Tailoring the visible light photoactivity of un-doped defective TiO2 anatase nanoparticles through a simple two-step solvothermal process.

Anatase TiO2 has become a material of great interest for photocatalytic production of hydrogen, environmental purification and solar energy conversion. Among the key parameters boosting the photocatalytic efficiency of the anatase nanoparticles, an increased light absorption to expand its optical response to the visible region, together with an improved charge separation of the photo-generated electrons and holes, can be enumerated. In this work, yellow-coloured, single-phase anatase nanoparticles have been obtained using a simple two-step solvothermal routine which requires no external addition of dopants, nor the use of a harassing/aggressive synthesis atmosphere. The obtained powders display a lowered bandgap (<3.0 eV) and significantly reduce the recombination processes, eventually leading to an improved photocatalytic performance under visible light, as exemplified by an enhanced degradation of phenol. This exceptional response is linked to the presence of intrinsic defects in the yellowish particles and, hence, the specific conditions of the proposed methodology become crucial to produce a propitious TiO2-defective nanomaterial capable of photo-degrade the phenol molecule, in contrast with the lack of photocatalytic activity currently exhibited by commercial photocatalysts under visible light.

[Grooming, Cyberbullying and Sexting in Chile according of sex and school management or administrative dependency]. / Grooming, Ciberbullying y Sexting en estudiantes en Chile según sexo y tipo de administración escolar.

INTRODUCTION: Children, teenagers and young men are increasingly experiencing their well-being related to the internet and the new digital technologies. The objective of this study is to describe the presence of Cyberbullying, Sexting and Grooming in students in Chile according to gender and type of school management or administrative dependency. SUBJECTS AND METHOD: Exploratory and descriptive study. The sample design was non-probabilistic by quotas in 60 transactional establish ments. The sample was weighted considering the age range and gender according to national data. The Digital Literacy Questionnaire "Divergente-SerDigital" (2010) was applied to a sample of 12,926 students, aged 5 to 18 years. 4,790 men and 8,136 women. Average age 13.17 years. Frequencies were analyzed and the Chi-squared contrast statistic was used to determine statistically significant differences. RESULTS: The item Total Grooming (cheating) is presented as the main risk, 12.6% in municipal dependent schools (MDS), 8.2% in subsidized private schools (SPS), and 8.4% in private schools (PS). When considering gender, Grooming is observed mainly in Men, 20.4% in MDS, 19.9% in SPS and, 16.9% in PS. It is noteworthy that Women perform less Cyberbullying (active) according to school administration with 4.2% in MDS, 2.4% in SPS and, 2.6% in PS, with statistically significant differences (p < 0.05) in relation to Men. It also highlights the indicator Sexting (send) in Men, higher in PS with 10.6%. CONCLUSION: Grooming, Cyberbullying and Sexting risks are presented in the three types of administration with specific characteristics. These data can be a guide to work in promotion and prevention as well as in the schematization of cases according to type of school administration.

Genetic variability and structure of jaguar (Panthera onca) in Mexican zoos.

Genealogical records of animals (studbook) are created to avoid reproduction between closely related individuals, which could cause inbreeding, particularly for such endangered species as the Panthera onca (Linnaeus, 1758). Jaguar is the largest felid in the Americas and is considered an important ecological key species. In Mexico, wild jaguar populations have been significantly reduced in recent decades, and population decline typically accompany decreases in genetic variation. There is no current census of captive jaguars in Mexico, and zoos do not follow a standardized protocol in breeding programs based on genetic studies. Here, we emphasise the importance of maintaining an adequate level of genetic variation and propose the implementation of standardised studbooks for jaguars in Mexico, mainly to avoid inbreeding. In addition, achieving the aims of studbook registration would provide a population genetic characterisation that could serve as a basis for ex situ conservation programmes.

Coexistence of sympatric carnivores in relatively homogeneous Mediterranean landscapes: functional importance of habitat segregation at the fine-scale level.

