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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.

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.

© 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)

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.

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.

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.

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.

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

Extension of a description of mass diffusion in binary fluids based on Fick's law to multicomponent fluids requires introduction of diffusion matrices. A problem is that Fick diffusion matrices commonly adopted for multicomponent fluids depend on the velocity frame of reference. In this paper we show how one can define Fick diffusion matrices for multicomponent fluids that are frame invariant.

This paper follows on from the Concluding Remarks presentation of the 3rd Faraday Discussion Meeting on Artificial Photosynthesis, Cambridge, UK, 25-27th March 2019. It aims to discuss the context for the research discussed at this meeting, starting with an overview of the motivation for research on artificial photosynthesis. It then goes onto analysing the composition and trends in the field of artificial photosynthesis, and its scale relative to other related research areas, primarily using the results of searches of publication data bases. As such, we hope it provides helpful insights to researchers in the field.

Made available in DSpace on 2019-10-06T17:12:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-01-01 The development of supported catalysts based on simple procedures without waste products and time-consuming steps is highly desirable. In this paper, self-supported nickel-based nanoparticles were obtained at the surface of the germanophosphate glasses by bottom-up process and evaluated as potential catalysts for the benzyl alcohol oxidation and bis(indolyl)methanes synthesis. A classical melt-quenching technique was used for preparing the nickel-doped germanophosphate glasses, followed by annealing under a hydrogen atmosphere at 400 °C for two different times. The approach enabled the synthesis of self-supported nanoparticles as a homogeneous film, covering the glass surface. The physical and chemical properties of synthesized glasses were characterized by UV-vis and Raman spectroscopies and thermal analysis. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were performed to monitor the growth process, morphology and chemical bonding structure of the nanoparticles surface. Universidade Federal Do Paraná - UFPR Departamento de Engenharias e Exatas Universidade Tecnológica Federal Paraná - UTFPR Group of Polymers and Nanostructures Universidade Federal de São Carlos Departamento de Química Universidade de Brasília - UNB Instituto de Química Universidade Do Estado de São Paulo - UNESP Instituto de Química Universidade Estadual Do Oeste Do Paraná - UNIOESTE Departamento de Química Universidade de Brasília - UNB Instituto de Física Núcleo de Física Aplicada Universidade Do Estado de São Paulo - UNESP Instituto de Química

Due to the importance of the Gibbs free energy of solvation in understanding many physicochemical phenomena, including lipophilicity, phase equilibria and liquid-phase reaction equilibrium and kinetics, there is a need for predictive models that can be applied across large sets of solvents and solutes. In this paper, we propose two quantitative structure property relationships (QSPRs) to predict the Gibbs free energy of solvation, developed using partial least squares (PLS) and multivariate linear regression (MLR) methods for 295 solutes in 210 solvents with total number of data points of 1777. Unlike other QSPR models, the proposed models are not restricted to a specific solvent or solute. Furthermore, while most QSPR models include either experimental or quantum mechanical descriptors, the proposed models combine both, using experimental descriptors to represent the solvent and quantum mechanical descriptors to represent the solute. Up to twelve experimental descriptors and nine quantum mechanical descriptors are considered in the proposed models. Extensive internal and external validation is undertaken to assess model accuracy in predicting the Gibbs free energy of solvation for a large number of solute/solvent pairs. The best MLR model, which includes three solute descriptors and two solvent properties, yields a coefficient of determination (R2) of 0.88 and a root mean squared error (RMSE) of 0.59 kcal mol-1 for the training set. The best PLS model includes six latent variables, and has an R2 value of 0.91 and a RMSE of 0.52 kcal mol-1. The proposed models are compared to selected results based on continuum solvation quantum chemistry calculations. They enable the fast prediction of the Gibbs free energy of solvation of a wide range of solutes in different solvents.

This paper presents the design, optimisation and fabrication of a mechanically robust 3D printed microfluidic device for the high time resolution online analysis of biomarkers in a microdialysate stream at microlitre per minute flow rates. The device consists of a microfluidic channel with secure low volume connections that easily integrates electrochemical biosensors for biomarkers such as glutamate, glucose and lactate. The optimisation process of the microfluidic channel fabrication, including for different types of 3D printer, is explained and the resulting improvement in sensor response time is quantified. The time resolution of the device is characterised by recording short lactate concentration pulses. The device is employed to record simultaneous glutamate, glucose and lactate concentration changes simulating the physiological response to spreading depolarisation events in cerebrospinal fluid dialysate. As a proof-of-concept study, the device is then used in the intensive care unit for online monitoring of a brain injury patient, demonstrating its capabilities for clinical monitoring.

