Uthrene, a radically new molecule?

We have studied uthrene with a large range of quantum chemical models. Uthrene is predicted to be naturally twisted and to possess a triplet ground state, making it the smallest non-planar polycyclic biradical that can be derived from graphene.The present work was carried out with support by the Portuguese ‘‘Fundação para a Ciência e a Tecnologia’’ through the program Ciência 2008 and project scope UID/CEC/00319/2013, as well as with resources from the project SeARCH (Services and Advanced Research Computing with HTC/HPC clusters) funded under contract CONC-REEQ/ 443/2005. A visiting scholarship and computer time from the HPC-EUROPA2 project is also gratefully acknowledged.Fundação para a Ciência e a Tecnologia (FCT

Diameter selective characterization of single-wall carbon nanotubes

A novel method is presented which allows the characterization of diameter selective phenomena in SWCNTs. It is based on the transformation of fullerene peapod materials into double-wall carbon nanotubes and studying the diameter distribution of the latter. The method is demonstrated for the diameter selective healing of nanotube defects and yield from C$_{70}$ peapod samples. Openings on small diameter nanotubes are closed first. The yield of very small diameter inner nanotubes from C$_{70}$ peapods is demonstrated. This challenges the theoretical models of inner nanotube formation. An anomalous absence of mid-diameter inner tubes is observed and explained by the suppressed amount of C$_{70}$ peapods due to the competition of the two almost equally stable standing and lying C$_{70}$ peapod configurations

Microencapsulation of herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives : an experimental and theoretical investigation

When a pesticide is released into the environment, most of it is lost before it reaches its target. An effective way to reduce environmental losses of pesticides is by using controlled release technology. Microencapsulation becomes a promising technique for the production of controlled release agricultural formulations. In this work, the microencapsulation of chlorophenoxy herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives was investigated. The phase solubility study showed that both native and β-CD derivatives increased the water solubility of the herbicide and inclusion complexes are formed in a stoichiometric ratio of 1:1. The stability constants describing the extent of formation of the complexes have been determined by phase solubility studies. 1H NMR experiments were also accomplished for the prepared solid systems and the data gathered confirm the formation of the inclusion complexes. 1H NMR data obtained for the MCPA/CDs complexes disclosed noticeable proton shift displacements for OCH2 group and H6 aromatic proton of MCPA provided clear evidence of inclusion complexation process, suggesting that the phenyl moiety of the herbicide was included in the hydrophobic cavity of CDs. Free energy molecular mechanics calculations confirm all these findings. The gathered results can be regarded as an essential step to the development of controlled release agricultural formulations containing herbicide MCPA.Fundação para a Ciência e a Tecnologia (FCT

Two high-performance alternatives to ZLIB scientific-data compression

ZLIB is used in diverse frameworks by the scientific community, both to reduce disk storage and to alleviate pressure on I/O. As it becomes a bottleneck on multi-core systems, higher throughput alternatives must be considered, exploring parallelism and/or more effective compression schemes. This work provides a comparative study of the ZLIB, LZ4 and FPC compressors (serial and parallel implementations), focusing on CR, bandwidth and speedup. LZ4 provides very high throughput (decompressing over 1GB/s versus 120MB/s for ZLIB) but its CR suffers a degradation of 5-10%. FPC also provides higher throughputs than ZLIB, but the CR varies a lot with the data. ZLIB and LZ4 can achieve almost linear speedups for some datasets, while current implementation of parallel FPC provides little if any performance gain. For the ROOT dataset, LZ4 was found to provide higher CR, scalability and lower memory consumption than FPC, thus emerging as a better alternative to ZLIB.This work is funded by National Funds through the FCT Fundacao para a Ciencia e a Tecnologia (Portuguese Foundation for Science and Technology) within project PEst-OE/EEI/UI0752/2014, UT Austin - Portugal FCT grant SFRH/ BD/47840/2008, and the resources from the project SeARCH funded under contract CONC- REEQ/443/2005. We would also like to thank Nuno Castro and Rafael Silva for their contributions

Thermoelectric properties of polypropylene carbon nanofiber melt-mixed composites: exploring the role of polymer on their Seebeck coefficient