One of the main objectives of community ecology is to understand the conditions allowing species to coexist. However, few studies have investigated the role of fine-scale habitat use segregation in the functioning of guild communities in relatively homogeneous landscapes where opportunities for coexistence are likely to be the most restrictive. We investigate how the process of habitat use differentiation at the home range level according to the degree of specialism/generalism of species can lead to coexistence between guild species. We examine differences in fine-scale habitat use and niche separation as potential mechanisms explaining the coexistence of five sympatric carnivore species that differ in life history traits (Iberian lynx, Eurasian badger, Egyptian mongoose, common genet and red fox) by collecting data from systematic track censuses in a relatively homogeneous Mediterranean landscape. We found that a higher degree of specialism determines the segregation of species among the fine-scale ecological niche dimensions defined using quantitative elements associated with vegetation, landscape, prey availability and human disturbance. The species with the lowest total performance over the set of variables did not exhibit segregation in the use of habitat at this level. Our study indicates that in relatively homogeneous landscapes, there exist subtle patterns of habitat partitioning over small-scale gradients of habitat determinants as a function of the degree of specialism of carnivore species within a guild. Our results also suggest that coexistence between generalist species may be permitted by fine-scale spatial-temporal segregation of activity patterns or trophic resource consumption, but not fine-scale habitat use differentiation.

Revisiting food-based models of territoriality in solitary predators.

Food availability is considered a major factor determining spacing behaviour in territorial species, especially for females. Theoretically, spatial overlap (considered the opposite of territoriality) and food availability are related in a nonlinear manner (hypothesized inverted-U function), with high overlap levels at the extremes of a food availability gradient and low overlap at intermediate levels of this gradient. Similar patterns are expected for encounter frequencies owing to its expected correlation with spatial overlap. However, these predictions have rarely been tested in highly structured social systems on a broad gradient of food availability, which implicitly requires experimental manipulation. We test these predictions in a solitary, territorial and trophic specialist, the Iberian lynx Lynx pardinus, taking advantage of a three-decade data set of spatial behaviour in different scenarios of food availability (i.e. rabbit density). In contrast with expectations, home range overlap among resident females was low (median overlap index = 0.08, range 0-0.57) and core area overlap was nearly nil (median overlap index = 0, range 0-0.22) throughout the entire gradient of prey availability. Furthermore, spatial associations between pairs of females were negligible regardless marked variation in prey availability. Therefore, we did not find support for a model of flexible lynx territoriality driven by food availability. Our results suggest that the exclusive use of space in the Iberian lynx was not related to food. Lack of influence of prey availability on lynx territoriality may be adaptive to cope with the consequences of frequent drought-induced periods of prey scarcity or other disturbance typically affecting wild rabbit populations in Mediterranean environments. Thus, lynx would adopt an obstinate strategy of territoriality that consists in defending exclusive areas across a broad range of resource availability ensuring an exclusive access to the minimum amount of prey necessary for survival and eventually reproduction even during periods of prey scarcity. However, we found signs that territoriality was influenced by lynx density in a nonlinear fashion. Our results suggest the occurrence of population regulation through territoriality in this species.

Graphene oxide films as a novel tool for the modulation of myeloid-derived suppressor cell activity in the context of multiple sclerosis.

