Fast evaluation of the adsorption energy of organic molecules on metals via graph neural networks

Modeling in heterogeneous catalysis requires the extensive evaluation of the energy of molecules adsorbed on surfaces. This is done via density functional theory but for large organic molecules it requires enormous computational time, compromising the viability of the approach. Here we present GAME-Net, a graph neural network to quickly evaluate the adsorption energy. GAME-Net is trained on a well-balanced chemically diverse dataset with C1–4 molecules with functional groups including N, O, S and C6–10 aromatic rings. The model yields a mean absolute error of 0.18 eV on the test set and is 6 orders of magnitude faster than density functional theory. Applied to biomass and plastics (up to 30 heteroatoms), adsorption energies are predicted with a mean absolute error of 0.016 eV per atom. The framework represents a tool for the fast screening of catalytic materials, particularly for systems that cannot be simulated by traditional methods

Conformational polymorphic changes in the crystal structure of the chiral antiparasitic drug praziquantel and interactions with calcium carbonate

Praziquantel is an antiparasitic drug used for decades. Currently, the praziquantel commercial preparation is a racemic mixture, in which only the levo-enantiomer possesses anthelmintic activity. The knowledge of its properties in the solid state and other chemical-physical properties is necessary for improving its efficacy and applications. Drug solid dispersions were prepared with calcium carbonate at 1:5 drug to excipient weight ratio by solvent evaporation method. Then, the modification of the crystal structure of the racemic polymorph of praziquantel in presence of calcium carbonate has been studied by means of several analytical techniques (DSC,TGA, XRD, SEM, FTIR, Raman spectroscopy and chiral liquid chromatography). This study has been completed with atomistic calculations based on empirical interatomic force fields and quantum mechanics methods applied to the crystal structure of praziquantel and of intermolecular interactions. The results evidenced that calcium carbonate provoked a conformational change in the praziquantel molecule yielding the formation of different polymorphs of praziquantel crystal. These alterations were not observed replacing calcium carbonate with colloidal silica as excipient in the solid dispersion

Schwartz - Zippelov teorem i neke njegove primjene

U ovom radu izložen je rezultat poznat pod nazivom Schwartz - Zippelova lema ili Schwartz - Zippelov teorem. Tema rada pripada pretežno algebri, ali ima značajne primjene u drugim matematičkim područjima kao što je na primjer teorija algoritama, te kombinatorika. Rad se sastoji od tri poglavlja. U uvodu je ukratko opisana tema i cilj rada. Prvo poglavlje sadrži kratku povijest nastanka teorema, različite oblike rezultata pojedinih autora, te kratki opis pojmova korištenih u samom radu. Drugo poglavlje sastoji se od iskaza i dokaza Schwartz - Zippelovog teorema, a u trećem poglavlju izložene su neke primjene tog teorema na probleme koji se mogu svesti na testiranje jednakosti polinoma. Takvi su, primjerice, problem postojanja savršenog sparivanja u grafu i ispitivanje svojstva asocijativnosti u grupoidu. Uz svaku primjenu navedeni su i prikladni primjeri.In this diploma thesis we present the result usually called the Schwartz-Zippel lemma or the Schwartz-Zippel theorem. The nature of this theorem is basically algebraic, but it has significant applications in other areas of mathematics, such as the theory of algorithms and combinatorial theory. The thesis consists of three chapters. The main theme and objective are briefly described in the introduction. The first chapter contains a short history of the theorem’s origins, various forms of the main results by different authors and some comments of basic concepts related to this topic. The statement and a proof of the Schwartz-Zippel theorem are given in the second chapter, together with the general outline of its applications. The third and final chapter consists of some applications to problems which can be reduced to polynomial identity testing, including the existence of a perfect matching in a graph and testing of the associativity property in a groupoi

Ethanol induction of laccase depends on nitrogen conditions of Pycnoporus sanguineus

