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In this chapter, the molecules that it is usually possible to detect in paper and paperboard samples are investigated. In addition to the additives and production aids that can be used in the production as listed in different national regulations, some other substances can also be found, particularly when the test involves recycled material. These substances must be evaluated with respect to the toxicological risk for the consumer, in order to assess the safety of the consumer.

Sustainability is essential for future technologies to harmonize with our living environment. Cellulose is one of nature's most abundant natural polymers, being the main chemical components of wood and plants. It recycles back to nature by composting over a short period of time. Recently, cellulose has been rediscovered as an active material, namely electroactive paper (EAPap). This chapter reviews the fabrication and actuation principles of EAPap and its three subareas in terms of piezoelectric EAPap, ionic EAPap and hybrid EAPap, along with their applications. Cellulose is known to have piezoelectric and ion migration effects and these two effects can be maximized, which results in piezoelectric EAPap and ionic EAPap. To further improve the functionality of cellulose, hybrid composites of inorganic functional materials are introduced by incorporating carbon nanotubes (CNTs), titanium dioxide (TiO2) and tin oxide (SnO2) with cellulose. Since cellulose is biocompatible, sustainable, biodegradable, capable of broad chemical modification, hydrophilic and has high mechanical strength and stiffness, various cellulose-based devices are possible.

This paper aims to evaluate the reduction in greenhouse gas emissions of rice and wheat and their supply chains by incorporating carbon capture, utilisation and storage into fertiliser production mainly from the ammonia process, which is a part of the fertiliser that produces most of the carbon dioxide. Greenhouse gas emissions of these grains without carbon capture, utilisation and storage are provided from the results of life cycle assessment in the literature. After that, carbon dioxide emission from fertiliser production is quantified. The alternative considered for utilisation is enhanced oil recovery and it is compared with the conventional way of oil production. The effects of carbon capture, utilisation, and storage on greenhouse gas reduction are presented in terms of the supply chains of rice and wheat to make people conscious about the use and optimisation of food. The reduction of greenhouse gas is around 6–7% in the rice supply chain e.g. rice milk, spoons of uncooked rice and 14–16% in the wheat supply chain e.g. pasta, one slice of bread. Although the alternative for carbon dioxide storage demonstrates marginally higher greenhouse gas reduction, enhanced oil recovery may offer an economic incentive from additional oil production that could reduce the cost of rice and wheat.

In this chapter, corn coproducts produced by the fuel ethanol industry, Dried Distiller's Grain with Solubles (DDGS), containing natural nanocellulose fibres and non-degradable protein, have been applied as formaldehyde-free bioadhesive for manufacturing biocomposite board. Various biocomposites based on wood fibres and other types of biomass fibres were produced. The results demonstrated the importance of the selection of the correct fibre to produce lightweight, high-performance sustainable natural bio-based boards using the DDGS bioadhesive system. The products exhibit a smooth surface, lightweight, high performance and microbial- and moisture-resistant structure. The selected natural fibres for this study included wood, bamboo, pineapple leaf and reed fibres to produce MDF, OSB, particleboard and pressed wood pallets. The end products are environmentally friendly alternatives to traditional plastic and wood biocomposites that meet industrial standards.

Algae, which has high photosynthetic efficiency, non-arable land requirement and the ability to utilize salt or brackish water, is a promising renewable source for biofuel and other value-added biochemical production. Examination of the economic viability of such algae-based bioproducts is trending. The results of the examinations indicate that many parameters are decreasing the viability of the commercialization of algal biofuels and other commodity products. This chapter covers several different components of an integrated algal biorefinery, as an alternative approach to democratize algal products by decreasing the costs of production. The main sections touch base on strain improvements and other upstream components followed by sustainability issues. The chapter is finalized with the techno-economic assessments (TEA) of algal biorefineries with various production scenarios. The major components affecting the total cost of algal biochemical production are indicated by TEA, and their effect on the viability of the biorefineries are discussed.

The paper industry has a long history of harvesting, processing, and making products from wood. As we look to the future, the paper industry's processing methods and attempts to obtain value from lignin may provide guidance for the emerging lignin industry. This chapter provides a broad overview of the history and chemistry of pulping, and describes processes that have provided lignosulfonates, vanillin, and kraft lignin to the marketplace.

Despite the rapid increase of anaerobic co-digestion works over the last years, the very small number of pilot- and full-scale studies available in the literature is a major barrier to its full-scale implementation. In this paper, a control strategy methodology was applied in a full-scale sludge digester to safely steer the transition from anaerobic mono- to co-digestion and to maximize methane production. Traditional wastewater treatment plants (WWTPs) are electrical consumers, with a usual high demand in the range of 0.3 to 0.6 kWh/m3 of wastewater treated. Their digesters are commonly oversized, and consequently operated at low organic loading rates (OLRs). This opens a great opportunity for anaerobic co-digestion (AcoD) as an interesting technology to increase methane productivity and the electrical self-production in WWTPs. However, there is a quite limited implementation of AcoD at full-scale plants, since the transition from mono- to co-digestion and the further AcoD optimisation is a crucial and delicate step that could lead to the inhibition of the process if not thoroughly controlled. In this study, a methodology based on an optimum control strategy is explained in detail and it was applied to safely and optimally steer the transition from mono- to co-digestion and to maximize methane production during AcoD. A lab-scale anaerobic digester of 14 L mimicking the full-scale one (3,500 m3) was operated 30 days in advance to anticipate and if needed correct any operational destabilization that might occurr. As a result, the treatment of sewage sludge with two co-substrates (coming from a pig slaughterhouse and from a frying industry), which accounted for just 11% of the feeding flowrate, at a hydraulic retention time of 20 days allowed to raise the OLR and the methane production by 2-fold and 3-fold, respectively, increasing the self-produced electricity from 25% to 75% of the total demand of the WWTP. The diagnosis indicators proved to be accurate to take decisions concerning wastes blending and the strategy of increasing OLR. Besides, the proposed control system provides the steps to ensure a safe transition from anaerobic mono- to co-digestion and further optimisation at full-scale plants This work was supported by SmartGreenGas project (Spanish Government, AEI, 2014-CE224). The authors from Universidade de Santiago de Compostela belong to the Galician Competitive Research Group ED431C 2017/029 and to the CRETUS Strategic Partnership (AGRUP2017/01). All these programs are co-funded by FEDER (EU) SI

