How to Predict Excited State Geometry by Using Empirical Parameters Obtained from Franck-Condon Analysis of Optical Spectrum

Excited state geometries of molecules can be calculated with highly reliable wavefunction schemes. Most of such schemes, however, are applicable to small molecules and can hardly be viewed as error-free for excited state geometries. In this study, a theoretical approach is presented in which the excited state geometries of molecules can be predicted by using vibrationally resolved experimental absorption spectrum in combination with the theoretical modelling of vibrational pattern based on Franck-Condon approximation. Huang-Rhys factors have been empirically determined and used as input for revealing the structural changes occurring between the ground and the excited state geometries upon photoexcitation. Naphthalene molecule has been chosen as a test case to show the robustness of the proposed theoretical approach. Predicted 1B_2u excited state geometry of the naphthalene has similar but slightly different bond length alternation pattern when compared with the geometries calculated with CIS, B3LYP, and CC2 methods. Excited state geometries of perylene and pyrene molecules are also determined with the presented theoretical approach. This powerful method can be applied to other molecules and specifically to relatively large molecules rather easily as long as vibrationally resolved experimental spectra are available to use.     

Chemo‐ and Enantioselective Oxidative α‐Azidation of Carbonyl Compounds

We report high‐performance I⁺/H₂O₂ catalysis for the oxidative or decarboxylative oxidative α‐azidation of carbonyl compounds by using sodium azide under biphasic neutral phase‐transfer conditions. To induce higher reactivity especially for the α‐azidation of 1,3‐dicarbonyl compounds, we designed a structurally compact isoindoline‐derived quaternary ammonium iodide catalyst bearing electron‐withdrawing groups. The nonproductive decomposition pathways of I⁺/H₂O₂ catalysis could be suppressed by the use of a catalytic amount of a radical‐trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late‐stage α‐azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α‐azidation of 1,3‐dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.     

Nutritional Analysis of Red-Purple and White-Fleshed Pitaya (Hylocereus) Species

Pitaya is one of the most preferred and produced tropical fruit species recently introduced to the Mediterrranean region in Turkey. Due to its nutritional fruits with high economic value, the popularity of pitaya increases steadily in Turkey as an alternative crop. No detailed nutritional analysis has been undertaken in Turkey so far on fruits of the pitaya species. In this study, we determined and compared some nutritional parameters in fruit flesh of two pitaya (dragon fruit) species (Hylocereus polyrhizus: Siyam and Hylocereus undatus: Vietnam Jaina) grown in the Adana province located in the eastern Mediterranean region in Turkey. The individual sugars, antioxidant activity, total phenolic content, phenolic compounds and volatiles were determined for the first time in Turkey on two pitaya species. The results showed that total phenol content and antioxidant capacity are notably higher in red-fleshed fruits than white-fleshed ones and the predominant phenolic compound in fruits of both species was quercetin. The total sugar content and most of the phenolic compounds in fruits of two pitaya species were similar. A total of 51 volatile compounds were detected by using two Solid Phase Micro Extraction (SPME) fibers, coupled with Gas Chromatography Mass Spectrometry (GC-MS) techniques, and more volatile compounds were presented in the white-fleshed species. Total phenolic content (TPC) of the red-fleshed and white-fleshed pitaya species were 16.66 and 17.11 mg GAE/100 g FW (fresh weight). This study provides a first look at the biochemical comparison of red-fleshed and white-fleshed pitaya species introduced and cultivated in Turkey. The results also showed, for the first time, the biochemical content and the potential health benefit of Hylocereus grown in different agroecological conditions, providing important information for pitaya researchers and application perspective.     

Thermoelectric properties of CoSb3 with maize‐like structure

Maize‐like CoSb₃ powders were obtained via the chemical alloying method. After the consolidation of the nanopowder using hot press, the CoSb₃ compact shows a higher Seebeck coefficient and lower thermal conductivity. For the investigated CoSb₃, a ZT of 0.15 at 673 K is shown. Though the achieved ZT does not reach the optimal value (0.17 to 0.18) for pure CoSb₃, due to its lower electrical conductivity, the novel structure fabrication provides an interesting and promising approach to enhancing the thermoelectric performance. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On Artinian generalized local cohomology modules

Let R be a commutative Noetherian ring with non-zero identity and a be a maximal ideal of R. An R-module M is called minimax if there is a finitely generated submodule N of M such that M/N is Artinian. Over a Gorenstein local ring R of finite Krull dimension, we proved that the Socle of H _a ⁿ (R) is a minimax R-module for each n ≥ 0.     

