not significantly affect the foams' density and morphology, their mechanical properties are strongly affected, for example from a rigid foam with 10 wt% keratin (compression modulus (E) = 21.9 MPa) to a flexible one with chitosan (E = 0.2 MPa). Preliminary studies indicate that the biofiller does not prevent the foam recycling into polymer films by hot pressing. Virtually any kind of moisture-containing biowaste can be used as a water reservoir to foam the formulations while increasing the bio-based content of the material, which reaches 97% when selecting bio-based monomers. This process valorizes abundant waste stream-sourced biofillers for producing more sustainable PU foams. [ABSTRACT FROM AUTHOR]

The cycloaddition of carbon dioxide to epoxide (CCE) reaction stands out as one of the few feasible chemical processes for catalytically fixing CO2. Traditionally, halide anions were frequently used as cocatalysts for catalysing the CCE reaction owing to their excellent nucleophilic and leaving abilities. However, halides are known for their corrosive effects on process reactors, and their treatment is challenging. Consequently, there is a substantial increase in the demand for halide-free catalysis in the CCE reaction. Herein, a series of bifunctional catalysts were designed for CCE reactions. The reactions were assessed under conditions of 120 °C and 1 MPa employing a catalyst loading of 0.5 mol% over 24 hours. The dual activation mechanism of the catalyst was confirmed through NMR titration and control experiments. As a bifunctional catalyst, the ion pair polarized the oxygen atom of epoxide via H-bonding with N+–H while the phenolate anion activated carbon dioxide simultaneously. This study introduces a pyridinium base binary organocatalyst as a halide-free hydrogen bond donor (HBD) anion organocatalyst with broad applicability for CO2 utilization. [ABSTRACT FROM AUTHOR]

With the use of quantum-chemical and kinetic methods, the influence of free amino groups in amine monomers on the rate of their reaction with ethylene carbonate is studied. It was stated that the catalytic effect in diamine appears at the length of the chain of 3–7 atoms. A decrease in activation barriers is associated with the formation of less strained proton transfer and stabilization cycles in transition states. The theoretically found dependence of the rates of aminolysis of ethylenecarbonate on the structure of amines is confirmed experimentally by kinetic measurements. [ABSTRACT FROM AUTHOR]

This study aims to determine bamboo agroforestry system in maintaining sustainability of privately owned forest and contribution of bamboo community forests to the farmers' economy. Research on the composition of privately owned forest species was carried out using a survey method. There were 37 observation plots evenly distributed in the study location villages. Land cover image data obtained from Sentinel-2 Imagery were compared based on land-cover classification. Thirty respondents were interviewed to obtain social and economic data. Data related to the pattern and composition of species diversity of privately owned forest were displayed in an ordinal space and processed by employing Non-metric Multi-Dimensional Scaling analysis. Data from interviews were analyzed using descriptive methods which were presented in the form of tables and graphs. Results showed that privately owned forest were able to increase tree vegetation cover in Ciamis Regency by 3.367%. The bamboo privately owned forest was composed of wood and bamboo, fruit plants, plantation crops, horticulture, and food plants. Privately owned forest contribute 24.49% to farmers' income with coffee as the main commodity. Bamboo has contributed 15.42% of the income from privately owned forest. Farmers will keep maintaining bamboo trees because they have provided economic, social, and environmental benefits. [ABSTRACT FROM AUTHOR]

Psychological characterization of patients affected by Inflammatory Bowel Disease (IBD) focuses on comorbidity with psychiatric disorders, somatization or alexithymia. Whereas IBD patients had higher risk of stable anxiety and depression for many years after the diagnosis of the disease, there is a lack of studies reporting a comprehensive psychosomatic assessment addressing factors of disease vulnerability, also in the long-term. The objective of this investigation is to fill this gap in the current literature. The aims were thus to assess: a) changes between baseline and a 4-year follow-up in psychiatric diagnoses (SCID), psychosomatic syndromes (DCPR), psychological well-being (PWB-I), lifestyle, gastrointestinal symptoms related to IBD and Irritable Bowel Syndrome (IBS)-like symptoms b) stability of psychiatric and psychosomatic syndromes at 4-year follow-up. A total of 111 IBD outpatients were enrolled; 59.5% of them participated at the follow-up. A comprehensive assessment, including both interviews and self-report questionnaires, was provided at baseline and follow-up. Results showed increased psychiatric diagnoses, physical activity, consumption of vegetables and IBS-like symptoms at follow-up. Additionally, whereas psychiatric diagnoses were no longer present and new psychopathological pictures ensued at follow-up, more than half of the sample maintained psychosomatic syndromes (particularly allostatic overload, type A behavior, demoralization) from baseline to follow-up. Long-term presence/persistence of such psychosocial burden indicates the need for integrating a comprehensive psychosomatic evaluation beyond traditional psychiatric nosography in IBD patients. Moreover, since psychosomatic syndromes represent vulnerability factors of diseases, further studies should target subgroups of patients presenting with persistent psychosomatic syndromes and worse course of the disease. [ABSTRACT FROM AUTHOR]

