Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution

The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.     

Activation-analysis investigation of the behaviour of biological trace elements during wound healing: The roles of calcium and iron

Summary Instrumental neutron-activation analysis was used for the determination of Ca, Cr, Fe, Co, Ni, Zn, Mo, Ag, Sb, and Hg. Blood and tissue samples of 70 mg each were analysed and, from these, changes in the concentrations of calcium, iron, and zinc in affected tissue were established. In this article the results of the behaviour of calcium and iron are reported. The calcium concentration of the fracture haematoma blood (FHB) is about 20 times higher than that of arterial or venous blood (rabbits). The level and the change with time of the calcium concentration in FHB-deposits (rabbits) can be explained by the participation of calcium in the haemolysis of the erythrocytes of the FHB which has been injected for the formation of the deposits. The behaviour of the iron in the FHB-deposits is in agreement with this explanation. The change in calcium concentration in the crust of punch-hole wounds in the skin (rats) can be attributed to the mobilization of calcium for fibrin formation. As a reason for the level and the change with time of the iron concentration in the tissue in the area of fascia and muscle incision wounds (rabbits) the participation of iron in the formation of collagen is discussed. From comparison of the behavoiur of the iron in the FHB-deposits with that in the area of incision wounds it follows that iron enrichments in the area of a complication-free wound are not predominantly caused by a wound haematoma.

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Zusammenfassung Die Untersuchungen erfolgten mit Hilfe der instrumentellen Neutronenaktivierungsanalyse. Das Verfahren war für die Erfassung der Gehalte an Ca, Cr, Fe, Co, Ni, Zn, Mo, Ag, Sb und Hg ausgelegt. Es wurden Blut bzw. Gewebeproben von jeweils etwa 70 mg analysiert und dabei Änderungen der Calcium-, Eisen- und Zinkgehalte des betroffenen Gewebes festgestellt. In diesem Artikel wird über das Verhalten des Calciums und Eisens berichtet. Der Calciumgehalt des Frakturhämatombluts (FHB) ist etwa 20mal höher als der von arteriellem oder venösem Blut (Kaninchen). Höhe und zeitlicher Verlauf der Calciumgehalte von FHB-Depots (Kaninchen) lassen sich mit der Beteiligung des Calciums an der Hämolyse der Erythrozyten des FHB erklären, das zur Bildung der Depots injiziert wurde. Das Verhalten des Eisens in den FHB-Depots stimmt mit dieser Erklärung überein. Der Verlauf der Calciumgehalte des Schorfes von Hautstanzwunden (Ratten) kann auf die Mobilisierung von Calcium für die Fibrinbildung zurückgeführt werden. Als Ursache für Höhe und zeitlichen Verlauf der Eisengehalte des Gewebes im Bereich von Faszie- und Muskelschnittwunden (Kaninchen) wird die Beteiligung des Eisens an der Kollagenbildung diskutiert. Aus dem Vergleich des Verhaltens des Eisens in FHB-Depots und im Bereich von Schnittwunden folgt, daß die Eisenanreicherungen im Bereich einer komplikationslosen Schnittwunde nicht vorwiegend durch ein Wundhämatom bedingt sind.

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Auszug aus der Dissertation des Herrn Danilo Boani, Technische Universität München. This work was supported by the Bundesministerium für Forschung und Technologie and the Fonds der Chemischen Industrie, and the paper was presented at the International Symposium on Microchemical Techniques, Davos, May 1977.     

An Informational Theory of Counterfactuals

Backtracking counterfactuals are problem cases for the standard, similarity based, theories of counterfactuals e.g., Lewis (Noûs13.4, 455–476, 1979). These theories usually need to employ extra-assumptions to deal with those cases (e.g., Lewis’ “standard resolution of vagueness”). Hiddleston (Noûs 39(4), 632–657, 2005) proposes a causal theory of counterfactuals that, supposedly, deals well with backtracking. The main advantage of the causal theory is that it provides a unified account for backtracking and non-backtracking counterfactuals (no extra-assumption is needed). In this paper, I present a backtracking counterfactual that is a problem case for Hiddleston’s account. Then I propose an informational theory of counterfactuals, which deals well with this problem case while maintaining the main advantage of Hiddleston’s account (the unified account for backtracking and non-backtracking counterfactuals). In addition, the informational theory offers a general theory of backtracking that provides clues for the semantics and epistemology of counterfactuals. I propose that backtracking is reasonable when the (possibly non-actual) state of affairs expressed in the antecedent of a counterfactual transmits less information about an event in the past than the actual state of affairs.     

