Synthesis and Visible Spectral Behaviour of Some New N‐Bridgehead Heterocyclic Cyanine Dyes Incorporating Pyrazolo (4,5‐b) Indolizine (Benzoindolizine)

The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and ¹³C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol.     

Syntheses of Some 3—[1′（1′H）—Substituent—pyrazol—5′—yl] benzo [5,6] coumarins

3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.     

Characterisation and cryomagnetic study of a hydrothermally synthesised hydrogen bonded L–M–L type co-ordination polymer

A ligand–metal–ligand type co-ordination polymer [Ni (C₆H₁₂N₄)(NCS)₂(H₂O)₂] _n has been synthesised under controlled hydrothermal conditions. Here 1,3,5,7-tetraazatricyclo[3.3.1]decane [or hexamethylenetetramine (hmt)] has been used as a μ-(N,N′) bidentate spacer molecule. The prepared polymeric complex has been characterised by elemental and spectral analyses. The structure has been confirmed by a single crystal X-ray diffraction study. Magneto-structural correlation has been drawn from cryomagnetic susceptibility measurements (2–300 K) which unequivocally reflects very weak magnetic spin interactions among the long distant octahedral Ni(II) metal centres mediated by hmt and weak hydrogen bonding interactions between the adjacent zigzag one-dimensional polymeric chains carrying into a two-dimensional infinite polymeric framework.     

Emulsion liquid membrane extraction of fission products promoted by polyvalent and organic acids

Emulsion liquid membranes (ELM) with di-2-ethylhexylphosphoric acid in n-alkane, and dipicrylamine and cobalt(III) dicarbollide in nitrobenzene stabilized in double emulsions by SPAN 80/85 surfactant were used for preconcentration of radioactive fission products (¹³⁷Cs,⁹⁰Sr,¹³⁹Ce, and¹⁵²Eu) from slightly acidic nitrate solutions. The efficiency of sulfuric, phosphotungstic and silicotungstic acids as stripping agents, and picric acid as the bulky anion additive was investigated. A group separation of the fission products is possible by the ELM technique and can be considered for their removal from waste water solutions.     

Synthesis and elaboration of functionalised carbohydrate-derived spiroketals

The scope of a stereoselective three-step approach for the synthesis of sugar derived spiroketals is presented. The methodology consists of Grignard addition of vinyl- or allylmagnesium bromide to a carbohydrate lactone, followed by K-10 clay mediated glycosidation with a terminal alkenol and subsequent ring-closing metathesis of the resulting diene. The generality of this procedure is demonstrated by the synthesis of various pyranose- and furanose-derived spiroketals, as well as more advanced tricyclic spiroketal derivatives. It is shown that functionalisation of the double bond in the resulting spiroketals leads to fused polycyclic ethers.     

The physical properties of pressure sensitive rubber composites

Nitrile butadiene rubber, NBR, structural foam of different apparent densities was obtained by using different concentrations of foaming agent, azodicarbonamide, ADC/K. The true stress-strain characteristics, in case of compression, of foamed samples after the application of cyclic stress-strain were measured. The effect of the cyclic stress-strain on strain energy density of ADC/K foaming agent-filled NBR rubber composites was studied. The mechanical parameters were found to depend on the foaming agent concentration and on the pre-cyclic fatigue number. Results also indicated that the strain energy decreased with filler concentration.The effects of the cyclic stress-strain on the conductivity of ADC/K foaming agent-filled NBR rubber composites were studied. The electrical properties were found to depend on the foaming agent concentration, the strain amplitude and the number of stress-strain cycles of pre-strain. This study was assisted by the current-voltage characteristics which were measured under the effect of different compression ratios: 0%, 5%, 10%, 15%, 20%, 25% and 30%. The free current carrier mobility and the equilibrium concentration of charge carriers in the conduction band were produced as functions of compressive strain. Results also indicate that there is a linear variation between pressure and conductivity for all samples, which means that these samples can be used as a pressure sensor.     

Chloroplast Biogenesis 77: Two Novel Monovinyl and Divinyl Light-Dark Greening Groups of Plants and Their Relationship to the Chlorophyll a Biosynthetic Heterogeneity of Green Plants

Abstract— On the basis of the steady-state accumulation of divinyl (DV) or monovinyl (MV) protochlorophyllide (Pchlide) a in darkness (D) or in the light (L), green plants have been classified into three different greening groups namely dark divinyl-light divinyl (DDV-LDV), dark monovinyl-light divinyl (DMV-LDV) and dark monovinyl-light monovinyl (DMV-LMV) (Ionannides et al., Biochem. Syst. Ecol. 22, 211-220,1994). Interruption of the L phase of the photoperiod by a brief period of darkness (LD condition) revealed a predominance of different chlorophyll (Chl) a biosynthetic routes, depending upon the greening group affiliation of the plant species. For example, in DMV-LDV and DMV-LMV plants, the predominant Chl a biosynthetic routes under the LD condition appear to be the MV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Pchlide a. On the basis of DV and MV Pchlide a accumulation rates after re-darkening, this greening group is designated as a light-dark MV (LDMV) subgroup. In DDV-LDV plants, the predominant LD Chi a biosynthetic routes appear to be the DV Chi a biosynthetic route and/or a mixed DV-MV Chi a biosynthetic route that bifurcates at the level of DV Chlide a. This greening group is designated as a light-dark DV (LDDV) subgroup. It is proposed that upon inhibiting the conversion of Pchlide a to Chi a by interruption of the L phase of the photoperiod by a brief period of D, the rates of DV and MV Pchlide a regeneration may reflect the carryover rates of DV and MV Pchlide a biosynthesis in L instead of reflecting a differential use of DV and MV carboxylic biosynthetic rates in D. It is also shown that in LDMV plants, MV Chlide a and MV Chi a are formed without the participation of [4-vinyl] Chlide a reductase. On the basis of recently published evidence, it is also argued that Pchlide oxidoreductase-A (POR-A) may be active in LDDV plants, while POR-B may predominate in LDMV plant species. The evolutionary significance of the LDDV and LDMV greening subgroups is discussed.     

Low coordinate germanium and tin compounds (ArO)2ME and (ArO)2MM′Ln M=Ge, Sn; E=S, Se, –NSiMe3 M′=Cr, W, Fe, Pt [Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]

The reactions of the divalent species (ArO)₂M (Ar=2,4,6-[(CH₃)₂NCH₂]₃C₆H₂; M=Ge, Sn) with either Me₃SiN₃, elemental S₈, Se or transition metal complexes M′(CO)_n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph₃P)₂Pt·C₂H₄ have resulted in the isolation of either the new stable formal metallanimines (ArO)₂M=N–SiMe₃, germanethione, -selone (ArO)₂Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)₂M=M′(CO)_n, (ArO)₂M=Pt(PPh₃)₂ complexes, respectively. The direct oxidation of the (ArO)₂M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)₂M–O–]₂. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)₂Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)₂M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione.     

Synthesis of π‐conjugated oligomer that can form metallo polymers

An oligo(p‐phenylene vinylene) that contains terpyridine ligands has been synthesized. Upon addition of metal ions, a π‐conjugated metallo polymer is formed in which the well‐defined character of oligomers and the material properties of polymers are combined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4020–4023, 2002