Energy efficiency in buildings requires adequate materials for thermal insulation. Given the enormous number of buildings worldwide needing a retrofit to improve their energy efficiency, it is of capital importance to identify materials suitable for sustainable thermal insulation. Among the many available insulators, polyurethanes occupy a preeminent role, given their versatility and effectiveness, and are thus expected to be extensively used in retrofitting buildings for improving their energy efficiency. Herein, the currently available bio‐derived or recyclable polyurethane‐based composites, considering them as either foams (i.e., with gaseous filler) or fully solid (i.e., with solid filler) composites, are assessed. The first section of the review is devoted to bioderived PUs as matrices for thermally insulating composites; the second section focuses on bio‐derived/recyclable fillers adopted with PUs as matrices, with specific reference to silica‐based aerogels. The main issues of the surveyed bio‐based composites are analyzed, and the future prospects of these materials, that are actually sustainable but at the same time performance effective, are discussed. [ABSTRACT FROM AUTHOR]

Polyhydroxyurethanes (PHUs) are promising polymers to replace polyurethanes (PUs), classically obtained by the isocyanate‐alcohol route. Various application fields of PUs, for example, foams or coatings, require the use of thermosetting polymers. Hence, a great deal of effort is devoted to the development of PHU thermosets in the recent literature. This review highlights the different strategies developed through the years to synthesize plurifunctional cyclic carbonates, also called poly(cyclic carbonate)s, and whose functionality ≥3 is a prerequisite for the synthesis of thermosetting PHUs. A special emphasize is accorded to the safe and eco‐friendly synthetic approaches (e.g., phosgene‐free, use of renewable reactants). In addition, the curing strategies implemented to overcome the low reactivity of the monomers and the limitations related to the transitions of the growing networks (i.e., viscosification, gelation, vitrification) are described. In the end, the curing of PHUs under mild thermal conditions, down to room temperature, is described. Such curing conditions are uncommon for PHU thermosets and are paving the way to much anticipated applications such as coatings, adhesives, or 3D‐printing. [ABSTRACT FROM AUTHOR]

Currently, conventional plastics are necessary for a variety of aspects of modern daily life, including applications in the fields of healthcare, technology, and construction. However, they could also contain potentially hazardous compounds like isocyanates, whose degradation has a negative impact on both the environment and human health. Therefore, researchers are exploring alternatives to plastic which is sustainable and environmentally friendly without compromising its mechanical and physical features. This review study highlights the production of highly eco‐friendly bioplastic as an efficient alternative to non‐biodegradable conventional plastic. Bioplastics are produced from various renewable biomass sources such as plant debris, fatty acids, and oils. Poly‐addition of di‐isocyanates and polyols is a technique employed over decades to produce polyurethanes (PUs) bioplastics from renewable biomass feedstock. The toxicity of isocyanates is a major concern with the above‐mentioned approach. Novel green synthetic approaches for polyurethanes without using isocyanates have been attracting greater interest in recent years to overcome the toxicity of isocyanate‐containing raw materials. The polyaddition of cyclic carbonates (CCs) and polyfunctional amines appears to be the most promising method to obtain non‐isocyanate polyurethanes (NIPUs). This method results in the creation of polymeric materials with distinctive and adaptable features with the elimination of harmful compounds. Consequently, non‐isocyanate polyurethanes represent a new class of green polymeric materials. In this review study, we have discussed the possibility of creating novel NIPUs from renewable feedstocks in the context of the growing demand for efficient and ecologically friendly plastic products. [ABSTRACT FROM AUTHOR]

Excessive carbon dioxide (CO2) emissions pose a serious threat to the natural environment; hence CO2 capture and utilization have been widely concerned in industrial production. At present, the high value‐added utilization of CO2 after capture has become a hot issue. Bio‐based carbonate materials with high commercial value can be generated by the reaction of CO2 and bio‐based compounds, which provides a promising, green, and sustainable material synthetic route. Bio‐based carbonate materials, which are suitable for applications in various industries, have excellent thermodynamic and mechanical properties compared with those prepared from petroleum. In this manuscript, the synthesis and utilization of bio‐based carbonates from a variety of bio‐based compounds and CO2 were briefly described, and the existing problems were put forward in the field. It provided a direction for the green utilization of CO2. [ABSTRACT FROM AUTHOR]