Despite the pharmacological arsenal approved for Multiple Sclerosis (MS), there are treatment-reluctant patients for whom cell therapy appears as the only therapeutic alternative. Myeloid-derived suppressor cells (MDSCs) are immature cells of the innate immunity able to control the immune response and to promote oligodendroglial differentiation in the MS animal model experimental autoimmune encephalomyelitis (EAE). However, when isolated and cultured for cell therapy purposes, MDSCs lose their beneficial immunomodulatory properties. To prevent this important drawback, culture devices need to be designed so that MDSCs maintain a state of immaturity and immunosuppressive function similar to that exerted in the donor organism. With this aim, we select graphene oxide (GO) as a promising candidate as it has been described as a biocompatible nanomaterial with the capacity to biologically modulate different cell types, yet its immunoactive potential has been poorly explored to date. In this work, we have fabricated GO films with two distintive redox and roughness properties and explore their impact in MDSC culture right after isolation. Our results show that MDSCs isolated from immune organs of EAE mice maintain an immature phenotype and highly immunosuppressive activity on T lymphocytes after being cultured on highly-reduced GO films (rGO200) compared to those grown on conventional glass coverslips. This immunomodulation effect is depleted when MDSCs are exposed to slightly rougher and more oxidized GO substrates (rGO90), in which cells experience a significant reduction in cell size associated with the activation of apoptosis. Taken together, the exposure of MDSCs to GO substrates with different redox state and roughness is presented as a good strategy to control MDSC activity in vitro. The versatility of GO nanomaterials in regards to the impact of their physico-chemical properties in immunomodulation opens the door to their selective therapeutic potential for pathologies where MDSCs need to be enhanced (MS) or inhibited (cancer).

Responses of a top and a meso predator and their prey to moon phases.

We compared movement patterns and rhythms of activity of a top predator, the Iberian lynx Lynx pardinus, a mesopredator, the red fox Vulpes vulpes, and their shared principal prey, the rabbit Oryctolagus cuniculus, in relation to moon phases. Because the three species are mostly nocturnal and crepuscular, we hypothesized that the shared prey would reduce its activity at most risky moon phases (i.e. during the brightest nights), but that fox, an intraguild prey of lynx, would avoid lynx activity peaks at the same time. Rabbits generally moved further from their core areas on darkest nights (i.e. new moon), using direct movements which minimize predation risk. Though rabbits responded to the increased predation risk by reducing their activity during the full moon, this response may require several days, and the moon effect we observed on the rabbits had, therefore, a temporal gap. Lynx activity patterns may be at least partially mirroring rabbit activity: around new moons, when rabbits moved furthest and were more active, lynxes reduced their travelling distances and their movements were concentrated in the core areas of their home ranges, which generally correspond to areas of high density of rabbits. Red foxes were more active during the darkest nights, when both the conditions for rabbit hunting were the best and lynxes moved less. On the one hand, foxes increased their activity when rabbits were further from their core areas and moved with more discrete displacements; on the other hand, fox activity in relation to the moon seemed to reduce dangerous encounters with its intraguild predator.

First Capture of a Jaguar Using a Minimally Invasive Capture System for GPS Tracking in an Isolated Patch of Atlantic Forest in Southern Brazil.

This study presents the first successful capture using GPS tagging of a jaguar (Panthera onca) using a minimally invasive capture system (MICS). We used snare-foot traps and a MICS during two capture campaigns in a fragment of Atlantic Forest in southeastern Brazil. The specimen disarmed snares on different occasions, and capture was only possible with the MICS. The captured jaguar, an estimated 16-year-old adult male, was monitored using a GPS Vertex Plus Iridium collar with an optimal performance of 86% in expected locations. The jaguar's home range (659 km2 by MPC and 174 km2 by 95%K) was within the observed range for the species and the animal was primarily maintained in protected areas. The habitat types most frequently used were native grassland (27.2% of 4798 fixes), marsh (24.8%), and dense lowland forest (24.7%). The use of a MICS for trapping jaguars is a promising technique that shows advantages in terms of efficiency, selectivity, portability, reduced potential risk of injury to animals or trappers, and animal stress compared to other capture methods used for the species.

Cubic Mesocrystal Magnetic Iron Oxide Nanoparticle Formation by Oriented Aggregation of Cubes in Organic Media: A Rational Design to Enhance the Magnetic Hyperthermia Efficiency.

