Topological analysis of the electron localisation function (ELF) applied to the electronic structure of oxaziridine: the nature of N-O bond

Topological analysis of the electron localisation function (ELF), natural bond orbital and Wiberg bond index calculations have been applied to study the electronic structure of the oxaziridine molecule with a special focus on the nitrogen-oxygen bond. The calculations have been performed at the DFT(B3LYP, CAM-B3LYP, ωB97XD, M06-L, M06-2X) and post-Hartree-Fock (CCSD(T) and CASSCF) computational levels with applied aug-cc-pVTZ basis set. Nature of N-O bonding has been characterised by two resonance forms, N+ O− and N−O+, owing to a very small population (< 0.60e) of the bonding basin V(N,O), localised in the ELF field for the N-O region. The importance of electron correlation effects for the description of the N-O bonding has been observed in the CASSCF calculations. The orbital description (Wiberg, NBO) differs from topological characterisation, indicating a single N-O bond

The nature of the T=T double bond (T = B, Al, Ga, In) in dialumene and its derivatives: topological study of the electron localization function (ELF)

The local electronic structure of the Al=Al bond was studied in dialumene and derivatives of dialumene in which the Al atoms were substituted by B, Ga, or In atoms. DFT calculations were performed using the B3LYP, B3PW91, PBE0, M06-L, and M06-2X functionals. Topological analysis of the electron localization function described the covalent bonds mentioned above using the disynaptic basins Vi=1,2(B,B), Vi=1,2(Al,Al), V(Ga,Ga), and Vi=1,2(In,In). The basin populations were smaller than 4 e, as expected for a double bond: B=B 2.97 e, Al=Al 3.44–3.5 e, Ga=Ga 3.58 e, and In=In 3.86 e. The Al=Al, Ga=Ga, and In=In bonds were found to be intermediate in character between single and double bonds. Topological analysis of the ρ(r) field for dialumene showed a non-nuclear attractor along the Al=Al bond, with a pseudoatom basin population of 0.937 e. NBO analysis suggested that a double bond occurred only in the molecules containing Al, Ga, or In atoms. The character of the Ga=Ga bond was observed to be strongly dependent on the effective core potential used in the calculations

Remote detection of past habitability at Mars-analogue hydrothermal alteration terrains using an ExoMars Panoramic Camera emulator

JKH is funded by a Birkbeck University of London Graduate Teaching Assistantship. CRC is funded by a Royal Society of Edinburgh Personal Research Fellowship co-funded by Marie Curie Actions. The Aberystwyth research leading to these results has been funded by the UK Space Agency, ExoMars Panoramic Camera (PanCam) Grant Nos. ST/G003114/1, ST/I002758/1, STL001454/1, and the UK Space Agency CREST2 PanCam-2020 research Grant No. ST/L00500X/1. Additional Aberystwyth funding has come from The European Community’s Seventh Framework Programme (FP7/2007-2013), Grant Agreement Nos. 21881 PRoVisG, 241523 PRoViScout, and Grant Agreement No. 312377 PRoViDE. PMG is funded by a UK Space Agency Aurora Fellowship (grants ST/J005215/1 and ST/L00254X/1).A major scientific goal of the European Space Agency’s ExoMars 2018 rover is to identify evidence of life within the martian rock record. Key to this objective is the remote detection of geological substrates that are indicative of past habitable environments, which will rely on visual (stereo wide-angle, and high resolution images) and multispectral (440–1000 nm) data produced by the Panoramic Camera (PanCam) instrument. We deployed a PanCam emulator at four hydrothermal sites in the Námafjall volcanic region of Iceland, a Mars-analogue hydrothermal alteration terrain. At these sites, sustained acidic–neutral aqueous interaction with basaltic substrates (crystalline and sedimentary) has produced phyllosilicate, ferric oxide, and sulfate-rich alteration soils, and secondary mineral deposits including gypsum veins and zeolite amygdales. PanCam emulator datasets from these sites were complemented with (i) NERC Airborne Research and Survey Facility aerial hyperspectral images of the study area; (ii) in situ reflectance spectroscopy (400–1000 nm) of PanCam spectral targets; (iii) laboratory X-ray Diffraction, and (iv) laboratory VNIR (350–2500 nm) spectroscopy of target samples to identify their bulk mineralogy and spectral properties. The mineral assemblages and palaeoenvironments characterised here are analogous to neutral–acidic alteration terrains on Mars, such as at Mawrth Vallis and Gusev Crater. Combined multispectral and High Resolution Camera datasets were found to be effective at capturing features of astrobiological importance, such as secondary gypsum and zeolite mineral veins, and phyllosilicate-rich substrates. Our field observations with the PanCam emulator also uncovered stray light problems which are most significant in the NIR wavelengths and investigations are being undertaken to ensure that the flight model PanCam cameras are not similarly affected.Publisher PDFPeer reviewe

The chemical compound 'Heatin' stimulates hypocotyl elongation and interferes with the Arabidopsis NIT1-subfamily of nitrilases

