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The steep increase in carbon dioxide (CO 2 ) emissions has created great concern due to its role in the greenhouse effect and global warming. One approach to mitigate CO 2 levels involves its application in specific technologies. In this context, CO 2 can be used for a more sustainable synthesis of polycarbonates (CO 2 -PCs). In this research, CO 2 -PC films and composites with multiwalled carbon nanotubes (MWCNTs, ranging from 0.2 to 7.0 wt.%) have been prepared to achieve more sustainable multifunctional sensing devices. The inclusion of the carbonaceous fillers allows for the electrical conductivity to be enhanced, reaching the percolation threshold (P c ) at 0.1 wt.% MWCNTs and a maximum electrical conductivity of 0.107 S·m -1 for the composite containing 1.5 wt.% MWCNTs. The composite containing 3.0 wt.% MWCNTs was also studied, showing a stable and linear response under temperature variations from 40 to 100 °C and from 30 to 45 °C, with a sensitivity of 1.3 × 10 -4 °C -1 . Thus, this investigation demonstrates the possibility of employing CO 2 -derived PC/MWCNT composites as thermoresistive sensing materials, allowing for the transition towards sustainable polymer-based electronics.

Electron tomography is an imaging technique that allows for the elucidation of three-dimensional structural information of biological specimens in a very general context, including cellular in situ observations. The approach starts by collecting a set of images at different projection directions by tilting the specimen stage inside the microscope. Therefore, a crucial preliminary step is to precisely define the acquisition geometry by aligning all the tilt images to a common reference. Errors introduced in this step will lead to the appearance of artifacts in the tomographic reconstruction, rendering them unsuitable for the sample study. Focusing on fiducial-based acquisition strategies, this work proposes a deep-learning algorithm to detect misalignment artifacts in tomographic reconstructions by analyzing the characteristics of these fiducial markers in the tomogram. In addition, we propose an algorithm designed to detect fiducial markers in the tomogram with which to feed the classification algorithm in case the alignment algorithm does not provide the location of the markers. This open-source software is available as part of the Xmipp software package inside of the Scipion framework, and also through the command-line in the standalone version of Xmipp., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

We propose two new measures of resolution anisotropy for cryogenic electron microscopy maps: Fourier shell occupancy (FSO), and the Bingham test (BT). FSO varies from 1 to 0, with 1 representing perfect isotropy, and lower values indicating increasing anisotropy. The threshold FSO = 0.5 occurs at Fourier shell correlation resolution. BT is a hypothesis test that complements the FSO to ensure the existence of anisotropy. FSO and BT allow visualization of resolution anisotropy. We illustrate their use with different experimental cryogenic electron microscopy maps., (© 2023. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Image-processing pipelines require the design of complex workflows combining many different steps that bring the raw acquired data to a final result with biological meaning. In the image-processing domain of cryo-electron microscopy single-particle analysis (cryo-EM SPA), hundreds of steps must be performed to obtain the three-dimensional structure of a biological macromolecule by integrating data spread over thousands of micrographs containing millions of copies of allegedly the same macromolecule. The execution of such complicated workflows demands a specific tool to keep track of all these steps performed. Additionally, due to the extremely low signal-to-noise ratio (SNR), the estimation of any image parameter is heavily affected by noise resulting in a significant fraction of incorrect estimates. Although low SNR and processing millions of images by hundreds of sequential steps requiring substantial computational resources are specific to cryo-EM, these characteristics may be shared by other biological imaging domains. Here, we present Scipion, a Python generic open-source workflow engine specifically adapted for image processing. Its main characteristics are: (a) interoperability, (b) smart object model, (c) gluing operations, (d) comparison operations, (e) wide set of domain-specific operations, (f) execution in streaming, (g) smooth integration in high-performance computing environments, (h) execution with and without graphical capabilities, (i) flexible visualization, (j) user authentication and private access to private data, (k) scripting capabilities, (l) high performance, (m) traceability, (n) reproducibility, (o) self-reporting, (p) reusability, (q) extensibility, (r) software updates, and (s) non-restrictive software licensing., Competing Interests: The authors declare no competing interests exist., (© The Author(s) 2023.)

Objective: The first-order absorption is a common model used in Pharmacokinetics. The absorption of some drugs follows carrier mediated transport. It has been proposed that the amount of drug available may saturate the transport mechanism resulting in an absorption slower than the one predicted by the first-order model. Saturable absorption has been modeled at the differential equation level by substituting the constant rate absorption by a Hill kinetics absorption. However, its exact solution is so far unknown. The goal of this is to know the exact solution of different Hill kinetic absorption models., Methods: We start defining different absorption models and increasing then their complexity. The simplest case is the first-order absorption model and the most complex will be a generalized Hill kinetic absorption model. The differential equation of each model is integrated., Results: The complexity of the models their solutions may be not expressed in a close-form, or in term of elementary functions. We obtain and discuss the exact solutions of the different Hill kinetics absorption models. To do that, the solutions are studied according to the possible values of the free parameters of the models. We show the differences between models through simulations., Conclusions: The knowledge of closed-form solutions allows to illustrate the differences between the different absorption models and minimizes the errors of numerical integration., (© 2022. The Author(s).)