The process of stabilization is essential in the production of carbon fibers from lignins. During stabilization, the initially thermoplastic lignin polymer is converted to a thermoset polymer allowing for high-temperature treatment without a change in shape. In this work, hardwood (HKL) and softwood (SKL) Kraft lignins were stabilized in air at temperatures between 190 and 340 °C before carbonization at 800 °C in a nitrogen atmosphere. Due to the differences in side-chain linkages, functional groups and molar mass, the lignins exhibit different structural changes upon stabilization and hence develop different porosities upon carbonization. Both lignins undergo major crosslinking reactions in the side chains at low temperatures and degradation reactions at high temperatures during stabilization. Crosslinking gives rise to narrow pore size distributions with mainly (sub-) nanometer pores, whereas degradation reactions lead to a more open pore structure with additional mesoporosity (>2 nm). When both types of reactions take place simultaneously, highly accessible (sub-) nanoporosity can be effectively created, which boosts the performance of supercapacitors operating in 6 M KOH(aq). This effect terminates when the crosslinking reactions cease and mainly degradation reactions take place, which occurs in HKL at 340 °C. SKL shows both a lower degree of crosslinking and degradation and hence develops less specific surface area. The optimum performance in an aqueous alkaline supercapacitor is achieved with HKL stabilized at 310 °C. It shows a specific gravimetric capacitance of 164 F g−1 at 0.1 A g−1 and 119 F g−1 at 250 A g−1 with a capacitance retention of more than 90% after 10 000 cycles. M. J. M. L. and D. C. A. thank Spanish Ministry of Science, Innovation and Universities and FEDER (project RTI2018-095291-B-I00) for financial support. C. P. G. and C. O'K. thank Shell. MMT and PS thank RISE AB for co-funding Philipp Schlee's PhD position.

Softwood is an abundantly available feedstock for the bio-based industry. However, achieving cost-effective sugar release is particularly challenging, owing to its guaiacyl-only lignin. Here, we report the highly effective pretreatment of the softwood pine (Pinus sylvestris) using ionoSolv pretreatment, a novel ionic liquid-based lignocellulose fractionation technology. Three protic, low-cost ionic liquids, 1-butylimidazolium hydrogen sulfate, triethylammonium hydrogen sulfate and N,N-dimethylbutylammonium hydrogen sulfate, were used to fractionate the biomass into a carbohydrate-rich pulp and a lignin. The carbohydrate-rich pulp was hydrolysed into fermentable sugars by enzymatic saccharification. Under the most successful pretreatment conditions, quantitative glucose release from the pulp was achieved, which equates to a projected glucose release of 464 mg per gram of pine wood entering the process. We further intensified the process by increasing the solid to solvent ratio up to 1 : 2 g g−1 while maintaining saccharification yields of 75% of the theoretical maximum. We also demonstrate for the first time that N,N-dimethylbutylammonium hydrogen sulfate, [DMBA][HSO4], is an excellent low-cost pretreatment solvent, surpassing the pretreatment effectiveness of its symmetrically substituted analogue triethylammonium hydrogen sulfate. This shows that ionoSolv pretreatment with protic hydrogen sulfate ionic liquids is a truly feedstock-independent pretreatment option, further increasing the commercial potential of this pretreatment technology.

An increase in biodiesel production has seen a dramatic increase in the production of glycerol, the main by-product. To maintain biodiesel production as economically viable, processes for valorising the 10 wt% glycerol waste stream need to be developed. The content of this chapter discusses recent work which examines potential catalytic processes for producing value added chemicals using glycerol as a platform chemical. Significant research has focussed on catalytic reactions tailored to selectively convert oxygenates from biological resources to produce valuable chemicals. While homogenous and biological catalytic processes are important, heterogeneously catalysed reactions are considered to be more desirable and potentially more economically viable due to advantages in feedstock processing. The current transesterification process associated with biodiesel production results in a number of contaminants in the glycerol stream, such as free fatty acids and residual catalyst salts, which affects downstream processing. Special emphasis is given to understand how contaminants of various by-products interact with surfaces and identify robust catalysts while examining alternative catalytic processes for producing biodiesel with purer product streams.

Green coffee beans decaffeination and irradiation are important coffee post-harvest processing steps that allow to produce decaffeinated coffee products and raw material after insect and microbial disinfestation, respectively. Insects can cause damage to food as well as leading to consumer objections. The decaffeination process aims at producing coffee products without the caffeine referred to by many as the main motive for not consuming coffee. In addition, it is important to control microbial contamination of the green coffee during all stages of processing, including the raw crop stage, harvesting, processing, packing and exportation, avoiding the production of mycotoxins. The aim of this chapter is to briefly discuss the post-harvest processing steps and their impact on the quality of the final product.

The first part of this chapter will discuss the composition of lignocellulose, and the structures of the cellulose, hemicellulose and lignin components. Degradation of lignocellulose in soil and the microorganisms and enzymes responsible for degradation of these components will be overviewed. Degradation of lignin is aerobic and slow; therefore, lignin degradation is a slow step in breakdown of lignocellulosic waste. Microbial production of biogas will be overviewed along with its role in commercial anaerobic digestion for production of biogas from lignocellulosic biomass. Pathways for lignin biodegradation will be described, including delignification by addition of lignin-degrading fungi and bacteria, delignification by lignin-oxidising enzymes and enhancement of biogas formation. The use of metabolic engineering for production of renewable chemicals from lignin degradation will also be described.

Coffee is one of the most consumed beverages in the world, and its consumption increases every year. The quality of a cup of coffee depends on many factors related to coffee, water and the coffeemaker. Coffee species, variety and origin have a clear influence on the chemical composition and quality of coffee brew, but many other factors from harvesting to roasting, grinding and brewing processes can contribute to maintain the high quality of the coffee beans or, on the contrary, to decrease or even ruin it. Each coffee brewing method has specific requirements in order to prepare a good quality cup. According to the methodology used for coffee brewing, the physico-chemical characteristics and chemical composition of coffee brews can substantially vary from one method to another. This chapter describes the different brewing methods and the requirements on water pressure, grinding grade, extraction time and water quality. Further, physico-chemical characteristics and chemical composition of brews will be discussed in detail.