© The Royal Society of Chemistry. As defects significantly affect the properties of metal-organic frameworks (MOFs)—from changing their mechanical properties to enhancing their catalytic ability—obtaining synthetic control over defects is essential to tuning the effects on the properties of the MOF. Previous work has shown that synthesis temperature and the identity and concentration of modulating acid are critical factors in determining the nature and distribution of defects in the UiO family of MOFs. In this paper we demonstrate that the amount of water in the reaction mixture in the synthesis of UiO family MOFs is an equally important factor, as it controls the phase which forms for both UiO-67(Hf) and UiO-66(Hf) (F4BDC). We use this new understanding of the importance of water to develop a new route to the stable defect-ordered hcp UiO-66(Hf) phase, demonstrating the effectiveness of this method of defect-engineering in the rational design of MOFs. The insights provided by this investigation open up the possibility of harnessing defects to produce new phases and dimensionalities of other MOFs, including nanosheets, for a variety of applications such as MOF-based membranes.

In a seminal work the photodissociation of IBr has been controlled using a strong non-resonant IR pulse [Sussman et al., Science, 2006, 314, 274], changing the branching ratio of products in different final states via the relative timing of pump and control pulses. In this paper, we revisit the control of this molecule. Potential surfaces for the complete spin-orbit manifold of IBr states dissociating into the ground and first excited states of the constituent atoms have been calculated at the multi-reference configuration interaction (MRCI) level of theory as a function of applied field. Both the strength and direction of field have been taken into account and it is seen how the avoided crossing between the states thought to be key in the control mechanism shift as a function of field strength. These surfaces will enable full calculations of the molecule in the pump-control field. Preliminary dynamics calculations with the field placed along the molecular axis show that a Hamiltonian including all 36-states agrees with earlier results and is able to model the basic features of the control. However, just like earlier results, this restricted model is not able to reproduce the timescale of the control.

In this paper we report the synthesis and characterization of hybrid molecular-inorganic systems composed of superparamagnetic iron oxide nanoparticles coated with a shell of oleic acid (NP) and (Pr2NH2)5[Dy12(OH)16(SALO)4(SALOH)8(NO3)8(H2O)0.5]NO3 (Dy12) single-molecule magnets. The hybrid NP-Dy12 system presents an enhancement of the magnetization hysteresis with respect to the isolated components while retaining the morphological characteristics of the parent NPs.

Self-assembled cationic micelles are an attractive platform for binding biologically-relevant polyanions such as heparin. This has potential applications in coagulation control, where a synthetic heparin rescue agent could be a useful replacement for protamine, which is in current clinical use. However, micelles can have low stability in human serum and unacceptable toxicity profiles. This paper reports the optimi- sation of self-assembled multivalent (SAMul) arrays of amphiphilic ligands to bind heparin in competitive conditions. Specifically, modification of the hydrophobic unit kinetically stabilises the self-assembled nanostructures, preventing loss of binding ability in the presence of human serum – cholesterol hydro- phobic units significantly outperform systems with a simple aliphatic chain. It is demonstrated that serum albumin disrupts the binding thermodynamics of the latter system. Molecular simulation shows aliphatic lipids can more easily be removed from the self-assembled nanostructures than the cholesterol ana- logues. This agrees with the experimental observation that the cholesterol-based systems undergo slower disassembly and subsequent degradation via ester hydrolysis. Furthermore, by stabilising the SAMul nano- structures, toxicity towards human cells is decreased and biocompatibility enhanced, with markedly improved survival of human hepatoblastoma cells in an MTT assay.