Resurrection plants are able to deal with complete dehydration of their leaves and then recover normal metabolic activity after rehydration. Only a few resurrection species are exposed to freezing temperatures in their natural environments, making them interesting models to study the key metabolic adjustments of freezing tolerances. Here, we investigate the effect of cold and freezing temperatures on physiological and biochemical changes in the leaves of Haberlea rhodopensis under natural and controlled environmental conditions. Our data shows that leaf water content affects its thermodynamical properties during vitrification under low temperatures. The changes in membrane lipid composition, accumulation of sugars, and synthesis of stress-induced proteins were significantly activated during the adaptation of H. rhodopensis to both cold and freezing temperatures. In particular, the freezing tolerance of H. rhodopensis relies on a sucrose/hexoses ratio in favor of hexoses during cold acclimation, while there is a shift in favor of sucrose upon exposure to freezing temperatures, especially evident when leaf desiccation is relevant. This pattern was paralleled by an elevated ratio of unsaturated/saturated fatty acids and significant quantitative and compositional changes in stress-induced proteins, namely dehydrins and early light-induced proteins (ELIPs). Taken together, our data indicate that common responses of H. rhodopensis plants to low temperature and desiccation involve the accumulation of sugars and upregulation of dehydrins/ELIP protein expression. Further studies on the molecular mechanisms underlying freezing tolerance (genes and genetic regulatory mechanisms) may help breeders to improve the resistance of crop plants.

The number of maps deposited in public databases (Electron Microscopy Data Bank, EMDB) determined by cryo-electron microscopy has quickly grown in recent years. With this rapid growth, it is critical to guarantee their quality. So far, map validation has primarily focused on the agreement between maps and models. From the image processing perspective, the validation has been mostly restricted to using two half-maps and the measurement of their internal consistency. In this article, we suggest that map validation can be taken much further from the point of view of image processing if 2D classes, particles, angles, coordinates, defoci, and micrographs are also provided. We present a progressive validation scheme that qualifies a result validation status from 0 to 5 and offers three optional qualifiers (A, W, and O) that can be added. The simplest validation state is 0, while the most complete would be 5AWO. This scheme has been implemented in a website https://biocomp.cnb.csic.es/EMValidationService/ to which reconstructed maps and their ESI can be uploaded.

Cryo-electron microscopy (CryoEM) has become a vital technique in structural biology. It is an interdisciplinary field that takes advantage of advances in biochemistry, physics, and image processing, among other disciplines. Innovations in these three basic pillars have contributed to the boosting of CryoEM in the past decade. This work reviews the main contributions in image processing to the current reconstruction workflow of single particle analysis (SPA) by CryoEM. Our review emphasizes the time evolution of the algorithms across the different steps of the workflow differentiating between two groups of approaches: analytical methods and deep learning algorithms. We present an analysis of the current state of the art. Finally, we discuss the emerging problems and challenges still to be addressed in the evolution of CryoEM image processing methods in SPA.

Phase control is a critical parameter in polarization measurements. It is well known that a proper combination of wave plates allows to obtain achromatic phase shift, i.e., a constant retardation in certain spectral ranges. This paper is focused on a different, but more useful, goal, as it is to achieve customized variable retarders in broad spectral ranges. To do that, a merit function was used to measure the similarity between the overall phase shift of the wave plate combinations and the desired target. The control variables are the thicknesses and orientations of the wave plates. All possible combinations with four and five wave plates of quartz and M g F 2 were analyzed, but our approach can be perfectly extended to deal with more wave plates. The result of an optimization process determines the thicknesses and orientations of the wave plates, which results in the closest retarder to the desired one. Numerical results show deviations below 10% between the target and the obtained retardation. These systems are of special interest in those fields and instruments in which polarization control plays a fundamental role.

Image processing in cryogenic electron tomography (cryoET) is currently at a similar state as Single Particle Analysis (SPA) in cryogenic electron microscopy (cryoEM) was a few years ago. Its data processing workflows are far from being well defined and the user experience is still not smooth. Moreover, file formats of different software packages and their associated metadata are not standardized, mainly since different packages are developed by different groups, focusing on different steps of the data processing pipeline. The Scipion framework, originally developed for SPA (de la Rosa-Trevín et al., 2016), has a generic python workflow engine that gives it the versatility to be extended to other fields, as demonstrated for model building (Martínez et al., 2020). In this article, we provide an extension of Scipion based on a set of tomography plugins (referred to as ScipionTomo hereafter), with a similar purpose: to allow users to be focused on the data processing and analysis instead of having to deal with multiple software installation issues and the inconvenience of switching from one to another, converting metadata files, managing possible incompatibilities, scripting (writing a simple program in a language that the computer must convert to machine language each time the program is run), etcetera. Additionally, having all the software available in an integrated platform allows comparing the results of different algorithms trying to solve the same problem. In this way, the commonalities and differences between estimated parameters shed light on which results can be more trusted than others. ScipionTomo is developed by a collaborative multidisciplinary team composed of Scipion team engineers, structural biologists, and in some cases, the developers whose software packages have been integrated. It is open to anyone in the field willing to contribute to this project. The result is a framework extension that combines the acquired knowledge of Scipion developers in close collaboration with third-party developers, and the on-demand design of functionalities requested by beta testers applying this solution to actual biological problems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Inc.)

The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH 3 ) 3 CNH 3 ] 4 [V 4 O 12 ] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which the initial and the final stages are structurally characterized by sc-XRD. Now, we observed the ability of the same compound to undergo an additional single-crystal-to-single-crystal (SCSC) transformation upon thermal stimuli, but this time at low temperatures (153 K). Compound 1h_RT contains a discrete unprotonated [V 4 O 12 ] 4- tetrahedral anion in which V and O bridging atoms are coplanar. In both phases, these tetrameric anions are linked through tert-butylammonium cations in an extensive network of hydrogen bonds, but at low temperatures, this phase loses its characteristic O-V-O coplanarity, with the resulting rearrangement of the crystal packing and hydrogen-bond network which provide its reversibility at low temperatures. Again, the initial and final stages have been characterized structurally by sc-XRD.

