Abstract Nature has been producing cellulose since long before man walked the surface of the earth. Millions of years of natural design and testing have resulted in cellulose-based structures that are an inspiration for the production of synthetic materials based on cellulose with properties that can mimic natural designs, functions, and properties. Here, five sections describe cellulose-based materials with characteristics that are inspired by gratings that exist on the petals of the plants, structurally colored materials, helical filaments produced by plants, water-responsive materials in plants, and environmental stimuli-responsive tissues found in insects and plants. The synthetic cellulose-based materials described herein are in the form of fibers and films. Fascinating multifunctional materials are prepared from cellulose-based liquid crystals and from composite cellulosic materials that combine functionality with structural performance. Future and recent applications are outlined.

In article number 1703655, Maria H. Godinho and co-workers review cellulose and cellulose-based materials which have properties that mimic natural designs and functions. Such materials are inspired by gratings, helical filaments, structurally colored water, and stimuli-responsive materials that exist in insects and plants. Synthetic cellulose-based materials in the form of fibers and films are considered. The inside front cover shows a eurodium awn cross section, by scanning electron microscopy, displaying the helical arrangements of cellulose fibrils.

Glass objects are common in shipwrecks since they are associated with ordinary glassware or commercial products. The alteration pathologies of historical glasses from two wrecks from the Mediterranean Sea were analyzed to characterize their alteration mechanisms. The results of this research proved that the alteration layers presented a moderate content of Na2O, similar to the average salinity of the ocean, and a high content of Al2O3 due to an extremely basic environment during the corrosion process. The biofouling layer protected the glass surfaces. Dark deposits with a high content of MnO were observed in the most instable glass.

Despite great advances in the fight against cancer, traditional chemotherapy has been hindered by the dose dependent adverse side effects that reduce the usable doses for effective therapy. This has been associated to drug resistance in tumor cells that often cause relapse and therapy failure. These drawbacks have been tackled by combining different therapeutic regiments that prevent drug resistance while decreasing the chemotherapy dose required for efficacious ablation of cancer. In fact, new metallic compounds have been in a continuous development to extend the existing chemotherapy arsenal for these combined regimens. Here, we demonstrate that combination of a metallic compound (TS265), previously characterized by our group, with photothermy circumvents cells resistant to Doxorubicin (DOX). We first engendered a colorectal carcinoma cell line (HCT116) highly resistant to DOX, whose viability was diminished after administration of TS265. Cancer cell death was potentiated by challenging these cells with 14 nm spherical gold nanoparticles followed by laser irradiation at 532 nm. The combination of TS265 with photothermy lead to 65% cell death of the DOX resistant cells without impacting healthy cells. These results support the use of combined chemotherapy and photothermy in the visible spectrum as an efficient tool for drug resistant tumors.

MicroRNAs (miRNAs) regulate a wide variety of biological processes, including tumourigenesis. Altered miRNA expression is associated with deregulation of signalling pathways, which in turn cause abnormal cell growth and de-differentiation, contributing to cancer. miR-143 and miR-145 are anti-tumourigenic and influence the sensitivity of tumour cells to chemotherapy and targeted therapy. Comparative proteomic analysis was performed in HCT116 human colon cancer cells stably transduced with miR-143 or miR-145. Immunoblotting analysis validated the proteomic data in stable and transient miRNA overexpression conditions in human colon cancer cells. We show that approximately 100 proteins are differentially expressed in HCT116 human colon cancer cells stably transduced with miR-143 or miR-145 compared to Empty control cells. Further, Gene Ontology and pathway enrichment analysis indicated that proteins involved in specific cell signalling pathways such as cell death, response to oxidative stress, and protein folding might be modulated by these miRNAs. In particular, antioxidant enzyme superoxide dismutase 1 (SOD1) was downregulated by stable expression of either miR-143 or miR-145. Further, SOD1 gain-of-function experiments rescued cells from miR-143-induced oxidative stress. Moreover, miR-143 overexpression increased oxaliplatin-induced apoptosis associated with reactive oxygen species generation, which was abrogated by genetic and pharmacological inhibition of oxidative stress. Overall, miR-143 might circumvent resistance of colon cancer cells to oxaliplatin via increased oxidative stress in HCT116 human colon cancer cells.