Herein, we present a facile synthetic process for producing biomass‐derived isosorbide (ISB) dioxides using dimethyl dioxirane (DMDO) as an efficient oxidizing agent, which was generated in situ from acetone and KHSO5. To achieve high conversion and product yield, the KHSO5 concentration, KHSO5 flow rate, and reaction temperature were optimized. Under the optimal conditions, rapid and efficient epoxidation using the in situ‐generated DMDO was observed under ultrasonication, yielding the desired product within 35 min at 0 °C. This study offers a convenient and efficient method for generating biomass‐derived ISB building blocks, which have significant potential for the fabrication of bioplastics. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of a series of polyurethane ionenes using a non‐isocyanate approach is disclosed. Imidazole‐capped, urethane‐containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3‐aminopropylimidazole (API). Polymerization with 1,4‐dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf2] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end‐group analysis. A single glass transition temperature (Tg), as determined by differential scanning calorimetry (DSC), is observed for each ionene (−38 to −64 °C) with the Tg decreasing with increasing PPG molecular weight. Thermogravimetric analysis (TGA) indicated a two‐step decomposition for each ionene, with the first being degradation of the PPG segment, followed by the urethane/ionic segment. Microphase separation is observed from x‐ray scattering profiles with Bragg distances that increased with increasing PPG molecular weight. Ionic conductivity is found to be inversely dependent upon DSC Tg at lower temperatures (RT and below); however, at higher temperatures, conductivity appears to be more dependent upon the ability of ionic aggregates caused by phase separation to interact. [ABSTRACT FROM AUTHOR]

A series of calcined Chitosan (CS) photothermal catalysts are prepared by heating the biopolymer at different temperatures. The photothermal conversion (light to heat) ability of these calcined CS materials is evaluated by measuring the temperature change with respect to time and lamp power. The material prepared at 300 °C (Cal‐CS‐300) shows excellent photothermal conversion ability which is explored for the CO2 cycloaddition reaction with epoxides to produce cyclic carbonates under mild reaction parameters (1 atm CO2 pressure, 25 °C). The study reveals the importance of defects present in the material on both photothermal conversion and CO2 fixation efficiency. Under optimized reaction conditions, Cal‐CS‐300 is able to convert a range of epoxides into their respective cyclic carbonates (>97 % selectivity) and retains its catalytic activity (~86 %) for 5 cycles of catalysis without losing its chemical integrity. The use of ubiquitously available biopolymer together with light makes this approach sustainable for preparing value added chemicals. [ABSTRACT FROM AUTHOR]

The influence of the substituents inductive effect and the proton-donor OH group in the substituted cyclocarbonates differing in the alkyl chain length on the activation barrier of their aminolysis reaction, which underlies the process of urethane formation without the participation of isocyanates, has been studied. Account for the solvent molecules has allowed quantitative interpretation of the process regularities. Kinetics of the model aminolysis reaction of a series of monomers in DMSO has been investigated. [ABSTRACT FROM AUTHOR]

A hybrid methodology is used to combine the favorable properties of non‐isocyanate polyurethanes (NIPUs) in the side chains with poly(methacrylates) as the backbone into thermoset hybrid resins with hydroxyurethane linkages (HNIPU)s. Using NIPUs linkages avoids the use of toxic isocyanates in the poly(urethane) segments. The backbone is synthesized from cyclic carbonated copolymer templates derived from atom transfer radical polymerization (ATRP) of an alkyl methacrylate (C13MA with average side‐chain length of 13)/glycidyl methacrylate (GMA) mixtures (initial GMA mol fraction = 0.1–0.4). The resulting flexible resins with pendent epoxy functional groups were subsequently carbonated and then reacted with 1,10‐diaminodecane (90°C, 24 h) to form rigid side chains via hydroxyurethane linkages. Manipulating template functionality (2–11 urethane linkages out of 35 backbone units) yielded crosslinked networks with Young's moduli from 0.1 to 71.9 MPa while decreasing tensile elongation at break from 105% to 10%. Swelling ratios (SR) of the networks in tetrahydrofuran (THF) decrease as urethane linkage concentration increases, indicating tighter networks, consistent with the rheologically obtained molecular weight between crosslinks. Gel content indicated less than 15% of the networks are soluble in THF. The HNIPU networks derived show their ready tunability by simply changing the precursor functionality. [ABSTRACT FROM AUTHOR]

Polyurethanes (PUs) are a class of materials usually synthesized from isocyanates, diols, and water. Water is essential for producing carbon dioxide (CO2) which is used for the self‐blowing of the foams. Due to safety concerns with the production of isocyanates, alternative chemistries have been evaluated and cyclic carbonate systems have shown great promise. In a recent advancement by Bourguignon, Grignard, and Detrembleur, a cyclic carbonate and diamine system is capable of generating CO2 for self‐blowing through hydrolysis of the carbonate‐based monomer. The authors demonstrate that with a simple variation of the diamine monomer a wide range of physical and thermo‐mechanical properties were achievable. This work represents a significant step towards safer and more environmentally friendly PUs. [ABSTRACT FROM AUTHOR]