Cryo-electron microscopy (cryoEM) has become a well established technique to elucidate the 3D structures of biological macromolecules. Projection images from thousands of macromolecules that are assumed to be structurally identical are combined into a single 3D map representing the Coulomb potential of the macromolecule under study. This article discusses possible caveats along the image-processing path and how to avoid them to obtain a reliable 3D structure. Some of these problems are very well known in the community. These may be referred to as sample-related (such as specimen denaturation at interfaces or non-uniform projection geometry leading to underrepresented projection directions). The rest are related to the algorithms used. While some have been discussed in depth in the literature, such as the use of an incorrect initial volume, others have received much less attention. However, they are fundamental in any data-analysis approach. Chiefly among them, instabilities in estimating many of the key parameters that are required for a correct 3D reconstruction that occur all along the processing workflow are referred to, which may significantly affect the reliability of the whole process. In the field, the term overfitting has been coined to refer to some particular kinds of artifacts. It is argued that overfitting is a statistical bias in key parameter-estimation steps in the 3D reconstruction process, including intrinsic algorithmic bias. It is also shown that common tools (Fourier shell correlation) and strategies (gold standard) that are normally used to detect or prevent overfitting do not fully protect against it. Alternatively, it is proposed that detecting the bias that leads to overfitting is much easier when addressed at the level of parameter estimation, rather than detecting it once the particle images have been combined into a 3D map. Comparing the results from multiple algorithms (or at least, independent executions of the same algorithm) can detect parameter bias. These multiple executions could then be averaged to give a lower variance estimate of the underlying parameters., (open access.)

Xmipp is an open-source software package consisting of multiple programs for processing data originating from electron microscopy and electron tomography, designed and managed by the Biocomputing Unit of the Spanish National Center for Biotechnology, although with contributions from many other developers over the world. During its 25 years of existence, Xmipp underwent multiple changes and updates. While there were many publications related to new programs and functionality added to Xmipp, there is no single publication on the Xmipp as a package since 2013. In this article, we give an overview of the changes and new work since 2013, describe technologies and techniques used during the development, and take a peek at the future of the package.

The presence of preferred orientations in single particle analysis (SPA) by cryo-Electron Microscopy (cryoEM) is currently one of the hurdles preventing many structural analyses from yielding high-resolution structures. Although the existence of preferred orientations is mostly related to the grid preparation, in this technical note, we show that some image processing algorithms used for angular assignment and three-dimensional (3D) reconstruction are more robust than others to these detrimental conditions. We exemplify this argument with three different data sets in which the presence of preferred orientations hindered achieving a 3D reconstruction without artifacts or, even worse, a 3D reconstruction could never be achieved., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Using a new consensus-based image-processing approach together with principal component analysis, the flexibility and conformational dynamics of the SARS-CoV-2 spike in the prefusion state have been analysed. These studies revealed concerted motions involving the receptor-binding domain (RBD), N-terminal domain, and subdomains 1 and 2 around the previously characterized 1-RBD-up state, which have been modeled as elastic deformations. It is shown that in this data set there are not well defined, stable spike conformations, but virtually a continuum of states. An ensemble map was obtained with minimum bias, from which the extremes of the change along the direction of maximal variance were modeled by flexible fitting. The results provide a warning of the potential image-processing classification instability of these complicated data sets, which has a direct impact on the interpretability of the results., (© Roberto Melero et al. 2020.)

The analysis of structure factors in 3D cryo-EM Coulomb potential maps and their "enhancement" at the end of the reconstruction process is a well-established practice, normally referred to as sharpening. The aim is to increase contrast and, in this way, to help tracing the atomic model. The most common way to accomplish this enhancement is by means of the so-called B-factor correction, which applies a global filter to boost high frequencies with some dampening considerations related to noise amplification. The results are maps with a better visual aspect and a quasiflat spectrum at medium and high frequencies. This practice is so widespread that most map depositions in the Electron Microscopy Data Base (EMDB) only contain sharpened maps. Here, the use in cryoEM of global B-factor corrections is theoretically and experimentally analyzed. Results clearly illustrate that protein spectra present a falloff. Thus, spectral quasi-flattening may produce protein spectra with distortions when compared with experimental ones, this fact, combined with the practice of reporting only sharpened maps, generates a sub-optimal situation in terms of data preservation, reuse and reproducibility. Now that the field is more advanced, we put forward two suggestions: (1) to use methods which keep more faithfully the original experimental signal properties of macromolecules when "enhancing" the map, and (2) to further stress the need to deposit the original experimental maps without any postprocessing or sharpening, not only the enhanced maps. In the absence of access to these original maps data is lost, preventing their future analysis with new methods., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Motivation: Recent technological advances and computational developments have allowed the reconstruction of Cryo-Electron Microscopy (cryo-EM) maps at near-atomic resolution. On a typical workflow and once the cryo-EM map has been calculated, a sharpening process is usually performed to enhance map visualization, a step that has proven very important in the key task of structural modeling. However, sharpening approaches, in general, neglects the local quality of the map, which is clearly suboptimal., Results: Here, a new method for local sharpening of cryo-EM density maps is proposed. The algorithm, named LocalDeblur, is based on a local resolution-guided Wiener restoration approach of the original map. The method is fully automatic and, from the user point of view, virtually parameter-free, without requiring either a starting model or introducing any additional structure factor correction or boosting. Results clearly show a significant impact on map interpretability, greatly helping modeling. In particular, this local sharpening approach is especially suitable for maps that present a broad resolution range, as is often the case for membrane proteins or macromolecules with high flexibility, all of them otherwise very suitable and interesting specimens for cryo-EM. To our knowledge, and leaving out the use of local filters, it represents the first application of local resolution in cryo-EM sharpening., Availability and Implementation: The source code (LocalDeblur) can be found at https://github.com/I2PC/xmipp and can be run using Scipion (http://scipion.cnb.csic.es) (release numbers greater than or equal 1.2.1)., Supplementary Information: Supplementary data are available at Bioinformatics online., (© The Author(s) 2019. Published by Oxford University Press.)

