Molecular structural features of unsymmetrical ortho analogs of POPOP

The electronic spectra and structures of sterically hindered molecules of unsymmetrical ortho-analogs of POPOP containing electron donor subsitituents in the oxadiazole part of the molecule have been studied (1-(5′-phenyloxazol-2-yl)-2-(5-phenyl-1,3,4-oxadiazol-2-yl)benzene derivatives (I)). X-Ray structural analysis was carried out on the dimethylamino derivative of I. It was found that the conformation of the molecules of the investigated compounds is determined by the conformation of the starting 2-(5-phenyloxazol-2-yl)benzoic acid and its acid chloride used in the synthesis of the ortho POPOP analogs. In the series of unsymmetrical ortho POPOP analogs there arises a unique possibility for changes in the structure of the oxadiazole part of the molecule to affect the position of the spectral emission almost without affecting the long wavelength absorption band in the process. There were thus prepared efficient organic luminophores having an anomalously large Stokes fluorescence shift. Kharkov State University, Kharkov 310077. Institutefor Monocrystals. National Academy of Sciences of Ukraine, Kharkov 310001. Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 11, pp. 1549–1558, November, 1997.     

Refined elliptic tropical enumerative invariants

We suggest a new refined (i.e., depending on a parameter) tropical enumerative invariant of toric surfaces. This is the first known enumerative invariant that counts tropical curves of positive genus with marked vertices. Our invariant extends the refined rational broccoli invariant invented by L. Göttsche and the first author, though there is a serious difference between the invariants: our elliptic invariant counts weights assigned partly to individual tropical curves and partly to collections of tropical curves, and our invariant is not always multiplicative over the vertices of the counted tropical curves as was the case for other known tropical enumerative invariants of toric surfaces. As a consequence we define elliptic broccoli curves and elliptic broccoli invariants as well as elliptic tropical descendant invariants for any toric surface.     

Long-term characteristics of analogical processing in high-school students with high fluid intelligence: an fMRI study

Intelligence is known to predict scholastic achievement and enables high performance in cognitive tasks. Fluid intelligence is strongly related to analogical reasoning abilities, which are fundamental to mathematical thinking. Geometric analogical reasoning is a prototypical measure of fluid intelligence. However, the cerebral correlates of geometric analogical reasoning and their developmental modulation over time are still rarely investigated. We report a 1-year follow-up functional magnetic resonance imaging study of a geometric analogical reasoning task in high fluid intelligence high-school students. This study was designed to characterise the cerebral correlates of geometric analogical reasoning and to improve our knowledge about the impact of general cognitive development on behavioural performance and on cerebral mechanisms underlying geometric analogical reasoning in adolescents. Our data indicate that a fronto-parietal network comprising the left and right parietal lobes and the left middle frontal gyrus was equally modulated by task difficulty at both measuring time points. At the behavioural level, however, participants showed improvements in performance at the second measuring time point. The behavioural improvements point to a more efficient task processing. As this is not accompanied by differential recruitment of fronto-parietal brain regions, the data suggest an increase in neural efficiency for these brain regions.     

Broccoli curves and the tropical invariance of Welschinger numbers

In this paper we introduce broccoli curves, certain plane tropical curves of genus zero related to real algebraic curves. The numbers of these broccoli curves through given points are independent of the chosen points — for arbitrary choices of the directions of the ends of the curves, possibly with higher weights, and also if some of the ends are fixed. In the toric Del Pezzo case we show that these broccoli invariants are equal to the Welschinger invariants (with real and complex conjugate point conditions), thus providing a proof of the independence of Welschinger invariants of the point conditions within tropical geometry. The general case gives rise to a tropical Caporaso–Harris formula for broccoli curves which suffices to compute all Welschinger invariants of the plane.     

Covalent‐Allosteric Inhibitors to Achieve Akt Isoform‐Selectivity

Isoforms of protein kinase Akt are involved in essential processes including cell proliferation, survival, and metabolism. However, their individual roles in health and disease have not been thoroughly evaluated. Thus, there is an urgent need for perturbation studies, preferably mediated by highly selective bioactive small molecules. Herein, we present a structure‐guided approach for the design of structurally diverse and pharmacologically beneficial covalent‐allosteric modifiers, which enabled an investigation of the isoform‐specific preferences and the important residues within the allosteric site of the different isoforms. The biochemical, cellular, and structural evaluations revealed interactions responsible for the selective binding profiles. The isoform‐selective covalent‐allosteric Akt inhibitors that emerged from this approach showed a conclusive structure–activity relationship and broke ground in the development of selective probes to delineate the isoform‐specific functions of Akt kinases.     

Functional Dithienopyrazines: Structure-Property Relationships**

Dithienopyrazines are only scarcely used as building blocks in organic electronic materials. Here, we report efficient preparation and investigation of syn- and anti-dithienopyrazines, which were functionalized with triaraylamine units to provide different series of donor-acceptor-donor-type materials. The characterization of the optoelectronic properties resulted in valuable structure-property relationships and allowed for the elucidation of the influence of structural effects such as core structure (syn vs anti), type of substituents (directly arylated vs ethynylated aryl), and substitution pattern (α,α’- vs β,β’- vs fourfold substitution). Finally, first application of a dithienopyrazine derivative as model for hole-transport materials tailored for organic electronic devices has been realized.     

Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding

Benzamide has been known for its polymorphism for almost 200 years. Three polymorphic forms are described. To date, it was only possible to crystallize a metastable form in a mixture together with the thermodynamically most stable form I. A complete transformation of form I into the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X‐ray diffraction.