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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.

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 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.

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.

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.

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.

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).