Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

Novel ethero atoms containing polyesters based on 2,6‐naphthalendicarboxylic acid: A comparative study with poly(butylene naphthalate)

Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the T_g value, a decrement of T_m, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Synthesis and chiroptical properties of optically active poly(ethynylcarbazole) derivatives: Substituent effect on the helix formation

Novel chiral acetylene monomers containing carbazole, 2‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 1 ), 3‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 2 ), 2‐ethynyl‐9‐[(S)‐2‐methylbutyl]carbazole ( 3 ), and 2‐ethynyl‐9‐[(S)‐4‐methylhexyl]carbazole ( 4 ) were synthesized and polymerized with [(nbd)RhCl]₂? Et₃N. The corresponding polyacetylenes with number‐average molecular weights ranging from 68,700 to 310,000 were obtained in good yields. Poly( 1 ) exhibited a large specific rotation and an intense Cotton effect in toluene, indicating that it formed a helix with predominantly one‐handed screw sense, while the other three polymers showed no evidence for taking a helical structure. Poly( 1 ) largely decreased the CD intensity upon heating from ?10 to 60 °C. Poly( 1 ) showed a Cotton effect in film state in a manner similar to solution state. No chiral amplification was observed in the copolymerization of 1 with achiral 2‐ethynyl‐9‐tert‐butoxycarbonylcarbazole ( 5 ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4450–4458, 2007     

Solid-phase oxidative halodecarboxylation of β-arylacrylic acids with the ceric ammonium nitrate—alkali halide system

The solid-phase oxidation of cinnamic, 4-methoxy- and 3,4-dimethoxycinnamic acids with Ce(NH₄)₂(NO₃)₆—MHal system leads to β-halostyrenes. Similar procedure in the absence of a metal halide results in a cleavage of the C=C bond giving the corresponding benzaldehydes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 114–118, January, 2008.     

Magnetic properties of lanthanum orthoferrite fine powders prepared by different chemical routes

Fine powders of lanthanum iron oxide, LaFeO₃, have been prepared by solid state reaction as well as sol-gel synthesis and nebulized spray pyrolysis. Structures, morphologies and magnetic susceptibility measurements of these powders have been examined. The powders prepared by all the three low-temperature routes contain nearly spherical particles with an average diameter of 40 nm. These samples show a lower Neel temperature than the powder prepared by solid state reaction besides showing much lower magnetic susceptibility at low temperatures. Dedicated to Professor C N R Rao on his 70th birthday     

Reversible 5′-end biotinylation and affinity purification of synthetic RNA

A reversible biotinylation phosphoramidite was synthesized and incorporated onto the 5′-end of an oligoribonucleotide on a solid phase synthesizer. After cleavage and deprotection, the crude synthetic oligomer mixture was incubated with NeutrAvidin^® coated microspheres, and the failure sequences removed by washing with a buffer followed by treating the microspheres with tetrabutylammonium fluoride to give a high quality unmodified full-length oligoribonucleotide.     

Alternating copolyfluorenevinyles with polynuclear aromatic moieties: Synthesis,photophysics, and electroluminescence

Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with η_EL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007