The introduction of local resolution has enormously helped the understanding of cryo-EM maps. Still, for any given pixel it is a global, aggregated value, that makes impossible the individual analysis of the contribution of the different projection directions. We introduce MonoDir, a fully automatic, parameter-free method that, starting only from the final cryo-EM map, decomposes local resolution into the different projection directions, providing a detailed level of analysis of the final map. Many applications of directional local resolution are possible, and we concentrate here on map quality and validation.

Resolution (global and local) is one of the most reported metrics of quality measurement in Single Particle Analysis (SPA). However, in electron tomography, the situation is different and its computation is not straightforward. Typically, resolution estimation is global and, therefore, reduces the assessment of a whole tomogram to a single number. However, it is known that tomogram quality is spatially variant. Still, up to our knowledge, a method to estimate local quality metrics in tomography is lacking. This work introduces MonoTomo , a method developed to estimate locally in a tomogram the highest reliable frequency component, expressed as a form of local resolution. The fundamentals lie in a local analysis of the density map via monogenic signals, which, in analogy to MonoRes , allows for local estimations. Results with experimental data show that the local resolution range that MonoTomo casts agrees with reported resolution values for experimental data sets, with the advantage of providing a local estimation. A range of applications of MonoTomo are suggested for further exploration., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2019 Published by Elsevier Inc.)

Electron microscopy of macromolecular structures is an approach that is in increasing demand in the field of structural biology. The automation of image acquisition has greatly increased the potential throughput of electron microscopy. Here, the focus is on the possibilities in Scipion to implement flexible and robust image-processing workflows that allow the electron-microscope operator and the user to monitor the quality of image acquisition, assessing very simple acquisition measures or obtaining a first estimate of the initial volume, or the data resolution and heterogeneity, without any need for programming skills. These workflows can implement intelligent automatic decisions and they can warn the user of possible acquisition failures. These concepts are illustrated by analysis of the well known 2.2 Å resolution β-galactosidase data set., (open access.)

The inclusion of electrospun nanofiber veils was revealed as an effective method for enhancing the mechanical properties of fiber-reinforced epoxy resin composites. These veils will eventually allow the incorporation of nanomaterials not only for mechanical reinforcement but also in multifunctional applications. Therefore, this paper investigates the effect of electrospun nanofibrous veils made of polyamide 6 modified with TiO 2 nanoparticles on the mechanical properties of a carbon-fiber/epoxy composite. The nanofibers were included in the carbon-fiber/epoxy composite as a single structure. The effect of positioning these veils in different composite positions was investigated. Compared to the reference, the use of unmodified and TiO 2 modified veils increased the flexural stress at failure and the fracture toughness of composites. When TiO 2 modified veils were incorporated, new antibacterial properties were achieved due to the photocatalytic properties of the veils, widening the application area of these composites.

The development of strategies to mimic the natural environment of tissues with engineered scaffolds remains one of the biggest challenges of tissue engineering. Hydrogels appear as suitable materials for this purpose due to their substantial water content, biocompatibility, and for being able to carry nanomaterials that introduce new functionalities to the hydrogel. The incorporation of magnetically responsive and, in particular, magnetoelectric materials into the hydrogel-based scaffolds are a promising approach for bone tissue engineering applications once it can promote not only tissue regeneration through magnetic to mechanic to electrical conversion/stimuli but also the external control of the scaffold by the application of magnetic fields. This work reports on a new CoFe 2 O 4 / Methacrylated Gellan Gum (GGMA)/poly(vinylidene fluoride) (PVDF) hydrogel-based scaffold with 20 kPa Young's modulus and cell viability superior to 80%. The ≈ 1 μm thick PVDF/CoFe 2 O 4 spheres added to GGMA gel (2 wt.%) exhibit 20 emu.g -1 magnetization saturation, 2.7 kOe magnetic coercivity and β-phase contents ≈ 78%, leading to a piezoelectric response |d 33 | of ≈ 22 pC N -1 and a magnetoelectric response of Δ|d 33 | ≈ 6 pC N -1 at a DC magnetic field of 220 m T, as verified for the CoFe 2 O 4 /PVDF spheres with 20 wt.% filler content. Such characteristics allow novel tissue regeneration strategies approaches once CoFe 2 O 4 /GGMA/PVDF has a porous 3-D structure, biocompatibility, bioresorbability, and mechanical/electrical dynamic responses that can be triggered by an applied external magnetic field., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Motivation: Cryo electron microscopy (EM) is currently one of the main tools to reveal the structural information of biological macromolecules. The re-construction of three-dimensional (3D) maps is typically carried out following an iterative process that requires an initial estimation of the 3D map to be refined in subsequent steps. Therefore, its determination is key in the quality of the final results, and there are cases in which it is still an open issue in single particle analysis (SPA). Small angle X-ray scattering (SAXS) is a well-known technique applied to structural biology. It is useful from small nanostructures up to macromolecular ensembles for its ability to obtain low resolution information of the biological sample measuring its X-ray scattering curve. These curves, together with further analysis, are able to yield information on the sizes, shapes and structures of the analyzed particles., Results: In this paper, we show how the low resolution structural information revealed by SAXS is very useful for the validation of EM initial 3D models in SPA, helping the following refinement process to obtain more accurate 3D structures. For this purpose, we approximate the initial map by pseudo-atoms and predict the SAXS curve expected for this pseudo-atomic structure. The match between the predicted and experimental SAXS curves is considered as a good sign of the correctness of the EM initial map., Availability and Implementation: The algorithm is freely available as part of the Scipion 1.2 software at http://scipion.i2pc.es/., (© The Author(s) 2018. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

This work has been focused on the one-step fabrication by electrospinning of polyamide 6 (PA6) nanofibre membranes modified with titanium dioxide nanoparticles (TiO 2 ), where these TiO 2 nanoparticles aggregates could induce a photocatalytic activity. The main potential application of these membranes could be the purification of contaminated water. Thus, it is important to analyse the contaminant degradation capability since in these membranes this is based on their photocatalytic activity. In this work, the effect of the photocatalysis has been studied both on the degradation of an organic model contaminant and on the removal of Escherichia coli and other coliform bacteria. As a result, it was observed that these membranes present excellent photocatalytic activity when they are irradiated under UV light, allowing a 70% reduction of an organic model pollutant after 240 min. In addition, these membranes successfully removed Escherichia coli and other coliform bacteria in artificially inoculated water after 24 h of contact with them. Moreover, the stand-alone structure of the membranes allowed for the reusing of the immobilized catalyst. The experimental evidence indicated that developed nanofibre membranes are a fast and efficient solution for polluted water decontamination based on photocatalysis. Their use could contribute to guarantee a fresh water level and quality, mitigating the water scarcity problem worldwide.