The effect of polypropylene (PP) on the Seebeck coefficient (S) of carbon nanofibers (CNFs) in melt-extruded PP composites filled with up to 5 wt. % of CNFs was analyzed in this study. The as-received CNFs present an electrical conductivity of ~320 S m−1 and an interesting phenomenon of showing negative S-values of −5.5 μVK−1, with 10−2 µW/mK2 as the power factor (PF). In contrast, the PP/CNF composites with 5 wt. % of CNFs showed lower conductivities of ~50 S m−1, less negative S-values of −3.8 μVK−1, and a PF of 7 × 10−4 µW/mK2. In particular, the change in the Seebeck coefficient of the PP/CNF composites is explained by a slight electron donation from the outer layers of the CNFs to the PP molecules, which could reduce the S-values of the as-received CNFs. Our study indicates that even insulating polymers such as PP may have a quantifiable effect on the intrinsic Seebeck coefficient of carbon-based nanostructures, and this fact should also be taken into consideration to tailor conductive polymer composites with the desired thermoelectric (TE) properties.The authors affiliated with 2C2T acknowledge support from FCT-Foundation for Science and Technology within the scope of project UID/CTM/00264/2020. In addition, support through project IF/ A. J. Paleo et al. 00894/2015 and within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020 and access to the Navigator platform (LCA-UC) through the Advanced Computing Project CPCA/A2/2524/2020, financed by national funds through the Portuguese Foundation for Science and Technology I.P./ MCTES, is gratefully acknowledged

Thermoelectric properties of n-type poly (ether ether ketone)/carbon nanofiber melt-processed composites

The thermoelectric properties, at temperatures from 30 °C to 100 °C, of melt-processed poly(ether ether ketone) (PEEK) composites prepared with 10 wt.% of carbon nanofibers (CNFs) are discussed in this work. At 30 °C, the PEEK/CNF composites show an electrical conductivity (σ) of ~27 S m−1 and a Seebeck coefficient (S) of −3.4 μV K−1, which means that their majority charge carriers are electrons. The origin of this negative Seebeck is deduced because of the impurities present in the as-received CNFs, which may cause sharply varying and localized states at approximately 0.086 eV above the Fermi energy level (EF) of CNFs. Moreover, the lower S, in absolute value, found in PEEK/CNF composites, when compared with the S of as-received CNFs (−5.3 μV K−1), is attributed to a slight electron withdrawing from the external layers of CNFs by the PEEK matrix. At temperatures from 30 °C to 100 °C, the σ (T) of PEEK/CNF composites, in contrast to the σ (T) of as-received CNFs, shows a negative temperature effect, understood through the 3D variable-range hopping (VRH) model, as a thermally activated hopping mechanism across a random network of potential wells. Moreover, their nonlinear S (T) follows the same behavior reported before for polypropylene composites melt-processed with similar CNFs at the same interval of temperatures.A. J. Paleo gratefully acknowledges support from FCT-Foundation for Science and Technology by the project UID/CTM/00264/2021 of 2C2T under the COMPETE and FCT/MCTES (PIDDAC) cofinanced by FEDER through the PT2020 program and “plurianual” 2020–2023 Project UIDB/00264/2020. E. Muñoz acknowledges financial support from ANID Anillo ACT/192023 and Fondecyt No 1190361. M. Melle-Franco acknowledges support from the project IF/00894/2015 and within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC)

Engineering spin exchange in nonbipartite graphene zigzag edges

The rules that govern spin exchange interaction in pristine graphene nanostructures are constrained by the bipartite character of the lattice, so that the sign of the exchange is determined by whether magnetic moments are on the same sublattice or not. The synthesis of graphene ribbons with perfect zigzag edges and a fluoranthene group with a pentagon ring, a defect that breaks the bipartite nature of the honeycomb lattice, has been recently demonstrated. Here we address how the electronic and spin properties of these structures are modified by such defects, both for indirect exchange interactions as well as the emergent edge magnetism, studied both with density functional theory and mean-field Hubbard model calculations. In all instances we find that the local breakdown of the bipartite nature at the defect reverts the sign of the otherwise ferromagnetic correlations along the edge, introducing a locally antiferromagnetic intraedge coupling and, for narrow ribbons, also revert the antiferromagnetic interedge interactions that are normally found in pristine ribbons. Our findings show that these pentagon defects are a resource that permits us to engineer the spin exchange interactions in graphene-based nanostructures