Air gasification of poultry litter was experimentally investigated in a laboratory scale bubbling fluidised bed gasifier. Gasification tests were conducted at atmospheric pressure using silica sand as the bed material. This paper examines the effect of the equivalence ratio (ER) in the range of 0.18-0.41, temperature between 700 and 800 °C, and the addition of limestone blended with the poultry litter on the yield and composition of tar. An off-line solid phase adsorption method was employed in order to quantify tar compounds heavier than styrene, whereas lighter species such as benzene and toluene were measured by means of on-line micro gas chromatography. Total tar yields were in the range from 15.7 to 30.7 g total tar kg poultry litter (dry and ash free basis) -1 . These values are considered low with respect to the feedstocks with a higher organic fraction. It also needs to be noted that the yields of benzene and toluene were measured by on-line micro gas chromatography, a technique which inherently delivers higher tar values compared to commonly employed off-line techniques. By varying the ER, poultry litter blended with limestone showed a reduction in total tar yield whereas poultry litter on its own showed an increasing tar yield over the ER range tested. In the presence of limestone, polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, toluene and benzene showed a tendency to reduce over the ER range tested. Since the ER also plays a crucial role in tar reduction, the reduction in tar cannot be unambiguously attributed to calcined limestone/lime (CaCO 3 /CaO). Increasing the temperature was shown to be effective for reducing the total tar yield but the amounts of polycyclic aromatic hydrocarbons increased. However, no definitive correlation could be established between limestone/lime catalytic activity for tar reduction and elevated gasification temperature, because there was no possibility to study their effects separately. The chemical composition of the tar arising from poultry litter is distinctive compared with conventional lignocellulosic fuels linked to the fact that poultry litter has a higher nitrogen content (≈6.5% w/w (dry and ash free basis)). Nitrogen-containing hydrocarbons such as pyridine, 2-methylpyridine, 2-methyl-1H-pyrrole and benzonitrile were identified in significant amounts. This study has demonstrated that poultry litter gasified in a bubbling fluidised bed yielded a product gas with relatively low tar content while its composition reflects the chemical nature of the feedstock. European Union FP7/2007-201 289887 INTERREG IVB NEW REsource Innovation Network 317J-RENEW Spanish Ministry of Economy and Competitiveness CTM2016-78089-R, AEI/FEDER, UE

The use of coarse-grained models is important in many fields, especially those that use computer simulation to analyze large systems in processes that span long-time scales, as happens in protein folding. Among those approaches, structure-based models have been widely and successfully used for a few decades now. They usually take a single native conformation, experimentally solved, of the protein studied to determine the native contacts, which subsequently define the interaction potential for the simulation. The characteristics of the folding transition can then be analyzed from the computed trajectories. In this paper, we consider the possibility of enriching these models by considering the structural fluctuations present in the native state of a globular protein at room temperature in an aqueous environment. We use the different conformers experimentally provided when the protein structure was determined by nuclear magnetic resonance (NMR) spectroscopy as an approximate ensemble to test our methodology, which includes the definition of a global interaction potential and the analysis of the thermodynamic and structural characteristics of the folding process. The results are compared with traditional, single structure models.

We demonstrate a rapid, 2-step, and ultrasensitive assay approach for quantification of target protein molecules from a single droplet test sample. The assay is comprised of antibody-conjugated gold nanoparticles (AuNPs) that are “activated” when they are mixed with the test sample and bind their targets. The resulting liquid is passed through a microfluidic channel with a photonic crystal (PC) biosensor that is functionalized with secondary antibodies to the target biomarker, so that only activated AuNPs are captured. Utilizing recently demonstrated hybrid optical coupling between the plasmon resonance of the AuNP and the resonance of the PC, each captured AuNP efficiently quenches the resonant reflection of the PC, thus enabling the captured AuNPs to be digitally counted with high signal-to-noise. To achieve a 2-step assay process that is performed on a single droplet test sample without washing steps or active pump elements, controlled single-pass flow rate is obtained with an absorbing paper pad waste reservoir embedded in a microfluidic cartridge. We use the activate capture and digital counting (AC + DC) approach to demonstrate HIV-1 capsid antigen p24 detection from a 40 μL spiked-in human serum sample at a one thousand-fold dynamic range (1–103 pg mL−1) with only a 35-minute process that is compatible with point-of-care (POC) analysis. The AC + DC approach allows for ultrasensitive and ultrafast biomolecule detection, with potential applications in infectious disease diagnostics and early stage disease monitoring. This work is supported by the National Institutes of Health (NIH) R01 AI20683, F30AI122925, and the Carl Woese Institute for Genomic Biology postdoctoral fellowship.