Magnetic iron oxide mesocrystals have been reported to exhibit collective magnetic properties and consequently enhanced heating capabilities under alternating magnetic fields. However, there is no universal mechanism to fully explain the formation pathway that determines the particle diameter, crystal size, and shape of these mesocrystals and their evolution along with the reaction. In this work, we have analyzed the formation of cubic magnetic iron oxide mesocrystals by thermal decomposition in organic media. We have observed that a nonclassical pathway leads to mesocrystals via the attachment of crystallographically aligned primary cubic particles and grows through sintering with time to achieve a sizable single crystal. In this case, the solvent 1-octadecene and the surfactant agent biphenyl-4-carboxylic acid seem to be the key parameters to form cubic mesocrystals as intermediates of the reaction in the presence of oleic acid. Interestingly, the magnetic properties and hyperthermia efficiency of the aqueous suspensions strongly depend on the degree of aggregation of the cores forming the final particle. The highest saturation magnetization and specific absorption rate values were found for the less aggregated mesocrystals. Thus, these cubic magnetic iron oxide mesocrystals stand out as an excellent alternative for biomedical applications with their enhanced magnetic properties.

Epitaxial growth and characterization of SnSe phases on Au(111).

Two-dimensional (2D) layered group IV-VI semiconductors attract great interest due to their potential applications in nanoelectronics. Depending on the dimensionality, different phases of the same material can present completely different electronic and optical properties, expanding its applications. Here, we present a combined experimental and theoretical study of the atomic structure and electronic properties of epitaxial SnSe structures grown on a metallic Au(111) substrate, forming almost defect-free 2D layers. We describe a coverage-dependent transition from a metallicß-SnSe to a semiconductingα-SnSe phase. The combination of scanning tunneling microscopy/spectroscopy, non-contact atomic force microscopy, x-ray photoelectron spectroscopy/diffraction and angle-resolved photoemission spectroscopy, complemented by density functional theory, provides a comprehensive study of the geometric and electronic structure of both phases. Our work demonstrates the possibility to grow two distinct SnSe phases on Au(111) with high quality and on a large scale. The strong interaction with the substrate allows the stabilization of the previously experimentally unreportedß-SnSe, while the ultra-thin films of orthorhombicα-SnSe are structurally and electronically equivalent to bulk SnSe.

Dying like rabbits: general determinants of spatio-temporal variability in survival.

1. Identifying general patterns of how and why survival rates vary across space and time is necessary to truly understand population dynamics of a species. However, this is not an easy task given the complexity and interactions of processes involved, and the interpopulation differences in main survival determinants. 2. Here, using European rabbits (Oryctolagus cuniculus) as a model and information from local studies, we investigated whether we could make inferences about trends and drivers of survival of a species that are generalizable to large spatio-temporal scales. To do this, we first focused on overall survival and then examined cause-specific mortalities, mainly predation and diseases, which may lead to those patterns. 3. Our results show that within the large-scale variability in rabbit survival, there exist general patterns that are explained by the integration of factors previously known to be important at the local level (i.e. age, climate, diseases, predation or density dependence). We found that both inter- and intrastudy survival rates increased in magnitude and decreased in variability as rabbits grow old, although this tendency was less pronounced in populations with epidemic diseases. Some causes leading to these higher mortalities in young rabbits could be the stronger effect of rainfall at those ages, as well as, other death sources like malnutrition or infanticide. 4. Predation is also greater for newborns and juveniles, especially in population without diseases. Apart from the effect of diseases, predation patterns also depended on factors, such as, density, season, and type and density of predators. Finally, we observed that infectious diseases also showed general relationships with climate, breeding (i.e. new susceptible rabbits) and age, although the association type varied between myxomatosis and rabbit haemorrhagic disease. 5. In conclusion, large-scale patterns of spatio-temporal variability in rabbit survival emerge from the combination of different factors that interrelate both directly and through density dependence. This highlights the importance of performing more comprehensive studies to reveal combined effects and complex relationships that help us to better understand the mechanisms underlying population dynamics.

