Post-Synthetic Modification of a Porous Hydrocarbon Cage to Give a Discrete C024 Organometallic Complex**

First published: 21 July 2022A new alkyne-based hydrocarbon cage was synthesized in high overall yield using alkyne-alkyne coupling in the cage forming step. The cage is porous and displays a moderately high BET surface area (546 m2 g−1). The cage loses crystallinity on activation and thus is porous in its amorphous form, while very similar cages have been either non-porous, or retained crystallinity on activation. Reaction of the cage with Co2(CO)8 results in exhaustive metalation of its 12 alkyne groups to give the Co24(CO)72 adduct of the cage in good yield.Chriso M. Thomas, Weibin Liang, Dan Preston, Christian J. Doonan, and Nicholas G. Whit

Pseudomonas expression of an oxygen sensing prolyl hydroxylase homologue regulates neutrophil host responses in vitro and in vivo

Background: Pseudomonas species are adapted to evade innate immune responses and can persist at sites of relative tissue hypoxia, including the mucus-plugged airways of patients with cystic fibrosis and bronchiectasis. The ability of these bacteria to directly sense and respond to changes in local oxygen availability is in part consequent upon expression of the 2-oxoglutarate oxygenase, Pseudomonas prolyl hydroxylase (PPHD), which acts on elongation factor Tu (EF-Tu), and is homologous with the human hypoxia inducible factor (HIF) prolyl hydroxylases. We report that PPHD expression regulates the neutrophil response to acute pseudomonal infection. Methods: In vitro co-culture experiments were performed with human neutrophils and PPHD-deficient and wild-type bacteria and supernatants, with viable neutrophil counts determined by flow cytometry. In vivo consequences of infection with PPHD deficient P. aeruginosa were determined in an acute pneumonia mouse model following intra-tracheal challenge. Results: Supernatants of PPHD-deficient bacterial cultures contained higher concentrations of the phenazine exotoxin pyocyanin and induced greater acceleration of neutrophil apoptosis than wild-type PAO1 supernatants in vitro. In vivo infection with PPHD mutants compared to wild-type PAO1 controls resulted in increased levels of neutrophil apoptosis and impaired control of infection, with higher numbers of P. aeruginosa recovered from the lungs of mice infected with the PPHD-deficient strain. This resulted in an overall increase in mortality in mice infected with the PPHD-deficient strain. Conclusions: Our data show that Pseudomonas expression of its prolyl hydroxylase influences the outcome of host-pathogen interactions in vitro and in vivo, demonstrating the importance of considering how both host and pathogen adaptations to hypoxia together define outcomes of infection. Given that inhibitors for the HIF prolyl hydroxylases are in late stage trials for the treatment of anaemia and that the active sites of PPHD and human HIF prolyl hydroxylases are closely related, the results are of current clinical interest

Correlation inequalities for classical and quantum XY models

We review correlation inequalities of truncated functions for the classical and quantum XY models. A consequence is that the critical temperature of the XY model is necessarily smaller than that of the Ising model, in both the classical and quantum cases. We also discuss an explicit lower bound on the critical temperature of the quantum XY model.Comment: 13 pages. Submitted to the volume "Advances in Quantum Mechanics: contemporary trends and open problems" of the INdAM-Springer series, proceedings of the INdAM meeting "Contemporary Trends in the Mathematics of Quantum Mechanics" (4-8 July 2016) organised by G. Dell'Antonio and A. Michelangel

Quantifying the impact of microbes on soil structural development and behaviour in wet soils

There is evidence that microbial populations play an important role in altering soil pore geometry, but a full understanding of how this affects subsequent soil behaviour and function is still unclear. In particular the role of microorganisms in soil structural evolution and its consequence for pore morphological development is lacking. Using a combination of bio-chemical measurements and X-ray Computed Tomography (CT) imaging, a temporal comparison of microscale soil structural development in contrasting soil environments was made. The aim was to quantify the effect of microbial activity in the absence of other features likely to cause soil deformation (e.g. earthworms, roots etc.) on soil structural development in wet soils, defined by changes in the soil porous architecture i.e. pore connectivity, pore shape and pore volume during a 24 week period. Three contrasting soil textures were examined and changes compared between field soil, sterilised soil and a glucose enhanced soil treatment. Our results indicate that soil biota can significantly alter their microhabitat by changing soil pore geometry and connectivity, primarily through localised gaseous release. This demonstrates the ability of microorganisms to modify soil structure, and may help reveal the scope by which the microbial-rich rhizosphere can locally influence water and nutrient delivery to plant roots

Sustainability, certification, and regulation of biochar

Biochar has a relatively long half-life in soil and can fundamentally alter soil properties, processes, and ecosystem services. The prospect of global-scale biochar application to soils highlights the importance of a sophisticated and rigorous certification procedure. The objective of this work was to discuss the concept of integrating biochar properties with environmental and socioeconomic factors, in a sustainable biochar certification procedure that optimizes complementarity and compatibility between these factors over relevant time periods. Biochar effects and behavior should also be modelled at temporal scales similar to its expected functional lifetime in soils. Finally, when existing soil data are insufficient, soil sampling and analysis procedures need to be described as part of a biochar certification procedure.O “biochar” tem um tempo de meia-vida no solo relativamente longo e pode alterar substancialmente as propriedades, processos e funções do solo. A perspectiva da aplicação de “biochar” aos solos, em escala global, evidencia a importância de se lhe atribuir um processo de certificação sofisticado e rigoroso. O objetivo deste trabalho foi discutir o conceito da integração das propriedades do “biochar” com os fatores ambientais e socioeconômicos relevantes do local de aplicação selecionado, como parte de um procedimento de certificação sustentável que otimize a complementaridade e a compatibilidade entre esses fatores, em períodos de tempo relevantes. Os efeitos e o comportamento do “biochar” devem, também, ser modelados em escalas temporais similares às de seu tempo de vida funcional nos solos do local selecionado. Finalmente, onde os dados existentes sobre as características do solo forem insuficientes, procedimentos de amostragem e análise do solo devem ser descritos como parte do procedimento de certificação do “biochar”.publishe

