Single Crystalline,Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks

Porous frameworks composed of non-stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives ( CP-Hp and CP-Py , respectively) yields non-stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP-Hp and CP-Py in the framework was determined by single crystalline X-ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.     

Preferential inactivation of paediatric solid tumour cells by sequential exposure to Merocyanine 540-mediated photodynamic therapy and Edelfosine: implications for the ex vivo purging of autologous haematopoietic stem cell grafts

Paediatric solid tumours exhibit steep dose-response curves to alkylating agents and are therefore considered candidates for high-dose chemotherapy and autologous stem cell support. There is growing evidence that autologous stem cell grafts from patients with solid tumours are frequently contaminated with live tumour cells. The objective of this study was to perform, in a preclinical purging model, an initial assessment of the safety and efficacy of a two-step purging procedure that combined Merocyanine 540-mediated photodynamic therapy (MC540-PDT) with a brief exposure to the alkyl-lysophospholipid, Edelfosine. Human and murine bone marrow cells and Neuro-2a murine neuroblastoma, SK-N-SH human neuroblastoma, SK-ES-1 and U-2 OS human osteosarcoma, G-401 and SK-NEP-1 human Wilms' tumour, and A-204 human rhabdomyosarcoma cells were exposed to a fixed dose of MC540-PDT followed by a brief incubation with graded concentrations of Edelfosine. Survival was subsequently assessed by in vitro clonal assay or, in the case of CD34-positive haematopoietic stem cells, by an immunohistochemical method. Combination purging with MC540-PDT and Edelfosine depleted all tumour cells by >4 log while preserving at least 15% of murine granulocyte/macrophage progenitors (CFU-GM), 34% of human CFU-GM, and 31% of human CD34-positive cells. The data suggest that combination purging with MC540-PDT and Edelfosine may be useful for the ex vivo purging of autologous stem cell grafts from patients with paediatric solid tumours.     

ESR study of Mn2+ in GeTe and GeTeSi glasses

The electron spin resonance spectra of Mn²⁺ ions have been studied in Ge_xTe_100?x with x = 15, 17.5 and 20, and Ge_20?xTe₈₀Si_x with 0 ?x? 20. All samples are found to exhibit six hyperfine lines centered at g = 4.3 with hyperfine interaction constant A = 56 × 10^?4cm^?1. The g = 4.3 line is interpreted as being caused by Mn²⁺ ions incorporated in the amorphous network and surrounded by four Te atoms in an arrangement of orthorhombic symmetry. Some of the samples of GeTe show a g = 2.0 line. This line also appears after heat treatment in air at temperatures above the glass transition temperature. It is concluded that the g = 2.0 line is caused by Mn²⁺ ions in phase separated microcrystalline or concentrated regions of MnO in the glass.     

Alternating copolymerization of polar vinyl monomers in the presence of zinc chloride. I. Propagation and initiation of the copolymerization of acrylonitrile with styrene copolymer

Copolymerization of acrylonitrile with styrene spontaneously occurred on addition of zinc chloride without addition of any other radical initiator. The composition of the copolymer approached that of strictly alternating copolymer as zinc chloride added to the copolymerization system increased. The significance of the apparent monomer reactivity ratios of this copolymerization system was studied from a kinetic point of view, and it was shown that the monomer sequence distribution is indicated by the apparent monomer reactivity ratios. Further, equations which represent the relation between the apparent monomer reactivity ratios and Q,e values at a given salt concentration were derived. These equations reasonably accounted for the decrease of the apparent monomer reactivity ratios of the copolymerization of acrylonitrile with styrene in the presence of zinc chloride and the behavior of the other acrylonitrile copolymerization systems in the presence of zinc chloride. The initiation step of the spontaneous radical copolymerization of acrylonitrile with styrene in the presence of zinc chloride was explained by a cross-initiation mechanism.