Possible extinction vortex for a population of Iberian lynx on the verge of extirpation.

Theory suggests that demographic and genetic traits deteriorate (i.e., fitness and genetic diversity decrease) when populations become small, and that such deterioration could precipitate positive feedback loops called extinction vortices. We examined whether demographic attributes and genetic traits have changed over time in one of the 2 remaining small populations of the highly endangered Iberian lynx (Lynx pardinus) in Doñana, Spain. From 1983 to 2008, we recorded nontraumatic mortality rates, litter size, offspring survival, age at territory acquisition, and sex ratio. We combined these demographic attributes with measures of inbreeding and genetic diversity at neutral loci (microsatellites) and genes subjected to selection (major histocompatibility complex). Data on demographic traits were obtained through capture and radio tracking, checking dens during breeding, track surveys, and camera trapping. For genetic analyses, we obtained blood or tissue samples from captured or necropsied individuals or from museum specimens. Over time a female-biased sex ratio developed, age of territory acquisition decreased, mean litter size decreased, and rates of nontraumatic mortality increased, but there were no significant changes in overall mortality rates, standardized individual heterozygosity declined steadily, and allelic diversity of exon 2 of class II major histocompatibility complex DRB genes remained constant (2 allelic variants present in all individuals analyzed). Changes in sex ratio and age of territory acquisition may have resulted from demographic stochasticity, whereas changes in litter size and nontraumatic mortality may be related to observed increases in inbreeding. Concomitant deterioration of both demographic attributes and genetic traits is consistent with an extinction vortex. The co-occurrence, with or without interaction, of demographic and genetic deterioration may explain the lack of success of conservation efforts with the Doñana population of Iberian lynx.

Assessment of the conservation efforts to prevent extinction of the Iberian lynx.

The Iberian lynx (Lynx pardinus) may be the first charismatic felid to become extinct in a high-income country, despite decades of study and much data that show extinction is highly probable. The International Union for Conservation of Nature categorizes it as critically endangered; about 200 free-ranging individuals remain in two populations in southern Spain. Conservation measures aimed at averting extirpation have been extensively undertaken with 4 of the former 10 Iberian lynx populations recorded 25 years ago. Two of the four populations have been extirpated. The number of individuals in the third population have declined by 83%, and in the fourth the probability of extirpation has increased from 34% to 95%. Major drivers of the pending extinction are the small areas to which conservation measures have been applied; lack of incorporation of evidence-based conservation, scientific monitoring, and adaptive management into conservation efforts; a lack of continuity in recovery efforts, and distrust by conservation agencies of scientific information. In contrast to situations in which conservation and economic objectives conflict, in the case of the Iberian lynx all stakeholders desire the species to be conserved.

The differential genetic signatures related to climatic landscapes for jaguars and pumas on a continental scale.

Modern and paleoclimate changes may have altered species dynamics by shifting species' niche suitability over space and time. We analyze whether the current genetic structure and isolation of the two large American felids, jaguar (Panthera onca) and puma (Puma concolor), are mediated by changes in climatic suitability and connection routes over modern and paleoclimatic landscapes. We estimate species distribution under 5 climatic landscapes (modern, Holocene, last maximum glaciations [LMG], average suitability, and climatic instability) and correlate them with individuals' genetic isolation through causal modeling on a resemblance matrix. Both species exhibit genetic isolation patterns correlated with LMG climatic suitability, suggesting that these areas may have worked as "allele refuges." However, the jaguar showed higher vulnerability to climate changes, responding to modern climatic suitability and connection routes, whereas the puma showed a continuous and gradual transition of genetic variation. Despite differential responsiveness to climate change, both species are subjected to the climatic effects on genetic configuration, which may make them susceptible to future climatic changes, since these are progressing faster and with higher intensity than changes in the paleoclimate. Thus, the effects of climatic changes should be considered in the design of conservation strategies to ensure evolutionary and demographic processes mediated by gene flow for both species.

