Horizons in Asymmetric Organocatalysis: En Route to the Sustainability and New Applications

Nowadays, the development of new enantioselective processes is highly relevant in chemistry due to the relevance of chiral compounds in biomedicine (mainly drugs) and in other fields, such as agrochemistry, animal feed, and flavorings. Among them, organocatalytic methods have become an efficient and sustainable alternative since List and MacMillan pioneering contributions were published in 2000. These works established the term asymmetric organocatalysis to label this area of research, which has grown exponentially over the last two decades. Since then, the scientific community has attended to the discovery of a plethora of organic reactions and transformations carried out with excellent results in terms of both reactivity and enantioselectivity. Looking back to earlier times, we can find in the literature a few examples where small organic molecules and some natural products could act as effective catalysts. However, with the birth of this type of catalysis, new chemical architectures based on amines, thioureas, squaramides, cinchona alkaloids, quaternary ammonium salts, carbenes, guanidines and phosphoric acids, among many others, have been developed. These organocatalysts have provided a broad range of activation modes that allow privileged interactions between catalysts and substrates for the preparation of compounds with high added value in an enantioselective way. Here, we briefly cover the history of this chemistry, from our point of view, including our beginnings, how the field has evolved during these years of research, and the road ahead.

Identification and mapping of ancient pigments in a Roman Egyptian funerary portrait by application of reflectance and luminescence imaging spectroscopy

Imaging spectroscopy (IS) is an important tool in the comprehensive technical analysis required of archaeological paintings. The complexity of pigment mixtures, diverse artistic practices and painting technologies, and the often-fragile and weathered nature of these objects render macroscale, non-invasive chemical mapping an essential component of the analytical protocol. Furthermore, the use of pigments such as Egyptian blue and madder lake, featuring diagnostic photoluminescence emission, provides motivation to perform photoluminescence mapping on the macroscale. This work demonstrates and advances new applications of dual-mode imaging spectroscopy and data analysis approaches for ancient painting. Both reflectance (RIS) and luminescence (LIS) modes were utilized for the study of a Roman Egyptian funerary portrait from second century CE Egypt. The first derivative of the RIS image cube was analyzed and found to significantly improve materials separation, identification, and the extent of mapping. Egyptian blue and madder lake were mapped across a decorated surface using their luminescence spectral signatures in the region of 540–1000 nm as endmembers in LIS analyses. Linear unmixing of the LIS endmembers and subsequent derivative analyses resulted in an improved separation and mapping of the luminescence pigments. RIS and LIS studies, combined with complementary, single-spot collection elemental and molecular spectroscopy, were able to successfully characterize the portrait’s painting materials and binding media used by the ancient artist, providing key insight into their material use, stylistic practices, and technological choices.

Silk Protein Composite Bioinks and Their 3D Scaffolds and In Vitro Characterization

This paper describes the use of silk protein, including fibroin and sericin, from an alkaline solution of Ca(OH)2 for the clean degumming of silk, which is neutralized by sulfuric acid to create calcium salt precipitation. The whole sericin (WS) can not only be recycled, but completely degummed silk fibroin (SF) is also obtained in this process. The inner layers of sericin (ILS) were also prepared from the degummed silk in boiling water by 120 °C water treatment. When the three silk proteins (SPs) were individually grafted with glycidyl methacrylate (GMA), three grafted silk proteins (G-SF, G-WS, G-ILS) were obtained. After adding I2959 (a photoinitiator), the SP bioinks were prepared with phosphate buffer (PBS) and subsequently bioprinted into various SP scaffolds with a 3D network structure. The compressive strength of the SF/ILS (20%) scaffold added to G-ILS was 45% higher than that of the SF scaffold alone. The thermal decomposition temperatures of the SF/WS (10%) and SF/ILS (20%) scaffolds, mainly composed of a β-sheet structures, were 3 °C and 2 °C higher than that of the SF scaffold alone, respectively. The swelling properties and resistance to protease hydrolysis of the SP scaffolds containing sericin were improved. The bovine insulin release rates reached 61% and 56% after 5 days. The L929 cells adhered, stretched, and proliferated well on the SP composite scaffold. Thus, the SP bioinks obtained could be used to print different types of SP composite scaffolds adapted to a variety of applications, including cells, drugs, tissues, etc. The techniques described here provide potential new applications for the recycling and utilization of sericin, which is a waste product of silk processing.