Background: Ethanol has been pointed out as a laccase inducer. However, there are controversial reports about its efficiencywith some fungi. In this study,we hypothesized that ethanol laccase induced in Pycnoporus sanguineus depends on nitrogen nutriment conditions. To prove this,we assessed laccase production in submerged cultures of P. sanguineus,with different nitrogen concentrations andwith, orwithout ethanol added in a factorial designed experiment. Results: In order to analyze the effects of factors on the response variables, a factorial ANOVA, and response-surface models were performed. It was found that the nitrogen source was the main factor that affected laccase production in P. sanguineus. The treatments with yeast extract (2 g/L) and ethanol (3 g/L) induced the highest laccase activity (31.01 \ub1 4.9 U/L), while the treatments with urea reached the lowest activity (less than 1.6 U/L). Ethanol had positive and synergic effects on laccase production, in accordance with the surface response model, as long as simple nitrogen sources (urea) were not available. Conclusions: We suggest that laccase in P. sanguineus is regulated by a catabolic nitrogen repressionmechanism; laccase activity is strongly inhibited by urea used as nitrogen source and it decreases when the amount of urea increases; contrarily, a synergic positive effect was observed between yeast extract and ethanol on laccase production

VALES VI: ISM enrichment in star-forming galaxies up to z∼\sim0.2 using 12^{12}CO(1-0), 13^{13}CO(1-0) and C18^{18}O(1-0) line luminosity ratios

We present Atacama Large Millimeter/sub-millimeter Array (ALMA) observations towards 27 low-redshift ($0.02< z<0.2$) star-forming galaxies taken from the Valpara\'iso ALMA/APEX Line Emission Survey (VALES). We perform stacking analyses of the $^{12}$CO($1-0$), $^{13}$CO($1-0$) and C$^{18}$O($1-0$) emission lines to explore the $L'$ ($^{12}$CO($1-0$))/$L'$($^{13}$CO($1-0$))) (hereafter $L'$($^{12}$CO)/$L'$($^{13}$CO)) and $L'$($^{13}$CO($1-0$))/$L'$(C$^{18}$O($1-0$)) (hereafter $L'$($^{13}$CO)/$L'$(C$^{18}$O) line luminosity ratio dependence as a function of different global galaxy parameters related to the star formation activity. The sample has far-IR luminosities $10^{10.1-11.9}$L$_{\odot}$ and stellar masses of $10^{9.8-10.9}$M$_{\odot}$ corresponding to typical star-forming and starburst galaxies at these redshifts. On average we find a $L'$($^{12}$CO)/$L'$($^{13}$CO) line luminosity ratio value of 16.1$\pm$2.5. Galaxies with evidences of possible merging activity tend to show higher $L'$($^{12}$CO)/$L'$($^{13}$CO) ratios by a factor of two, while variations of this order are also found in galaxy samples with higher star formation rates or star formation efficiencies. We also find an average $L'$($^{13}$CO)/$L'$(C$^{18}$O) line luminosity ratio of 2.5$\pm$0.6, which is in good agreement with those previously reported for starburst galaxies. We find that galaxy samples with high $L_{\text{IR}}$, SFR and SFE show low $L'$($^{13}$CO)/$L'$(C$^{18}$O) line luminosity ratios with high $L'$($^{12}$CO)/$L'$($^{13}$CO) line luminosity ratios, suggesting that these trends are produced by selective enrichment of massive stars in young starbursts.Comment: 16 pages, 10 figures to be published in MNRA

Synthesis of Densely Packaged, Ultrasmall Pt02Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature

The gram\u2010scale synthesis, stabilization, and characterization of well\u2010defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X\u2010ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal\u2013organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140\u2009\ub0C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal clusters in solids for technically easier, cheaper, and dramatically less\u2010dangerous industrial reactions

Mass calibration of distant SPT galaxy clusters through expanded weak-lensing follow-up observations with HST, VLT, & Gemini-South