The highly reactive erythritol dicarbonate (EDC) allows facile design and preparation of solvent‐ and catalyst‐free epoxyurethane polymers. Diglycidyl ether of bisphenol‐A (DGEBA) and oligo polyhydroxyurethanes are used to produce epoxyurethane polymers (o‐PHUs). The o‐PHUs are prepared using cyclic carbonates derived from erythritol and various diamines (aliphatic amine and polyether amine) or polyamines (diethylene triamine (DETA) and triethylne tetramine (TETA)). Active secondary amino groups derived from o‐PHUs polyamines form hydrogen bonds between urethane carbonyls in epoxy hybrid networks with the highest cross‐linking density (1293 mol m−3), glass transition temperature Tg (93 °C), and ultimate tensile strength (34 MPa). And the ether bond provides a significant potential for hydrogen bonding between hydroxyl group and ether oxygen, forming strong hydrogen bond cross‐linking between molecular chains, with cross‐linking density and ultimate tensile strength comparable to polyepoxyurethane derived from polyamines, except for a lower Tg (27 °C). In addition, these polyepoxyurethanes have superior adhesion to wood, aluminum alloy, and polymethyl methacrylate (PMMA) substrates. This versatile oligo PHUs would provide a wide range of fabrication options for adhesive epoxyurethane polymers. [ABSTRACT FROM AUTHOR]

Pyrogenic dissolved organic matter (pyDOM) is derived from black carbon, which is important in the global carbon cycle and other biogeochemical redox processes. The electron-exchange capacity (EEC) of pyDOM has been characterized in water using mediated chronoamperometry (MCA), which gives precise results under specific operational conditions, but the broader significance of these EECs is less clear. In this study, we described a novel but complementary electrochemical approach to quantify EECs of pyDOM without mediation using square-wave voltammetry (SWV) in dimethyl sulfoxide (DMSO). Using both the SWV and MCA methods, we determined EECs for 10 pyDOMs, 6 natural organic matter (NOM) samples, and 2 model quinones. The two methods gave similar EECs for model quinones, but SWV gave larger EECs than MCA for NOM and pyDOM (by several-fold and 1–2 orders of magnitude, respectively). The differences in the EECs obtained by SWV and MCA likely are due to multiple factors, including the potential range of electrons sampled, kinetics of electron transfer from (macro)molecular structures, and coupling of electron and proton transfer steps. Comparison of the results obtained by these two methods should provide new insights into important environmental processes such as carbon-cycling, wildfire recovery, and contaminant mitigation using carbon-based amendments. [ABSTRACT FROM AUTHOR]

Hybrid non‐isocyanate poly(urethanes) (HNIPUs) are designed from a precursor whose carbonate functionality is derived from epoxy‐functional statistical copolymers. Specifically, a bio‐based diene (β‐myrcene) is copolymerized via conventional free radical polymerization with glycidyl methacrylate (GMA) at different molar ratios, producing flexible copolymers with epoxy pendant groups, which are then reacted with carbon dioxide to yield the precursors with cyclic carbonate functionality. Subsequent addition of an amine‐terminated telechelic poly(propylene glycol) (PPG) forms urethane linkages in the side chains, whose concentration is tuned by varying the GMA initial molar fraction. The NIPUs are end‐capped with silanes to enable moisture curing, resulting in HNIPUs with elongations at break up to 150%, and relatively low elastic moduli varying from 32 kPa to 50 kPa as the number of urethane side linkages increases from 6 to 22. The swelling ratio of the NIPUs is also measured in tetrahydrofuran (THF). As the number of urethane side chains increases, the swelling ratio of the NIPUs decreases (710% to 620%), indicating a higher crosslinking density. All samples have gel contents higher than 50% in THF, indicating non‐crosslinked species in the hybrid samples which confirms the relatively low reported tensile moduli. [ABSTRACT FROM AUTHOR]

This review is devoted to the role of 3D printing in the development of a new high‐tech field, smart biohybrid microsystems. The motivation behind the development of this field is the intention to integrate the capabilities of biological systems optimized in the course of evolution with the achievements of modern methods of forming micro‐ and nanostructures. Biohybrid technologies have demonstrated enormous potential for creating new materials and devices intended for a wide range of applications, primarily in the fields of medicine and biology. In this review, attention is focused on 3D printing as the main driver of the development of technologies for the formation of biohybrid systems. Methods featuring micro‐ and nanoresolution, which make it possible to efficiently integrate artificial structures and biosystems at the cellular level, are discussed. The formation of smart biohybrid microsystems—complex multifunctional devices designed for the medical treatment and study of tissues and organs in vitro and in vivo—is analyzed. Particular attention is given to the most promising, breakthrough trends in the development of biohybrid systems—microrobots, organ‐on‐a‐chip systems, and brain–computer interfaces. The main strategies in designing such systems and the near‐future opportunities offered by them are outlined. [ABSTRACT FROM AUTHOR]