Biomass Valorization of Walnut Shell for Liquefaction Efficiency

Globally, lignocellulosic biomass has great potential for industrial production of materials and products, but this resource must be used in an environmentally friendly, socially acceptable and sustainable manner. Wood and agricultural residues such as walnut shells as lignocellulosic biomass are one of the most affordable and important renewable resources in the world, which can partially replace fossil resources. The overall objective of the research is to provide background information that supports new applications of walnut shells in a biorefinery context and to increase the economic value of these non-wood forest products. This paper presents the properties characterization of liquefied biomass according to their chemical composition. All results were compared to liquefied wood. In this study, the liquefaction properties of five different walnut shell particle sizes were determined using glycerol as the liquefaction reagent under defined reaction conditions. The liquefied biomass was characterized for properties such as percentage residue, degree of liquefaction, and hydroxyl OH numbers. The chemical composition of the same biomass was investigated for its influence on the liquefaction properties. Accordingly, the main objective of this study was to determine the liquefaction properties of different particle sizes as a function of their chemical composition, also in comparison with the chemical composition of wood. The study revealed that walnut shell biomass can be effectively liquefied into glycerol using H2SO4 as the catalyst, with liquefaction efficiency ranging from 89.21 to 90.98%.

The Lithium (Li) Doping Effect for Enhancing Thermoelectric and Optoelectronic Performances of Co2NbAl

Cobalt -rich Heusler compounds represent a very interesting family among Heusler alloys due to their performance in the field of spintronics and magnetic devices. The quaternary Heusler created by swapping of an anti-atom site by an alkali element improves the performance of physical properties for new applications. In this study, the electronic structures and magnetic properties before and after swapping cobalt (Co) by lithium (Li) in the Co2NbAl compound have been investigated using first-principle computational calculations. Our findings revealed that the swapping Co antisite by Li keeps the half-metallic character in the CoLiNbAl. Analysis of band structures show that ternary Heusler compound is ferromagnetic half-metallic with half metallic gap (band gap in minority channel ) equal 0.134 eV but the swapping Co with Li leads the material to change its behavior and becomes a semiconductor with a gap equal 1.043 eV using HSE06 approach. The results of optical and thermoelectric properties such as absorption coefficient, reflectivity or thermopower and figure of merit are very interesting in the optoelectronic field and encourages the researchers to realize photovoltaic cell and thermoelectric generator with a higher efficiency. These interesting features suggest that Co2NbAl and LiNbAlCo Heusler compounds could be good candidates for applications of antiferromagnetic spintronics and optoelectronics in commercial semiconductor industry.

Small RNAs Participate in Plant–Virus Interaction and Their Application in Plant Viral Defense

Small RNAs are significant regulators of gene expression, which play multiple roles in plant development, growth, reproductive and stress response. It is generally believed that the regulation of plants’ endogenous genes by small RNAs has evolved from a cellular defense mechanism for RNA viruses and transposons. Most small RNAs have well-established roles in the defense response, such as viral response. During viral infection, plant endogenous small RNAs can direct virus resistance by regulating the gene expression in the host defense pathway, while the small RNAs derived from viruses are the core of the conserved and effective RNAi resistance mechanism. As a counter strategy, viruses evolve suppressors of the RNAi pathway to disrupt host plant silencing against viruses. Currently, several studies have been published elucidating the mechanisms by which small RNAs regulate viral defense in different crops. This paper reviews the distinct pathways of small RNAs biogenesis and the molecular mechanisms of small RNAs mediating antiviral immunity in plants, as well as summarizes the coping strategies used by viruses to override this immune response. Finally, we discuss the current development state of the new applications in virus defense based on small RNA silencing.