A series of 14 isostructural [Cu(cyclam)] 2 [{Cu(cyclam)} 4 {(α-GeW 11 O 39 )Ln(H 2 O)(OAc)} 2 ]·18H 2 O (1-Ln, where Ln = La-Lu; cyclam = 1,4,8,11-tetraazacyclotetradecane) polyoxometalate-based hybrids reported herein represent (i) the first example of a two-dimensional covalent hybrid lattice involving the [{(α-XW 11 O 39 )Ln(H 2 O)(OAc)} 2 ] n- archetype and (ii) the first structural characterization of such a dimeric polyoxotungste for Ln = La and Pr as well as for the combination of X = Ge and Ln = Ce, Nd, Sm, or Lu. Compounds 1-Ln have been characterized by elemental analyses, infrared spectroscopy, and thermogravimetric analysis, and their thermostructural behavior has been monitored by powder and single-crystal X-ray diffraction. The title compounds undergo two single-crystal-to-single-crystal transformations triggered by thermal dehydration leading to the [{Cu(cyclam)} 6 {(α-GeW 11 O 39 )Ln(H 2 O)(OAc)} 2 ]·4H 2 O intermediate (2-Ln, where Ln = Eu or Er) and [Cu(cyclam)] 0.5 [{Cu(cyclam)} 5.5 {(α-GeW 11 O 39 )Ln(OAc)} 2 ] (3-Ln, where Ln = Ce or Eu) final anhydrous phases, the latter evidencing a coordinatively unsaturated derivative of the dimeric archetype for the first time. These transitions involve formation and disruption of Cu-O POM bonds that result in different {Cu(cyclam)} 2+ moieties grafting onto and being released from Keggin surfaces, which reduces the dimensionality of 1-Ln to one-dimensional covalent assemblies for 2-Ln and 3-Ln. While all 3-Ln phases rehydrate fully upon exposure to air for 24 h, the kinetics governing the crystal transitions back toward 1-Ln through 2-Ln depend on the nature of Ln. Under ambient moisture, the anhydrous structures fully revert back to the parent framework for Ln = La-Sm, while the samples containing Eu to Lu afford mixtures of 1-Ln and 2-Ln and require immersion in water for the structural reversion to reach completion. Single-crystal X-ray diffraction analyses of the rehydrated 1R-Ln samples (Ln = Ce, Eu, and Er) support these observations.

Single-particle analysis by electron microscopy is a well established technique for analyzing the three-dimensional structures of biological macromolecules. Besides its ability to produce high-resolution structures, it also provides insights into the dynamic behavior of the structures by elucidating their conformational variability. Here, the different image-processing methods currently available to study continuous conformational changes are reviewed.

Three dimensional electron microscopy is becoming a very data-intensive field in which vast amounts of experimental images are acquired at high speed. To manage such large-scale projects, we had previously developed a modular workflow system called Scipion (de la Rosa-Trevín et al., 2016). We present here a major extension of Scipion that allows processing of EM images while the data is being acquired. This approach helps to detect problems at early stages, saves computing time and provides users with a detailed evaluation of the data quality before the acquisition is finished. At present, Scipion has been deployed and is in production mode in seven Cryo-EM facilities throughout the world., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The Map Challenge organized by the Electron Microscopy Data Bank has prompted the development of an Xmipp high resolution reconstruction protocol (which we will refer to as highres) that is integrated in the software platform Scipion. In this work we describe the details of the image angular alignment and map reconstruction steps in our new method. This algorithm is similar to the standard projection matching approach with some important modifications, especially in the area of detecting significant features in the reconstructed volume. We show that the new method is able to produce higher resolution maps than the current de facto standard as measured by the Fourier Shell Correlation, the Monogenic Local Resolution and EMRinger., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Delamination and brittle matrix fracture have long since been the biggest problems in fibre-reinforced composites. Recently, the incorporation of electrospun nanofibre veils has been shown to be an effective method for improving the mechanical properties of these composites, without causing process problems and negatively affecting other mechanical properties. Thus, these nanofibres have the potential to be used as thickness-reinforcing materials in composites. This paper investigates the effect of incorporating standalone electrospun nanofibre veils made of two different types of polyamide 6 (PA6) on the mechanical properties of carbon fibre/epoxy composites. The influence of positioning the electrospun veils at different interlaminar positions of the laminate has also been investigated.

