Theoretical investigation of carboranylpyrrole structures and the thermal resistance and conducting properties of carboranylpyrrole polymers

The carboranylpyrrole polymers are functional materials with superior thermal resistance and conducting performances. The carboranylpyrrole structures and Laplacian bond order (LBO) of carborane moiety, as well as the thermal resistance and conducting properties of carboranylpyrrole dimers or polymers, were investigated theoretically. The ¹¹B NMR chemical shifts of 3-(2-methyl-o-carboranyl)alkyl-1H-pyrrole monomers (CP-1 to CP-5) were calculated and analyzed. The average LBO values of some characteristic chemical bonds in the carborane cages of CP-1 to CP-5 molecules were calculated. It is found that the average LBO values of carborane moieties change slightly with the increase in alkyl chain length. The temperature resulting in about 15–20 % weight loss for CP-1, CP-3, CP-4 and CP-5 polymers is predicted to be more than 700 °C. Apart from the C–C bonds in carborane moieties of 3-(2-R-o-carboranyl)propyl-1H-pyrrole (R = CH₂OH, CH₂OCH₃, CN, COCl, Ph) substituents, the LBO values of other bonds in these cages change slightly relative to that in the molecule of 3-(2-methyl-o-carboranyl)propyl-1H-pyrrole (CP-3). The C–C bond LBO values in the carborane cages of these substituents with electron-donating groups (R = CH₂OH, CH₂OCH₃) are bigger than that in CP-3, while those values in those substituents with electron-withdrawing groups (R = CN, COCl, Ph) are smaller than that in CP-3. The polymerization activity calculated for CP-1 to CP-5 monomers increases with the increase in alkyl chain length. The calculated orbital energy gap (?E _LUMO?HOMO) of CP-1 to CP-5 dimers decreases with the increase in alkyl chain length, and accordingly, the electronic conductivity has the potential to increase. In addition, the calculated band gaps of CP-1 to CP-5 dimers cell models also decrease with the increase in alkyl chain length.     

Two cadmium(II) complexes with polymeric 2D layer and discrete mononuclear motifs: Syntheses,crystal structures,and fluorescent properties

Two new 1,3-bi(4-pyridyl)propane-based cadmium(II) complexes, [Cd(Bpp)₂(Nas)₂] _n (I) and [Cd(Bpp)₂(Na)₂(H₂O)₂] (II) (Bpp = 1,3-bi(4-pyridyl)propane, Nas^– = 2-aminonaphthalene-1-sulfonate, and Na^– = 1-naphthoate) (CIF files CCDC nos. 1429589 (I), 1429590 (II)) have been hydrothermally synthesized by varying carboxylate- or sulfonate-containing coligands. Structural analyses reveal that, complex I with monodentate Nas^– ligands exhibits a two-dimensional (2D) layered motif extended by equatorial Bpp connectors. By contrast, complex II modified by monodentate Na^– ligands exhibit discrete mononuclear structure. Althouth the Nas^–/Na^– coligands showed the same monodentate binding modes, the Bpp ligand exhibits bridging or terminal binding modes in I and II, respectively. So it is obvious that the competitive coordination in the present mixed-ligands system is responsible for the aggregation or dissociation of mononuclear structural units. Furthermore, both of the two compounds are linked to 3D supramolecular architecture by intermolecular C–H···O hydrogen bonding or C–H···π stacking interactions, exhibiting strong fluorescent emissions resulting from the ligand-to-metal or Na^?-based intraligand charge transfer at room temperature, which can be hopefully used as fluorescent materials.     

Existence of one weak solution for p(x)-biharmonic equations with Navier boundary conditions

We study the existence of at least one weak solution for a class of elliptic Navier boundary value problems involving the p(x)-biharmonic operator. Our technical approach is based on variational methods. In addition, an example to illustrate our results is given.     

Hydrothermal reactions from sodium hydrogen carbonate to phenol

We report here experimental evidence for the hydrothermal formation of a pure organic molecule, phenol, from the reaction of carbonate with water in the presence of iron powders.     

Expeditious synthesis of indolizine derivatives via iodine mediated 5-endo-dig cyclization

Iodine-mediated 5-endo-dig cyclization of propargylic esters 2 at room temperature proceeded smoothly to give highly functionalized indolizines 3 in excellent yields. A pyridine group was employed as a nucleophilic partner in this facile process for the first time.     

General frame constructions for Z-cyclic triplewhist tournaments

Frames are useful in dealing with resolvable designs such as resolvable balanced incomplete block designs and triplewhist tournaments. Z-cyclic triplewhist tournament frames are also useful in the constructions of Z-cyclic triplewhist tournaments. In this paper, the concept of an (h₁,h₂,…,hn;u)-regular Z-cyclic triplewhist tournament frame is defined, and used to establish several quite general recursive constructions for Z-cyclic triplewhist tournaments. As corollaries, we are able to unify many known constructions for Z-cyclic triplewhist tournaments. As an application, some new Z-cyclic triplewhist tournament frames and Z-cyclic triplewhist tournaments are obtained. The known existence results of such designs are then extended.     

Structure analysis of triterpene saponins in Polygala tenuifolia by electrospray ionization ion trap multiple-stage mass spectrometry

Eighteen different triterpene saponins isolated from Polygala tenuifolia were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMS(n)) in positive and negative ion modes. MS(1)-MS(3)/MS(4) spectra of the both modes were analyzed, and they all gave fragments in line and shared common fragmentation patterns. Key fragments from MS(n) spectra of both the modes and their proposed fragmentation pathways were constructed with examples illustrated for the formation of characteristic fragments in the saponins. Two special fragmentation patterns were proposed: (1) the formation of fragments by cleavage of CH(2)O from Delta(12)-14alpha-CH(2)OH of the oleanene-type saponin aglycone in both positive and negative MS(n) (n > or = 2) modes; (2) the occurrence of fragments by cleavage of CO(2) and 3-glucose as the characteristic structure feature of 23-COOH at the oleanene-type saponin aglycones coupled with 3-Glc substitutes in the negative MS(n) (n > or = 2) modes. Peak intensities in MS(n) spectra were also correlated with structural features and fragmentation preferences of the investigated saponins, which are discussed in detail. In general, fragments formed predominantly by cleavages of glycosidic bonds in the positive mode, while selective cleavages of acyl bonds preceded that of glycosidic bonds in negative MS(n) (n > or = 2) mode, both of which could well be applied to the structural analysis of these saponins. Interpretation of MS(n) spectra presented here provided diagnostic key fragment ions important for the structural elucidation of saponins in P.tenuifolia.