Graphocrown—A Novel, Two-Dimensional Oxocarbon: A Theoretical Study

An innovative 2D-material, graphocrown, was designed and studied. Our graphocrown computations revealed a higher stability compared to previous materials studied with the same generalized C$_2$O formula. The energetic benefit of the graphocrown formation from benzenehexol was also evaluated. The structure and properties of graphocrowns with various layer arrangements were analysed and compared. In addition, the formation of potassium complexes with the new material was studied. It was found that graphocrown binds potassium better than 18-crown-6, and the intercalation of graphocrown with potassium is more favourable, compared to graphite. Finally, the band structure, as well as the mobility of the charge carriers in the graphocrown, were investigated

An Indacenopicene‐based Buckybowl Catcher for Recognition of Fullerenes

A novel buckybowl catcher with an extended π-surface has been synthesized via cross-coupling of two bowl shaped bromoindacenopicene moieties with a tolyl linker. The obtained catcher has been unambiguously characterized by 2D-NMR and mass spectrometry. DFT calculations indicate that the curved shape of the receptor moieties is favourable for binding fullerenes. Effective binding was confirmed for interactions with C$_{60}$ and C$_{70}$ utilizing NMR spectroscopy and isothermal titration calorimetry (ITC). The resulting binding values show a higher affinity of the catcher towards C$_{70}$ over C$_{60}$. The designed catcher demonstrated the fundamental possibility of creating sensors for spherical aromaticity

Disruptive Selection of Human Immunostimulatory and Immunosuppressive Genes Both Provokes and Prevents Rheumatoid Arthritis, Respectively, as a Self-Domestication Syndrome

Using our previously published Web service SNP_TATA_Comparator, we conducted a genome-wide study of single-nucleotide polymorphisms (SNPs) within core promoters of 68 human rheumatoid arthritis (RA)-related genes. Using 603 SNPs within 25 genes clinically associated with RA-comorbid disorders, we predicted 84 and 70 candidate SNP markers for overexpression and underexpression of these genes, respectively, among which 58 and 96 candidate SNP markers, respectively, can relieve and worsen RA as if there is a neutral drift toward susceptibility to RA. Similarly, we predicted natural selection toward susceptibility to RA for 8 immunostimulatory genes (e.g., IL9R) and 10 genes most often associated with RA (e.g., NPY). On the contrary, using 25 immunosuppressive genes, we predicted 70 and 109 candidate SNP markers aggravating and relieving RA, respectively (e.g., IL1R2 and TGFB2), suggesting that natural selection can simultaneously additionally yield resistance to RA. We concluded that disruptive natural selection of human immunostimulatory and immunosuppressive genes is concurrently elevating and reducing the risk of RA, respectively. So, we hypothesize that RA in human could be a self-domestication syndrome referring to evolution patterns in domestic animals. We tested this hypothesis by means of public RNA-Seq data on 1740 differentially expressed genes (DEGs) of pets vs. wild animals (e.g., dogs vs. wolves). The number of DEGs in the domestic animals corresponding to worsened RA condition in humans was significantly larger than that in the related wild animals (10 vs. 3). Moreover, much less DEGs in the domestic animals were accordant to relieved RA condition in humans than those in the wild animals (1 vs. 8 genes). This indicates that the anthropogenic environment, in contrast to a natural one, affects gene expression across the whole genome (e.g., immunostimulatory and immunosuppressive genes) in a manner that likely contributes to RA. The difference in gene numbers is statistically significant as confirmed by binomial distribution (p < 0.01), Pearson’s χ2 (p < 0.01), and Fisher’s exact test (p < 0.05). This allows us to propose RA as a candidate symptom within a self-domestication syndrome. Such syndrome might be considered as a human’s payment with health for the benefits received during evolution

Simultaneous retrieval of atmospheric CO_2 and light path modification from space-based spectroscopic observations of greenhouse gases: methodology and application to GOSAT measurements over TCCON sites

This paper presents an improved photon path length probability density function method that permits simultaneous retrievals of column-average greenhouse gas mole fractions and light path modifications through the atmosphere when processing high-resolution radiance spectra acquired from space. We primarily describe the methodology and retrieval setup and then apply them to the processing of spectra measured by the Greenhouse gases Observing SATellite (GOSAT). We have demonstrated substantial improvements of the data processing with simultaneous carbon dioxide and light path retrievals and reasonable agreement of the satellite-based retrievals against ground-based Fourier transform spectrometer measurements provided by the Total Carbon Column Observing Network (TCCON)

Study of the footprints of short-term variation in XCO₂ observed by TCCON sites using NIES and FLEXPART atmospheric transport models

The Total Carbon Column Observing Network (TCCON) is a network of ground-based Fourier Transform Spectrometers (FTS) that record near-infrared (NIR) spectra of the Sun. From these spectra, accurate and precise observations of CO2 column-averaged dry-air mole fraction (denoted XCO2) are retrieved. TCCON FTS observations have previously been used to validate satellite estimations of XCO2; however, our knowledge of the short-term spatial and temporal variations in XCO2 surrounding the TCCON sites is limited. In this work, we use the National Institute for Environmental Studies (NIES) Eulerian three-dimensional transport model and the FLEXPART (FLEXible PARTicle) Lagrangian Particle Dispersion Model (LPDM) to determine the footprints of short-term variations in XCO2 observed by operational, past, future, and possible TCCON sites. We propose a footprint-based method for the colocation of satellite and TCCON XCO2 observations, and estimate the performance of the method using the NIES model and five GOSAT XCO2 product datasets. Comparison of the proposed approach with a standard geographic method shows higher number of colocation points and average bias reduction up to 0.15 ppm for a subset of 16 stations for the period from January 2010 to January 2014. Case studies of the Darwin and La Réunion sites reveal that when the footprint area is rather curved, non-uniform and significantly different from a geographical rectangular area, the differences between these approaches are more noticeable. This emphasizes that the colocation is sensitive to local meteorological conditions and flux distributions