Electron cryomicroscopy (cryoEM) is essential for the study and functional understanding of non-crystalline macromolecules such as proteins. These molecules cannot be imaged using X-ray crystallography or other popular methods. CryoEM has been successfully used to visualize macromolecular complexes such as ribosomes, viruses, and ion channels. Determination of structural models of these at various conformational states leads to insight on how these molecules function. Recent advances in imaging technology have given cryoEM a scientific rebirth. As a result of these technological advances image processing and analysis have yielded molecular structures at atomic resolution. Nevertheless there continue to be challenges in image processing, and in this article we will touch on the most essential in order to derive an accurate three-dimensional model from noisy projection images. Traditional approaches, such as k-means clustering for class averaging, will be provided as background. We will then highlight new approaches for each image processing subproblem, including a 3D reconstruction method for asymmetric molecules using just two projection images and deep learning algorithms for automated particle picking., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The introduction of Direct Electron Detector (DED) videos in the Electron Microscope field has boosted Single Particle Analysis to a point in which it is currently considered to be a key technique in Structural Biology. In this article we introduce an approach to estimate the DED camera gain at each pixel from the movies themselves. This gain is needed to have the set of recorded frames into a coherent gray level range, homogeneous over the whole image. The algorithm does not need any other input than the DED movie itself, being capable of providing an estimate of the camera gain image, helping to identify dead pixels and cases of incorrectly calibrated cameras. We propose the algorithm to be used either to validate the experimentally acquired gain image (for instance, to follow its possible change over time) or to verify that there is no residual gain image after experimentally correcting for the camera gain. We show results for a number of DED camera models currently in use (DE, Falcon II, Falcon 3, and K2)., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Polymer-based piezoelectric biomaterials have already proven their relevance for tissue engineering applications. Furthermore, the morphology of the scaffolds plays also an important role in cell proliferation and differentiation. The present work reports on poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), a biocompatible, biodegradable, and piezoelectric biopolymer that has been processed in different morphologies, including films, fibers, microspheres, and 3D scaffolds. The corresponding magnetically active PHBV-based composites were also produced. The effect of the morphology on physico-chemical, thermal, magnetic, and mechanical properties of pristine and composite samples was evaluated, as well as their cytotoxicity. It was observed that the morphology does not strongly affect the properties of the pristine samples but the introduction of cobalt ferrites induces changes in the degree of crystallinity that could affect the applicability of prepared biomaterials. Young's modulus is dependent of the morphology and also increases with the addition of cobalt ferrites. Both pristine and PHBV/cobalt ferrite composite samples are not cytotoxic, indicating their suitability for tissue engineering applications.

The dispersion of nanoparticles having different size-, shape-, and composition-dependent properties is an exciting approach to design and synthesize multifunctional materials and devices. This work shows a detailed investigation of the preparation and properties of free-standing nanocomposite films based on cellulose nanocrystals (CNC) loaded with three different types of metal nanoparticles. CNC-based nanocomposites having zinc oxide (ZnO), titanium dioxide (TiO 2 ), and silver oxide (Ag 2 O) have been obtained through evaporation-induced self-assembly (EISA) in acqueous solution. Morphological and optical characteristics, chemical properties, wettability, and antimicrobial assays of the produced films were conducted. Furthermore, disintegrability in composting condition of CNC based nanocomposites was here investigated for the first time. The morphological observations revealed the formation of a chiral nematic structure with uniformly distributed nanoparticles. The bionanocomposite films based on the metal nanoparticles had effective antimicrobial activity, killing both Escherichia coli RB ( E. coli RB) and Staphylococcus aureus 8325-4 ( S. aureus 8325-4). The simplicity method of film preparation, the large quantity of cellulose in the world, and the free-standing nature of the nanocomposite films offer highly advantageous characteristics that can for the new development of multifunctional materials.

Herein we describe the preparation of hybrid polymer-inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene- b -poly(acrylic acid)/polystyrene (PS- b -PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [Ln III (α-SiW 11 O 39 )] 5- polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface., Competing Interests: The authors declare no conflict of interest.

Poly(2-ethyl-2-oxazoline) has become an excellent alternative to the use of poly(ethylene glycol) in pharmaceutical formulations due to its valuable physicochemical and biological properties. This work presents a formulation of poorly-water soluble drug, hydrocortisone, using interpolymer complexes and physical blends of poly(2-ethyl-2-oxazoline)s and two Carbopols ® (Carbopol 974 and Carbopol 971) for oromucosal administration. The swelling, hydrocortisone release and mucoadhesive properties of a series of tablet formulations obtained by combination of different Carbopols with poly(2-ethyl-2-oxazoline)s of different molecular weights have been evaluated in vitro., Competing Interests: The authors declare no conflict of interest.

