Synthesis and reactivity profiles of phosphinated poly(alkyl aryl ether) dendrimers

Poly(alkyl aryl ether) dendrimers were utilized to synthesize a series of new triphenylphosphine functionalized dendrimers. Zero, first, second and third generation dendrimers, carrying 3, 6, 12 and 24 triphenylphosphine units, were prepared and characterized. The new triphenylphosphine containing dendrimers were assessed for their reactivity profiles and in this instance, the dendrimers were used as reagents to mediate Mitsunobu etherification reaction between phenol and various primary, secondary and benzylic alcohols. In addition, dendritic poly-phenols were also tested in an O-benzylation reaction. A monomeric methoxy group attached triphenylphosphine acted as a control for comparison of reactivity profiles of dendrimers. It was observed that the etherification reaction was mediated efficiently by the dendritic reagent, and in addition, the dendritic phosphine oxide reagents could be recovered quantitatively by precipitation methods. The recovered dendritic phosphine oxides were reduced subsequently to the corresponding phosphines and used as reagents for the Mitsunobu reaction, repetitively.     

Efficient halogen-lithium exchange reactions to functionalize poly(alkyl aryl ether) dendrimers

Poly(alkyl aryl ether) dendrimers were functionalized with bromophenyl groups at their peripheries, so as to have 3, 6, 12, and 24 groups in the zero, first, second, and third generation dendrimers, respectively. The new bromophenyl functionalized dendrimers were assessed for their reactivities in C-heteroatom and C-C bond forming reactions. For this purpose, the bromophenyl functionalized dendrimers were converted quantitatively to their polylithiated derivatives, using n-BuLi in benzene. The polylithiated dendrimers were reacted either with D₂O or with CO₂, so as to afford the corresponding deuterated and carboxylic acid functionalized dendrimers, respectively. The carboxylic acid functionalized dendrimers were modified further to the methyl esters during their characterization.     

D-A-D-based Unsymmetrical Thiosquaraine Dye for the Dye-Sensitized Solar Cells†

In dye-sensitized solar cell, modulating the electronic properties of the sensitizer by varying the donor, π-spacer, acceptor and anchoring groups help optimizing the structure of the dye for better device performance. Here, a donor–acceptor–donor-based unsymmetrical thiosquaraine sensitizer ( SQ5S ) has been designed and synthesized. Photophysical, electrochemical, theoretical and photovoltaic characterizations of SQ5S dye have been compared with its oxygen analog, SQ5 . The incorporation of the sulfur atom in the acceptor unit of SQ5S dye showed an intense peak at 688 nm, which was 38 nm of red-shifted and showed the panchromatic light harvesting response with the onset of 850 nm compared with SQ5 dye. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO₂ and the redox potential of electrolyte for the charge injection and the dye-regeneration processes, respectively. Photovoltaic efficiency of 1.51% (V_OC 610 mV, J_SC 3.07 mA cm⁻², ff 81%) has been achieved for SQ5S dye, whereas SQ5 showed the device performance of 5.43% (V_OC 723 mV, J_SC 9.3 mA cm⁻², ff 80%). The decreased device performance for the dye SQ5S has been attributed to the favorable intersystem crossing process associated with the photoexcited SQ5S that reduces the driving force for the charge injection process.     

RETRACTED: Simultaneous flow-through determination of nitrites, nitrates and their mixtures in environmental and biological samples using spectrophotometry

This article has been retracted at the request of the Editors-in-Chief. Please see Elsevier Policy on Article Withdrawal (http://www.elsevier.com/locate/withdrawalpolicy). REASON: Considerable concern was raised about the research purportedly conducted at Sri Venkateswara University, India with the alleged involvement of Professor P. Chiranjeevi. Questions were raised as to the volume of publications, the actual capacity (equipment, orientation and chemicals) of the laboratory in which Professor Chiranjeevi worked, the validity of certain of the research data identified in the articles, the fact that a number of papers appear to have been plagiarized from other previously published papers, and some aspects of authorship. Professor Chiranjeevi was given the opportunity to respond to these allegations. Thereafter, a committee was constituted by the University to look into these allegations. Based on the enquiry committee report, we have been informed by the head of the Department of Chemistry at Sri Venkateswara University that the university authorities have taken disciplinary action against Professor Chiranjeevi, as the university considers that there are grounds for such action. Therefore, based on the results of this investigation, the Editors-in-Chief are retracting this article.     