To increase disease survival rates, there is a vital need for diagnosis at very preliminary stages. Then, low concentrations of biomarkers are present which must be effectively detected and quantified for reliable diagnosis. Fluorescent biosensing is commonly enabled through the labelling of these biomarkers with nanostructures and fluorophores. Metal Enhanced Fluorescence (MEF) is a phenomenon whereby the intensity of a fluorescent biosensor signal can be considerably enhanced by placing a metallic nanostructure and fluorophore in close proximity. Importantly, this allows for an even lower detection limit and thus earlier diagnosis. In recent years, extraordinary efforts have been made in the understanding of how the chemical and physical properties of nanomaterials may be exploited advantageously. Via precise nanoscale engineering, it is possible to optimize the optical properties of plasmonic nanomaterials, which now need to be refined and applied in diagnostics. Through MEF, the intensity of this signal can be related in direct proportion to analyte concentration, allowing for diagnosis of disease at an earlier stage than previously. This review paper outlines the potential and recent progress of applied MEF biosensors, highlighting their substantial clinical potential. MEF biosensors are presented both upon assay-based platforms and in solution, with comments on the various metallic nanoparticle morphologies available. This is explored across various emission wavelengths from ultra-violet to the second near infrared window (NIR-II), emphasising their wide applicability. Further to this, the importance of near infrared (NIR-I and NIR-II) biosensing is made clear as it allows for higher penetration in biological media. Finally, by developing multiplexing techniques, multiple and simultaneous analyses of analytes can be achieved. Through the incorporation of metal enhanced fluorescence into biosensing, it will be possible to diagnose disease more rapidly and more reliably than before, with the potential to save countless lives.

Carbon capture and storage (CCS) is broadly recognised as having the potential to play a key role in meeting climate change targets, delivering low carbon heat and power, decarbonising industry and, more recently, its ability to facilitate the net removal of CO2 from the atmosphere. However, despite this broad consensus and its technical maturity, CCS has not yet been deployed on a scale commensurate with the ambitions articulated a decade ago. Thus, in this paper we review the current state-of-the-art of CO2 capture, transport, utilisation and storage from a multi-scale perspective, moving from the global to molecular scales. In light of the COP21 commitments to limit warming to less than 2 °C, we extend the remit of this study to include the key negative emissions technologies (NETs) of bioenergy with CCS (BECCS), and direct air capture (DAC). Cognisant of the non-technical barriers to deploying CCS, we reflect on recent experience from the UK's CCS commercialisation programme and consider the commercial and political barriers to the large-scale deployment of CCS. In all areas, we focus on identifying and clearly articulating the key research challenges that could usefully be addressed in the coming decade.

The safety assessment of a flavour substance examines several factors, including metabolic and physiological disposition data. The present article provides an overview of the metabolism and disposition of flavour substances by identifying general applicable principles of metabolism to illustrate how information on metabolic fate is taken into account in their safety evaluation. The metabolism of the majority of flavour substances involves a series both of enzymatic and non-enzymatic biotransformation that often results in products that are more hydrophilic and more readily excretable than their precursors. Flavours can undergo metabolic reactions, such as oxidation, reduction, or hydrolysis that alter a functional group relative to the parent compound. The altered functional group may serve as a reaction site for a subsequent metabolic transformation. Metabolic intermediates undergo conjugation with an endogenous agent such as glucuronic acid, sulphate, glutathione, amino acids, or acetate. Such conjugates are typically readily excreted through the kidneys and liver. This paper summarizes the types of metabolic reactions that have been documented for flavour substances that are added to the human food chain, the methodologies available for metabolic studies, and the factors that affect the metabolic fate of a flavour substance.

© 2018 The Royal Society of Chemistry. Carbon capture and storage (CCS) is broadly recognised as having the potential to play a key role in meeting climate change targets, delivering low carbon heat and power, decarbonising industry and, more recently, its ability to facilitate the net removal of CO2 from the atmosphere. However, despite this broad consensus and its technical maturity, CCS has not yet been deployed on a scale commensurate with the ambitions articulated a decade ago. Thus, in this paper we review the current state-of-the-art of CO2 capture, transport, utilisation and storage from a multi-scale perspective, moving from the global to molecular scales. In light of the COP21 commitments to limit warming to less than 2 °C, we extend the remit of this study to include the key negative emissions technologies (NETs) of bioenergy with CCS (BECCS), and direct air capture (DAC). Cognisant of the non-technical barriers to deploying CCS, we reflect on recent experience from the UK's CCS commercialisation programme and consider the commercial and political barriers to the large-scale deployment of CCS. In all areas, we focus on identifying and clearly articulating the key research challenges that could usefully be addressed in the coming decade.