Anaerobic digestion (AD) is a well-established technology widely used for waste management and production of biogas. Biogas, mainly composed of methane and carbon dioxide, is the final product generated by anaerobic microbial degradation of organic materials. The general view is that it is mainly the carbohydrate, protein, and lipid fractions of organic materials that is degraded during AD, while the lignin fraction is difficult to degrade. However, AD of lignin has been observed in various natural environments and here we highlight the mechanisms of depolymerization and solubilization into small molecular weight aromatic compounds and their subsequent conversion into biogas. This degradation requires close cooperation between several groups of microorganisms, where the key step is the enzymatic depolymerization of lignin. The industrial applicability of AD for lignin valorization may be limited due to the slow rate of lignin depolymerization. However, various pretreatment and bioaugmentation methods are identified that may enhance lignin depolymerization. Furthermore, co-digestion and microbial acclimation are suggested for reducing the possible inhibitory effects of aromatic compounds on the microbial community.

The success of the biorefinery will depend on deriving value from the lignin fraction of lignocellulosic feedstocks. Thus, it will be necessary to develop procedures that provide a separate and usable lignin stream for chemical transformation. A wide range of processes have been developed that afford isolated lignin, but very few of these methods are practical for the biorefinery, as they target lignin analysis or lignin removal, and are largely impractical for large scale use or introduce severe structural changes in the lignin that significantly reduces its potential as a chemical feedstock. This chapter will introduce several methods that isolate lignin for analytical purposes, or for its removal from lignocellulose. The majority of the chapter then discusses processes for biomass fractionation – methodology that gives lignin streams in high yield and purity, and which offer potential utility within the biorefinery.

Conversion of abundant biomass to bioproducts, biomaterials and bioenergy is essential for accomplishment of the biorefinery concept. The first challenge involved in biorefinery processing is biomass fractionation into individual components. One of the most commonly used methods of biomass deconstruction at industrial level is hydrothermal pre-treatment. However, improvements in this technology by use of low cost and widely available solvents are highly desirable. Supercritical CO2 (scCO2) is a good candidate and its use can result in more efficient biomass processing. The advantage of scCO2 use is that the pre-treated material presents no solvent residues after the pre-treatment and CO2 can be easily recovered and reused. Moreover, CO2 in the presence of water generates an acidic environment that offers several benefits in biomass fractionation and chemical transformations. Therefore, this chapter aims to demonstrate the use of scCO2 and water in biomass pre-treatment, highlighting the effects on hemicellulose and starch hydrolysis, as well as the influence on cellulose hydrolysis and lignin extraction. In addition, the benefits of scCO2 in the conversion of biomass-related monosaccharides (hexoses and pentoses) into value-added products are presented. Finally, the influence of pre-treatments on the enzymatic hydrolysis of pre-treated biomass is discussed.

Lignin is an alkyl-aromatic polymer found in the cell walls of terrestrial plants. Lignin provides structure and rigidity to plants, is a natural, highly effective barrier against microbial attack, and enables water and nutrient transport through plant tissues. Depending on the plant species, the constituents of lignin can vary considerably, leading to substantial diversity in lignin chemistry and structure. Despite nearly a century of research and development attempting to convert lignin into valuable products, lignin in most current and planned biorefinery contexts remains underutilized, most often being burned to generate heat and power. However, the drive towards effective lignin valorization processes has witnessed a significant resurgence in the past decade, catalyzed by advances in improved understanding of lignin chemistry, structure, and plasticity in parallel with new catalytic and biological approaches to valorize this important, prevalent biopolymer. As a preface to the subsequent chapters in this book, this chapter briefly highlights the known aspects of lignin structure.

PETROBRAS efforts in biocatalysis are overviewed. Research and development at either bench or pilot scale includes the use of enzymes in synthesis reactions (fatty acid alkyl esters for biodiesel, biolubricants, polyester and solvents such as glycerol carbonate and butyl acetate), in biomass (mostly lignocellulosic) deconstruction and in polyester depolymerization for recycling purposes. In the areas of interest for PETROBRAS, the key enzymes are cellulases and lipases.

3D MoS2/Graphene hybrid layer materials were prepared by in situ synthesizing molybdenum sulfide on 3D honeycomb-like structured graphene sheets via a hydrothermal approach. Furthermore, the composite materials were explored as counter electrodes for dye-sensitized solar cells (DSSCs). It was found that the DSSC with 3D MoS2/Graphene hybrid counter electrode exhibited a high energy conversion efficiency of 7.31%, which is larger than those with either MoS2 (2.81%) or graphene counter electrode (6.72%). The excellent electrocatalytic activity of the hybrid counter electrode was further demonstrated by cyclic voltammograms, namely, the MoS2/Graphene hybrid electrode showed higher peak current density and lower peak-to-peak separation positions than either MoS2 or graphene counter electrode.

© The Royal Society of Chemistry 2017. Denitrification processes have been widely recognised as the key processes in biological nitrogen removal from wastewater. In this chapter, the traditional and emerging denitrification processes in wastewater treatment were reviewed in order to illuminate their stoichiometry, microbial community, kinetics, affecting factors, mathematical models and technological applications, including heterotrophic denitrification, anaerobic ammonia oxidation, denitrifying anaerobic methane oxidation, sulphur or hydrogen-based autotrophic denitrification and bioelectrochemical denitrification. Although existing technological denitrification processes still have limitations, their applications will undoubtedly increase in the near future because of increasing attention that is being paid to high-rate, cost-effective nitrogen removal from wastewater.