For 80 years, polyisocyanates and polyols were central building blocks for the industrial fabrication of polyurethane (PU) foams. By their partial hydrolysis, isocyanates release CO2 that expands the PU network. Substituting this toxic isocyanate‐based chemistry by a more sustainable variant—that in situ forms CO2 by hydrolysis of a comonomer—is urgently needed for producing greener cellular materials. Herein, we report a facile, up‐scalable process, potentially compatible to existing infrastructures, to rapidly prepare water‐induced self‐blown non‐isocyanate polyurethane (NIPU) foams. We show that formulations composed of poly(cyclic carbonate)s and polyamines furnish rigid or flexible NIPU foams by partial hydrolysis of cyclic carbonates in the presence of a catalyst. By utilizing readily available low cost starting materials, this simple but robust process gives access to greener PU foams, expectedly responding to the sustainability demands of many sectors. [ABSTRACT FROM AUTHOR]

Naturally occurring 2-picolinic acid was uncovered as an off-the-shelf, non-toxic, commercially available, cost-effective and sustainable hydrogen bond donor (HBD) catalyst with a suitable halide co-catalyst for the cycloaddition of CO2 to both terminal and internal epoxides to prepare cyclic carbonates. The catalytic ability of the 2-picolinic acid/n-Bu4NI binary system was noticed when it was used to induce the insertion of CO2 into internal di-substituted epoxides as substrates. This is a rare instance of naturally sourced hydrogen bond donor catalyzed cycloaddition of CO2 to internal epoxides. Notably, 8 crucial internal di-substituted epoxides were converted to the corresponding cyclic carbonates with up to 97% yield and >99% selectivity with only 2 mol% catalyst loading. Additionally, 15 terminal mono-substituted epoxides were transformed under mild reaction conditions in the presence of CO2 (1 bar) to the related cyclic carbonates with up to 98% yield and >99% selectivity, with a low catalyst loading (1 mol%) and high turnover numbers (TON) and frequencies (TOF); TON/TOF (h−1) up to 97/5.4. The catalyst reusability experiment in which the reuse of 2-picolinic acid up to 5 times without significant loss of reactivity and a scale-up reaction with only 1 mol% catalyst loading was performed to highlight the practicality of this catalytic system. Density functional theory (DFT) calculations provided the reaction barriers for the different pyridine carboxylic acid catalysts employed in the title reaction and revealed that finding a suitable hydrogen bond donor catalyst hinges upon the interplay between the acidic strength and catalytic activity. [ABSTRACT FROM AUTHOR]

Globalization propelled human migration and commercial exchanges at the global level, but woefully led to the introduction of non-indigenous organisms into several agroecological systems. These include pathogenic bacteria with devastating consequences for numerous crops of agronomical importance for food production worldwide. In the last decade, research efforts have focused on these noxious organisms, aiming to understand their evolutionary processes, degree of pathogenicity, and mitigation strategies, which have allowed stakeholders and policymakers to develop evidence-based regulatory norms to improve management practices and minimize production losses. One of these cases is the bacterium Pseudomonas syringae pv. actinidiae (Psa), the causal agent of the kiwifruit bacterial canker, which has been causing drastic production losses and added costs related to orchard management in the kiwifruit industry. Although Psa is presently considered a pandemic pathogen and far from being eradicated, the implementation of strict regulatory norms and the efforts employed by the scientific community allowed the mitigation, to some extent, of its negative impacts through an integrated pest management approach. This included implementing directive guidelines, modifying cultural practices, and searching for sources of plant resistance. However, bacterial pathogens often have high spatial and temporal variability, with new strains constantly arising through mutation, recombination, and gene flow, posing constant pressure to agroecosystems. This review aims to critically appraise the efforts developed to mitigate bacterial pathogens of agronomical impact, from orchard management to genome analysis, using Psa as a case study, which could allow a prompter response against emerging pathogens in agroecosystems worldwide. [ABSTRACT FROM AUTHOR]

Non-isocyanate polyurethanes (NIPUs) from renewable resources have attracted much attention owing to their significant benefits towards sustainable development and green production. However, the low molar mass and poor mechanical properties of NIPUs greatly restrict their large-scale production and practical application as alternatives to conventional polyurethanes. In this study, a series of bio-based carbonated linseed oil (CLSO) films were synthesized via the carbon dioxide (CO2) coupling reaction of epoxidized linseed oil (ELSO) followed by efficient conversion into novel renewable NIPU thermosetting networks by curing CLSO with different diamines. In the coupling reaction between ELSO and CO2 (denoted as CO2@ELSO), the reactivity of epoxy groups at different sites on the ELSO was revealed by density functional theory (DFT) calculations. Furthermore, the reaction conditions for CLSO and NIPU films were optimized to achieve high atom efficiency and tailorable performance. The tensile strength of the resulting NIPU films was high up to 69.2 MPa and the elongation at breaking could be maintained at 15.4% due to their high crosslinking density and hydrogen bonding content. The novel bio-based NIPU materials developed in this work demonstrate various advantages, including excellent mechanical properties and thermal stability, which could find various applications in coatings, adhesives, elastomers and other industries. [ABSTRACT FROM AUTHOR]