Temperature passively affects biological processes involved in plant growth. Therefore, it is challenging to study the dedicated temperature signalling pathways that orchestrate thermomorphogenesis, a suite of elongation growth-based adaptations that enhance leaf-cooling capacity. We screened a chemical library for compounds that restored hypocotyl elongation in the pif4-2-deficient mutant background at warm temperature conditions in Arabidopsis thaliana to identify modulators of thermomorphogenesis. The small aromatic compound 'Heatin', containing 1-iminomethyl-2-naphthol as a pharmacophore, was selected as an enhancer of elongation growth. We show that ARABIDOPSIS ALDEHYDE OXIDASES redundantly contribute to Heatin-mediated hypocotyl elongation. Following a chemical proteomics approach, the members of the NITRILASE1-subfamily of auxin biosynthesis enzymes were identified among the molecular targets of Heatin. Our data reveal that nitrilases are involved in promotion of hypocotyl elongation in response to high temperature and Heatin-mediated hypocotyl elongation requires the NITRILASE1-subfamily members, NIT1 and NIT2. Heatin inhibits NIT1-subfamily enzymatic activity in vitro and the application of Heatin accordingly results in the accumulation of NIT1-subfamily substrate indole-3-acetonitrile in vivo. However, levels of the NIT1-subfamily product, bioactive auxin (indole-3-acetic acid), were also significantly increased. It is likely that the stimulation of hypocotyl elongation by Heatin might be independent of its observed interaction with NITRILASE1-subfamily members. However, nitrilases may contribute to the Heatin response by stimulating indole-3-acetic acid biosynthesis in an indirect way. Heatin and its functional analogues present novel chemical entities for studying auxin biology

The nature and distribution of flowing features in a weakly karstified porous limestone aquifer

The nature and distribution of flowing features in boreholes in an area of approximately 400 km2 in a weakly karstic porous limestone aquifer (the Chalk) was investigated using single borehole dilution tests (SBDTs) and borehole imaging. One-hundred and twenty flowing features identified from SBDTs in 24 boreholes have densities which decrease from ∼0.3 m−1 near the water table to ∼0.07 m−1 at depths of more than 40 m below the water table; the average density is 0.20 m−1. There is some evidence of regional lithological control and borehole imaging of three boreholes indicated that most flowing features are associated with marls, hardgrounds and flints that may be developed at a more local scale. Borehole imaging also demonstrated that many flowing features are solutionally enlarged fractures, suggesting that even in carbonate aquifers where surface karst is developed on only a small scale, groundwater flow is still strongly influenced by dissolution. Fully connected solutional pathways can occur over 100s, sometimes 1000s of metres. However, conduits, tubules and fissures may not always be individually persistent along a flowpath, instead being connected together and also connected to unmodified fractures to create a relatively dense network of voids with variable apertures (15 cm). Groundwater therefore moves along flowpaths made up of voids with varying shape and character. Local solutional development of fractures at significant depths below the surface suggests that mixing corrosion and in situ sources of acidity may contribute to solutional enhancement of fractures. The study demonstrates that single borehole dilution testing is a useful method of obtaining a large dataset of flowing features at catchment-regional scales. The Chalk is a carbonate aquifer with small-scale surface karst development and this study raises the question of whether other carbonate aquifers with small-scale surface karst have similar characteristics, and what hydrological role small-scale dissolutional features play in highly karstic aquifers

Intersexuality in a crab-eating fox (Cerdocyon thous)

Intersexuality is a reproductive pathology that has been described in wild animals in recent years. However, its occurrence and consequences remain obscure and therefore all aspects of this reproductive disorder deserve attention. The aim of this study is to report a case of intersexuality with probable absence of gonadal tissue in the crab-eating fox (Cerdocyon thous) native to Brazil. The animal has male external genitalia, but its prepuce and penis were both hypoplastic. Because of a clinical suspicion of bilateral cryptorchidism, a laparotomy was performed and the absence of prostate and gonads were revealed. The procedure also revealed vas deferentia, extending laterally from the each side of the bladder basis to the right and left abdominal wall muscles. The animal died one month later, and post mortem examination confirmed the absence of prostatic and gonadal tissues. Muscular structures similar to uterine horns and cervix were founded macroscopically and confirmed by optic microscopy. In addition, post mortem findings corroborate with penis hypoplasia, since penile bone presence was observed. The vasa deferentia had a normal tissue structure, although hypoplastic. In conclusion, the case of a crab-eating fox (Cerdocyon thous) reported here represents a proved intersexual animal with probable absence of gonadal tissue.A intersexualidade é uma das patologias reprodutivas, hereditária e/ou congênita, que têm sido mais reportada em animais selvagens nos últimos anos. Entretanto, suas ocorrências e conseqüências permanecem obscuras, sendo que todos os aspectos relacionados a este distúrbio reprodutivo merecem atenção. O objetivo deste estudo foi relatar um caso de intersexualidade com provável ausência de tecido gonadal em uma raposa (Cerdocyon thous) do Brasil. O animal apresentava sexo fenotípico masculino, mas seu prepúcio e pênis eram pequenos. Devido a uma suspeita clínica de criptorquidismo bilateral, foi realizada uma laparotomia, sendo, no procedimento cirúrgico, revelada a ausência de próstata e gônadas. Os ductos deferentes foram localizados lateralmente à bexiga, entendendo-se desde a sua base, inserindo-se na musculatura da parede abdominal direita e esquerda. Um mês após, o animal morreu e os achados necroscópicos confirmaram a ausência de tecidos prostático e gonadal. Entretanto, uma estrutura muscular histologicamente semelhante a cornos e cérvix uterinos foram encontradas. Além disso, pelo mesmo método, ratificou-se a ausência de próstata e o pênis exibiu aspecto normal contendo osso peniano. Os ductos deferentes apresentaram estrutura tecidual normal, porém hipoplásicos. Concluiu-se que o caso reportado no presente trabalho representa um exemplo de intersexualidade com provável ausência de tecido gonadal em um animal da espécie Cerdocyon thous