Time-dependent density functional theory study of the spectroscopic properties related to aggregation in the platinum(II) biphenyl dicarbonyl complex

Singlet ground-state geometry optimization of the monomer, four dimers, and the trimer of [Pt(bph)(CO)(2)], where bph = biphenyl dianion, was performed at the B3LYP level of density functional theory (DFT) with a mixed basis set (6-311G** on C, O, and H atoms; the Stuttgart/Dresden (SDD) effective core potential (ECP) on the Pt core; [6s5p3d] on the Pt valence shell). The aggregation was based on Pt[bond]Pt binding as well as on pi[bond]pi and electrostatic interactions. The lowest-lying triplet-state geometries of the monomer, one dimer, and the trimer of the complex were also optimized using the above theory. Significant shortening of the Pt[bond]Pt bond was recorded in the triplet state compared to the singlet one. A number of low-energy singlet and triplet allowed excited states were calculated using time-dependent density functional theory (TDDFT) and analyzed with respect to absorption, excitation, and emission spectra collected under various conditions. Simulated spectra of the monomer and dimer based on the singlet excited states were correlated with the absorption spectrum. The emission in concentrated solution was due to the triplet dimer, and the emitting states were (3)MLCT and Pt-centered states.     

A concise synthesis of 3-substituted-7-amino-6-carboxyl-8-azachromones

We report on an approach to truncate the tricyclic 5H-chromeno[2,3-b]pyridin-5-one core of amlexanox, an approved drug under investigation for the treatment of obesity, to the bicyclic 4H-pyrano[2,3-b]pyridin-4-one (8-azachromone) core. A short, concise synthesis generates a key intermediate with requisite functionality on the pyridyl A-ring and iodo functionality on the 4-pyrone B-ring upon which palladium-catalyzed cross-coupling and subsequent reactions generate representative analogues. One of these shows a 14.2-fold increase in aqueous solubility over amlexanox.     

Separation and Analysis of Nucleic Acids and Their Constituents by Ion-Exclusion and Ion-Exchange Column Chromatography

The recent commercial development of high pressure liquid chromatographic instruments, and the availability of small and uniformly sized resin beads has enhanced the role of column chromatography for the rapid assay of nucleic acid components. A major advancement in the purification and analysis has been due to the recent demonstration that the ion exclusion is more or equally effective than the ion exchange as a separation principle for the resolution of purine and pyrimidine bases, nucleosides, deoxynucleosides and nucleotides^1–3. This article deals with the recent applications of separation principles that have been employed for the separation of nucleic acid constituents. The reader is referred to two review articles of Cohn for the earlier works on this subject^{4, 5}. Separations by chromatography and electrophoresis on paper and thin layers are not described here; several monographs and review articles are available in the literature^6–12.The reader is also referred to a recent methodological study for the base analysis of ribopolynucleotides by chemical tritium labeling which utilizes two dimensional chromatography on thin layers of cellulose as a separation means^{13, 14}.     

Time and distance constraints on accelerating cosmological models

The absence of guidance from fundamental physics about the mechanism behind cosmic acceleration has given rise to a number of alternative cosmological scenarios. These are based either on modifications of general relativistic gravitation theory on large scales or on the existence of new fields in Nature. In this Letter we investigate the observational viability of some accelerating cosmological models in light of 32 age measurements of passively evolving galaxies as a function of redshift and recent estimates of the product of the cosmic microwave background acoustic scale and the baryonic acoustic oscillation peak scale. By using information-criteria model selection, we select the best-fit models and rank the alternative scenarios. We show that some of these models may provide a better fit to the data than does the current standard cosmological constant dominated (ΛCDM) model.     

Categorification and Group Extensions

We review several known categorification procedures, and introduce a functorial categorification of group extensions (Section 4.1) with applications to non-Abelian group cohomology (Section 4.2). The obstruction to the existence of group extensions (Section 4.2.4, Equation (9)) is interpreted as a coboundary condition (Proposition 4.5).     

A note on idempotents in finite AW*-factors

We prove that the value of the quasi-trace on an idempotent element in an AW*-factor of type is the same as the dimension of its left (or right) support.

     

Functionalized heteropolyanions: high-valent metal nitrido fragments incorporated into a Keggin polyoxometalate structure

Three examples of nitrido-functionalized polyoxometalate species are reported, namely (n-Bu4N)4[PW11O39(OsN)] (1), (n-Bu4N)4[PW11O39(ReN)] (2), and (n-Bu4N)3[PW11O39(ReN)] (3), which feature the incorporation of [OsVI identical to N]3+, [ReVI identical to N]3+ and [ReVII identical to N]4+ fragments, respectively, into the framework of a Keggin-type heteropolyanion.