Seismic Advances in Process Geomorphology

One of the pillars of geomorphology is the study of geomorphic processes and their drivers, dynamics, and impacts. Like all activity that transfers energy to Earth's surface, a wide range of geomorphic process types create seismic waves that can be measured with standard seismic instruments. Seismic signals provide continuous high-resolution coverage with a spatial footprint that can vary from local to global, and in recent years, efforts to exploit these signals for information about surface processes have increased dramatically, coalescing into the emerging field of environmental seismology. The application of seismic methods has the potential to drive advances in our understanding of the occurrence, timing, and triggering of geomorphic events, the dynamics of geomorphic processes, fluvial bedload transport, and integrative geomorphic system monitoring. As new seismic applications move from development to proof of concept to routine application, integration between geomorphologists and seismologists is key for continued progress. ▪ Geomorphic activity on Earth's surface produces seismic signals that can be measured with standard seismic instruments. ▪ Seismic methods are driving advances in our understanding of the occurrence, triggering, and internal dynamics of a range of geomorphic processes. ▪ Dedicated seismic-based observatories offer the potential to comprehensively characterize geomorphic activity and its impacts across a landscape. ▪ Collaboration between seismologists and geomorphologists is fostering the development of new applications, models, and analysis techniques for geomorphic seismology. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 50 is May 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Investigation of Thermal, Mechanical and Acoustic Performance of Bio-Materials Based on Plaster-Gypsum and Cork

The building sector is one of the biggest consumers of energy in the world and it is pushing the scientific community to find various alternative solutions to solve the problem of thermal insulation of buildings. Therefore, the selection of appropriate building materials is a major challenge for improving the thermal comfort and energy performance of buildings. In this scenario, the interest of plaster-based composites as insulating materials increases, in particular for new applications, as insulators for the building envelope, and this deserves to be studied. In this investigation, new plaster-based composites with cork were produced and tested at lab scale, in order to obtain cheap solutions with improved thermo-physical and acoustic performance. The results show that it is possible to improve the thermal, mechanical, and acoustic performance of construction biomaterials by using plaster as a binder and cork as a natural reinforcement: thermal conductivity was equal to 0.097 W/m.K, the compressive strength to about 2.30 MPa, and the transmission loss to about 40 dB. Keywords: Plaster-Gypsum; Cork; Thermal, Mechanical and Acoustic Properties.

Approximate field measures for ionic polymer-metal composite Materials and a simplified Order-of-magnitude actuator model

As the field of soft robotics grows and new applications for this technology are discovered, the use of simplified models for the soft actuators found in these devices will be critical. In this study we explore arguments based on the magnitude of field gradients that arise in the ionic polymer-metal composite under large applied voltages and their use for approximating measures of the fields inside the polymer. Using the order-of-magnitude based arguments provides exceptional results for quantifying the field measures of maximum ionic concentration and electric potential within the bulk of the polymer. These measures are leveraged to reconstruct the fields themselves in such a way that the internal bending moments generated inside the actuator may be approximated. With the internal moments, a simplified kinematic model may be used to formulate the steady-state actuator response of the IPMC. This actuator model shows a great deal of accuracy as compared to a full multiphysics model, and we discuss the prospects for future development of this model to account for dynamic actuation.

Nanomaterials and nanotechnology for the delivery of agrochemicals: strategies towards sustainable agriculture

Nanomaterials (NMs) have received considerable attention in the field of agrochemicals due to their special properties, such as small particle size, surface structure, solubility and chemical composition. The application of NMs and nanotechnology in agrochemicals dramatically overcomes the defects of conventional agrochemicals, including low bioavailability, easy photolysis, and organic solvent pollution, etc. In this review, we describe advances in the application of NMs in chemical pesticides and fertilizers, which are the two earliest and most researched areas of NMs in agrochemicals. Besides, this article concerns with the new applications of NMs in other agrochemicals, such as bio-pesticides, nucleic acid pesticides, plant growth regulators (PGRs), and pheromone. We also discuss challenges and the industrialization trend of NMs in the field of agrochemicals. Constructing nano-agrochemical delivery system via NMs and nanotechnology facilitates the improvement of the stability and dispersion of active ingredients, promotes the precise delivery of agrochemicals, reduces residual pollution and decreases labor cost in different application scenarios, which is potential to maintain the sustainability of agricultural systems and improve food security by increasing the efficacy of agricultural inputs. Graphical Abstract