The crystallization and electrical characterization of the semiconducting polymer poly(3‐hexylthiophene) (P3HT) on a single layer graphene sheet is reported. Grazing incidence X‐ray diffraction revealed that P3HT crystallizes with a mixture of face‐on and edge‐on lamellar orientations on graphene compared to mainly edge‐on on a silicon substrate. Moreover, whereas ultrathin (10 nm) P3HT films form well oriented face‐on and edge‐on lamellae, thicker (50 nm) films form a mosaic of lamellae oriented at different angles from the graphene substrate. This mosaic of crystallites with π–π stacking oriented homogeneously at various angles inside the film favors the creation of a continuous pathway of interconnected crystallites, and results in a strong enhancement in vertical charge transport and charge carrier mobility in the thicker P3HT film. These results provide a better understanding of polythiophene crystallization on graphene, and should help the design of more efficient graphene based organic devices by control of the crystallinity of the semiconducting film.

Swelling of Hummers graphene oxide (HGO) membranes in a set of progressively longer liquid alcohols (methanol to 1-nonanol) was studied using synchrotron radiation XRD after air ageing over prolonged periods of time.

BackgroundThe emerging relationship between microRNAs (miRNA) and viral-control is a topic of interest in the field of HIV. Host-genome might play an important role in the control of viremia. The aim of this study was to assess the specific miRNA profile that could contribute to the control of HIV replication in Elite ControllersResultsAfter adequate normalization, expression profile of 286 human miRNAs (hsa-miR) was evaluated in phytohaemagglutinin-stimulated PBMCs from 29 individuals classified in 4 groups: 8 elite controllers (EC; viral load <50 cp/ml without treatment), 8 viremic progressors (VP; VL>5000 cp/ml without treatment), 8 patients under antiretroviral treatment (ART; VL<200 cp/ml) and 5 uninfected individuals (HIV-) through TaqMan Array Human microRNA Cards v3.0. A differential expression pattern consisting of 23 miRNAs became significantly different when comparing EC and VP. Profiling analysis segregated the population in two different blocks: while EC and HIV- clustered together in the same block (EC/HIV-_block 1), VP and ART individuals clustered together in a second block (VP/ART_block 2). Two inversely expressed miRNA patterns were determined within those two blocks: a set of 4 miRNAs (hsa-miR-221, -27a, -27b and -29b) was up-expressed in EC/HIV-_block and down-expressed in VP/ART_block while 19 miRNAs were down-expressed in block 1 and up-expressed in block 2. Differential miRNAs were successfully validated through individual RT-qPCR assays.ConclusionsProfile in EC resembled HIV- and differentially clusters with VP and ART. Therefore, differential clustering does not rely on undetectable viremia.

Extremely defect graphene oxide (dGO) is proposed as an advanced sorbent for treatment of radioactive waste and contaminated natural waters. dGO prepared using a modified Hummers oxidation procedure, starting from reduced graphene oxide (rGO) as a precursor, shows significantly higher sorption of U(VI), Am(III), and Eu(III) than standard graphene oxides (GOs). Earlier studies revealed the mechanism of radionuclide sorption related to defects in GO sheets. Therefore, explosive thermal exfoliation of graphite oxide was used to prepare rGO with a large number of defects and holes. Defects and holes are additionally introduced by Hummers oxidation of rGO, thus providing an extremely defect-rich material. Analysis of characterization by XPS, TGA, and FTIR shows that dGO oxygen functionalization is predominantly related to defects, such as flake edges and edge atoms of holes, whereas standard GO exhibits oxygen functional groups mostly on the planar surface. The high abundance of defects in dGO results in a 15-fold increase in sorption capacity of U(VI) compared to that in standard Hummers GO. The improved sorption capacity of dGO is related to abundant carboxylic group attached hole edge atoms of GO flakes as revealed by synchrotron-based extended X-ray absorption fine structure (EXAFS) and high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy.

To exploit the full potential of hematite (α-FeO) as an efficient photoanode for water oxidation, the redox processes occurring at the FeO/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb states in Sb-doped FeO photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 10 vs 1.3 × 10 cm) and decreased photoanode/electrolyte charge transfer resistance (∼990 vs ∼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb can activate multiple Fe ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.