In the present paper we report experimental and theoretical evidence for lithium biphenyl disproportionation in solution. The presence of an absorption band (at 250 nm), which corresponds to neutral biphenyl in the spectra of dissolved crystalline [Li+(THP)4][Bph˙−] (1), clearly suggests the disproportionation of the biphenyl radical anion into neutral biphenyl plus the corresponding dianion, 2Bph˙− ⇄ Bph2− + Bph0. The experimental spectrum of 1 displays four main groups of bands at 834, 644, 408 and 250 nm. Upon addition of an excess of lithium, the biphenyl band becomes diminished revealing a hidden lower intensity band at 262 nm, this one truly belonging to the dianion. Highly accurate time-dependent density functional theory (TDDFT) calculations of the electronic spectra of a series of contact as well as solvent separated ionic associate models, performed at the wB97XD/6-311++G(3df,3pd) level of theory in dimethoxyethane (DME) solution, revealed that the contact lithium biphenyl dianion [(Li+DME)2Bph2−] predicts all the main absorption bands fairly well, while the corresponding radical anion does not reproduce the experimental spectral pattern. Analysis of the electron density distribution performed by means of Quantum Theory of Atoms in Molecules (QTAIM) confirms that the studied ionic associates represent the correct resonance structures since the charges of the lithium cations are close to +1 in all the cases. Solvation usually plays a key role in these types of equilibria; however the underlying cause of this disproportionation seems to lie on the inherent electronic stabilities of the anionic species involved, as could be inferred from the reported free energy calculations of the nude ion associates, neglecting any solvent effects. Financial support by the Spanish Ministry of Economy and Competitiveness (Grant No. MAT2016-78625-C2-2-P), the Ministry of Education and Science of Ukraine, Research Fund (Grant No. 0117U003908), the Generalitat Valenciana (Grant PROMETEO/2017/139) and the University of Alicante (VIGROB-285) is gratefully acknowledged. MC thanks the VIDI of the University of Alicante for a predoctoral grant.

This paper addresses the synthesis and a detailed electrical analysis of individual copper nanowires (CuNWs). One dimensional CuNWs are chemically grown using Bromide ions (Br-) as a co-capping agent. By partially replacing alkyl amines with Br-, the isotropic growth on Cu seeds was suppressed during the synthesis. To study the electrical properties of individual CuNWs, a fabrication method is developed which does not require any e-beam lithography process. Chemically grown CuNWs have an ampacity of about 30 million amps per cm2, which is more than one order of magnitude larger than the bulk Cu. These good qualities easy to synthesize CuNWs are an excellent candidate for creating high ampacity wires and flexible printable electronics.

Accurate and efficient methods for predicting the alignment between a semiconductor's electronic energy levels and electrochemical redox potentials are needed to facilitate the computational discovery of photoelectrode materials. In this paper, we present an approach that combines many-body perturbation theory within the GW method with continuum solvation models. Specifically, quasiparticle levels of the bulk photoelectrode are referenced to the outer electric potential of the electrolyte by calculating the change in electric potential across the photoelectrode–electrolyte and the electrolyte–vacuum interfaces using continuum solvation models. We use this method to compute absolute energy levels for the prototypical rutile (TiO2) photoelectrode in contact with an aqueous electrolyte and find good agreement with predictions from atomistic simulations based on molecular dynamics. Our analysis reveals qualitative and quantitative differences of the description of the interfacial charge density in atomistic and continuum solvation models and highlights the need for a consistent treatment of electrode–electrolyte and electrolyte–vacuum interfaces for the determination of accurate absolute energy levels.

Carbon capture and storage (CCS) is a vital technology for the cost-effective mitigation of anthropogenic CO2 emissions. However, a key obstacle to its deployment on a large scale remains its cost – both capital and operating costs. In this context, the development of improved sorbents is a key research priority. Consequently, there is a vast global effort to develop new materials for this purpose, with literally thousands of new materials having been proposed since the beginning of the millennium. One common element of these contributions is that they focus on the equilibrium capacity of the material to absorb CO2 and rarely, if ever, other key factors such as transport properties. To date, the majority of this effort has cost significant amounts of time and resources and has almost exclusively focused on developing sorbents with increased CO2 capacity and/or reduced heat of regeneration. Given that sorbent regeneration largely dictates operational cost, this would, on the surface, appear rational. However, it is vital to recall that the cost structure of $ per MWh of electricity generated is composed of contributions from both capital and operational costs. Consequently, this single-minded focus on equilibrium CO2 capacity and heat of regeneration excludes the contribution of transport and kinetic properties which determine the equipment size and thus the capital cost. Therefore, in order to develop sorbents which will result in a non-negligible cost reduction, it is essential to move beyond equilibrium-based metrics of sorbent performance. In this paper, we present a new methodological approach for sorbent screening which explicitly includes rate-based phenomena. Our approach uses both monetised and non-monetised performance indicators. Our results suggest that whilst equilibrium CO2 capacity is a key determinant of process performance, transport properties (e.g., viscosity) and other thermophysical properties (e.g., heat capacity) have a significant effect on the capital cost, and thus on the price of the carbon captured. The key contribution of this work is the identification of the minimum set of thermophysical and kinetic parameters which must be reported in order to justify the claim of adequacy for a new sorbent for CO2 capture in particular and gas separations in general.

