Non-covalent assemblies of negatively charged boronated porphyrins with different cationic moieties

A unique approach to non-covalent electron and energy transfer is described that is based on the formation of salt bridges between oppositely charged porphyrin units. A new class of electrostatically linked dimeric and pentameric porphyrins was synthesized by interaction of novel anionic boron containing porphyrins such as 5-(benzamidodecahydro-closo-dodecaborate)-10,15,20-triphenylporphyrin (N1) and meso-tetrakis-benzamidodecahydro-closo-dodecaborate)porphyrin (N2) and a variety of cationic meso-tetraarylporphyrin units. A bipyridine linked dimer (N1 · bpy · N1) was also prepared by employing N,N′-dimethyl-4,4′-bipyridinium (bpy) as a spacer between two mono-anionic species. A quinone-porphyrin dyad was also prepared for electron or energy transfer demonstration. All the synthesized assemblies were characterized by NMR, IR, UV-Vis, and mass spectroscopy. Significant spectral changes occurred in the absorption spectra of these non-covalent porphyrin assemblies compared to those of the reference monomers, indicating the presence of electronic interaction between the adjacent porphyrin units. Resonance light scattering was also used to study the formation of these assemblies in solution.     

The chemistry of the azanonaborane cluster RNH2---B8H11NHR

The preparation and properties of the R¹R²NH---B₈H₁₁NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.     

Spectrophotometric study of the charge transfer complexation of some porphyrin derivatives as electron donors with tetracyanoethylene

Charge transfer complexes (CTC) of 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetra(4-tolyl)porphyrin (TTP), 5,10,15,20-tetra(4-methoxyphenyl)porphyrin (TMP), Zn-5,10,15,20-tetraphenylporphyrin (Zn-TPP), and Zn-5,10,15,20-tetra(4-tolyl)porphyrin (Zn-TTP) with tetracyanoethylene (TCNE) have been studied at various temperatures in CH(2)Cl(2) and CCl(4). The data are discussed in terms of equilibrium constant (K(CT)), molar extinction coefficient (varepsilon(CT)), thermodynamic standard reaction quantities (DeltaG degrees , DeltaH degrees and DeltaS degrees ), oscillator strength (f), and transition dipole moment (mu). The spectrum obtained for TPP/TCNE, TTP/TCNE, and TMP/TCNE systems shows two main absorption bands at 475 and 690nm, which are not due to the absorption of any of the reactants. These bands are characteristic of an intermolecular charge transfer involving the overlap of the lowest unoccupied molecular orbital (LUMO) of the acceptor with the highest occupied molecular orbital (HOMO) of the donor. The results reveal that the interaction between the donors and acceptor is due to pi-pi(*) transitions by the formation of radical ion pairs. The stoichiometry of the complexes was found to be 1:1 ratio by the Job and straight line methods between donors and acceptor with the maximum absorption bands at wavelengths of 475 and 690nm. The observed data show salvation effects on the spectral and thermodynamics properties of CTC. The ionization potential of the donors and the dissociation energy of the CTC were also determined and are found to be constant.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

Azanonaboranes containing imidazole derivatives for boron neutron capture therapy: synthesis, characterization, and in vitro toxicity evaluation

A number of azanonaboranes containing imidazole derivatives have been synthesized by a ligand-exchange reaction. The exo-NH(2)R group of the azanonaborane of the type [(RH(2)N)B(8)H(11)NHR] can be exchanged by one hetero-nitrogen atom of the imidazole ring. In the case of histamine, the exchange takes place on the aliphatic amino group, the hetero-nitrogen atom of the imidazole ring or both of them. The products were confirmed by NMR, IR spectroscopy, elemental analysis, and mass spectrometry. The electron-withdrawing effect of the nitro group in 2-nitroimidazole is the main hindrance to achieve the exchange reaction. In vitro experiments were performed with B16 melanoma cells. A comparison of the biological properties of the products in which the B(8)N cluster is connected to the hetero-nitrogen atom of imidazole ring or the aliphatic NH(2) group showed that incorporation of B(8)N cluster unit into primary amino group increases the compound's toxicity. In contrast, this specificity for cytotoxicity effect was not observed in the case of histamine containing two B(8)N clusters which was relatively nontoxic and did not inhibit colony formation up to concentrations of 2 mM.     

羧甲基纤维素钠水凝胶的制备及其生物降解性研究

用羧甲基纤维素钠(CMC—Na)制得了含水量高达98％的水凝胶，考察了防腐剂、交联剂、无机态氮素、有机态氮素、碳水化合物的加入量以及环境中pH值等因素对生物降解性的影响。结果表明：制备条件不同，水凝胶的生物降解性不同；环境中一定量铵根离子的存在有利于水凝胶的生物降解；在pH=5．2的环境中纤维素酶活性最高，降解程度最大。