Producción Científica, High temperature annealing is the only method known to date that allows the complete repair of a defective lattice of graphenes derived from graphite oxide, but most of the relevant aspects of such restoration processes are poorly understood. Here, we investigate both experimentally (scanning probe microscopy) and theoretically (molecular dynamics simulations) the thermal evolution of individual graphene oxide sheets, which is rationalized on the basis of the generation and the dynamics of atomic vacancies in the carbon lattice. For unreduced and mildly reduced graphene oxide sheets, the amount of generated vacancies was so large that they disintegrated at 1773–2073 K. By contrast, highly reduced sheets survived annealing and their structure could be completely restored at 2073 K. For the latter, a minor atomic-sized defect with six-fold symmetry was observed and ascribed to a stable cluster of nitrogen dopants. The thermal behavior of the sheets was significantly altered when they were supported on a vacancy-decorated graphite substrate, as well as for the overlapped/stacked sheets. In these cases, a net transfer of carbon atoms between neighboring sheets via atomic vacancies takes place, affording an additional healing process. Direct evidence of sheet coalescence with the step edge of the graphite substrate was also gathered from experiments and theory., Ministerio de Economía, Industria y Competitividad (Project AT2011-26399 and MAT2011-22781), Junta de Castilla y León (programa de apoyo a proyectos de investigación - Ref. VA158A11-2)

Energy security, environmental concerns, and business opportunities in the emerging bio-economy have generated strong interest in the production of n-butanol by fermentation. The acetone butanol ethanol (ABE or solvent) batch fermentation process is product limiting because butanol, even at low concentrations, inhibits the growth of fermenting microorganisms resulting in (i) low ABE yield, usually 0.33, (ii) use of dilute sugar solutions as substrates, (iii) low concentration of butanol in the bioreactor, (iv) energy intensive recovery of butanol due to low concentration in the fermentation broth, and (v) generation of large effluent streams. Indeed, the inhibitory property of butanol largely accounts for the long batch fermentation time (60–72 h) thus resulting in low ABE productivity. The cumulative effects of these factors hamper the energy efficient production of butanol and hence scale-up and commercialization. Proficient production of butanol can be accomplished by the application of ‘‘cutting edge’’ science and technologies. This chapter describes novel bioreactors for butanol fermentation using different advanced fermentation systems such as free cell continuous, immobilized cell continuous and cell recycle continuous membrane reactors, and integrated continuous processes where product can be simultaneously recovered using energy efficient product recovery techniques.

Lignocellulosic biomass is a potentially valuable resource for transformation into biofuels and bio-based products. The transformation of biomass into bioethanol involves four basic steps: pre-treatment, hydrolysis, fermentation and distillation. The hydrolysis of cellulose to yield fermentable sugars is an essential step in any practical cellulosic-ethanol process before the microbial action to produce ethanol. The application of ionic liquids as media for the dissolution, pre-treatment and hydrolysis of biomass is a novel alternative method that follows the green chemistry concept and makes the process to obtain biofuels and high-value chemicals more efficient, resulting in improved overall productivity. However, there are still many challenges in order to put these potential applications into practical use: the high price of ionic liquids and lack of basic physicochemical and toxicological data. This chapter focuses on the applications and challenges to use ionic liquids as an aid to carry out biomass hydrolysis.

A major challenge to producing cost-competitive biobased organic acids is the high cost of product recovery from the bioreactor due to the low product titers that are achievable in state-of-the-art bioconversion processes. A new approach in bioprocessing that integrates upstream bioconversion and downstream product separation into a continuous process, called a separative bioreactor (SB), is described. Incorporating an innovative membrane technology, resin wafer electrodeionization (RW-EDI), with SB results in a simpler bioprocess train with fewer unit operations, better pH control, reduced product inhibition from the organic acids, higher organic acid product concentrations and, most importantly, enhanced bioconversion rates and yields. The design and operation of SB-based organic acid processes are described, and the performance of representative processes investigated and demonstrated at bench-scale and pilot-scale tests are reported. The processes include enzymatic, anaerobic and aerobic fermentations to produce sorbitol, gluconic acid and succinic acid. Compared to conventional fermentation processes, SB processes show excellent productivity and high titers of the organic acid products. In long-term operational tests, SB processes were found to be robust with respect to fermentation contamination and membrane fouling issues. Finally, the technical and economic viability for commercial production of organic acids from biomass feedstocks using the SB technology is discussed.

This paper describes the development of a test kit for the selective detection of glyphosate (GlyP). A copper(ii)-pyrocatechol violet complex was selected by a screening approach from a pool of 96 combinations of metal ions and commercially available indicators and subsequently incorporated as a detection zone into a hydrophobic C18 solid support. With this kit, detection of 20 μM GlyP in tap water by the “naked eye” is possible and quantifications by smartphone analysis with a limit of detection as low as 2.66 μM (450 μg L−1) have been demonstrated in a proof-of-principle study., This paper describes the development of a test kit for the naked-eye detection of glyphosate (GlyP) using a copper(ii)-pyrocatechol violet complex immobilized on a C18 solid support.

This paper focuses on the complex conservation of the multi-material sculpture Love Me (1998) made by the British artist Sarah Lucas. The fragility of the constituent materials, combined with frequent transportations and installation/de-installation in art shows worldwide, had produced a deformation on one leg of the artwork. The goal of this experimental study was to develop a treatment methodology to ease out the dent and find a consolidant able to secure the area from further damage. A novel traction system, borrowed from medical limb-lengthening surgery, was developed and several types of tie rods and protecting layers were tested. Moreover, innovative materials based on nanocellulose particles were evaluated as strengthening agents for the papier-mâche layers and compared to traditional strengthening products. Due to the lack of information obtained from the experimentation, the use of nanocellulose particles was not considered safe for the treatment, which was done using more traditional materials, namely wheat starch and Kozo Japanese paper. Nevertheless, the results of the preliminary trials laid the foundation for the use of these novel products for conservation purposes.