Simple strategies for stable aqueous suspensions of carbon nanotubes

Carbon nanotubes (CNT) are attractive nanoparticles for biological applications due to their broad absorption of light in the UV-Vis-NIR, NIR photoluminescence, unique Raman signature, photothermal response, and large surface area for the covalent and non-covalent conjugation of contrast agents and drugs, DNA/RNA. However, pristine CNT are highly hydrophobic and not biocompatible, requiring functionalization with hydrophilic molecules in order to form stable aqueous suspensions. Here, simple functionalization methods of perylene bisimides and pyrene, to render these polyaromatic molecules amphiphilic, will be presented. Bolaamphiphilic perylene bisimides (PBI) were prepared by the reaction of perylenetetracarboxylic dianhydride with -amino acids in good yield, using a simple protocol and avoiding complex purification methods. [1] Pyrene was modified by nitration followed by amination, and further reacted with maleic anhydride yielding carboxylic acid-functionalized pyrene. The CNT aqueous suspensions were studied by absorption and emission spectroscopy. Theoretical calculations were used to support the experimental observations. The possibility of CNT double functionalization (covalent and non-covalent) will be discussed based on CNT solubility studies in surfactant aqueous solutions. Pristine and covalently functionalized CNT, at different functionalization yields, were compared. The CNT were functionalized by the 1,3-dipolar cycloaddition of azomethine ylides. [2] The ability of CNT to adsorb surfactant molecules was reduced by the covalent functionalization. Nevertheless, depending on the extent of covalent functionalization, a high concentration of CNT in water could be attained, in comparison to that of pristine CNT.Fundação para a Ciência e a Tecnologia (FCT

Effect of carbon nanotubes on methane production in pure cultures of methanogens and in a syntrophic co-culture

ICBM-3 - 3rd International Conference on Biogas MicrobiologyConductive materials have been reported to enhance methane production by anaerobic microbial communities from a wide diversity of substrates 1 . The mechanisms involved are far from being fully understood. Many studies suggest that these materials facilitate direct interspecies electron transfer (DIET) between electrogenic bacteria and methanogens and that this mechanism is even dominant over interspecies hydrogen and formate transfer 2,3. The effect of conductive materials in pure cultures of methanogens or in co-cultures of typical fatty acid-degrading syntrophs with methanogenic partners was never studied. In this work, the effect of carbon nanotubes (CNT) on the activity of pure cultures of Methanobacterium formicicum, Methanospirillum hungatei, Methanosarcina mazei and Methanosaeta concilii, and in the co-culture of Syntrophomonas wolfei and Methanospirillum hungatei was evaluated. The results showed that CNT affect methane production by methanogens. Initial methane production rate (MPR) increased 17 and 6 times when M. formicicum and M. hungatei were incubated with 5g·L-1 CNT, respectively. M. mazei and M. concilii‘ activities were higher when exposed to CNT concentrations of 0.1 to 1g·L-1 , but lower with 5g·L-1 . Increasing CNT concentrations resulted in more negative redox potentials, which correlated with the increased methanogenic activity. Remarkably, in the absence of a reducing agent, but in the presence of CNT, the MPR was higher than in incubations with reducing agent, while no growth was observed without reducing agent and without CNT. MPR from butyrate increased 1.5 fold in the presence of CNT (5g.L-1 ), showing a positive effect of CNT on the syntrophic coculture. Indications of DIET by the presence CNT were not obtained. Rather, CNT directly affects the activity of methanogens, which creates new opportunities to improve methane production from waste and wastewater in anaerobic digesters.info:eu-repo/semantics/publishedVersio

Stable hydrogenated graphene edge types: Normal and reconstructed Klein edges

Hydrogenated graphene edges are assumed to be either armchair, zigzag or a combination of the two. We show that the zigzag is not the most stable fully hydrogenated structure along the direction. Instead hydrogenated Klein and reconstructed Klein based edges are found to be energetically more favourable, with stabilities approaching that of armchair edges. These new structures "unify" graphene edge topology, the most stable flat hydrogenated graphene edges always consisting of pairwise bonded C2H4 edge groups, irrespective the edge orientation. When edge rippling is included, CH3 edge groups are most stable. These new fundamental hydrogen terminated edges have important implications for graphene edge imaging and spectroscopy, as well as mechanisms for graphene growth, nanotube cutting, and nanoribbon formation and behaviour.Fundação para a Ciência e a Tecnologia (FCT