Aldehyde oxidases are molybdenum and flavin dependent enzymes characterized by a very wide substrate specificity and performing diverse reactions that include oxidations (e.g., aldehydes and aza-heterocycles), hydrolysis of amide bonds, and reductions (e.g., nitro, S-oxides and N-oxides). Oxidation reactions and amide hydrolysis occur at the molybdenum site while the reductions are proposed to occur at the flavin site. AOX activity affects the metabolism of different drugs and xenobiotics, some of which designed to resist other liver metabolizing enzymes (e.g., cytochrome P450 monooxygenase isoenzymes), raising its importance in drug development. This work consists of a comprehensive overview on aldehyde oxidases, concerning the genetic evolution of AOX, its diversity among the human population, the crystal structures available, the known catalytic reactions and the consequences in pre-clinical pharmacokinetic and pharmacodynamic studies. Analysis of the different animal models generally used for pre-clinical trials and comparison between the human (hAOX1), mouse homologs as well as the related xanthine oxidase (XOR) are extensively considered. The data reviewed also include a systematic analysis of representative classes of molecules that are hAOX1 substrates as well as of typical and well characterized hAOX1 inhibitors. The considerations made on the basis of a structural and functional analysis are correlated with reported kinetic and metabolic data for typical classes of drugs, searching for potential structural determinants that may dictate substrate and/or inhibitor specificities.

A simple process of commercial paper functionalisation via in situ polymerisation of conductive polymers onto cellulose fibres was investigated and applied as electrodes in paper-based batteries. The functionalisation involved polypyrrole (PPy) and Poly (3,4-ethylenedioxythiophene) (PEDOT) as conductive polymers with the process of functionalisation optimised for each polymer individually with respect to oxidant-to-monomer ratios and polymerisation times and temperature. Paper with conductivity values of 44 mS/cm was obtained by exposing the samples to pyrrole vapour for a period of 30 min at room temperature; however, polymerisation at temperatures of 40 °C lead to higher conductivity values to up 141 mS/cm. Consequently, functionalised PPy and PEDOT papers were applied as cathodes in batteries with Al foil anodes and commercial paper soaked in an electrolyte solution of NaCl.

A simple process of commercial paper functionalisation via in situ polymerisation of conductive polymers onto cellulose fibres was investigated and applied as electrodes in paper-based batteries. The functionalisation involved polypyrrole (PPy) and Poly (3,4-ethylenedioxythiophene) (PEDOT) as conductive polymers with the process of functionalisation optimised for each polymer individually with respect to oxidant-to-monomer ratios and polymerisation times and temperature. Paper with conductivity values of 44 mS/cm was obtained by exposing the samples to pyrrole vapour for a period of 30 min at room temperature; however, polymerisation at temperatures of 40 °C lead to higher conductivity values to up 141 mS/cm. Consequently, functionalised PPy and PEDOT papers were applied as cathodes in batteries with Al foil anodes and commercial paper soaked in an electrolyte solution of NaCl.

A novel cellulose-based bio-battery made of electrospun fibers activated by biological fluids has been developed. This work reports a new concept for a fully organic bio-battery that takes advantage of the high surface to volume ratio achieved by an electrospun matrix composed of sub-micrometric fibers that acts simultaneously as the separator and the support of the electrodes. Polymer composites of polypyrrole (PPy) and polyaniline (PANI) with cellulose acetate (CA) electrospun matrix were produced by in situ chemical oxidation of pyrrole and aniline on the CA fibers. The structure (CA/PPy|CA|CA/PANI) generated a power density of 1.7 mW g−1 in the presence of simulated biological fluids, which is a new and significant contribution to the domain of medical batteries and fully organic devices for biomedical applications.

A novel cellulose-based bio-battery made of electrospun fibers activated by biological fluids has been developed. This work reports a new concept for a fully organic bio-battery that takes advantage of the high surface to volume ratio achieved by an electrospun matrix composed of sub-micrometric fibers that acts simultaneously as the separator and the support of the electrodes. Polymer composites of polypyrrole (PPy) and polyaniline (PANI) with cellulose acetate (CA) electrospun matrix were produced by in situ chemical oxidation of pyrrole and aniline on the CA fibers. The structure (CA/PPy|CA|CA/PANI) generated a power density of 1.7 mW g−1 in the presence of simulated biological fluids, which is a new and significant contribution to the domain of medical batteries and fully organic devices for biomedical applications.