Both difunctional five‐membered cyclic carbonate (E5CC) and trithiocarbonate (E5CTC) were synthesized via the reactions of diglycidyl ether of bisphenol A (DGEBA) with carbon dioxide (CO2) and carbon disulfide (CS2), respectively. These two monomers were employed to synthesize linear poly(hydroxyurethane‐co‐mecaptotrithiourethane) [P(HU‐co‐MTU)] copolymers via the polymerization with an α,ω‐diamino‐terminated poly(propylene oxide). By controlling the mole ratios of E5CC to E5CTC, the P(HU‐co‐MTU) copolymers were synthesized with variable contents of thiol groups. It was found that the linear P(HU‐co‐MTU) copolymers were readily cross‐linked with the disulfide bonds which were in situ generated via the radical coupling of the side thiol groups. The cross‐linking exerted a profound impact on the thermomechanical properties of the materials. The glass transition temperature (Tg's), Young's moduli and tensile strengths were significantly enhanced with increasing the contents of disulfide bonds. More importantly, the networks significantly displayed the self‐healing and reprocessing properties, which are attributable to the dynamic exchanges of disulfide bonds. [ABSTRACT FROM AUTHOR]

Nonisocyanate polyurethane (NIPU) was synthesized using different concentrations of C36‐alkylenediamine (C36DDA), hexamethylene diamine, and a cyclic carbonate monomer synthesized from bisphenol A epoxy resin and carbon dioxide. The structures, molecular weights, thermal behaviors, and stabilities of the NIPU copolymers were evaluated using 1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry measurements. All synthesized NIPUs were amorphous and exhibited good Td−5% thermal stabilities above 250°C; Tg decreased from 73 to 51°C as C36DDA content increased from 0% to 10% based on dynamic mechanical analysis tests. Furthermore, ethylenediamine (EDA) as a chain extender incorporating a small amount of crosslinker 1,2,4,5‐benzenetetracarboxylic acid (PMA) can enhance the melt strength of a partially three‐dimensional network, and the attained NIPU showed elastic properties. Thus, the NIPU synthesized with 7.5% and 10% C36DDA containing small amounts of EDA and PMA were suitable choices for supercritical CO2 foaming; their morphologies and mechanical behaviors were examined by scanning electron microscopy and DMA, and the densities of foamed NIPU with 7.5% and 10% C36DDA were calculated as 432 and 215 kg m−3 with pore sizes of 10–20 μm, respectively. The maximum stresses were attained at 149.5 and 123.4 kPa, and the foamed NIPU displayed rigid foam behaviors owing to the compression behaviors of the stress–strain curves. [ABSTRACT FROM AUTHOR]

Microlens arrays (MLAs) have a variety of applications in, e.g., display systems, projection optics, and sensors. They can be manufactured by various fabrication methods. Among all, inkjet printing stands out because it offers a straightforward, versatile, and low‐cost fabrication route. However, extra manufacturing steps such as photolithography are so far involved to pre‐structure the substrate in order to improve the uniformity of the printed MLAs and achieve a high fill factor (FF). In this study, the fabrication of MLAs is reported on unstructured substrates by inkjet printing using an optimized UV‐curable ink on top of self‐assembled monolayers (SAMs). The latter allows for tuning the surface free energy and thus the aspect ratio of the microlenses. The high uniformity of the printed MLAs is demonstrated by the automatic quantitative evaluations, where the standard deviations of the radii are below 2.5% and of the sag heights are less than 3.9%. An unprecedented FF of 88% amongst all inkjet‐printed MLAs on unstructured substrates is achieved. Digitally controlled large area fabrication is demonstrated, both, on rigid as well as on flexible substrates, opening a pathway for customized microoptics by additive manufacturing. [ABSTRACT FROM AUTHOR]

Aim: This study was conducted to increase knowledge on the actuality of resilience, social support and quality of life among inflammatory bowel disease patients in China to provide evidence for psychological support. Design: Using convenience sampling, 249 outpatients and inpatients with inflammatory bowel disease from a hospital who completed the questionnaires were enrolled in the analytic questionnaire‐based study. Methods: Demographic information forms, Resilience Scale for Inflammatory Bowel Disease, Social Support Rating Scale and Short Health Scale were administered. Results: It was found that the resilience of patients with inflammatory bowel disease should be enhanced. When considering factors that influence resilience, the place of residence (living in rural areas) and utilization of social support should be considered. Resilience demonstrated a positive correlation with utilization of social support, and different place of residence was related to resilience. Targeted interventions should be implemented to increase patients' resilience and quality of life. [ABSTRACT FROM AUTHOR]