Expanding from previous work, we present weak-lensing (WL) measurements for a total sample of 30 distant (zmedian = 0.93) massive galaxy clusters from the South Pole Telescope Sunyaev-Zel'dovich (SPT-SZ) Survey, measuring galaxy shapes in Hubble Space Telescope (HST) Advanced Camera for Surveys images. We remove cluster members and preferentially select z 73 1.4 background galaxies via V - I colour, employing deep photometry from VLT/FORS2 and Gemini-South/GMOS. We apply revised calibrations for the WL shape measurements and the source redshift distribution to estimate the cluster masses. In combination with earlier Magellan/Megacam results for lower-redshifts clusters, we infer refined constraints on the scaling relation between the SZ detection significance and the cluster mass, in particular regarding its redshift evolution. The mass scale inferred from the WL data is lower by a factor $0.76^{+0.10}_{-0.14}$ (at our pivot redshift z = 0.6) compared to what would be needed to reconcile a flat Planck \u3bd\u39bCDM cosmology (in which the sum of the neutrino masses is a free parameter) with the observed SPT-SZ cluster counts. In order to sensitively test the level of (dis-)agreement between SPT clusters and Planck, further expanded WL follow-up samples are needed

Cytotoxic Acetogenins from the Roots of Annona purpurea

Annona purpurea, known in Mexico as "cabeza de negro" or "ilama", belongs to the Annonaceae family. Its roots are employed in folk medicine in several regions of Mexico. Taking that information into account, a chemical and biological analysis of the components present in the roots of this species was proposed. Our results demonstrated that the dichloromethane (DCM) extract was exclusively constituted by a mixture of five new acetogenins named annopurpuricins A-E (1-5). These compounds have an aliphatic chain of 37 carbons with a terminal \u3b1,\u3b2 unsaturated \u3b3-lactone. Compounds 1 and 2 belong to the adjacent bis-THF (tetrahydrofuran) \u3b1-monohydroxylated type, while compounds 3 and 4 belong to the adjacent bis-THF \u3b1,\u3b1'-dihydroxylated type; only compound 5 possesses a bis-epoxide system. Complete structure analysis was carried out by spectroscopy and chemical methods. All compounds were evaluated for their antiproliferative activity on three human tumor cell lines (MSTO-211H, HeLa and HepG2). Compounds 1-4 inhibited significantly the growth of HeLa and HepG2 cells, showing GI50 values in the low/subnanomolar range, while 5 was completely ineffective under the tested conditions. The investigation of the mechanism of action responsible for cytotoxicity revealed for the most interesting compound 1 the ability to block the complex I activity on isolated rat liver mitochondria (RLM)

Corrigendum: Analysis of the common genetic component of large-vessel vasculitides through a meta-Immunochip strategy.

Giant cell arteritis (GCA) and Takayasu's arteritis (TAK) are major forms of large-vessel vasculitis (LVV) that share clinical features. To evaluate their genetic similarities, we analysed Immunochip genotyping data from 1,434 LVV patients and 3,814 unaffected controls. Genetic pleiotropy was also estimated. The HLA region harboured the main disease-specific associations. GCA was mostly associated with class II genes (HLA-DRB1/HLA-DQA1) whereas TAK was mostly associated with class I genes (HLA-B/MICA). Both the statistical significance and effect size of the HLA signals were considerably reduced in the cross-disease meta-analysis in comparison with the analysis of GCA and TAK separately. Consequently, no significant genetic correlation between these two diseases was observed when HLA variants were tested. Outside the HLA region, only one polymorphism located nearby the IL12B gene surpassed the study-wide significance threshold in the meta-analysis of the discovery datasets (rs755374, P\u2009=\u20097.54E-07; ORGCA\u2009=\u20091.19, ORTAK\u2009=\u20091.50). This marker was confirmed as novel GCA risk factor using four additional cohorts (PGCA\u2009=\u20095.52E-04, ORGCA\u2009=\u20091.16). Taken together, our results provide evidence of strong genetic differences between GCA and TAK in the HLA. Outside this region, common susceptibility factors were suggested, especially within the IL12B locus