NOTICE: This is the peer reviewed version of the following article: Fuertes A, Juanes M, Granja J, Montenegro J. Supramolecular functional assemblies: dynamic membrane transporters and peptide nanotubular composites. Chem Commun. 2017;53(56):7861-7871. [doi: 10.1039/C7CC02997G]. This article may be used for non-commercial purposes in accordance with RSC Terms and Conditions for self-archiving The fabrication of functional molecular devices constitutes one of the most important current challenges for chemical sciences. The complex processes accomplished by living systems continuously demand the assistance of non-covalent interactions between molecular building blocks. Additionally, these building blocks (proteins, membranes, nucleotides) are also constituted by self-assembled structures. Therefore, supramolecular chemistry is the discipline required to understand the properties of the minimal self-assembled building blocks of living systems and to develop new functional smart materials. In the first part of this feature article, we highlight selected examples of the preparation of supramolecular membrane transporters with special emphasis in the application of dynamic covalent bonds. In the second section of the paper we review recent breakthroughs in the preparation of peptide nanotubes hybrids with functional applications. The development of these devices constitutes an exciting process from where we can learn how to understand and manipulate supramolecular functional assemblies We acknowledge funding from the Spanish Agencia Estatal de Investigación (AEI) (CTQ2014-59646-R and CTQ2016-78423-R), the Xunta de Galicia (ED431G/09 and 2016-AD031) and the ERDF. A. F. and M. J. received F. P. U. and F. P. I. fellowships from MECD and MINECO. J. M. received a Ramon y Cajal Grant (RYC-2013-13784), an ERC Starting Investigator Grant (DYNAP-677786) and a Young Investigator Grant from the Human Frontier Research Program (RGY0066/2017) SI

Halide perovskite derivatives present unprecedented physical phenomena among those materials which are suitable for photovoltaics, such as a fast ion diffusion coefficient. In this paper it is reported how the benefits of this property can be used during the growth of halide perovskites in order to control the morphological and optoelectronic properties of the final thin film. Using a large enough halide reservoir, the nature of the halides present in the final perovskite layer can be exchanged and this depends on the initial salt used in the two-step deposition method. In particular, the preparation of a methylammonium lead bromide (MAPbBr3) thin film is reported, using a two-step method based on the transformation of lead(II) iodide (PbI2), lead(II) bromide (PbBr2) and lead(II) chloride (PbCl2) salts into MAPbBr3 perovskite after dipping in a methylammonium bromide (MABr) solution. The films prepared from different salts present different properties in terms of morphology and optoelectronic properties, thus providing significantly different performance when they are used for the preparation of photovoltaic devices. Interestingly, the use of PbI2 and PbCl2 salts reduce the charge recombination and increase the open circuit potential obtained, especially in the former case. However, the highest photocurrent is obtained when PbBr2 is used. For PbI2 and PbCl2 salts no traces of the former salt are observed in the MAPbBr3 layer obtained after 10 minutes of dipping time, however, the presence of PbBr2 has still been detected (using X-ray diffraction) when this salt has been employed.

Paper aging and protection are of crucial interest for improving the preservations of library collections and archives. Highly aging-resistant cellulose fiber sheets were obtained by treatment with magnesium hydroxide nanoparticles (Mg(OH)2). The procedure was tested on the sheets made of bleached (B) and refined unbleached (UB) pine cellulose fibers as well as their 50%/50% mixture (M). The morphological and structural properties of the obtained sheets were studied by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) methods. Stress-strain, smoothness and pH measurements were employed to determine the changes in physical-chemical characteristics of the sheets after mixing two types of the fibers and subsequent treatment with Mg(OH)2. It has been shown that the sheets made of the fiber mixture show higher tensile index and smoothness. The modification with Mg(OH)2 nanoparticles induces an increase in the pH of the sheets to slightly basic values (around pH 8), facilitates the inter-fiber bonding and additionally enhances the smoothness of the sheets. Finally, by exposing the sheets to the thermo-hygrometric accelerated artificial ageing, it was found that the physical properties of the treated sheets were not significantly dependent on the environmental factors., This study was supported by the Geomaterials 2 Programme (S2013/MIT_2914), the Innovation and Education Ministry (ref. MAT2013-47460-C5-5-P) and the Autonomous Region Program of Madrid, MULTIMAT-CHALLENGE (ref. S2013/MIT-2862).