Environmental Effect on the Laser-Excited Fluorescence Spectra of Methylene Blue and Methylene Green Dyes

A laser-induced fluorescence investigation of the phenothiazine dyes Methylene Blue (MB⁺) and Methylene Green (MG⁺) is reported. To study the effect of environment, fluorescence spectra of these molecules in a variety of solvents with different polarity and various concentrations of an anionic surfactant were measured. The polarization and anisotropy analysis showed that there is no abrupt behavior except at the surfactant concentrations corresponding to the critical micellar concentration.     

Dynamic internal cavities of dendrimers as constrained media. A study of photochemical isomerizations of stilbene and azobenzene using poly(alkyl aryl ether) dendrimers

Dendritic microenvironments defined by dynamic internal cavities of a dendrimer were probed through geometric isomerization of stilbene and azobenzene. A third-generation poly(alkyl aryl ether) dendrimer with hydrophilic exterior and hydrophobic interior was used as a reaction cavity in aqueous medium. The dynamic inner cavity sizes were varied by utilizing alkyl linkers that connect the branch junctures from ethyl to n-pentyl moiety (C(2)G3-C(5)G3). Dendrimers constituted with n-pentyl linker were found to afford higher solubilities of stilbene and azobenzene. Direct irradiation of trans-stilbene showed that C(5)G3 and C(4)G3 dendrimers afforded considerable phenanthrene formation, in addition to cis-stilbene, whereas C(3)G3 and C(2)G3 gave only cis-stilbene. An electron-transfer sensitized trans-cis isomerization, using cresyl violet perchlorate as the sensitizer, also led to similar results. Thermal isomerization of cis-azobenzene to trans-azobenzene within dendritic microenvironments revealed that the activation energy of the cis- to trans-isomer was increasing in the series C(5)G3 < C(4)G3 相似文献   

Biofouling studies on nanoparticle-based metal oxide coatings on glass coupons exposed to marine environment

Titania, niobia and silica coatings, derived from their respective nanoparticle dispersions or sols and fabricated on soda lime glass substrates were subjected to field testing in marine environment for antimacrofouling applications for marine optical instruments. Settlement and enumeration of macrofouling organisms like barnacles, hydroides and oysters on these nanoparticle-based metal oxide coatings subjected to different heat treatments up to 400 °C were periodically monitored for a period of 15 days. The differences observed in the antifouling behaviour between the coated and uncoated substrates are discussed based on the solar ultraviolet light induced photocatalytic activities as well as hydrophilicities of the coatings in case of titania and niobia coatings and the inherent hydrophilicity in the case of silica coating. The effect of heat treatment on the photocatalytic activity of the coatings is also discussed.     

Aggregates of cucurbituril complexes in the gas phase

The self-organization of cucurbit[n]uril (n = 7 and 8, CBs) complexes was probed by electrospray mass spectrometry. The self-association of CB complexes is a general phenomenon but shows some dependence on the absence, presence, and type of included guest molecules.     

Synthesis and biological evaluation of 3-hydroxypyrazoles as aquaporin 9 inhibitors

A series of 3-hydroxypyrazole derivatives have been synthesized by a base-promoted reaction of nitro-substituted donor–acceptor cyclopropanes with hydrazines. The synthesized compounds have been investigated for their ability to inhibit aquaporin 9 (AQP9) in rat Leydig cells (LC-540). The protein data bank structure for AQP9 was predicted using homology modeling; and the protein–ligand interaction for the synthesized hydroxyl pyrazole derivatives were analyzed using molecular modeling and docking studies. The results of in silico analyses showed that compound 5b had a higher binding affinity with AQP9 than other compounds. Further, in vitro studies conducted in LC-540 cells confirmed that compound 5b effectively inhibits AQP9. Hence, compound 5b may be used as an inhibitor in enhancing our understanding of AQP9 function, and in the treatment of several diseases.