Microwave-assisted and conventional synthesis and stereogenic properties of monospirocyclotriphosphazene derivatives

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆, with N/O donor type N-alkyl or (aryl)-o-hydroxybenzylamines HO(C₆H₄)CH₂NHR(Ar), [R(Ar) = C(CH₃)₃ (1), Ph (2)] produce monospirocyclic tetrachlorocyclotriphosphazenes (1a and 2a). The geminal substituted cyclotriphosphazenes (1b, 1d, 2b and 2d) are obtained from the reactions of 1 equiv. of 1a and 2a with 2 equiv. of pyrrolidine or morpholine in THF, while the fully substituted phosphazenes (1c, 1e, 2c and 2e) are formed from the reactions of 1a and 2a with the excess pyrrolidine or morpholine in toluene, between 24 and 48 h. The microwave-assisted reactions of 1a and 2a with excess pyrrolidine or morpholine in toluene afford the fully substituted products with higher yields than those which were obtained by conventional methods. The structural investigations of the compounds have been verified by elemental analyses, ESI-MS, FTIR, ¹H, ¹³C, ³¹P NMR and HETCOR techniques. The crystal structure of 2a is determined by X-ray crystallography and the phosphazene ring is in the flattened boat form. Compounds 1b, 1d, 2b and 2d in which the spiro aryloxy moiety provides the one centre of chirality exist as racemates and the chirality has been confirmed by ³¹P NMR spectroscopy on addition of a chiral solvating agent (CSA), (S)-(+)-2,2,2-trifluoro-1-(9′-anthryl)ethanol.     

Multifunctional core–shell nanoparticles: superparamagnetic,mesoporous, and thermosensitive

Multifunctional core–shell composite nanoparticles (NPs) have been developed by the combination of three functionalities into one entity, which is composed of a single Fe₃O₄ NP as the magnetic core, mesoporous silica (mSiO₂) with cavities as the sandwiched layer, and thermosensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) copolymer as the outer shell. The mSiO₂-coated Fe₃O₄ NPs (Fe₃O₄@mSiO₂) are monodisperse and the particle sizes were varied from 25 to 95 nm by precisely controlling the thickness of mSiO₂-coating layer. The P(NIPAAm-co-AAm) were then grown onto surface-initiator-modified Fe₃O₄@mSiO₂ NPs through free radical polymerization. These core–shell composite NPs (designated as Fe₃O₄@mSiO₂@P(NIPAAm-co-AAm)) were found to be superparamagnetic with high r ₂ relaxivity. To manipulate the phase transition behavior of these thermosensitive polymer-coated NPs for future in vivo applications, the characteristic lower critical solution temperature (LCST) was subtly tuned by adjusting the composition of the monomers to be around the human body temperature (i.e. 37 °C), from ca. 34 to ca. 42 °C. The thermal response of the core–shell composite NPs to the external magnetic field was also demonstrated. Owing to their multiple functionality characteristics, these porous superparamagnetic and thermosensitive NPs may prove valuable for simultaneous magnetic resonance imaging (MRI), temperature-controlled drug release, and temperature-programed magnetic targeting and separation applications.     

Synthesis of uniform quasi-octahedral CeO<Subscript>2</Subscript> mesocrystals via a surfactant-free route

A facile surfactant-free nonaqueous method is presented to prepare uniform quasi-octahedral ceria, CeO₂, mesocrystals, in which only Ce(NO₃)₃ and octanol were used as the reactants at a reaction temperature of 150 °C. CeO₂ sample synthesized using this technique consists of well-dispersed quasi-octahedrons and exhibits an uniform size and morphology. Based on structural characterization, it is proposed that the CeO₂ mesostructure was formed by self-assembly of primary nanocrystals based on unique 3D oriented-attachment mechanism. Optical characterization exhibited a strong quantum confinement, revealing small size of primary nanocrystals. The thermal stability and UV–Vis study reveal CeO₂ mesocrystal has various potential for high temperature applications and optical apparatus applications.