Structures and electronic absorption spectra of a recently synthesised class of photodynamic therapy agents

A theoretical study was performed on a novel class of boron-containing molecules (various substituted tetraarylazadipyrromethenes), which show in vitro activity for application in photodynamic therapy. Geometric optimisation of the structures for the singlet and triplet electronic states was carried out on compounds in vacuo at the density functional level of theory, by employing the PBE0 hybrid functional and the split-valence plus polarisation basis set. The absorbance properties in the UV-visible region were examined by means of time-dependent density functional response theory, using the same functional as mentioned above. To evaluate the influence of the solvent on the excitation energies, the continuum polarisable model was applied. Calculated electronic excitations, such as those regarding the Q-like band, were found to be in good agreement (within 0.01-0.1 eV) with experimental values and experimental trends on changing both the substituents and solvent.     

UV polymerization of self-assembled monolayers of a novel diacetylene on silver: a spectroscopic analysis by surface plasmon resonance and surface enhanced Raman scattering

UV polymerization of self-assembled monolayers of a novel carbazolyl-diacetylene (CDS9) chemisorbed on silver films was demonstrated by surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) experiments. SPR tests performed during UV exposure permitted one to observe the growth of the absorption coefficient, associated with the formation of the polymeric backbone. The Raman spectra of polymerized monolayers exhibited the bands associated with the C=C stretching modes of the conjugated backbone, typical of the blue and red polymeric phases usually present in polydiacetylenes, with a clear predominance of the red form. Moreover, the strong surface enhancement of the Raman band corresponding to the aromatic C=C stretching modes suggested that carbazolyl groups arrange nearly perpendicularly to the metal surface. In contrast, the absence of a SERS signal in the region of conjugated C[triple bond]C bond stretchings confirmed a polymerization scheme with conjugated triple bonds nearly parallel to the plane of the metal.     

Consistency of the intensional level of the Minimalist Foundation with Church’s thesis and axiom of choice

Consistency with the formal Church’s thesis, for short CT, and the axiom of choice, for short AC, was one of the requirements asked to be satisfied by the intensional level of a two-level foundation for constructive mathematics as proposed by Maietti and Sambin (in Crosilla, Schuster (eds) From sets and types to topology and analysis: practicable foundations for constructive mathematics, Oxford University Press, Oxford, 2005). Here we show that this is the case for the intensional level of the two-level Minimalist Foundation, for short MF, completed in 2009 by the second author. The intensional level of MF consists of an intensional type theory à la Martin-Löf, called mTT. The consistency of mTT with CT and AC is obtained by showing the consistency with the formal Church’s thesis of a fragment of intensional Martin-Löf’s type theory, called \(\mathbf{MLtt}_1\), where mTT can be easily interpreted. Then to show the consistency of \(\mathbf{MLtt}_1\) with CT we interpret it within Feferman’s predicative theory of non-iterative fixpoints \(\widehat{ID_1}\) by extending the well known Kleene’s realizability semantics of intuitionistic arithmetics so that CT is trivially validated. More in detail the fragment \(\mathbf{MLtt}_1\) we interpret consists of first order intensional Martin-Löf’s type theory with one universe and with explicit substitution rules in place of usual equality rules preserving type constructors (hence without the so called \(\xi \)-rule which is not valid in our realizability semantics). A key difficulty encountered in our interpretation was to use the right interpretation of lambda abstraction in the applicative structure of natural numbers in order to model all the equality rules of \(\mathbf{MLtt}_1\) correctly. In particular the universe of \(\mathbf{MLtt}_1\) is modelled by means of \(\widehat{ID_1}\)-fixpoints following a technique due first to Aczel and used by Feferman and Beeson.     

Electron Spin Resonance (ESR) Dating of Calcareous Fault Gouge of the Ushikubi Fault, Central Japan

The ages of fault events of active faults have been estimated using electron spin resonance (ESR) signals of siliceous gouges. This technique of ESR method is limited by obtaining only ages that are greater than tens of millennia. So this study focuses on developing a new technique of using calcareous gouges to gain an insight into the ages of latest seismogenic event within the Holocene. For the first time, signal B of the ESR method has been used to estimate the age of the Ushikubi fault from calcareous gouge. This technique proved reliable because the mean age (1.9 ka) obtained agrees with previous works on indirect age determination of latest fault events by utilizing radiocarbon dating in the study area. However, the result from the ESR technique showed an increase relative to the age of 1 ka that was obtained by the radiocarbon dating method. This disparity may be due to a high dose rate value of 50 Gy/h of artificial irradiation that was used to determine the equivalent dose (ED). Moreover, isochronal experiment revealed that the gouge did not comprise pure carbonates but consisted of a mixture of calcite and quartz grains. A younger age value would have been obtained if a lower artificial irradiation dose rate and a relatively pure carbonate fault gouge were used in the ED determination.     

Enzymatic Macrocyclization of 1,2,3‐Triazole Peptide Mimetics

The macrocyclization of linear peptides is very often accompanied by significant improvements in their stability and biological activity. Many strategies are available for their chemical macrocyclization, however, enzyme‐mediated methods remain of great interest in terms of synthetic utility. To date, known macrocyclization enzymes have been shown to be active on both peptide and protein substrates. Here we show that the macrocyclization enzyme of the cyanobactin family, PatGmac, is capable of macrocyclizing substrates with one, two, or three 1,4‐substituted 1,2,3‐triazole moieties. The introduction of non‐peptidic scaffolds into macrocycles is highly desirable in tuning the activity and physical properties of peptidic macrocycles. We have isolated and fully characterized nine non‐natural triazole‐containing cyclic peptides, a further ten molecules are also synthesized. PatGmac has now been shown to be an effective and versatile tool for the ring closure by peptide bond formation.     

Über die Koexistenz der Aluminium- und Eisen(III)-hydroxide und Oxide

Analysis of the IR spectra reveals that traces of aluminium ions reduce the amount of goethite phase in the products of ageing of amorphous ferric hydroxide. X-ray studies showed that the unit-cell parameters of the hematite decrease during ageing, this decrease ceasing at the composition 0,2 Al₂O₃· · 0,8 Fe₂O₃. Electron microscopic examination showed that the hematite grains are always larger in the presence of Al³⁺. Thermal analysis showed the hydrohematite formed in the presence of 0,03 mole of Al₂O₃ to be almost anhydrous.In the concentration range 0,2–0,5 mole Al₂O₃ the processes of ageing show a trend towards the formation of hydrohematite and bayerite, of which the latter could not exist alone at the high ageing temperature. The formation of bayerite is most favoured when the composition is exactly 0,5 Al₂O₃· · 0,5 Fe₂O₃, as is proved by IR spectra, X-ray diffraction patterns, differential thermal analysis and electron microscopy. Study of the products of thermal decomposition of such a sample shows that following the decomposition of bayerite no crystalline hydroxide or oxide of aluminium appears until the temperature reaches 900°.When Al³⁺ predominates in the mixturexAl(OH)_3/y Fe(OH)₃ and boehmite is formed, no ferriboehmite can be detected.

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