BiVO4/CoPi photoanodes are studied using transient absorption spectroscopy and transient photocurrent methods. The cathodic shift of photocurrent onset potential is due to efficient suppression of back electron/hole recombination on the timescale of seconds., In this paper, we compared for the first time the dynamics of photogenerated holes in BiVO4 photoanodes with and without CoPi surface modification, employing transient absorption and photocurrent measurements on microsecond to second timescales. CoPi surface modification is known to cathodically shift the water oxidation onset potential; however, the reason for this improvement has not until now been fully understood. The transient absorption and photocurrent data were analyzed using a simple kinetic model, which allows quantification of the competition between electron/hole recombination and water oxidation. The results of this model are shown to be in excellent agreement with the measured photocurrent data. We demonstrate that the origin of the improvement of photocurrent onset resulting from CoPi treatment is primarily due to retardation of back electron/hole recombination across the space charge layer; no evidence of catalytic water oxidation via CoPi was observed.

A unique, but unifying, feature of ionic liquids (ILs) is that they are nanostructured on the length scale of the ions; in many ILs well-defined polar and apolar domains exist and may percolate through the liquid. Near a surface the isotropic symmetry of the bulk structure is broken, resulting in different nanostructures which, until now, have only been studied indirectly. In this paper, in situ amplitude modulated atomic force microscopy (AM-AFM) has been used to resolve the 3-dimensional nanostructure of five protic ILs at and near the surface of mica. The surface and near surface structures are distinct and remarkably well-defined, but are very different from previously accepted descriptions. Interfacial nanostructure is strongly influenced by the registry between cations and the mica surface charge sites, whereas near surface nanostructure is sensitive to both cation and anion structure. Together these ILs reveal how interfacial nanostructure can be tuned through ion structure, informing “bottom-up” design and optimisation of ILs for diverse technologies including heterogeneous catalysis, lubrication, electrochemical processes, and nanofluids.

Integrating gene expression profiles with certain proteins can improve our understanding of the fundamental mechanisms in protein-ligand binding. This paper spotlights the integration of gene expression data and target prediction scores, providing insight into mechanism of action (MoA). Compounds are clustered based upon the similarity of their predicted protein targets and each cluster is linked to gene sets using Linear Models for Microarray Data. MLP analysis is used to generate gene sets based upon their biological processes and a qualitative search is performed on the homogeneous target-based compound clusters to identify pathways. Genes and proteins were linked through pathways for 6 of the 8 MCF7 and 6 of the 11 PC3 clusters. Three compound clusters are studied; (i) the target-driven cluster involving HSP90 inhibitors, geldanamycin and tanespimycin induces differential expression for HSP90-related genes and overlap with pathway response to unfolded protein. Gene expression results are in agreement with target prediction and pathway annotations add information to enable understanding of MoA. (ii) The antipsychotic cluster shows differential expression for genes LDLR and INSIG-1 and is predicted to target CYP2D6. Pathway steroid metabolic process links the protein and respective genes, hypothesizing the MoA for antipsychotics. A sub-cluster (verepamil and dexverepamil), although sharing similar protein targets with the antipsychotic drug cluster, has a lower intensity of expression profile on related genes, indicating that this method distinguishes close sub-clusters and suggests differences in their MoA. Lastly, (iii) the thiazolidinediones drug cluster predicted peroxisome proliferator activated receptor (PPAR) PPAR-alpha, PPAR-gamma, acyl CoA desaturase and significant differential expression of genes ANGPTL4, FABP4 and PRKCD. The targets and genes are linked via PPAR signalling pathway and induction of apoptosis, generating a hypothesis for the MoA of thiazolidinediones. Our analysis show one or more underlying MoA for compounds and were well-substantiated with literature.