This paper highlights the important developments which have emerged from a collaboration between the University of Bari, University of Perugia and Paper Conservator Antonio Mirabile which seeks to explore multi-analytical investigation methods for the characterization of modern and contemporary inks. Specifically, the present work describes and explains a set of analysis carried out to characterize 20 Johann Faber felt-tip pens commercialized in the 1960s that actually belonged to and were used by the Italian-Brazilian architect and designer Lina Bo Bardi. Spectroscopic methods (i.e. X-ray fluorescence, conventional and coupled to thin-layer chromatography micro-Raman, SERS, and reflection infrared spectroscopy) combined with the use of chromatography techniques (GC-MS and Py-GC-MS) were exploited in order to provide a thorough chemical characterization of the ink formulations. Of particular interest, in the multi-analytical investigation employed, is the strong ability to distinguish and identify not only the dyes and their possible mixtures but also the specific use of solvents, binders and additives as other components of the ink formulation. This chapter contains additionally a preliminary investigation on the aging behaviour of the felt-tip pens' inks, a compressed history of felt-tip pens and of the synthetic dyes determined in addition to a brief introduction about Lina Bo Bardi's artistic personality, merge this research study.

11 pags., 5 figs., 3 tabs. -- We adknowledge support by the CSIC Open Access Publication Initiative through its Unit Information Resources for Research (URICI). -- Open Access funded by Creative Commons Atribution Licence 3.0, Absolute total electron scattering cross sections (TCS) for nitrobenzene molecules with impact energies from 0.4 to 1000 eV have been measured by means of two different electron-transmission experimental arrangements. For the lower energies (0.4–250 eV) a magnetically confined electron beam system has been used, while for energies above 100 eV a linear beam transmission technique with high angular resolution allowed accurate measurements up to 1000 eV impact energy. In both cases random uncertainties were maintained below 5–8%. Systematic errors arising from the angular and energy resolution limits of each apparatus are analysed in detail and quantified with the help of our theoretical calculations. Differential elastic and integral elastic, excitation and ionisation as well as momentum transfer cross sections have been calculated, for the whole energy range considered here, by using an independent atom model in combination with the screening corrected additivity rule method including interference effects (IAM-SCARI). Due to the significant permanent dipole moment of nitrobenzene, additional differential and integral rotational excitation cross sections have been calculated in the framework of the Born approximation. If we ignore the rotational excitations, our calculated total cross section agrees well with our experimental results for impact energies above 15 eV. Additionally, they overlap at 10 eV with the low energy Schwinger Multichannel method with Pseudo Potentials (SMCPP) calculation available in the literature (L. S. Maioli and M. H. F. Bettega, J. Chem. Phys., 2017, 147, 164305). We find a broad feature in the experimental TCS at around 1.0 eV, which has been related to the formation of the NO2 anion and assigned to the p*(b1) resonance, according to previous mass spectra available in the literature. Other local maxima in the TCSs are found at 4.0 0.2 and 5.0 0.2 eV and are assigned to core excited resonances leading to the formation of the NO2 and O2 anions, respectively. Finally, for energies below 10 eV, differences found between the present measurements, the SMCPP calculation and our previous data for non-polar benzene have revealed the importance of accurately calculating the rotational excitation contribution to the TCS before comparing theoretical and experimental data. This comparison suggests that our dipole-Born calculation for nitrobenzene overestimates the magnitude of the rotational excitation cross sections below 10 eV., This study has partially been supported by the Spanish Ministerio de Ciencia, Innovacion y Universidades (Project FIS2016-80440) and CSIC (Project LINKA 20085). F. C. acknowledges Radiation Biology and Biophysics Doctoral Training Programme (RaBBiT, PD/00193/2012); UCIBIO (UIDB/04378/2020) and together with P. L. V. the Portuguese National Funding Agency FCT through the Research Grants CEFITEC (UIDB/00068/2020) and PTDC/FISAQM/31281/2017. M. J. B. thanks the Australian Research Council for funding through grants DP160102787 and DP180101655. The authors acknowledge Dr N. C. Jones for providing her full experimental TCS data on NBz molecules and Dr L. S. Maioli and Prof. M. H. F. Bettega for providing numerical tables of their SMCPP calculation and taking part in helpful discussions related to this paper. We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI). Finally we also acknowledge Dr L. Campbell for his contributions to the final version of this paper.

Contemporary drawings incorporate a series of artistic techniques and unconventional materials, which sometimes make it difficult not only to identify the exact nature, medium and substrates of the drawings, but also to determine their chemical and physical characteristics. The three artists chosen for this contribution—Stefano Arienti, Sandra Vasquez de la Horra and Beatriz Milhazes—are representative of contemporary creations on paper and were also selected due to the originality of their artistic techniques. Their techniques and unorthodox materials have been characterized through a series of analyses and scientific investigations, which for the most part were non-invasive. The results gathered have permitted a better understanding of their creative approach through the identification of constituent materials and execution techniques employed, in particular the identification of heated lemon juice used by Stefano Arienti, the impregnation of paper with wax resulting in different paper thickness by Sandra Vasquez de la Horra and the utilization of wrapping papers used by Beatriz Milhazes. Furthermore, beyond the analytical investigations, direct contact with the artist and historical fonts aided the documented results.

Electronic Laboratory Notebooks (ELNs) have the potential to not only replace paper notebooks for recording our research and our day-to-day activities, but they can also provide a myriad of additional capabilities for supporting scientists that go far beyond what is possible in a paper notebook. However, we know that many scientists are sceptical of the technology and have anxieties about the complexity of the software, and perceived ease of use is of primary importance to users in selecting an ELN provider. It is essential to ensure that usability is at the forefront in the design of digital tools to encourage adoption and also to ensure that the users get the best value out of the functions that are provided. The design of interfaces for digital tools not only impacts whether users are willing to use them, but also whether users are able to make the best use of them. In this chapter, we discuss a variety of user experience design techniques, including interaction design, that are used to help make software both useful and usable for the intended audience. We will investigate how these techniques can be used to identify requirements for new tools based on user needs and present some examples of potential ELN capabilities based on the needs and behaviours of real-world researchers. This chapter also includes guidelines and best practices for designing interfaces for desktop, mobile, and Web-based software.

