Synthesis, crystal structure and magnetic property of the novel dinuclear nickel(II) complex with 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole

A novel dinuclear nickel(II) complex, [Ni₂(MOBPT)₂Cl₂(H₂O)₂]Cl₂ · 7H₂O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction methods. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planer in which each Ni^II ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex.     

Subsolidus phase relations and crystal structure of compounds in the PrOx-CaO-CuO system

The subsolidus phase relations of the PrO_x-CaO-CuO pseudo-ternary system sintered at 950-1000°C have been investigated by X-ray powder diffraction. In this system, there exist one compound Ca₁₀Pr₄Cu₂₄O₄₁, one Ca₂Pr₂Cu₅O₁₀-based solid solution, seven three-phase regions and two two-phase regions. The crystal structures of Ca₁₀Pr₄Cu₂₄O₄₁ and Ca₂Pr₂Cu₅O₁₀-based solid solution have been determined. Compound Ca₁₀Pr₄Cu₂₄O₄₁ crystallizes in an orthorhombic cell with space group D_2h²⁰−Cccm, Z=4. Its lattice parameters are a=11.278(2) Å, b=12.448(3) Å and c=27.486(8) Å. The crystal structure of Ca₂Pr₂Cu₅O₁₀-based solid solution is an incommensurate phase based on the orthorhombic NaCuO₂ type subcell. The lattice parameters of the subcell of the Ca_2.4Pr_1.6Cu₅O₁₀ are a₀=2.8246(7) Å, b₀=6.3693(5) Å, c₀=10.679(1) Å, and those of the orthorhombic superstructure are with a=5a₀, b=b₀, c=5c₀. The Ca_2.4Pr_1.6Cu₅O₁₀ structure can also be determined by using a monoclinic supercell with space group C_2h⁵−P2₁/c, Z=4, a=5a₀, b=b₀, and β=104.79(1)° or 136.60(1)°, V=5a₀b₀c₀.     

Ring-opening polymerization of 1-(p-substituted phenyl)-2-vinylcyclopropanes by Ziegler–Natta catalysts

1-(p-Substituted phenyl)-2-vinylcyclopropanes such as 1-phenyl-2-vinylcyclopropane (I_a), 1-(p-chlorophenyl)-2-vinylcyclopropane (I_b), 1-(p-anisyl)-2-vinylcyclopropane (I_c), and 1-(p-tolyl)-2-vinylcyclopropane (I_d) were prepared and polymerized radically, cationically and with Ziegler–Natta catalysts. I_a and I_b polymerized exclusively in 1,5-fashion with radical initiators. However, I_c and I_d polymerized in 1,5-fashion only with Ziegler–Natta catalysts. All polymers were soluble in ordinary organic solvent and solution-cast films were clear and flexible, showing T_g values in the range of 39–71°C. Spectral data indicated that the double bonds of the polymer chains were in trans form in all cases. The difference between the polymerizabilities of different monomers are interpreted in terms of electronic properties of substituents.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Rapid separation of phenylthiohydantoin amino acids: ambient pressure ion-mobility mass spectrometry (IMMS)

An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids.     

Synthesis,crystal structure and luminescent property of a novel H<Subscript>2</Subscript>O-bridged cobalt(II) polymer with one-dimensional chain structure

The coordination compound [Co(C₁₀H₇COO)₂(H₂O)₃]_2n · 4nH₂O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions. The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can be assigned to the intraligand electronic transfer.     

Zeolite NaY-mediated oxidation of dyes with H2O2: unique heterogeneous non-transition metal center cleavage of H2O2 under visible light irradiation

This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H₂O₂. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H₂O₂ to produce ^·OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown.     

Conversion of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol by arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3-diarylpyrazoles and their fragmentation under electron impact

It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007.     

The Effect of Alkane Chain Length on the Liquid–Liquid Critical Temperatures of Oligostyrene/Linear-Alkane Mixtures

Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N ₁=5) to pentacontane (N ₁=50)) with an oligostyrene (1241amu, N ₂=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains.     

Encoding method for OBOC small molecule libraries using a biphasic approach for ladder-synthesis of coding tags

In the "one-bead one-compound" (OBOC) combinatorial library method, each compound bead displays only one compound entity. Hundreds of thousands to millions of compound beads can be synthesized rapidly and screened simultaneously. Positive compound beads are then isolated for structural analysis. To fully exploit the power of OBOC combinatorial small molecule libraries, a robust and high throughput encoding method is needed to decode the positive compound beads. In this paper, we report on the development of a novel encoding strategy that combines the concepts of ladder-synthesis and chemical encoding on bilayer beads. In these encoded libraries, small molecule compounds are displayed on the bead surface, and cleavable coding tags consisting of a series of truncated molecules reside in the bead interior. Such a library can be easily constructed using the biphasic approach (J. Am. Chem. Soc.2002, 124, 7678) to topologically segregate the functionalities of the beads during library synthesis. The ladder members and coding tags are then released for MALDI-TOF-MS analysis. To simplify the interpretation of the mass spectra, we purposely add bromine into the cleavable linker so that the cleavage products generate a characteristic isotope fingerprint. The chemical structure of library compounds can be determined by analyzing the mass differences between adjacent peaks on the mass spectra. This encoding strategy also provides valuable information on the quality of the testing compound on the surface of the bead. To validate this methodology, a model OBOC small molecule library with 12,288 members was synthesized on TentaGel beads and screened against streptavidin. The chemical structures of the compound on each positive bead were unambiguously identified.