The adsorption of choline benzoate ([CH][BE]) ionic liquid (IL) on the surface of different hexagonal nanosheets has been studied using Density Functional Theory (DFT) methods. For this, the interaction mechanism, binding energies and electronic structure of [CH][BE] ionic liquid on four types of nanosheets, i.e., graphene, silicene, germanene and boron-nitride, were estimated and compared. The adsorption of [CH][BE] ionic liquid on different nanosheets is mainly featured by van der Waals forces, leading to strong benzoate ion–surface π-stacking. Likewise, there is also an important charge transfer from the anion to the sheet. The electronic structure analysis shows that Si- and Ge-based sheets lead to the largest changes in the HOMO and LUMO levels of choline benzoate. This paper provides new insights into the capability of DFT methods to provide useful information about the adsorption of ionic liquids on nanosheets and how ionic liquid features could be tuned through the adsorption on the suitable nanosheet., Ministerio de Economı´a y Competitividad (Spain, project CTQ2013-40476-R) and Junta de Castilla y León (Spain, project BU324U14).

In this paper, we have combined the various experimental results and first-principles calculations with a new and interesting discussion to explain the photocatalytic and antibacterial activities of α-Ag2WO4 crystals, which were obtained using the microwave-hydrothermal (MH) method with anionic surfactants. The advantages of the insights gained through the present work are two-fold. First, the mechanism and origin of the photocatalytic and antibacterial activities can be rationalized. Second, this facile and controllable synthetic method is expected to encourage the synthesis of complex metal oxides with specific active facets, and these insights can contribute to the rational design of new materials for multifunctional applications. X-ray diffraction and Rietveld refinement analysis confirmed that all the crystals have an orthorhombic structure without deleterious phases. Ultraviolet–visible diffuse reflectance spectroscopy indicated the presence of intermediary energy levels and a variation in the optical band gap values (3.09–3.14 eV) with the crystal growth process. The geometry, electronic properties of the bulk, and surface energies of these crystals were evaluated using first-principles quantum mechanical calculations based on the density functional theory. The crystal shapes was experimentally and theoretically modeled based on Rietveld refinement data, emission scanning electron microscopy images, and Wulff construction. To obtain a wide variety of crystal shapes, the morphologies were gradually varied by tuning the surface chemistry, i.e., the relative stability of the faceted crystals. The growth mechanisms of different α-Ag2WO4 crystals and their facet-dependent photocatalytic and antibacterial performances were explored in details. The combination of experimental and theoretical data revealed the presence of (110) and (011) planes with high surface energies together with the disappearance of faces related to the (010)/(0[1 with combining macron]0) planes in α-Ag2WO4 crystals are key factors that can rationalize both the photocatalytic and antibacterial activities. The different activities may be attributed to the different number of unsaturated superficial Ag and W atoms capable of forming the main active adsorption sites. Finally, we discuss how knowledge of surface-specific properties can be utilized to design a number of crystal morphologies that may offer improved performance in various applications. The authors acknowledge the financial support of the following Brazilian research funding institutions: the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP; 2012/14004-5 and 2013/07296-2), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq; 479644/2012-8 and 304531/2013-8) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). J.A. and L.G. are grateful to Prometeo/2009/053 (GeneralitatValenciana), Ministerio de Economia y Competitividad (Spain; CTQ2012-36253-C03-02), and the Spanish Brazilian program (PHB2009-0065-PC). We also acknowledge the Servei Informática, Universitat Jaume I for the generous allotment of computer time.

In the last decade, photovoltaics (PV) has experienced an important transformation. Traditional solar cells formed by compact semiconductor layers have been joined by new kinds of cells that are constituted by a complex mixture of organic, inorganic and solid or liquid electrolyte materials, and rely on charge separation at the nanoscale. Recently, metal organic halide perovskites have appeared in the photovoltaic landscape showing large conversion efficiencies, and they may share characteristics of the two former types. In this paper we provide a general description of the photovoltaic mechanisms of the single absorber solar cell types, combining all-inorganic and hybrid and organic cells into a single framework. The operation of the solar cell relies on a number of internal processes that exploit internal charge separation and overall charge collection minimizing recombination. There are two main effects to achieve the required efficiency, first to exploit kinetics at interfaces, favouring the required forward process, and second to take advantage of internal electrical fields caused by a built-in voltage and by the distribution of photogenerated charges. These principles represented by selective contacts, interfaces and the main energy diagram, form a solid base for the discussion of the operation of future types of solar cells. Additional effects based on ferroelectric polarization and ionic drift provide interesting prospects for investigating new PV effects mainly in the perovskite materials. This work was supported by MINECO of Spain under a project (MAT2013-47192-C3-1-R), and the Helmholtz-Energy-Alliance ‘‘Hybrid-Photovoltaics’’.