Improving the sustainability of polymer networks is a crucial challenge in polymer science due to their important role in industry. Their traditional syntheses conflict with several principles of green chemistry as the employed monomers are petroleum‐based, their production involves the use of toxic reagents, and their permanently cross‐linked structures impede their chemical recycling and reshaping. The development of vitrimers represents a unique solution to address the issue of polymer network end‐of‐life by enabling reprocessability while maintaining good thermomechanical properties and solvent resistance. Although over the last decades biomass has proved to be an excellent feedstock for the production of permanently cross‐linked polymers, the field of biobased vitrimers is still in its infancy. In this review, a comprehensive overview of vitrimers synthesized from biobased monomers is presented. The emphasis is set on the compatibility of the biomass structure with the nature of the dynamic covalent chemistry, as well as the sustainability of the synthetic approaches. Implementing renewable feedstocks and recyclability in the production of polymer networks paves the way for the development of the next generation of sustainable materials. [ABSTRACT FROM AUTHOR]

Polyurethane (PU) foams are very common materials that have found many applications over the years. Their use is constantly improving due to their unique physical properties and easy blowing which does not require the addition of a blowing agent. Greener routes have been explored in the recent years to replace isocyanates. One of the most promising routes is leading to polyhydroxyurethanes (PHU). However, with PHUs, external blowing agent are usually required to obtain a foam. Thus, the work focuses on PHU foam synthesis using in situ reaction to produce NIPU foam. Hence, the aminolysis of thiocyclic carbonate triggers Pearson reaction between released thiols and cyclic carbonates which serves as a chemical blowing agent. [ABSTRACT FROM AUTHOR]

Today, plastics are ubiquitous in everyday life, problem solvers of modern technologies, and crucial for sustainable development. Yet the surge in global demand for plastics of the growing world population has triggered a tidal wave of plastic debris in the environment. Moving from a linear to a zero‐waste and carbon‐neutral circular plastic economy is vital for the future of the planet. Taming the plastic waste flood requires closing the carbon loop through plastic reuse, mechanical and molecular recycling, carbon capture, and use of the greenhouse gas carbon dioxide. In the quest for eco‐friendly products, plastics do not need to be reinvented but tuned for reuse and recycling. Their full potential must be exploited regarding energy, resource, and eco‐efficiency, waste prevention, circular economy, climate change mitigation, and lowering environmental pollution. Biodegradation holds promise for composting and bio‐feedstock recovery, but it is neither the Holy Grail of circular plastics economy nor a panacea for plastic littering. As an alternative to mechanical downcycling, molecular recycling enables both closed‐loop recovery of virgin plastics and open‐loop valorization, producing hydrogen, fuels, refinery feeds, lubricants, chemicals, and carbonaceous materials. Closing the carbon loop does not create a Perpetuum Mobile and requires renewable energy to achieve sustainability. [ABSTRACT FROM AUTHOR]

Non‐isocyanate polyurethanes (NIPUs) synthesized from biodiesel‐derived diglycerol dicarbonate (DGC) and triamine functional poly(propylene glycol) (Jeffamine) are investigated to improve upon poor water resistance and slow curing kinetics observed in (DGC/diamine functional Jeffamine) NIPUs. The structural, thermal, and rheological properties of the prepolymer formulations match those of their diamine‐prepared analog previously reported. The NIPU prepolymers (number average molecular weight, MN between 4200 and 6400 g mol−1) are subsequently functionalized with trimethoxy silane end‐cappers to yield moisture‐curable hybrid NIPUs. The prepolymers are both successfully end‐capped and subsequently cured under ambient conditions. The sol/gel curing kinetics of the prepolymers are extensively studied, and the effects of the capping methodology, moisture, and the amount of catalyst are quantified so that gel times are observed in as little as 1.4 h at room temperature. The developed curing methods are effective leading to final hybrid films with high gel contents (>86%). The tensile properties of the final films resulting are considerably better compared to previously reported DGC/Jeffamine‐based NIPUs, which are too soft to undergo mechanical testing. Also, the films are found to exhibit a tenfold decrease in water absorption compared to the latter (5% vs 70%, respectively). [ABSTRACT FROM AUTHOR]

A nonlinear interface circuit, known as synchronized switch harvesting on inductor (SSHI), for in-plane rotational electret kinetic energy harvesters (EHs) was developed. An explicit generator model is derived to verify the applicability of SSHI, which was originally proposed for the piezoelectric EH, on an in-plane electret EH. Experimentally, 505 μW was harvested with SSHI at a rectified voltage of 142 V for an in-plane rotational electret EH rotating at 1 rps, which is 2.47 times of that with a full-bridge rectifier, and which is in good agreement with the simulation result. The circuit efficiency and criteria for the inductor selection were clarified through circuit analysis based on spice simulation. It is found that the power dissipation of voltage-divider and rectification diodes becomes pronounced as the load voltage increases, constraining the efficiency. The inductor, which usually dominates the circuit volume, can be miniaturized for electret EHs, because the voltage inversion ratio, a benchmark of the SSHI performance, turns out to be insensitive to the series resistance of the inductor. The self-powering ability of the proposed circuit is also presented. [ABSTRACT FROM AUTHOR]