Method for Measurements of Terrestrial Ultraviolet Radiation on Inclined Surfaces in Personal Dosimetry Field Studies

Understanding personal ultraviolet radiation (UVR) exposure is essential for the evaluation of the health risks and benefits; however, personal dosimetry could be challenging in large‐scale or/and long‐term population studies. Alternatively, personal exposure could be simulated using three‐dimensional models and lifestyle surveys together with data on a body position with respect to the sun. These models require a real‐time input on local environmental UVR. The main challenge in using this method is retrieval of the diffuse irradiance as it requires an often‐expensive tracking of solar position. In this study, a hypothesis that UVR measured on a vertical plane in the north direction can be used in the UK as a proxy for diffuse radiation was tested against direct measurements and compared with models based on solar tracker data in Chilton, UK, (51.57°N) in June–July 2018. The statistical analysis over 17 days under all weather conditions showed that for 45° and 90° tilted surfaces the proposed method performed as well as the best of the models based on solar tracker data. A proposed system could offer a portable and low‐cost alternative to measurements of diffuse radiation by solar tracking radiometers for spatial distribution of terrestrial erythema effective UVR in population field studies.     

Strukturelle Untersuchungen einiger neutraler Komplexe des zweiwertigen Molybdäns

Unit cell parameters have been calculated from x-ray powder diffraction data of Mo₂Br₄ Py ₄ (A), Mo₂I₄ Py ₄ (B), Mo₂I₄ Pic ₄ (C), Mo₂(SCN)₄ Py ₄ (D) and Mo₂(SCN)₄ Pic ₄ (E), A, B and C crystallize tetragonal. A witha=9,4₂,c=15,O₂ Å; B witha=9,4₆,c=14,9₈ Å and C witha=9,6₆ andc=15,7₂ Å D and E crystallize orthorhombic. D witha=10,0₉,b=9,1₄,c=15,0₈ Å; E witha=10,2₂,b=9,4₁ andc=15,1₅ Å.Py=pyridine,Pic=4-methylpyridine.

     

Periodic and Non-Periodic Oscillations of a Class of Hysteretic Two Degree of Freedom Systems

The equations governing the response of hysteretic systems to sinusoidal forces, which are memory dependent in the classical phase space, can be given as a vector field over a suitable phase space with increased dimension. Hence, the stationary response can be studied with the aids of classical tools of nonlinear dynamics, as for example the Poincaré map. The particular system studied in the paper, based on hysteretic Masing rules, allows the reduction of the dimension of the phase space and the implementation of efficient algorithms. The paper summarises results on one degree of freedom systems and concentrates on a two degree of freedom system as the prototype of many degree of freedom systems. This system has been chosen to be in 1:3 internal resonance situation. Depending on the energy dissipation of the elements restoring force, the response may be more or less complex. The periodic response, described by frequency response curves for various levels of excitation intensity, is highly complex. The coupling produces a strong modification of the response around the first mode resonance, whereas it is negligible around the second mode. Quasi-periodic motion starts bifurcating for sufficiently high values of the excitation intensity; windows of periodic motions are embedded in the dominion of the quasi-periodic motion, as consequence of a locking frequency phenomenon.     

Computer simulations study of biomolecules in non-aqueous or cosolvent/water mixture solutions

Pure organic solvents or mixtures with water are very common environments for studying protein and peptide in solution. These milieu conditions are used either for improving the catalytic performance of enzymes or for studying the effect of solvent on the protein stability and hence gaining insight into the protein folding mechanism. The atomic details of these processes are mainly addressed using computer simulation approaches. In particular, Molecular Dynamics simulation represents the most powerful and versatile tool to investigate the details of solvation processes at atomic level. In the last few years, the number of publications peptide and protein simulations in non-natural environments has proliferated. These studies are providing important contributions to shed light on the nature of non-aqueous solvent effects. In this review, the achievements and the future prospects in this field of computational biochemistry are reviewed by summarizing the most important theoretical results published in the last 10 years.     

On finite groups with automorphisms whose fixed points are Engel

The main result of the paper is the following theorem. Let q be a prime, n a positive integer, and A an elementary abelian group of order q². Suppose that A acts coprimely on a finite group G and assume that for each \({a \in A^{\#}}\) every element of C_G(a) is n-Engel in G. Then the group G is k-Engel for some \({\{n,q\}}\)-bounded number k.