Since the beginning of electron microscopy, resolution has been a critical parameter. In this article, we propose a fully automatic, accurate method for determining the local resolution of a 3D map (MonoRes). The foundation of this algorithm is an extension of the concept of analytic signal, termed monogenic signal. The map is filtered at different frequencies and the amplitude of the monogenic signal is calculated, after which a criterion is applied to determine the resolution at each voxel. MonoRes is fully automatic without compulsory user parameters, with great accuracy in all tests, and is computationally more rapid than existing methods in the field. In addition, MonoRes offers the option of local filtering of the original map based on the calculated local resolution., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A magnetic cellulosic material composed of cellulose nanocrystals (CNC) and cobalt ferrite (CoFe 2 O 4 ) nanoparticles was developed through evaporation-induced self-assembly (EISA). Nanoparticles demonstrated good dispersibility within the cellulose nanocrystal template. The addition of glucose to CNC network allows the development of homogeneous crack-free CNC-based films and does no modify neither the morphology nor the optical properties. In contrast, the introduction of CoFe 2 O 4 nanoparticles produces a marked decrease in the amount of the transmitted light. 20wt.% of CoFe 2 O 4 nanoparticles inside the CNC matrix induced a maximum magnetization value of 12.96emug -1 , increased the real part of the dielectric constant (permittivity) from 10 (pure CNC film) to 12 and improved the thermostability of the nanocomposite as evidenced by the increase of the onset temperature from 165.1 to 220.4°C. Those features obtained in a non-petroleum-based composite provide insight into the development of the next generation of functional materials from natural origin., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The hybrid compound [{Cu(cyclam)} 3 (W 7 O 24 )]⋅15.5 H 2 O (1) (cyclam=1,4,8,11-tetraaza-cyclotetradecane) was synthesized by reacting the {Cu(cyclam)} 2+ complex with a tungstate source in water at pH 8. Compound 1 exhibits an unprecedented three-dimensional covalent structure built of heptatungstate clusters linked through metalorganic complexes in a POMOF-like framework that displays water-filled channels. This dynamic architecture undergoes two sequential single-crystal-to-single-crystal transformations upon thermal evacuation of water molecules to result in the partially dehydrated [{Cu(cyclam)} 3 (W 7 O 24 )]⋅12 H 2 O (2) and anhydrous [Cu(cyclam)] 0.5 [{Cu(cyclam)} 2.5 (W 7 O 24 )] (3) crystalline phases. These transitions are associated with cluster rotations and modifications in the Cu II coordination geometries, which reduce the dimensionality of the original lattice to layered systems but preserving the porous nature. Phase 3 reverts to 2 upon exposure to ambient moisture, whereas the transition between 1 and 2 proved to be irreversible. The permanent microporosity of 3 was confirmed by gas sorption measurements (N 2 , CO 2 ), which reveal a system of parallel channels made of wide cavities connected through narrow necks that limit the adsorption process. This observation is in good agreement with Grand Canonical Monte Carlo simulations., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Composites based on epoxy/graphene oxide (GO) and epoxy/reduced graphene oxide (rGO) were investigated for thermal-mechanical performance focusing on the effects of the chemical groups present on nanoadditive-enhanced surfaces. GO and rGO obtained in the present study have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and X-ray powder diffraction (XRD) demonstrating that materials with different oxidation degrees have been obtained. Thereafter, GO/epoxy and rGO/epoxy nanocomposites were successfully prepared and thoroughly characterized by dynamic mechanical thermal analysis (DMTA) and transmission electron microscopy (TEM). A significant increase in the glass transition temperature was found in comparison with the neat epoxy. The presence of functional groups on the graphene surface leads to chemical interactions between these functional groups on GO and rGO surfaces with the epoxy, contributing to the possible formation of covalent bonds between GO and rGO with the matrix. The presence of oxidation groups on GO also contributes to an improved exfoliation, intercalation, and distribution of the GO sheets in the composites with respect to the rGO based composites., Competing Interests: The authors declare no conflict of interest.

Due to the potential of CNC-based flexible materials for novel industrial applications, the aim of this work is to improve the thermal stability of cellulose nanocrystals (CNC) films through a straightforward and scalable method. Based of nanocomposite approach, five different metallic nanoparticles (ZnO, SiO 2 , TiO 2 , Al 2 O 3 and Fe 2 O 3 ) have been co-assembled in water with CNCs to obtain free-standing nanocomposite films. Thermogravimetric analysis (TGA) reveals an increased thermal stability upon nanoparticle. This increase in the thermal stability reaches a maximum of 75°C for the nanocomposites having 10wt% of Fe 2 O 3 and ZnO. The activation energies of thermodegradation process (E a ) determined according to Kissinger and Ozawa-Flynn-Wall methods further confirm the delayed degradation of CNC nanocomposites upon heating. Finally, the changes induced in the crystalline structure during thermodegradation were followed by wide angle X-ray diffraction (WAXD). It is also observed that thermal degradation proceeds at higher temperatures for nanocomposites having metallic nanoparticles. Overall, experimental findings here showed make nanocomposite approach a simple low-cost environmentally-friendly strategy to overcome the relatively poor thermal stability of CNCs when extracted via sulfuric acid assisted hydrolysis of cellulose., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Polymer inclusion membranes (PIM) used for selective transport and separation of metallic ions have emerged in recent times. Their expansion depends on the method of preparation and their suitable structure and physico-chemical characteristics. In this paper, a novel category of membranes for ions separation is reported. The membranes were synthesized by thermally induced phase separation using a mixture of polyvinylidene fluoride (PVDF) and cellulose triacetate (CTA) plasticized by tris(2-ethylhexyl) phosphate (TEHP) and with di-(2-ethylhexyl) phosphoric acid (D2EHPA) incorporated into the polymer as carrier to increase specific interactions between polymers. PIM membrane exhibited a hydrophobic (∼100°) and thermally stable up to ∼200°C porous homogenous structure. The transport of Ni(II), Zn(II) and Pb(II) from aqueous solutions was studied by competitive transport across polymer inclusion membranes (PIM). Competitive transport of ions in solution across PIM provide the selectivity order: Ni 2+ (45%)>Pb 2+ (35%)>Zn 2+ (5%). A long-term transport experiment was carried out to study the durability of the system., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work we fabricate porous PLLA and PLLA/ZnO scaffolds with porosities ranging from 10 to 90% and average pore diameter of 125-250μm by solvent casting/particulate leaching method. The structural evolution of PLLA/ZnO scaffolds during their in vitro degradation in phosphate buffered saline (PBS) at physiological pH (7.4) has been studied as a function of porosity and obtained results were compared to plain PLLA scaffolds. The changes induced upon the hydrolytic degradation of scaffolds have been explored by measuring the pH changes of the medium, the mass loss, thermal transitions, crystalline structure, thermal stability and the morphological changes. It is shown that the degradation profile of scaffolds could be successfully modified by tuning both the amount of ZnO nanoparticles and by varying the scaffold porosity. Results reveal that the water dissociated on ZnO nanoparticle surfaces initiate hydrolytic degradation reactions by reducing the strength of the chemical bonds of the adjacent PLLA chains, causing them to further divide into water-soluble oligomers. Obtained results may be useful towards the development of antibacterial porous structures with tuneable degradation rates to be used as a substrate for the growth of different kind of cells and tissues., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work we explore the effect of surface nanoarchitecture of polystyrene (PS) and polystyrene-b-poly(acrylic acid) (PS-b-PAA) diblock copolymer films on cell viability. PS and PS-b-PAA have been nanopatterned at temperatures of 110, 120 and 140°C using nanoporous aluminium oxide membranes (AAO) as a template. Surface architecture strongly depends on the infiltration temperature and the nature of the infiltrated polymer. High patterning temperatures yield hollow fibre shape architecture at the nanoscale level, which substantially modifies the surface hydrophobicity of the resulting materials. Up to date very scarce reports could be found in the literature dealing with the interaction of microstructured/nanostructured polymeric surfaces with cancer cells. Therefore, MCF-7 breast cancer cells have been selected as a model to conduct cell viability assays. The findings reveal that the fine-tuning of the surface nanoarchitecture contributes to the modification of its biocompatibility. Overall, this study highlights the potential of AAO membranes to obtain well-defined tailored morphologies at nanoscale level and its importance to develop novel soft functional surfaces to be used in the biomedical field., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Fourier Shell Correlation, Spectral Signal-to-Noise Ratio, Fourier Neighbour Correlation, and Differential Phase Residual are different measures that have been proposed over time to determine the spatial resolution achieved by a certain 3D reconstruction. Estimates of B-factors to describe the reduction in signal-to-noise ratio with increasing resolution is also a useful parameter. All these concepts are interrelated and different thresholds have been given for each one of them. However, the problem of resolution assessment in 3DEM is still far from settled and preferences are normally adopted in order to choose the "correct" threshold. In this paper we review the different concepts, their theoretical foundations and the derivation of their statistical distributions (the basis for establishing sensible thresholds). We provide theoretical justifications for some common practices in the field for which a formal justification was missing. We also analyze the relationship between SSNR and B-factors, the electron dose needed for achieving a given contrast and resolution, the number of images required, etc. Finally, we review the consequences for the number of particles needed to achieve a certain resolution and how to analyze the Signal-to-Noise Ratio for a sequence of imaging operations., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

