Transient photocurrents in a charge transfer complex of trinitrofluorenone with a carbazole substituted discotic liquid crystal

We describe transient photoconduction studies on a well known triphenylene discotic liquid crystal molecule modified to incorporate a single carbazole moiety on one side chain and doped with the acceptor, trinitrofluorenone. This material is found to show both electron and hole photocurrents when the transient photoconduction study is carried out in the time of flight geometry although no time of flight transits are observed. Of interest here is the fact that the temperature dependence of the hole and electron photocurrents are radically different, the electron photocurrent being strongly activated while the hole photocurrent decreases with increasing temperature. We suggest a mechanism whereby the electron photocurrent controls the hole photocurrent through recombination. Furthermore, the electron activation energy varies with the applied electric field, indicating the influence of the Poole Frenkel barrier lowering mechanism in the production of the charge carriers.     

DNA release dynamics from reducible polyplexes by atomic force microscopy

Controlled intracellular disassembly of polyelectrolyte complexes of polycations and DNA (polyplexes) is a crucial step for the success of nonviral gene delivery. Motivated by our previous observation of different gene delivery performances among multiblock reducible copolypeptide vectors ( Manickam, D. S. ; Oupicky, D. Bioconjugate Chem. 2006, 17, 1395- 1403 ), atomic force microscopy is used to visualize plasmid DNA in various decondensed states from reducible polypeptide polyplexes under simulated physiological reducing conditions. DNA decondensation is triggered by reductive degradation of disulfide-containing cationic polypeptides. Striking differences in DNA release dynamics between polyplexes based on polypeptides of histidine-rich peptide (HRP, CKHHHKHHHKC) and nuclear localization signal (NLS, CGAGPKKKRKVC) peptide are presented. The HRP and NLS polyplexes are similar to each other in their initial morphology with a majority of them containing only one DNA plasmid. Upon reductive degradation by dithiothreitol, DNA is released from NLS abruptly regardless of the initial polyplex morphology, while DNA release from HRP polyplexes displays a gradual decondensation that is dependent on the size of polyplexes. The release rate is higher for larger HRP polyplexes. The smaller HRP polyplexes become unstable when they are in contact with expanding chains nearby. The results reveal potentially rich DNA release dynamics that can be controlled by subtle variation in multivalent counterion binding to DNA as well as the cellular matrix.     

Triple domino reaction for the synthesis of pyrazole/indoline linked chromenes

A simple and convenient method towards the synthesis of highly diversified chromenopyrazole/indoline frameworks in excellent yields via iodine promoted triple domino reaction involving Michael addition followed by intramolecular cyclization and dehydrogenation sequence has been described for the first time.     

Synthesis and structural study of thiacyclophanes utilizing dibromides and methane dithiolate

The synthesis of a series of thiacyclophanes and optically active binaphthol-based chiral thiacyclophanes is reported with XRD structure. Two diastereomeric tetrathiacyclophanes are designed and synthesized. The two diastereomers are evidenced by crystal structure; the single-crystal X-ray studies reveal that one of the isomers possesses an inherent property of self-assembling into a vertical stack of tunnel-like structures.     

Effect of Substituents in the Syntheses of Phenyl‐Substituted Dibenzonaphthyridines

A facile and elegant syntheses of linear and angular phenyl‐substituted dibenzonaphthyridines from 2,4‐dichloroquinolines through anilinoquinolines have been developed. The substituents in the 4th position of the anilinoquinoline and the temperature were found to play a vital role in the regulation of the yield towards the synthesis of the final compounds. The methyl group in the 7th position of the naphthyridin‐11‐ones was found to hinder the N‐methylation reaction sterically, consequently increasing the reaction time than other derivatives.     

Segmented polyethylene oxides: A new class of polyethers prepared via melt transetherification

Several segmented polyethylene oxides (SPEOs) were prepared by a melt-transetherification process using 1,4-bis(methoxymethyl)-2,3,5,6-tetramethylbenzene and polyethylene glycols (PEGs) of different molecular weights (di-, tri-, and tetraethylene glycols and PEGs of molecular weights 300, 600, 1000, 1500, and 3400) as the monomers. The effect of polymerization temperature (185 and 150 °C) on the molecular weight of SPEOs was studied, and it was shown that the molecular weight is larger at a higher polymerization temperature. The reversal of the polycondensation (transetherification) equilibrium by treatment of the polyethers with excess methanol transformed them completely into the starting monomers. The analysis of the degraded products by mass and NMR spectroscopies revealed that side reactions, such as the self-condensation of diols, are insignificant. The polymers containing shorter PEG spacers are amorphous, whereas the ones with longer PEG spacers are semicrystalline. The glass-transition temperature (T_g) of the SPEOs decreased with increases in the spacer length and attained the value of PEO at PEG-600, whereas the melting transition (T_m), crystallization temperature (T_c), and their enthalpies of transition, (ΔH_m) and (ΔH_c), increased with increases in the spacer length. The introduction of “molecular kinks” into SPEOs by the use of another monomer, 1,3-bis(methoxymethyl)-2,4,5,6-tetramethylbenzene, surprisingly, showed little effect on their thermal properties. A “branched-PEO” analogue, containing pendant oligoethyleneoxy units, was also prepared, and its thermal properties were compared with its linear analogue. Preliminary ionic conductance measurements showed that some of these SPEOs could serve as potential candidates for solid polymer–electrolyte applications. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1615–1628, 2001     

An experimental study on the intense heat transfer and phase change during melt and water interactions

Accidental contact between hot melt and cold water poses fatal hazard in several industries. Vapor explosion during melt-water contact in nuclear power plant accident can result in catastrophic containment failure. The fast transient phenomena as vapor explosion is not comprehensively understood despite several advances in research. It is not clear why certain parameters of melt and water exhibit differences in fragmentation behavior. To examine the influential parameters, we perform a series of experiments. The interactions between melt and water is visualized by high-speed video and X-ray radiograph.     

Physical facets of ultrasonic cavitational synthesis of zinc ferrite particles

This paper addresses the physical features of the ultrasonic cavitational synthesis of zinc ferrite particles and tries to establish the relationship between cavitation physics and sonochemistry of the zinc ferrite synthesis. A dual approach of coupling experimental results with simulations of radial motion of cavitation bubbles has been adopted. The precursors for the zinc ferrite, viz. ZnO and Fe₃O₄ are produced in situ by the hydrolysis of Zn and Fe(II) acetates stimulated by OH radicals produced from the transient collapse of the cavitation bubbles. Experiments performed under different conditions create significant variation in the production of OH radicals, and hence, the rate of acetate hydrolysis. Correlation of the results of experiments and simulations sheds light on the important facets of the physical mechanism of ultrasonic cavitational zinc ferrite synthesis. It is revealed that too much or too little rate of acetate hydrolysis results in smaller particle size of zinc ferrite. The first effect of a higher rate of hydrolysis leads to excessively large growth of particles, due to which they become susceptible to the disruptive action of cavitation bubbles. Whereas, the second effect of too small rate of hydrolysis of Zn and Fe(II) acetates restricts the growth of particles. It has been observed that the initial reactant concentration does not influence the mean particle size or the size distribution of zinc ferrite particles. The present investigation clearly confirms that the rate-controlling step of zinc ferrite synthesis through ultrasonic cavitational route is the rate of formation of OH radicals from cavitation bubbles.