Ratiometric Near-Infrared Fluorescent Probes Based on Hemicyanine Dyes Bearing Dithioacetal and Formal Residues for pH Detection in Mitochondria.

Ratiometric near-infrared fluorescent probes (AH+ and BH+) have been prepared for pH determination in mitochondria by attaching dithioacetal and formal residues onto a hemicyanine dye. The reactive formyl group on probe BH+ allows for retention inside mitochondria as it can react with a protein primary amine residue to form an imine under slightly basic pH 8.0. Probes AH+ and BH+ display ratiometric fluorescent responses to pH changes through the protonation and deprotonaton of a hydroxy group in hemicyanine dyes with experimentally determined pKa values of 6.85 and 6.49, respectively. Calculated pKa values from a variety of theoretical methods indicated that the SMDBONDI method of accounting for solvent and van der Waals radii plus including a water molecule located near the site of protonation produced the closest overall agreement with the experimental values at 7.33 and 6.14 for AH+ and BH+ respectively.

A near-infrared fluorescent probe based on a hemicyanine dye with an oxazolidine switch for mitochondrial pH detection.

A near-infrared fluorescent probe (AH+) has been prepared by incorporating an oxazolidine switch into a near-infrared hemicyanine dye. The probe shows fast and sensitive responses to pH from an oxazolidine switch to the hemicyanine dye upon pH decreases from 10.0 to 5.0. The probe shows good photostability, low cytotoxicity, and reversible fluorescence responses to pH changes with a pKa value of 7.6. It has been successfully used to determine pH changes in mitochondria.

An Alternating D1-A-D2-A Conjugated Ternary Copolymer Containing [1,2,5]selenadiazolo[3,4-c]pyridine Unit With Photocurrent Response Up to 1,100 nm.

Two narrow band gap conjugated ternary copolymers comprising two electron-rich (donor, D) and one electron-deficient (acceptor, A) moieties regularly alternating along the polymer backbone were designed and synthesized. The polymers with the repeating unit in a D1-A-D2-A manner were constructed by copolymerizing a bisstannyled-D1 (D1 = n-alkyl-substituted cyclopentadithiophene) and a dibromo-monomer (Br-A-D2-A-Br, D2 = branched-alkyl-substituted cyclopentadithiophene, A =[1,2,5]selenadiazolo[3,4-c]pyridine or 5-fluorobenzo[c][1,2,5]selenadiazole) through a palladium-catalyzed Stille polymerization. This approach that enables variations in the donor fragment substituents can not only control the polymer regiochemistry but also the solubility. Two ternary copolymers exhibited absorbance up to near-infrared region along with relatively narrow band gap in the range of 1.02-1.26 eV. The polymeric photovoltaic cells based on CDTPSE/PC61BM show the short circuit density of 1.45 mA cm-2, open current voltage of 0.53 V, and photocurrent spectra response from 300 to 1,150 nm under AM 1.5 simulator (100 mW cm-2). It is indicated that it can be potentially applied to near infrared photodetectors.

Cell Membrane-Specific Fluorescent Probe Featuring Dual and Aggregation-Induced Emissions.

A cell membrane-specific fluorescent probe was prepared by conjugating a coumarin dye with a tetraphenylethene (TPE) derivative through an α,ß-unsaturated ketone connection. The probe has two absorptions: one from the TPE moiety at 300 nm and a second one due to the coumarin moiety at 458.5 nm. The probe fluoresces at 470 nm in tetrahydrofuran (THF) solution. The probe exhibits a useful aggregation-induced emission (AIE) property. A gradual increase in the water content of a THF solution causes a significant decrease and 12 nm red shift in the fluorescence peak at 470 nm, giving rise to a new strong fluorescence peak at 591 nm at a 95% water content. The probe is hydrophobic with an AIE property and binds to cell membranes, resulting in 591 nm fluorescence upon implantation into cells. The probe possesses a long retention time despite the lack of a long, cell membrane-anchored hydrophobic alkyl chain, which is typical for traditional membrane-specific probes. Our probe also displays low cytotoxicity and excellent photostability.

One-pot cascade synthesis of N-methoxyisoquinolinediones via Rh(III)-catalyzed carbenoid insertion C-H activation/cyclization.

Here a new, mild and versatile method for one-pot cascade synthesis of diverse N-methoxyisoquinolinediones via Rh(III)-catalyzed regioselective carbenoid insertion C-H activation/cyclization of N-methoxybenzamides with α-diazotized Meldrum's acid has been achieved. Extension of the developed Rh(III) catalysis for building new analogs of the marketed drug Edaravone has also been demonstrated.

Rhodium(III)-catalyzed C2-selective carbenoid functionalization and subsequent C7-alkenylation of indoles.

Here a new, mild and versatile method for efficient synthesis of a diverse range of 2-acetate substituted indoles via Rh(III)-catalyzed and alcohol-mediated C2-selective carbenoid insertion functionalization of indoles by α-diazotized Meldrum's acid has been developed. Furthermore, for the first time, a Rh(III)/Cu(II)-catalyzed direct C7-alkenylation of such functionalized products has also been demonstrated.

Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues.

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, (1)H NMR, (13)C NMR, MS or HRMS; their absorption coefficients (epsilon), maximum absorption lambda(amax), fluorescence emission maximum lambda(em), Stokes shifts and fluorescence quantum yields (Phi(F)) in ethyl acetate were determined; their fluorescent lifetimes (T(1) and T(2)) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.