Atropisomeric Dyes: Axial Chirality in Orthogonal BODIPY Oligomers

Cataloged from PDF version of article.A dissymmetrically substituted orthogonal BODIPY dimer and an orthogonal BODIPY trimer exist as two stable conformers, which are in fact atropisomeric enantiomers. The racemic mixture can be separated by HPLC using a chiral stationary phase. These enantiomeric derivatives hold great potential as chiral agents in asymmetric synthesis, fluorogenic/chromogenic sensing, and biological applications

PEGylated calix[4]arene as a carrier for a Bodipy-based photosensitizer

Cataloged from PDF version of article.Heavy atom substituted Bodipy compounds, unlike the parent chromophore, undergo rapid intersystem crossing to generate singlet oxygen, which is the primary cytotoxic agent exploited in PDT. In this work, we show that an organic soluble calix[4]arene can be functionalized by Knoevenagel reaction and then converted into an amphiphilic photosensitizer in a few steps. In addition to generating a potentially useful photosensitizer, the sequence of reactions is the first use of a Bodipy dye as a chromophoric/fluorogenic label without the typical reactive functional groups. 2013 Elsevier Ltd. All rights reserved

Proof of principle for a molecular 1:2 demultiplexer to function as an autonomously switching theranostic device

Cataloged from PDF version of article.Guided by the digital design concepts, we synthesized a two-module molecular demultiplexer (DEMUX) where the output is switched between emission at near IR, and cytotoxic singlet oxygen, with light at 625 nm as the input (I), and acid as the control (c). In the neutral form, the compound fluoresces brightly under excitation at 625 nm, however, acid addition moves the absorption bands of the two modules in opposite directions, resulting in an effective reversal of excitation energy transfer direction, with a concomitant upsurge of singlet oxygen generation and decrease in emission intensity

Design and synthesis of soluble dibenzosuberane-substituted fullerene derivatives for bulk-heterojunction polymer solar cells

Cataloged from PDF version of article.Two new dibenzosuberane-substituted fullerene derivatives, dibenzosuberane-C60 monoadduct (DBSCMA) and bis-adduct (DBSCBA) were synthesized using a classical cyclopropanation reaction via a tosylhydrazone route for application as acceptor materials in polymer solar cells (PSCs). DBSCBA shows good solubility in common organic solvents and both derivatives were characterized by 1HNMR, 13C NMR, MALD-TOF, elemental analysis and UV-vis absorption measurements. The shift of fullerene energy levels induced by the dibenzosuberane substitution was investigated by using theoretical simulations and ultraviolet photoelectron spectroscopy. Bulk-heterojunction PSCs based on poly (3-hexylthiophene) (P3HT) and dibenzosuberane-C60 derivatives were fabricated and optimized by adjusting the donor/acceptor ratio and using thermal annealing and solvent additive. The morphologies of the active layers processed under different conditions were also examined by atomic force microscopy. When tested under an illumination of AM 1.5 G at 100 mW/ cm2, the highest power conversion efficiency of the devices using DBSCBA is 3.70% which is superior to that of conventional P3HT:PCBM devices. © 2013 Elsevier B.V

Heavy atom free singlet oxygen generation: Doubly substituted configurations dominate S 1 states of bis-BODIPYs

S 0, S 1, and T 1 states of various orthogonal 8,8′ and 8,2′-bis-boradiaza-s-indacene (BODIPY) dyes, recently (Angew. Chem., Int. Ed.2011, 50, 11937) proposed as heavy atom free photosensitizers for O 2( 1Δ g) generation, were studied by multireference quantum chemical approaches. S 0→S 1 excitation characteristics of certain bis-BODIPYs are shown to be drastically different than the parent BODIPY chromophore. Whereas a simple HOMO→LUMO-type single substitution perfectly accounts for the BODIPY core, S 1 states of certain orthogonal bis-BODIPYs are described as linear combinations of doubly substituted (DS) configurations which overall yield four electrons in four singly occupied orbitals. Computed DS character of S 1, strongly correlated with facile 1O 2 production, was presumed to occur via S 1→T 1 intersystem crossing (ISC) of the sensitizer. Further confirmation of this relation was provided by newly synthesized BODIPY derivatives and comparison of spectroscopic properties of their dimers and monomers. Near-IR absorption, desired for potential photodynamic therapy applications, was not pursuable for bis-chromophores by the standard strategy of π-extension, as DS singlet states are destabilized. Decreased exchange coupling in π-extended cases appears to be responsible for this destabilization. Comparisons with iodine incorporated bis-BODIPYs suggest that the dynamics of 1O 2 generation via DS S 1 states are qualitatively different from that via ISC originating from heavy atom spin-orbit coupling. Although red-shifting the absorption wavelength to enter the therapeutic window does not seem attainable for orthogonal bis-BODIPYs with DS S 1 states, modifications in the chromophore cores are shown to be promising in fine-tuning the excitation characteristics. © 2012 American Chemical Society