Electronic Laboratory Notebooks (ELNs) have many features that can support the work of scientists, but their main purpose is to replace the paper notebook in the laboratory. When we capture notes in a paper notebook, we have the flexibility to record our research in any format we choose. When we capture notes using an electronic notebook, and particularly using ELNs, the way that we capture information changes. Many ELNs make use of templates to encourage the capture of standard information and provide the opportunity to prompt users to capture items of interest that they might otherwise omit or forget to record. Using the cues provided by the formal structure, templates should improve the consistency and quality of records. There is, however, the possibility that templates may have negative as well as positive impacts because they may restrict the content that is recorded, and information that is not specifically prompted for in the template may be omitted, even if it is significant to the record. In this chapter, we will examine research into the impacts of different kinds of interfaces on the information that is captured in the laboratory. We also take a look at the role of mobile applications in bridging the gap between paper notebooks and ELNs, and how other kinds of interfaces may better support users in capturing their research in electronic form.

As more and more scientific data is being created in digital formats, the need to be able to link together the data with the methods used to obtain it becomes ever more urgent. Digital data without the context provided by the notes we typically collect in our paper notebooks is meaningless. Electronic notebooks have the potential to revolutionise the way that scientists record their research. Not only can electronic notebooks enable us to create better links between the research activities recorded and the data they produce, but they are also easier to read, easier to search, enable sharing and collaboration, and can improve quality and efficiency in working practices. Despite the benefits, the majority of scientists are still relying on their trusty paper notebooks to capture the record of their research. In this chapter, we take a more in-depth look at electronic notebooks, and Electronic Laboratory Notebooks (ELNs) in particular. We take a look at the numerous benefits of electronic notebooks over paper notebooks and discuss a number of different ELNs to provide examples of differences and overlaps in their capabilities and target audience. We also look at some experiences of using an ELN from different disciplines, and how an ELN can facilitate and support scientific research in different ways. We also take a look at what some of the potential barriers are to the adoption of ELNs and why some scientists are reluctant to use them.

Until relatively recently, scientific data has mostly been captured in paper notebooks or on paper forms. With the proliferation of digital technologies has come an even greater proliferation in the amount of scientific data produced and that subsequently needs to be managed. Although there are some challenges in managing data in paper-based form, there are significantly larger challenges in managing data in both paper and digital format. There is also an increasing desire for scientific data to be shared more widely in order that research can be validated and data reused. Both the creators and users of scientific data need to be able to find the data and then make sense of it in order to use it. In this chapter, we will discuss the issues and challenges around research reproducibility, and how data management practices can help. We discuss the role of metadata, standards, identifiers, and provenance in data curation and their importance for discoverability and reuse. We also look at the vulnerability of digital data and the steps that need to be taken to ensure that data is preserved for future access and reuse.

This paper presents the use of tubing to store clinical microdialysis samples for delayed analysis with high temporal resolution, offering an alternative to traditional discrete offline microdialysis sampling. Samples stored in this way were found to be stable for up to 72 days at −80 °C. Examples of how this methodology can be applied to glucose and lactate measurement in a wide range of in vivo monitoring experiments are presented. This paper presents a general model, which allows for an informed choice of tubing parameters for a given storage time and flow rate avoiding high back pressure, which would otherwise cause the microdialysis probe to leak, while maximising temporal resolution.

This paper reports that various thermodynamic properties in aqueous media for certain individual ions and for compounds are linear functions of the inverse cube root of the solid respective ionic and compound solid state volumes, V m –1/3 . This is similar to the situation which has been fully exploited in solid state thermodynamics and out of which Volume–Based Thermodynamics, VBT evolved. A short resume of these various VBT applications is provided for the general reader and an improved lattice potential energy equation emerges using the state of the art data presented in this paper.

For rapid and efficient development of new phosphors, a suitable method that proposes promising candidates is expected to focus time-consuming trial-and-error experiments. A data-driven approach to discover new phosphor materials with a designed luminescence color is demonstrated in this paper. To screen compounds for a desirable luminescence color, a machine learning model has been developed for predicting emission peak wavelengths from a dataset composed of 129 Eu2+-activated phosphors. General-purpose compositional and structural features are used to represent host compounds of phosphors. Bootstrap aggregation with the gradient boosted regression trees method is adopted to obtain high predictive performance and to avoid overfitting. The predictive performance of the machine learning model is estimated to be 25 nm of mean absolute error (MAE) and 33 nm of root mean squared error (RMSE) by 10-fold cross validation. To discover new green-emitting Eu2+-activated phosphors, twenty candidate compounds have been selected to have predicted emission peak wavelengths of about 500–550 nm from a materials database, and the candidates have been synthesized and characterized by experiments. Three new Eu2+-activated phosphors, Li2Ca4Si4O13:Eu2+, Na2Ca2Si2O7:Eu2+, and SrLaGaO4:Eu2+, successfully show green or blue-green emissions as designed., Materials Advances. 4 [1] (2023)231-239

Nano-enabled products and their applications have continued to evolve in recent years. Indeed, nanotechnologies have been integrated into many academic and industrial sectors, and have spurred new directions in terms of research, patents, commercial opportunities and technology transfer. However, many nanopatents are of dubious scope and breadth yet continue to be granted by patent offices internationally. Underpinning many issues in the regulation and patenting of such technologies is the difficulty that has been encountered in agreeing a definition, and this continues to pose a significant problem to regulators, policy-makers, drug companies, ethicists and legal professionals. This chapter aims to provide an overview of the regulatory and scientific landscape for nanotechnologies applied to medicine. The first US Food and Drug Administration (FDA)-approved nanodrug, Doxil®, is discussed as a paradigm for some of the sentient points. The chapter also provides information on the utility of physiologically based pharmacokinetic modeling for nano-enabled regulatory submissions, and a view of important gaps in knowledge relating to the mechanistic basis for modeling in the context of efficacy and safety of novel materials. There are potentially serious and inhibitory consequences if nanodrugs are overregulated, and a balanced approach is required, at least on a case-by-case basis, that addresses the needs of commercialization against mitigation of inadvertent harm to patients or the environment. Obviously, not every nanotherapeutic or nano-enabled product needs to be regulated. However, more is clearly needed from regulatory agencies like the FDA and European Medicines Agency than a stream of guidance documents that are in draft format, position papers that lack any legal implication, presentations that fail to identify key regulatory issues and policy papers that are often short on specifics. There is a very real need for regulatory guidelines that follow a science-based approach that are responsive to the associated shifts in knowledge and risks.