High-surface area activated graphene has a threedimensional porous structure that makes it difficult to prepare dispersions. Here we report a general approach that allows the preparatioon of stable water-based dispersions/inks at concentrations of ≲20 mg/mL based on activated graphene using environmentally friendly formulations. Simple drying of the dispersion on the substrate allows the preparation of electrodes that maintain the high specific surface area of the precursor material (∼1700 m 2 /g). The electrodes are flexible because of the structure that consists of micrometer-sized activated graphene grains interconnected by carbon nanotubes (CNTs). The electrodes prepared using activated graphene demonstrate performance superior to that of reduced graphene oxide in supercapacitors with KOH and TEA BF 4 /acetonitrile electrolytes providing specific capacitance values of 180 and 137 F/g, respectively, at a specific current of 1 A/g. The high surface area of activated graphene in combination with the good conductivity of CNTs allows an energy density of 35.6 Wh/kg and a power density of 42.2 kW/kg to be achieved. The activated graphene dispersions were prepared in liter amounts and are compatible with most industrial deposition methods.

Considering the growing use of cellulose in various applications, knowledge and understanding of its physical properties become increasingly important. Thermal conductivity is a key property, but its variation with porosity and density is unknown, and it is not known if such a variation is affected by fiber size and temperature. Here, we determine the relationships by measurements of the thermal conductivity of cellulose fibers (CFs) and cellulose nanofibers (CNFs) derived from commercial birch pulp as a function of pressure and temperature. The results show that the thermal conductivity varies relatively weakly with density (ρ sample = 1340–1560 kg m –3 ) and that its temperature dependence is independent of density, porosity, and fiber size for temperatures in the range 80–380 K. The universal temperature and density dependencies of the thermal conductivity of a random network of CNFs are described by a third-order polynomial function (SI-units): κ CNF = (0.0787 + 2.73 × 10 –3 · T – 7.6749 × 10 –6 · T 2 + 8.4637 × 10 –9 · T 3 )·(ρ sample /ρ 0 ) 2 , where ρ 0 = 1340 kg m –3 and κ CF = 1.065·κ CNF . Despite a relatively high degree of crystallinity, both CF and CNF samples show amorphous-like thermal conductivity, that is, it increases with increasing temperature. This appears to be due to the nano-sized elementary fibrils of cellulose, which explains that the thermal conductivity of CNFs and CFs shows identical behavior and differs by only ca. 6%. The nano-sized fibrils effectively limit the phonon mean free path to a few nanometers for heat conduction across fibers, and it is only significantly longer for highly directed heat conduction along fibers. This feature of cellulose makes it easier to apply in applications that require low thermal conductivity combined with high strength; the weak density dependence of the thermal conductivity is a particularly useful property when the material is subjected to high loads. The results for thermal conductivity also suggest that the crystalline structures of cellulose remain stable up to at least 0.7 GPa.

Spermatozoa contain a complex population of RNAs including messenger RNAs (mRNAs) and small RNAs such as microRNAs (miRNA). It has been reported that these RNAs can be used to understand the mechanisms by which toxicological exposure affects spermatogenesis. The aim of our study was to compare mRNA and miRNA profiles in spermatozoa from eight smokers and eight non-smokers, and search for potential relationships between mRNA and miRNA variation. All men were selected based on their answers to a standard toxic exposure questionnaire, and sperm parameters. Using mRNA and miRNA microarrays, we showed that mRNAs from 15 genes were differentially represented between smokers and non-smokers (p<0.01): five had higher levels and 10 lower levels in the smokers. For the microRNAs, 23 were differentially represented: 16 were higher and seven lower in the smokers (0.004≤p<0.01). Quantitative RT-PCR confirmed the lower levels in smokers compared to non-smokers for hsa-miR-296-5p, hsa-miR-3940, and hsa-miR-520d-3p. Moreover, we observed an inverse relationship between the levels of microRNAs and six potential target mRNAs (B3GAT3, HNRNPL, OASL, ODZ3, CNGB1, and PKD2). Our results indicate that alterations in the level of a small number of microRNAs in response to smoking may contribute to changes in mRNA expression in smokers. We conclude that large-scale analysis of spermatozoa RNAs can be used to help understand the mechanisms by which human spermatogenesis responds to toxic substances including those in tobacco smoke.