Rare Earth Elements Alter Redox Balance in Methylomicrobium alcaliphilum 20ZR

Background: Rare Earth Elements (REEs) control methanol utilization in both methane- and methanol-utilizing microbes. It has been established that the addition of REEs leads to the transcriptional repression of MxaFI-MeDH [a two-subunit methanol dehydrogenase (MeDH), calcium-dependent] and the activation of XoxF-MeDH (a one-subunit MeDH, lanthanum-dependent). Both enzymes are pyrroquinoline quinone-dependent alcohol dehydrogenases and show significant homology; however, they display different kinetic properties and substrate specificities. This study investigates the impact of the MxaFI to XoxF switch on the behavior of metabolic networks at a global scale.Results: In this study we investigated the steady-state growth of Methylomicrobium alcaliphilum 20ZR in media containing calcium (Ca) or lanthanum (La, a REE element). We found that cells supplemented with La show a higher growth rate compared to Ca-cultures; however, the efficiency of carbon conversion, estimated as biomass yield, is higher in cells grown with Ca. Three complementary global-omics approaches–RNA-seq transcriptomics, proteomics, and metabolomics–were applied to investigate the mechanisms of improved growth vs. carbon conversion. Cells grown with La showed the transcriptional activation of the xoxF gene, a homolog of the formaldehyde-activating enzyme (fae2), a putative transporter, genes for hemin-transport proteins, and nitrate reductase. In contrast, genes for mxaFI and associated cytochrome (mxaG) expression were downregulated. Proteomic profiling suggested additional adjustments of the metabolic network at the protein level, including carbon assimilation pathways, electron transport systems, and the tricarboxylic acid (TCA) cycle. Discord between gene expression and protein abundance changes points toward the possibility of post-transcriptional control of the related systems including key enzymes of the TCA cycle and a set of electron-transport carriers. Metabolomic data followed proteomics and showed the reduction of the ribulose-monophosphate (RuMP) pathway intermediates and the increase of the TCA cycle metabolites.Conclusion: Cells exposed to REEs display higher rates of growth but have lower carbon conversion efficiency compared to cells supplemented with Ca. The most plausible explanation for these physiological changes is an increased conversion of methanol into formate by XoxF-MeDH, which further stimulates methane oxidation but limits both the supply of reducing power and flux of formaldehyde into the RuMP pathway

Study of the footprints of short-term variation in XCO_2 observed by TCCON sites using NIES and FLEXPART atmospheric transport models

The Total Carbon Column Observing Network (TCCON) is a network of ground-based Fourier transform spectrometers (FTSs) that record near-infrared (NIR) spectra of the sun. From these spectra, accurate and precise observations of CO_2 column-averaged dry-air mole fractions (denoted XCO_2) are retrieved. TCCON FTS observations have previously been used to validate satellite estimations of XCO_2; however, our knowledge of the short-term spatial and temporal variations in XCO_2 surrounding the TCCON sites is limited. In this work, we use the National Institute for Environmental Studies (NIES) Eulerian three-dimensional transport model and the FLEXPART (FLEXible PARTicle dispersion model) Lagrangian particle dispersion model (LPDM) to determine the footprints of short-term variations in XCO_2 observed by operational, past, future and possible TCCON sites. We propose a footprint-based method for the collocation of satellite and TCCON XCO_2 observations and estimate the performance of the method using the NIES model and five GOSAT (Greenhouse Gases Observing Satellite) XCO_2 product data sets. Comparison of the proposed approach with a standard geographic method shows a higher number of collocation points and an average bias reduction up to 0.15 ppm for a subset of 16 stations for the period from January 2010 to January 2014. Case studies of the Darwin and Reunion Island sites reveal that when the footprint area is rather curved, non-uniform and significantly different from a geographical rectangular area, the differences between these approaches are more noticeable. This emphasises that the collocation is sensitive to local meteorological conditions and flux distributions

Testiranje pokrivenog kamatnog pariteta: slučaj HRK/EUR

Cilj ovog rada je uspostaviti vezu između terminske premije/diskonta i kamatnog diferencijala koristeći model pokrivenog kamatnog pariteta (CIRP). Model je izgrađen na pretpostavkama visoke mobilnosti kapitala, savršene supstitucije valuta i odsutnosti transakcijskih troškova. Postojanje pokrivenog kamatnog pariteta testirano je na podacima tečaja eura i kune za Hrvatsku u 2010. godini. Rezultati su potvrdili skoro savršeno važenje pokrivenog kamatnog pariteta u kratkom roku koristeći referentne kamatnjake ZIBOR i EURIBOR kao i odgovarajuće vrijednosti spot i forward HRK/EUR tečaja odgovarajuće ročnosti od 1, 3, 6, 9 i 12 mjeseci. Ekonometrijski test je proveden kako bi se procijenio nagib linije pokrivenog kamatnog pariteta. Rezultati su pokazali kako je empirijska vrijednost nagiba linije kamatnog pariteta gotovo identična očekivanoj vrijednosti koristeći teorijski model pokrivenog kamatnog pariteta. Zbog relativno uske zone kamatnog pariteta kratkoročne mogućnosti arbitraže su minimizirane kao i vjerojatnost ostvarenja nerizičnog profita