Indirect spin–spin coupling constants are important NMR parameters, indispensable in structure elucidation of organic compounds, and as descriptors of bond character and interactions between coupled atoms. Moreover, the spin–spin coupling phenomenon is the base of numerous nuclear magnetic resonance techniques. The present chapter covers the key work on indirect spin–spin coupling constants published within the period from the end of April 2020 to the end of April 2021. The chapter includes papers concerning theoretical and practical aspects of indirect spin–spin coupling constants, among other calculations of coupling constants, applications of coupling constants in organic chemistry to structure elucidation, and coupling constants across non-covalent bonds.

The ability to easily and reliably predict quantum interference (QI) behaviour would facilitate the design of functional molecular wires with potential applications in switches, transistors and thermoelectric devices. A variety of predictive methods exist, but with the exception of computationally-expensive DFT-based charge transport simulations, these often fail to account for the experimentally observed behaviour of molecules that differ significantly in structure from alternant polycyclic aromatic hydrocarbons. By considering a range of prior studies we have developed an extension to predictive “curly arrow rules”. We show that, in most cases, these extended curly arrow rules (ECARs) can rationalise the type of QI exhibited by conjugated molecular wires containing heteroatoms, cross-conjugation and/or non-alternant structures. ECARs provide a straightforward “pen-and-paper” method to predict whether a molecular wire will display constructive, destructive or “shifted destructive” QI,i.e.whether or not its transmission function would be expected to show an antiresonance, and if this antiresonance would occur close to the Fermi energy or be shifted elsewhere.

Cellulose nanoparticles (CNP) are emerging as an essential class of biopolymers. Owing to their biodegradability, amphiphilicity, availability, mechanical strength, and low cost, CNPs are mostly employed in food processing, paper, coating, oil well cement, composite, oil and gas, adhesive, construction, cosmetics, and film applications. To process them for their intended use, particularly as a stabilizer for Pickering emulsion, CNPs usually take the form of aqueous suspensions and gels. However, optimizing the processing performance of CNP suspensions for the intended end-product, the design requires a detailed understanding of its flow and viscoelastic behaviours. These properties are usually studied and characterized using a dynamic mechanical analyser (DMA), capillary rheometer, and rotational rheometer. The rheological information obtained often provides the shear flow behaviour of the CNP suspension, which is highly dependent on the share rate, molecular weight, molecular structure, inclusions/impurities, additives, and temperature. In this chapter, the rheological principles governing both viscous and elastic materials are explained. Special attention is devoted to particulate suspensions which describe a system that embodies the features of both viscous and elastic rheological behaviours. This is followed by detailed discussion of the viscoelastic and shear flow characteristics of CNP suspensions. In addition, the discussion is geared towards CNP emulsions’ ability to store (elastic or storage modulus) and dissipates energy (viscous or loss modulus) as a function of time, temperature, frequency, and stress/strain. Finally, a section of this chapter is devoted to describing how CNPs promote the Payne effect, which arises from the filler network of gel-like suspensions.

Disposable sensors are affordable and easy-to-operate instruments for rapid determination in various fields such as biomedical, food, environmental, etc. The growing demand is due to rapid, easy to access and consistent data collection in clinical and environmental samples. The existing spectroscopy and microscopy techniques are sophisticated and require more time per analysis, which has motivated researchers to find an alternate sensing methodology. Amongst various developed sensing strategies, electrochemical sensing strategies attracted tremendous interest due to its rapid response, affordable, minimal sample requirement, easy-to-operate in a different medium. The nanostructured electrode materials play vital roles in electrochemical sensor performance. Recently, a series of stretchable, flexible (e.g., cellulose paper, polyethylene sheets, ITO, and FTO) and movement sensors occupy the central part for the development of medical sensors. In addition to the substrate matrix, 2D electrode materials i.e., metal chalcogenides derived from different synthetic methods are attracted much attention. This is due to the easy and tuneable preparation methods, controlled synthesis, high electrochemical activity, etc. Hence, the present chapter is designed in such a way to explore the disposable sensor based on metal chalcogenides, its opportunities and challenges.

Cellulose has been a valuable raw material throughout humankind's journey for advancement and technology as a food, fuel, paper, and cloth. The mechanical properties of cellulose nanoparticles and the quest to replace petro-based polymers with sustainable resources have heightened researchers’ interest in cellulose. Cellulose nanoparticles are mostly used as fillers in polymer matrices where they improve desirable properties such as tensile modulus and fatigue resistance among others. In this chapter, important applications of cellulose nanoparticles as reinforcements in several polymers are discussed, along with methods for the fabrication of polymer/cellulose composites which include solution casting, melt compounding, impregnation, electrospinning, freeze-drying, and polymer latex matrices. The mechanical improvement associated with impregnation of cellulose nanoparticles in polymers and functionality is also highlighted.

The required dynamic mechanical properties and/or viscoelastic behaviour of viable cellulose matrix can be considerably improved by using green nanofillers (GNFs), which have a high aspect ratio and high active surface area. Cellulose naturally exists as a linear biopolymer in the plant cells of wood and cotton. The growing interest in the study of cellulose-reinforced renewable green reinforcing nanofillers is due to their biodegradability, low density, high aspect ratio and excellent mechanical and viscoelastic properties. These optimal properties require a good nanoparticle dispersion in the polymeric matrix, and the extent of dispersion can be analysed by dynamic mechanical analysis (DMA). DMA is a characterization technique that gives insight into the bulk properties and thermal transitions of the material analysed. The chemical compatibility between green nanofiller and cellulose plays a key role in both the dispersion of nanoparticles in the matrix and the adhesion between these phases. By chemical or mechanical modification, cellulose nanofillers can be converted into cellulose nanofibres (CNFs), cellulose nanocrystals (CNCs) and bacterial nanocellulose (BNC), all of which possess outstanding dynamic mechanical properties compared with their individual constituents. This chapter comprehensively emphasizes the processing methods of sustainable polymer nanocomposites containing GNFs for potential industrial applications, in fields such as packaging, paper and paperboard, food industry, medical and hygiene products, paints, cosmetics and optical sensors. Various extraction methods and characterization techniques, including surface modification, compatibility and dispersion methods, are discussed in detail, coupled with their effects on the overall properties.