The transition towards safer and more sustainable production of polymers has led to a growing body of academic research into non-isocyanate polyurethanes (NIPUs) as potential replacements for conventional, isocyanate-based polyurethane materials. This perspective article focuses on the opportunities and current limitations of NIPUs produced by the reaction between biobased cyclic carbonates with amines, which offers an interesting pathway to renewable NIPUs. While it was initially thought that due to the similarities in the chemical structure, NIPUs could be used to directly replace conventional polyurethanes (PU), this has proven to be more challenging to achieve in practice. As a result, and in spite of the vast amount of academic research into this topic, the market size of NIPUs remains negligible. In this perspective, we will emphasize the main limitations of NIPUs in comparison to conventional PUs and the most significant advances made by others and us to overcome these limitations. Finally, we provide our personal view of where research should be directed to promote the transition from the academic to the industrial sector. [ABSTRACT FROM AUTHOR]

Objectives: Patients with inflammatory bowel disease (IBD) usually experience psychosocial impairment and psychiatric comorbidity related to the chronic course, relapsing activity (unpredictable risk of flare), and consequent physical symptoms. One of the psychological approaches which has gained more consideration as a coadjuvant therapy is mindfulness-based intervention (MBI). The purpose of this study was to examine the efficacy of a blended Internet-based MBI compared to standard medical therapy (SMT), in a sample of patients with IBD. Methods: A mixed-methods non-randomized controlled trial was conducted with 57 patients with IBD (35 in MBI condition and 22 in SMT condition). The MBI involved an 8-week program which comprised four face-to-face support sessions and four Internet-based therapy modules. Health-related quality of life (HRQoL), anxiety, depression, stress, mindfulness, and optimism were compared within and between groups. Qualitative methods were used to analyze the response of the patients to the treatment. Results: Results revealed that the MBI condition significantly increased HRQoL and optimism compared to the SMT condition. However, there were no significant between-group differences in anxiety, depression, perceived stress, pessimism, or mindfulness facets. In addition, the interviewed MBI participants (n = 19) assured that they had learned strategies to regulate their emotions (anxiety, depression, stress) and to manage both pain and fatigue. Conclusions: This study shows the effectiveness of a blended Internet-based MBI in increasing HRQoL and optimism in patients with IBD. It also highlights the use of MBIs to treat psychological impairment in IBD. Trial Registration.: NCT 02,963,246, 15/11/2016. [ABSTRACT FROM AUTHOR]

This work reports on the use of gallium aminotrisphenolate compounds as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The results show that they are highly active, and more so than the corresponding aluminium congeners. The catalyst system is applicable at low and elevated temperatures across a wide substrate scope including terminal, internal, multiple and fully deuterated epoxides. Applying low catalyst loadings has allowed for a TON of 344,000 to be obtained, highlighting their stability. A DFT investigation has confirmed that the gallium catalysts have lower energetic profiles compared to the aluminium congeners. Measurement of the Lewis acidity of both the gallium and aluminium aminotrisphenolate compounds using the Gutmann‐Beckett method provides the experimental proof that the gallium compounds are more Lewis acidic than their aluminium congeners. Finally, Ab‐Initio Molecular Dynamic (AIMD) simulations have investigated and quantified the dynamic behaviour of the catalytic systems, highlighting an important increase in fluxionality in some cases which helps to explain the increase in catalytic activity. [ABSTRACT FROM AUTHOR]

Tungstate catalysts are well established for olefin epoxidation reactions, while their catalytic activity for CO2 insertion in epoxides is a more recent discovery. This dual reactivity of tungstate prompted the present development of a catalytic tandem process for the direct conversion of olefins into the corresponding cyclic organic carbonates (COCs). Each of the two steps was studied in the presence of the ammonium tungstate ionic liquid catalyst – [N8,8,8,1]2[WO4] – obtained via a benign procedure starting from ammonium methylcarbonate ionic liquids. The catalytic epoxidation first step was optimised on 1-decene as model substrate, using H2O2 as benign oxidant, [N8,8,8,1]2[WO4] as catalyst and phosphoric acid as promoter affording quantitative conversion with 92% selectivity towards decene oxide. Unfortunately, the addition of CO2 from the start (auto-tandem catalysis) gave low yields of decene carbonate (<10%). On the contrary, the addition of 1 atm CO2 and tetrabutyl ammonium iodide after completion of the epoxidation first step without any intermediate work-up (assisted-tandem catalysis) afforded a 94% yield in decene carbonate. The protocol could be scaled up to a 10 gram scale. The scope of the reaction was demonstrated for primary aliphatic olefins with different alkyl chain lengths (C6–C16), while cyclic and aromatic activated olefins such as cyclohexene and styrene suffered from the formation of undesired overoxidation products in the first step. [ABSTRACT FROM AUTHOR]

New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Non‐isocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU′s urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post‐functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding. [ABSTRACT FROM AUTHOR]