One of the key steps in Electron Microscopy is the tomographic reconstruction of a three-dimensional (3D) map of the specimen being studied from a set of two-dimensional (2D) projections acquired at the microscope. This tomographic reconstruction may be performed with different reconstruction algorithms that can be grouped into several large families: direct Fourier inversion methods, back-projection methods, Radon methods, or iterative algorithms. In this review, we focus on the latter family of algorithms, explaining the mathematical rationale behind the different algorithms in this family as they have been introduced in the field of Electron Microscopy. We cover their use in Single Particle Analysis (SPA) as well as in Electron Tomography (ET).

Random conical tilt (RCT) and orthogonal tilt reconstruction (OTR) are two remarkable methods for reconstructing the three-dimensional structure of macromolecules at low resolution. These techniques use two images at two different sample tilts. One of the most demanding steps in these methods at the image processing level is to identify corresponding particles on both micrographs, and manual or semiautomatic matching methods are usually used. Here we present an approach to solve this bottleneck with a fully automatic method for assigning particle tilt pairs. This new algorithm behaves correctly with a variety of samples, covering the range from small to large macromolecules and from sparse to densely populated fields of view. It is also more rapid than previous approaches. The roots of the method lie in a Delaunay triangulation of the set of independently picked coordinates on both the untilted and tilted micrographs. These triangulations are then used to search an affine transformation between the untilted and tilted triangles. The affine transformation that maximizes the number of correspondences between the two micrographs defines the coordinate matching., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Commercial stabilized slurry of zero-valent iron nanoparticles (nZVI) as well as laboratory-synthesized polymer-stabilized NZVI nanoparticles were used for lindane (γ-hexachlorocyclohexane) degradation studies in aqueous solution. In the present study, polymer-stabilized iron nanoparticles were stabilized using polyethylene glycol (PEG, Mn ~400 and ~950-1050) and polytetrahydrofuran (PTHF, Mn ~650). To study the effectiveness of the different nanoparticles, a quantitative monitorization of lindane degradation by using solid-phase extraction (SPE) and a qualitative measurement of generated volatile by-products by headspace-solid phase microextraction (HS-SPME) followed by GC/MS were carried out. The obtained data were compared and contrasted with the results obtained in previous work. Results showed that the nanoparticles studied in this work possess superior dechlorination performance compared with previous observations. The freshly prepared Fe(0)-PEG400, Fe(0)-PEG1050 and Fe(0)-PTHF exhibited high reactivity during the dechlorination process of lindane in a very short time. The results obtained with the synthesized nanoparticles were similar to those obtained with commercial nanoparticles. However, in all cases reactivity decreased at reaction's late stage. Degradation of lindane by the studied nanoparticles removed 99.9% of the lindane initial concentration after 72h, except for Fe(0)-PTHF nanoparticles, for which the reaction stopped after 5min. In all cases, the reaction followed a second order kinetics. Finally, comparing the results from this study with our previous work, where different nature polymers were considered (Fe(0)-CMC, Fe(0)-PAA and Fe(0)-PAP), more gradual degradation profile of lindane was observed for Fe(0)-PAA and Fe(0)-CMC. It should be noted that in the present case, the reaction of lindane was speeded up with commercial and Fe(0)-PEG nanoparticles. Nevertheless, in the later case, the composition of by-products was affected by the presence of partially degraded intermediates. Taking into account the current technologies, the high removal rates obtained and the acceptable degradation times required, the proposed technology is suitable for its aimed purpose., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The temperature dependence of the birefringence in a suspended core fiber (SCF) has been experimentally analyzed by using a polarimetric setup. The used configuration consists of two linear polarizers and the SCF as birefringent medium. A theoretical study based on Jones matrices has been carried out to analyze the experimental observed behavior. For this, a polarimetric all-fiber configuration was used whose sensitivity depends on the wavelength variation with temperature. Results obtained show that it is strongly affected when the air holes of SCF are partially filled with ethanol.