Developments in thermoelectric (TE) transparent p-type materials are scarce and do not follow the trend of the corresponding n-type materials – a limitation of the current transparent thermoelectric devices. P-type thermoelectric thin films of CuI have been developed by three different methods in order to maximise optical transparency (>70% in the visible range), electrical (σ = 1.1 × 104 Sm−1) and thermoelectric properties (ZT = 0.22 at 300 K). These have been applied in the first planar fully transparent p-n type TE modules where gallium-doped zinc oxide (GZO) thin films were used as the n-type element and indium thin oxide (ITO) thin films as electrodes. A thorough study of power output in single elements and p-n modules electrically connected in series and thermally connected in parallel is inclosed. This configuration allows for a whole range of highly transparent thermoelectric applications.

Highly porous monolithic alumina columns find a wide variety of applications, including in chromatography, due to increased surface area and good accessibility to the ligands and reduced diffusional hindrances. Several modelling approaches have been applied to describe experimentally observed flow behaviour in such materials, which morphology plays a key role in determining their hydrodynamic and mass transfer properties. In this work, a direct computational fluid dynamics (CFD) modelling approach is proposed to simulate flow behaviour in monolithic porous columns. The morphological structure of a fabricated alumina monolith was first reconstructed using 3D X-ray tomography data and, subsequently, OpenFOAM, an open-source CFD tool, was used to simulate the essential parameters for monoliths’ performance characterisation and optimisation, i.e. velocity and pressure fields, fluid streamlines, shear stress and residence time distribution (RTD). Moreover, the tortuosity of the monolith was estimated by a novel method, using the computed streamlines, and its value (∼1.1) was found to be in the same range of the results obtained by known experimental, analytical and numerical equations. Besides, it was observed (for the case of the monolith studied) that fluid transport was dominated by flow heterogeneities and advection, while the shear stress at pore mouths was significantly higher than in other regions. The proposed modelling approach, with expected high potential for designing target materials, was successfully validated by an experimentally obtained residence time distribution (RTD).

The Cathedral of León has one of the most important ensembles of medieval stained glass windows in Europe; however, most of them have been altered by atmospheric weathering. The main objective of this study was the characterization of a set of glass samples from the Cathedral of León, the comparison with glasses from previous interventions in the cathedral and the study of the relation between the alteration pathologies, the chemical composition of the glasses and the environment in which they were placed. The samples were characterized by means of binocular microscopy, scanning electron microscopy and energy dispersive X-ray spectrometry, visible spectrophotometry, X-ray fluorescence spectrometry and X-ray diffraction. The main alteration of glasses exposed until the 19th century was the formation of pits by dealkalinization, while the glasses exposed until the present formed CaSO4 deposits as a consequence of the synergic effect of rainwater and gaseous pollutants. Glasses altered by the browning of manganese were also characterized. Resumen La Catedral de León posee una de las colecciones de vidrieras medievales más importantes de Europa; sin embargo, muchos de los vidrios se han alterado por degradación atmosférica. El objetivo principal de este estudio fue la caracterización de un conjunto de vidrios procedentes de la Catedral de León, su comparación con vidrios procedentes de intervenciones previas en la catedral y el estudio de la relación entre las patologías de alteración, la composición química del vidrio y el medio en el que estuvieron expuestas. Las muestras se caracterizaron mediante lupa binocular, microscopía electrónica de barrido y microanálisis de dispersión de energía de rayos X, espectrofotometría visible, espectrometría de fluorescencia de rayos X y difracción de rayos X. La alteración principal de los vidrios expuestos hasta el s. xix consistió en la formación de picaduras por desalcalinización, mientras que en los vidrios expuestos hasta la actualidad se formaron depósitos de CaSO4 como consecuencia del efecto sinérgico de la lluvia y los gases contaminantes. También se han caracterizado vidrios alterados por el enmarronamiento del manganeso.

Blends of rice waste streams were submitted to co-gasification assays. The resulting chars (G1C and G2C) were characterized and used in Cr(III) removal assays from a synthetic solution. A Commercial Activated Carbon (CAC) was used for comparison purposes. The chars were non-porous materials mainly composed by ashes (68.3–92.6% w/w). The influences of adsorbent loading (solid/liquid ratio – S/L) and initial pH in Cr(III) removal were tested. G2C at a S/L of 5 mg L−1 and an initial pH of 4.50 presented an uptake capacity significantly higher than CAC (7.29 and 2.59 mg g−1, respectively). G2C was used in Cr(III) removal assays from an industrial wastewater with Cr(III) concentrations of 50, 100 and 200 mg L−1. Cr(III) removal by precipitation (uptake capacity ranging from 11.1 to 14.9 mg g−1) was more effective in G2C, while adsorption (uptake capacity of 16.1 mg g−1) was the main removal mechanism in CAC.

