- Tunable Mechanical Response from a Crystal Undergoing Topochemical Dimerization: Instant Explosion at a Faster Rate and Chemical Storage of a Harvestable Explosion at a Slower Rate
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Strain developed in crystals in response to stimuli causes mechanical response. Methods to tune such mechanical response is important for practical applications. Crystals of a monomer having azide and alkyne units pre-organized in a ready-to-react orientation, undergo thermal topochemical dimerization and show rate-dependent mechanical response. When the reaction rate is fast, the crystals explode violently. When the reaction rate is slow, the crystals absorb water from the surroundings contemporaneously with the reaction to form the dimer-hydrate in a single-crystal-to-single-crystal (SCSC) manner. Crystals of the dimer-hydrate upon dehydration also undergo explosion. Thus, at slow reaction rate, the strain gets stored in crystals by hydration and the explosion can be harvested, at will, by dehydration. Use of this rate-dependent explosion in the automatic activation of a remedial electrical circuit in case of a sudden rise in temperature has been demonstrated.
- Ravi, Arthi,Sureshan, Kana M.
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- A concise synthesis of neo-inositol
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neo-Inositol was prepared on a multigram scale in five steps from myo-inositol without recourse to column chromatography. The synthesis includes a large-scale preparation of 1,6:3,4-bis-[O-(2,3-dimethoxybutane-2,3-diyl)]-myo-inositol and a high-yielding i
- Riley, Andrew M.,Jenkins, David J.,Potter, Barry V.L.
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- Single-crystal-to-single-crystal synthesis of a pseudostarchviatopochemical azide-alkyne cycloaddition polymerization
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There is high demand for polysaccharide-mimics as enzyme-stable substitutes for polysaccharides for various applications. Circumventing the problems associated with the solution-phase synthesis of such polymers, we report here the synthesis of a crystalline polysaccharide-mimic by topochemical polymerization. By crystal engineering, we designed a topochemically reactive crystal of a glucose-mimicking monomer decorated with azide and alkyne units. In the crystal, the monomers arrange in head-to-tail fashion with their azide and alkyne groups in a ready-to-react antiparallel geometry, suitable for their topochemical azide-alkyne cycloaddition (TAAC) reaction. On heating the crystals, these pre-organized monomer molecules undergo regiospecific TAAC polymerization, yielding 1,4-triazolyl-linked pseudopolysaccharide (pseudostarch) in a single-crystal-to-single-crystal manner. This crystalline pseudostarch shows better thermal stability than its amorphous form and many natural polysaccharides.
- Ravi, Arthi,Shijad, Amina,Sureshan, Kana M.
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- Rigid diol bearing 6-6-6 fused ring system derived from naturally occurring myo-inositol and its polyaddition with diisocyanates
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Naturally occurring myo-inositol was developed into a highly rigid diol by converting its 3,4- and 1,6-vicinal diols in trans configuration into the corresponding butane-2,3-diacetals. The resulting diol bearing 6-6-6 fused ring system, in which conformational change is strictly suppressed, was combined with diisocyanates to perform polyadditions. The resulting polyurethanes were analyzed by differential scanning calorimetry, and it was found that their glass transition temperatures were much higher than those of the previously reported myo-inositol-derived polyurethanes, which were synthesized from a myo-inositol-derived diol bearing 5-6-5 fused ring system.
- Yoshida, Arata,Sudo, Atsushi
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- Regioselective SN2 reactions for rapid syntheses of azido-inositols by one-pot sequence-specific nucleophilysis
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Triflates of myo-inositol undergo facile solvolysis in DMSO and DMF yielding SN2 products substituted with O-nucleophiles; DMF showed slower kinetics. Axial O-triflate undergoes faster substitution than equatorial O-triflate. By exploiting this
- Ravi, Arthi,Hassan, Syed Zahid,Vanikrishna, Ajithkumar N.,Sureshan, Kana M.
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supporting information
p. 3971 - 3973
(2017/04/11)
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- A Definitive Synthesis of D-myo-Inositol 1,4,5,6-Tetrakisphosphate and Its Enantiomer D-myo-Inositol 3,4,5,6-Tetrakisphosphate from a Novel Butane-2,3-diacetal-Protected Inositol
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New and rapid syntheses of the enantiomeric intracellular signalling molecules D-myo-inositol 1,4,5,6-tetrakisphosphate (1a) and D-myo-inositol 3,4,5,6-tetrakisphosphate (1b) are described. The synthetic strategy employs the novel butane-2,3-diacetal-prot
- Mills, Stephen J.,Riley, Andrew M.,Liu, Changsheng,Mahon, Mary F.,Potter, Barry V. L.
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p. 6207 - 6214
(2007/10/03)
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