Reproductive traits in captive and free-ranging males of the critically endangered Iberian lynx (Lynx pardinus).

The Iberian lynx (Lynx pardinus) is the most endangered felid in the world. Adequate genetic management of in situ and ex situ populations, and linkage between both, require knowledge on male reproductive biology and factors influencing it. We examined the influence of age, free-ranging versus captive conditions and seasonality on phenotypic, endocrine and semen traits, and links between reproductive traits and male fertility. Males had relatively small testes, produced low sperm numbers, a low proportion of normal sperm, and a high proportion of motile sperm. Young (2-year-old) males had lower testosterone levels, fewer sperm, and a lower proportion of motile and normal sperm than > or =4-year-old males. No major differences were found in semen traits before and after the mating season or between free-ranging and captive males, although the latter had better sperm motility. Males with larger relative testes weight and more sperm copulated more frequently, whereas males that produced more sperm with higher motility produced more cubs per female. In conclusion, small relative testes size and low sperm quality could indicate either low levels of sperm competition or high levels of inbreeding. Young males are probably subfertile; there is a slight trend for males in the captive breeding programme to have better semen quality than wild males, and males with higher sperm production are sexually more active and more fertile. These findings have major implications for decisions regarding which males should breed, provide samples for the genetic resource bank, or participate in programmes involving the use of assisted reproductive techniques.

Wireless Sensor Network deployment for monitoring wildlife passages.

Wireless Sensor Networks (WSNs) are being deployed in very diverse application scenarios, including rural and forest environments. In these particular contexts, specimen protection and conservation is a challenge, especially in natural reserves, dangerous locations or hot spots of these reserves (i.e., roads, railways, and other civil infrastructures). This paper proposes and studies a WSN based system for generic target (animal) tracking in the surrounding area of wildlife passages built to establish safe ways for animals to cross transportation infrastructures. In addition, it allows target identification through the use of video sensors connected to strategically deployed nodes. This deployment is designed on the basis of the IEEE 802.15.4 standard, but it increases the lifetime of the nodes through an appropriate scheduling. The system has been evaluated for the particular scenario of wildlife monitoring in passages across roads. For this purpose, different schemes have been simulated in order to find the most appropriate network operational parameters. Moreover, a novel prototype, provided with motion detector sensors, has also been developed and its design feasibility demonstrated. Original software modules providing new functionalities have been implemented and included in this prototype. Finally, main performance evaluation results of the whole system are presented and discussed in depth.

Shedding Light Onto the Nature of Iron Decorated Graphene and Graphite Oxide Nanohybrids for CO2 Conversion at Atmospheric Pressure.