Designing Excited States: Theory-Guided Access to Efficient Photosensitizers for Photodynamic Action

Cataloged from PDF version of article.The in silico design of tetraradical S 1 states was validated experimentally through synthesis, followed by characterization including phosphorescence measurements, use of trap molecules, and cell culture studies, leading to a series of orthogonal dimers of Bodipy chromophores with remarkable singlet oxygen efficiencies (see picture). A new path for the rational development of efficient photosensitizers is thus revealed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Locomotor differences in Mongolian gerbils with the effects of midazolam administration in the form of eye drops

Background: Midazolam is a sedative-hypnotic agent with amnestic and anticonvulsant properties that can be administrated to mammals through various routes, such as intravenous, intramuscular, oral, intrathecal, rectal, and buccal. Midazolam administration in the form of eye drops through the conjunctiva is not reported in the literature. Aim:This study aims to demonstrate the possible central nervous system effects of midazolam administration as eyes drops in Mongolian gerbils. Materials and Methods: Fourteen gerbils were randomly assigned to one of two equal sized groups. The active arm received 2 ml of 10 mg midazolam as eye drops in both eyes. Control group received a total of 2 ml of physiological saline(0.9% NaCl). We subjected the gerbils to an adapted “Open Field” to determine the possible effects on central nervous system of midazolam. Gerbils were allowed to move freely in the open field. Before and after the drug administration, locomotor activities of each gerbil have been recorded. Frequency of loss of righting reflex was quantified. Results: Conjunctival Midazolam administration resulted with the transient loss of righting reflex (p=0.017) and suppressed exploration motion (p=0.018) in the open field test compared to control subjects. Conclusions: In the present study, administration of conjunctival midazolam as an eye drop may affect gerbil’s locomotor activities and open field behaviors. We argue that, using a sedative and anticonvulsive drug such as midazolam via conjunctival route may be useful in some clinical situations. Therefore, it could be beneficial to develop a new conjunctival formulation of midazolam. Also, there is a need for trials in humans with pharmacokinetic studies.Keywords: Righting reflex; Conjunctival Midazolam; Gerbillinae; Midazolam; Eye drop; New administration routeAfrican Health sciences Vol 14 No. 1 March 201

Proof of principle for a molecular 1 : 2 demultiplexer to function as an autonomously switching theranostic device

Guided by the digital design concepts, we synthesized a two-module molecular demultiplexer (DEMUX) where the output is switched between emission at near IR, and cytotoxic singlet oxygen, with light at 625 nm as the input (I), and acid as the control (c). In the neutral form, the compound fluoresces brightly under excitation at 625 nm, however, acid addition moves the absorption bands of the two modules in opposite directions, resulting in an effective reversal of excitation energy transfer direction, with a concomitant upsurge of singlet oxygen generation and decrease in emission intensity. © The Royal Society of Chemistry 2013

Solid-state dye-sensitized solar cells using red and near-IR absorbing bodipy sensitizers

Boron-dipyrrin dyes, through rational design, yield promising new materials. With strong electron-donor functionalities and anchoring groups for attachment to nanocrystalline TiO2, these dyes proved useful as sensitizers in dye-sensitized solar cells. Their applicability in a solid-state electrolyte regime offers additional opportunities for practical applications. © 2010 American Chemical Society

Design and characterization of Bodipy derivatives for bulk heterojunction solar cells

Two electron rich Bodipy dyes with strong absorptivities in the visible region were designed and synthesized as potential electron donors in bulk heterojunction photovoltaic constructs. Overall efficiency is above 1%, with impressive responsiveness at both UV and near-IR ends of the visible spectrum. Computational studies reveal an unexpected effect of meso-substituents on the electron transfer efficiency. © 2014 Elsevier Ltd. All rights reserved