A BODIPY-O-glycoside based near-infrared fluorescent sensor for serum albumin.

Highly sensitive and selective near-infrared fluorescent bioprobes for serum albumin detection and quantification are in high demand for biomedical applications. Herein, we report a near-infrared emitting BODIPY-O-glycoside dye as a turn-on emission sensor for serum albumin. To the best of our knowledge, this is the first report of NIR-emitting BODIPY dyes for serum albumin sensing. Despite the various outstanding photophysical properties of the BODIPY dyes, their insolubility in water/biological media restricts their real biomedical applications. To overcome this issue, highly stable unadulterated BODIPY-O-glycoside nanoparticles (BDP-Glu-NPs) were prepared in aqueous solution by self-assembly of amphiphilic BODIPY-O-glycoside dyes. The BDP-Glu-NPs were characterized by spectroscopic, NMR, DLS and TEM studies. The ability of the BDP-Glu-NPs for the detection and quantification of serum albumin was demonstrated. It showed a 150-fold fluorescence enhancement in the presence of serum albumin, with excellent selectivity over other amino acids, porphyrin, proteins and various inorganic salts. Detection of human serum albumin (HSA) in urine samples showed that the bioprobe is applicable to a clinically significant range of the analytes with very low detection limit. These results suggested that the BDP-Glu-NPs can act as potential bioprobe to quantify albumin in biochemical and clinical samples.

Monitoring the formation of insulin oligomers using a NIR emitting glucose-conjugated BODIPY dye.

Protein oligomers, which are formed due to the aggregation of protein molecules under physiological stress, are neurotoxic and responsible for several neurological diseases. Early detection of protein oligomers is essential for the timely intervention in the associated diseases. Although several probes have been developed for the detection of insoluble matured protein fibrils, fluorescent probes with emission in the near infrared (NIR) region for probing protein oligomers are very rare. In the present study we have designed and synthesized a glucose-conjugated BODIPY dye with emission in the NIR spectral range. Our detailed studies show that the new probe is not only capable of detecting matured fibrils but can also probe the formation of oligomers from the native protein. The new probe shows a large increase in its emission intensity upon association with oligomers and matured fibrils. Hence, the present probe has a great potential for the in vivo imaging of protein oligomers and matured fibrils. Detailed spectroscopic properties of the new probes in molecular solvents have been performed to understand its oligomers- and fibril- sensing mechanism.

Tuning of electron tunneling: a case study using BODIPY molecular layers.

Redox active π-conjugated organic molecules have shown the potential to be used as electronic components such as diode and memory elements. Here, we demonstrate that using simple surface chemistry, rectification characteristics can be tuned to reproducible negative differential resistance (NDR) with a very high peak-to-valley ratio (PVR) up to 1000 in 2,6-diethyl-4,4-difluoro-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indecene (BODIPY) grafted on Si. The change in properties is related to oxidation and reduction of BODIPY, which results in the change in resonant to non-resonant tunneling of electrons under bias. This has been explained by the ab initio molecular-orbital theoretical calculations.

"To Twist or Not to Twist": Figure-of-Eight and Planar Structures of Octaphyrins.

Amongst the various porphyrinoids, octaphyrin has attracted significant attention owing to its diverse syntheses, conformations, and metal-ligation properties. Octaphyrin is a higher homologue of porphyrin and is formed by linking together heterocycles such as pyrrole, furan, thiophene, and selenophene through α-α or α-meso carbon bonds. The planar conformation is mainly achieved through inversion of the heterocyclic units from the center of macrocycle; avoiding meso-bridges; introducing a para-quinodimethane bridge; employing a neo-confusion approach; protonation; and by generating dianionic species. In this Focus Review, recent synthetic advancements in the field of octaphyrins are summarized. The twisted conformation of the octaphyrin binds to two metal ions in a tetracoordinate geometry. The diphosphorus complex of octaphyrin represents the first example of a stable expanded isophlorin.

Syntheses and photodynamic activity of some glucose-conjugated BODIPY dyes.

The syntheses of three water-soluble glucose-conjugated BODIPY dyes with different wavelength emissions and studies of their photodynamic therapeutic (PDT) action on human lung cancer A549 cell line are disclosed. Amongst the chosen compounds, the BODIPY dye 4 possessing a glycosylated styryl moiety at the C-3 position showed best PDT property against the A549 cell line. In particular, it induced reactive oxygen species-mediated caspase-8/caspase-3-dependent apoptosis as revealed from the increased sub G1 cell population and changes in cell morphology. These results along with its localization in the endoplasmic reticulum, as revealed by confocal microscopy suggested that mitochondria may not be directly involved in the photo-cytotoxicity of 4. Compound 4 did not induce any dark toxicity to the A549 cells, and was non-toxic to normal lung cells.

Quinone-Bodipy H-bonding interaction over π-stacking in toluene.

Quinone type compounds (o-chloranil, p-chloranil and DDQ) demonstrate excellent H-bonding interactions with a meso-phenol Bodipy dye (1) in both ground and excited state in a non-polar toluene medium. The spectroscopic detection of isosbestic absorption occurs with both quinones and fullerenes, but only quinones form isoemissive complexes with dye 1. (1)H NMR study and Monte Carlo global minima searching justified the above mentioned results with efficiency.

Change of boron substitution improves the lasing performance of Bodipy dyes: a mechanistic rationalisation.

Bodipy laser dyes are highly efficient but degrade rapidly in solution by reacting with in situ generated singlet oxygen ((1)O(2)). To increase the lasing lifetimes of these dyes, we have designed and synthesised two different congeners of the widely studied Pyrromethene 567 (PM567) by substitution at the boron centre and/or at both the boron centre and the meso position. The two new dyes showed high lasing efficiencies with increased photostability. The results of theoretical and pulse radiolysis studies revealed that the substitution at the boron centre reduced the (1)O(2) generation capacity of these dyes as well as their rate of reaction with (1)O(2), thereby enhancing their lifetimes even under lasing conditions.

Steric strain release-directed regioselective functionalization of meso-methyl Bodipy dyes.

Starting from some meso-methyl Bodipy dyes, the corresponding meso-styryl derivatives were synthesized by regioselective Knoevenagel-type condensation with different aromatic aldehydes. The reactions were driven by the alleviation of the structural strain of the alkyl substituted Bodipys that could override the differential acidities of the methyl protons at the pyrrole ring of the Bodipy moiety.