We report on the design and testing of new graphite and graphene oxide-based extended π-conjugated synthetic scaffolds for applications in sustainable chemistry transformations. Nanoparticle-functionalised carbonaceous catalysts for new Fischer Tropsch and Reverse GasWater Shift (RGWS) transformations were prepared: functional graphene oxides emerged from graphite powders via an adapted Hummer's method and subsequently impregnated with uniform-sized nanoparticles. Then the resulting nanomaterials were imaged by TEM, SEM, EDX, AFM and characterised by IR, XPS and Raman spectroscopies prior to incorporation of Pd(II) promoters and further microscopic and spectroscopic analysis. Newly synthesised 2D and 3D layered nanostructures incorporating carbon-supported iron oxide nanoparticulate pre-catalysts were tested, upon hydrogen reduction in situ, for the conversion of CO2 to CO as well as for the selective formation of CH4 and longer chain hydrocarbons. The reduction reaction was also carried out and the catalytic species isolated and fully characterised. The catalytic activity of a graphene oxide-supported iron oxide pre-catalyst converted CO2 into hydrocarbons at different temperatures (305, 335, 370 and 405 °C), and its activity compared well with that of the analogues supported on graphite oxide, the 3-dimensional material precursor to the graphene oxide. Investigation into the use of graphene oxide as a framework for catalysis showed that it has promising activity with respect to reverse gas water shift (RWGS) reaction of CO2 to CO, even at the low levels of catalyst used and under the rather mild conditions employed at atmospheric pressure. Whilst the γ-Fe2O3 decorated graphene oxide-based pre-catalyst displays fairly constant activity up to 405 °C, it was found by GC-MS analysis to be unstable with respect to decomposition at higher temperatures. The addition of palladium as a promoter increased the activity of the iron functionalised graphite oxide in the RWGS. The activity of graphene oxide supported catalysts was found to be enhanced with respect to that of iron-functionalised graphite oxide with, or without palladium as a promoter, and comparable to that of Fe@carbon nanotube-based systems tested under analogous conditions. These results display a significant step forward for the catalytic activity estimations for the iron functionalised and rapidly processable and scalable graphene oxide. The hereby investigated phenomena are of particular relevance for the understanding of the intimate surface morphologies and the potential role of non-covalent interactions in the iron oxide-graphene oxide networks, which could inform the design of nano-materials with performance in future sustainable catalysis applications.

Improvement in Heavy Metal Removal from Wastewater Using an External Magnetic Inductor.

Magnetite nanoparticles (Fe3O4) of 12 ± 4 nm diameter are electrochemically synthesized for the adsorption and magnetic harvesting of Cr(VI) from contaminated simulated solutions. The removal of Cr(VI) from aqueous media follows pseudo-second-order kinetics. The adsorption efficiency is evaluated in three different scenarios. In standard conditions, i.e., at room temperature; in a thermal bath working at 60 °C, where the temperature could be considered homogeneous within the solution; and finally, under magnetic induction heating, while adjusting the frequency and magnetic field used to attain the same temperature as in the bath experiments. Two benefits of using a magnetic inductor are demonstrated. First, the removal efficiency is almost doubled in comparison to that of the room temperature experiments, and it is higher by 30% compared to that of the bath setup. At the same time as the adsorption occurs, a redox reaction occurs on the surface of the nanoparticles, and Cr(VI), the predominant species in the contaminated solution, is significantly reduced to Cr(III). Through X-ray photoelectron spectroscopy, it is shown that a greater reduction effect is achieved when working in induction conditions than at room temperature. This is the first time that this synergistic effect using magnetic induction heating has been demonstrated for heavy metal decontamination of wastewater.

Ultra-thin NaCl films as protective layers for graphene.

The ageing of graphene is an important issue that limits its technological applications. Capping layers are a good option for circumventing this problem. In this work, we propose the use of ultra-thin NaCl films as easily-removable protective layers. We have carried out a detailed characterization of the NaCl/graphene interface on metal substrates, namely Cu(111) and Ir(111), by means of complementary microscopy, electron diffraction and spectroscopic techniques. Interestingly, we show that NaCl neither interacts in a chemical way with graphene nor intercalates through it. We demonstrate that the NaCl film is stable under ambient conditions, protecting the graphene surface from oxidation. In addition, after removing the protective layer, graphene remains intact.

Directed Molecular Stacking for Engineered Fluorescent Three-Dimensional Reduced Graphene Oxide and Coronene Frameworks.

Three-dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene-like domains present in the in situ-formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free-base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso- and ß-positions were employed in turn to act as directing entities for the assembly of new graphene-based and foam-like frameworks and of their corresponding coronene-based hybrids. Investigations in the dispersed phase and in thin-film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi-empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the "molecular glue". Single crystal X-ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter-planar distance between the rGO, coronene or graphene sheets. The host-guest chemistry involves the porphyrins acting as guests held through π-π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π-conjugated molecules and materials and their π-stacks may be relevant towards selective separation membranes, water purification and biosensing applications.