Modification of alumina matrices through chemical etching and electroless deposition of nano-Au array for amperometric sensing

Simple nanoporous alumina matrix modification procedure, in which the electrically highly insulating alumina barrier layer at the bottom of the pores is replaced with the conductive layer of the gold beds, was described. This modification makes possible the direct electron exchange between the underlying aluminum support and the redox species encapsulated in the alumina pores, thus, providing the generic platform for the nanoporous alumina sensors (biosensors) with the direct amperometric signal readout fabrication

The Science of Sungrazers, Sunskirters, and Other Near-Sun Comets

This review addresses our current understanding of comets that venture close to the Sun, and are hence exposed to much more extreme conditions than comets that are typically studied from Earth. The extreme solar heating and plasma environments that these objects encounter change many aspects of their behaviour, thus yielding valuable information on both the comets themselves that complements other data we have on primitive solar system bodies, as well as on the near-solar environment which they traverse. We propose clear definitions for these comets: We use the term near-Sun comets to encompass all objects that pass sunward of the perihelion distance of planet Mercury (0.307 AU). Sunskirters are defined as objects that pass within 33 solar radii of the Sun’s centre, equal to half of Mercury’s perihelion distance, and the commonly-used phrase sungrazers to be objects that reach perihelion within 3.45 solar radii, i.e. the fluid Roche limit. Finally, comets with orbits that intersect the solar photosphere are termed sundivers. We summarize past studies of these objects, as well as the instruments and facilities used to study them, including space-based platforms that have led to a recent revolution in the quantity and quality of relevant observations. Relevant comet populations are described, including the Kreutz, Marsden, Kracht, and Meyer groups, near-Sun asteroids, and a brief discussion of their origins. The importance of light curves and the clues they provide on cometary composition are emphasized, together with what information has been gleaned about nucleus parameters, including the sizes and masses of objects and their families, and their tensile strengths. The physical processes occurring at these objects are considered in some detail, including the disruption of nuclei, sublimation, and ionisation, and we consider the mass, momentum, and energy loss of comets in the corona and those that venture to lower altitudes. The different components of comae and tails are described, including dust, neutral and ionised gases, their chemical reactions, and their contributions to the near-Sun environment. Comet-solar wind interactions are discussed, including the use of comets as probes of solar wind and coronal conditions in their vicinities. We address the relevance of work on comets near the Sun to similar objects orbiting other stars, and conclude with a discussion of future directions for the field and the planned ground- and space-based facilities that will allow us to address those science topics

Horizontal Branch Stars: The Interplay between Observations and Theory, and Insights into the Formation of the Galaxy

We review HB stars in a broad astrophysical context, including both variable and non-variable stars. A reassessment of the Oosterhoff dichotomy is presented, which provides unprecedented detail regarding its origin and systematics. We show that the Oosterhoff dichotomy and the distribution of globular clusters (GCs) in the HB morphology-metallicity plane both exclude, with high statistical significance, the possibility that the Galactic halo may have formed from the accretion of dwarf galaxies resembling present-day Milky Way satellites such as Fornax, Sagittarius, and the LMC. A rediscussion of the second-parameter problem is presented. A technique is proposed to estimate the HB types of extragalactic GCs on the basis of integrated far-UV photometry. The relationship between the absolute V magnitude of the HB at the RR Lyrae level and metallicity, as obtained on the basis of trigonometric parallax measurements for the star RR Lyrae, is also revisited, giving a distance modulus to the LMC of (m-M)_0 = 18.44+/-0.11. RR Lyrae period change rates are studied. Finally, the conductive opacities used in evolutionary calculations of low-mass stars are investigated. [ABRIDGED]Comment: 56 pages, 22 figures. Invited review, to appear in Astrophysics and Space Scienc

Study of doubly strange systems using stored antiprotons

Bound nuclear systems with two units of strangeness are still poorly known despite their importance for many strong interaction phenomena. Stored antiprotons beams in the GeV range represent an unparalleled factory for various hyperon-antihyperon pairs. Their outstanding large production probability in antiproton collisions will open the floodgates for a series of new studies of systems which contain two or even more units of strangeness at the P‾ANDA experiment at FAIR. For the first time, high resolution γ-spectroscopy of doubly strange ΛΛ-hypernuclei will be performed, thus complementing measurements of ground state decays of ΛΛ-hypernuclei at J-PARC or possible decays of particle unstable hypernuclei in heavy ion reactions. High resolution spectroscopy of multistrange Ξ−-atoms will be feasible and even the production of Ω−-atoms will be within reach. The latter might open the door to the |S|=3 world in strangeness nuclear physics, by the study of the hadronic Ω−-nucleus interaction. For the first time it will be possible to study the behavior of Ξ‾+ in nuclear systems under well controlled conditions