This paper interprets a palette of spectroscopic data on tetracyano thienoquinoidal molecules of different sizes oriented towards the elucidation of their electronic behavior and other aspects of interest in materials chemistry. It also provides a contextualization of these properties between those of even oligoenes (carotene-like) and those of odd cyanines as a function of the reduction state. A complete UV-Vis-NIR electronic absorption, fluorescence emission and infrared spectroscopic study in part helped by quantum chemical calculations in the framework of the DFT theory has been carried out. The study encompasses the neutral and charged states. The optical properties of these compounds in the neutral state are controlled by the competition of bright (electric dipole–dipole allowed) and dark (electric dipole–dipole forbidden) singlet excited states. In the anionic state, the trimeric compounds disclose behaviors compatible with being either charge localized or delocalized mixed valence systems. Interestingly, we show the π-dimerization of a radical anion of a thienoquinoidal compound forming a π-dimer dianion as a manifestation of the delocalization of the charge in the charged monomer. The hexamer compound in the neutral state discloses incipient diradical character which permits the detection of a NIR emission band from the dark state at energies well below 1 eV. As thiophene benzo-annulation minimizes the diradical character, it forces the confinement of the charge in the vicinity of the terminal dicyanomethylene groups in the dianion. The oxidized species of the compounds have been also analyzed as models of charge localization states. The competition between doublet and quartet high spin states in the radical cations has been explored with the objective of visualizing potential molecules able to produce SOMO–HOMO energy inversion. (...) The authors thank the Spanish Ministry of Science, Innovation and Universities MCIU (PGC2018-098533-B-100 and RED2018-102815-T), and the Junta de Andalucı´a, Spain (UMA18FEDERJA057). We also thank the Research Central Services (SCAI) of the University of Málaga.

This paper investigates the control of effective magnetic anisotropy in Permalloy linear chain arrays, achieved by tuning the symmetry arrangement of the ellipsoidal nanomagnets and the film thickness. When the ellipsoidal nanomagnets are coupled along their easy axis, stronger effective magnetic anisotropy is achieved compared to when the nanomagnets are coupled along their hard axis. A clear transition from a single domain state to a combination of complex flux closure states such as a vortex or double vortices is observed at different applied field angles when the film thickness is varied in the range from 20 nm to 100 nm. Tunable microwave absorption spectra, obtained by ferromagnetic resonance spectroscopy, established the complex interplay between the shape anisotropy and magnetostatic interactions, which becomes more intriguing at different film thicknesses and applied field angles. The micromagnetic simulations are in good agreement with the experimental results. Our results demonstrate possible ways of manipulating the effective magnetic anisotropy in arrays of nanomagnets for magnonic and microwave applications.

The interaction between carbon monoxide and metal-based catalysts is important in several reactions such as CO hydrogenation, CO oxidation, and CO2 reduction. Consequently, CO adsorption on metal surfaces and nanoparticles largely has been investigated. Current understanding of the microscopic mechanism that governs the metal–CO binding has been enhanced by gas phase studies of well-defined small metal cluster model systems as a function of their size, charge state, and composition. In this highlight paper, key experimental and computational studies dealing with the interaction between CO and transition and coinage metal clusters are discussed, with particular emphasis on the influence of dopant atoms. ispartof: Crystengcomm vol:22 issue:29 pages:4807-4815 status: published

It has been amply constated that sugar ligand multivalency increases lectin-binding avidities dramatically, thereby modulating the capacity of carbohydrates to participate in supramolecular recognition processes involving transfer of biological information. The importance of this concept, the multivalent or glycoside cluster effect, in cell biology in general and in the glycosciences in particular is reflected in the ever-growing number of papers in the field. An impressive range of glycoarchitectures has been conceived to imitate the glycan coating of cells (the glycocalyx) in order to target complementary lectin receptors. However, these models rarely address the heterogeneity and the fluidity of the densely glycosylated cell membrane. They also disregard the impact that high-density nanosized arrangements could have in their interactions with the whole spectrum of carbohydrate-interacting proteins, among which glycosidases are notable representatives. For many years it has been tacitly assumed that: (i) efficient recognition by lectins generally requires high densities of the putative primary ligand and (ii) the mechanisms governing binding of a carbohydrate motif by a lectin or a glycosidase are totally disparate. Notwithstanding, an increasing amount of evidence seriously questions this paradigm. First, it was shown that secondary “innocent” ligands can play important roles in the recognition of heteroglycocluster constructs by lectins through synergistic or antagonistic contributions, a phenomenon termed the heterocluster effect. Second, the existence of multivalent effects in the inhibition of certain glycosidases by glycomimetic- and, even more disturbing, glyco-coated architectures (multivalent enzyme inhibition) was demonstrated. These observations call for a generalized multivalent effect governing the supramolecular chemistry of carbohydrate or glycomimetic structures in a biological context, with (hetero)multivalency acting as a multimodal switcher to drive the encoded information through different pathways. In this Feature Article we review the advancements made in the last few years in our understanding of the mechanisms underpinning the generalized multivalent effect, with an emphasis on the potential risks and opportunities derived from (hetero)multivalency-elicited promiscuity. Unión Europea, (MICIU, AEI, FEDER, UE). RTI2018- 097609-B-C21 Union Europea, MINECO, FEDER contract numbers SAF2016-76083-R

PARP1 is the founder and most abundant of a superfamily of 17 enzymes, it plays a key role in the repair of DNA single-strand breaks, the most common form of endogenous DNA damage. PARP inhibitors were first developed to inhibit DNA repair and resistance to DNA damaging anticancer therapy. In 2005 two landmark papers were published showing that PARP inhibitors as single agents selectively kill cells lacking homologous recombination DNA repair, including those with BRCA1 or BRCA2 mutations. Four PARP inhibitors are now approved for the treatment of cancer: 3 for ovarian cancer, 2 for breast cancer 2 for metastatic castrate-resistant prostate cancer and 1 for pancreatic cancer with other tumour types under investigation. This chapter describes the journey from identification of the enzyme to the present day.