The p53 tumor suppressor is widely found to be mutated in human cancer. This protein is regarded as a molecular hub regulating different cell responses, namely cell death. Compelling data have demonstrated that the impairment of p53 activity correlates with tumor development and maintenance. For these reasons, the reactivation of p53 function is regarded as a promising strategy to halt cancer. In the present work, the recombinant mutant p53R280K DNA binding domain (DBD) was produced for the first time, and its crystal structure was determined in the absence of DNA to a resolution of 2.0 Å. The solved structure contains four molecules in the asymmetric unit, four zinc(II) ions, and 336 water molecules. The structure was compared with the wild-type p53 DBD structure, isolated and in complex with DNA. These comparisons contributed to a deeper understanding of the mutant p53R280K structure, as well as the loss of DNA binding related to halted transcriptional activity. The structural information derived may also contribute to the rational design of mutant p53 reactivating molecules with potential application in cancer treatment.

Nearly 1.5 million people worldwide suffer from chronic myeloid leukemia (CML), characterized by the genetic translocation t(9;22)(q34;q11.2), involving the fusion of the Abelson oncogene (ABL1) with the breakpoint cluster region (BCR) gene. Early onset diagnosis coupled to current therapeutics allow for a treatment success rate of 90, which has focused research on the development of novel diagnostics approaches. In this review, we present a critical perspective on current strategies for CML diagnostics, comparing to gold standard methodologies and with an eye on the future trends on nanotheranostics.

Cellulose nanocrystals are isolated from plant cellulose structures, e.g., cotton. In article 1603560, M. H. Godinho and co-workers describe a tunable photonic material produced from these cellulose nanocrystals iridescent films, which reflects both right- and left-handed circularly polarized light, taking advantage of the gaps existing along the cellulose nanocrystals films that are filled with a nematic liquid crystal.

Six new copper(ii) complexes with 2,2[prime or minute]:6[prime or minute],2[prime or minute][prime or minute]-terpyridine (4[prime or minute]-Rn-terpy) [1 (R1 = furan-2-yl), 2 (R2 = thiophen-2-yl), and 3 (R3 = 1-methyl-1H-pyrrol-2-yl)] and 2,6-di(thiazol-2-yl)pyridine derivatives (Rn-dtpy) [4 (R1), 5 (R2), and 6 (R3)] have been synthesized by a reaction between copper(ii) chloride and the corresponding ligand. The complexes have been characterized by UV-vis and IR spectroscopy, and their structures have been determined by X-ray analysis. The antiproliferative potential of copper(ii) complexes of 2,2[prime or minute]:6[prime or minute],2[prime or minute][prime or minute]-terpyridine and 2,6-di(thiazol-2-yl)pyridine derivatives towards human colorectal (HCT116) and ovarian (A2780) carcinoma as well as towards lung (A549) and breast adenocarcinoma (MCF7) cell lines was examined. Complex 1 and complex 6 were found to have the highest antiproliferative effect on A2780 ovarian carcinoma cells, particularly when compared with complex 2, 3 with no antiproliferative effect. The order of cytotoxicity in this cell line is 6 > 1 > 5 > 4 > 2 [approximate] 3. Complex 2 seems to be much more specific towards colorectal carcinoma HCT116 and lung adenocarcinoma A549 cells. The viability loss induced by the complexes agrees with Hoechst 33258 staining and typical morphological apoptotic characteristics like chromatin condensation and nuclear fragmentation. The specificity towards different types of cell lines and the low cytotoxic activity towards healthy cells are of particular interest and are a positive feature for further developments. Complexes 1-6 were also tested in the oxidation of alkanes and alcohols with hydrogen peroxide and tert-butyl-hydroperoxide (TBHP). The most active catalyst 4 gave, after 120 min, 0.105 M of cyclohexanol + cyclohexanone after reduction with PPh3. This concentration corresponds to a yield of 23% and TON = 210. Oxidation of cis-1,2-dimethylcyclohexane with m-CPBA catalyzed by 4 in the presence of HNO3 gave a product of a stereoselective reaction (trans/cis = 0.47). Oxidation of secondary alcohols afforded the target ketones in yields up to 98% and TON = 630.