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Reversible CO2 binders under ambient conditions are of significant interest for multiple applications in sensing and capture technologies. In this paper, a general systematic way to evaluate CO2 re...

This study represents a successful approach toward employing polycaprolactone-polyamidoamine (PCL-PAMAM) linear dendritic block copolymer (LDBC) nanoparticles as small-molecule carriers in NIR imaging and photothermal therapy. A feasible and robust synthetic strategy was used to synthesize a library of amphiphilic LDBCs with well-controlled hydrophobic-to-hydrophilic weight ratios. Systems with a hydrophobic weight ratio higher than 70% formed nanoparticles in aqueous media, which show hydrodynamic diameters of 51.6 and 96.4 nm. These nanoparticles exhibited loading efficiencies up to 21% for a hydrophobic molecule and 64% for a hydrophilic molecule. Furthermore, successful cellular uptake was observed via trafficking into endosomal and lysosomal compartments with an encapsulated NIR theranostic agent (C3) without inducing cell death. A preliminary photothermal assessment resulted in cell death after treating the cells with encapsulated C3 and exposing them to NIR light. The results of this work confirm the potential of these polymeric materials as promising candidates in theranostic nanomedicine.

A NIR II emissive dye was synthesized by the C–H bond functionalization of 1-methyl-2-phenylindolizine with 3,6-dibromoxanthene. The rhodindolizine (RhIndz) spirolactone product was nonfluorescent;...

Reversible CO2 binders under ambient conditions are of significant interest for multiple applications in sensing and capture technologies. In this paper, a general systematic way to evaluate CO2 receptors with π-systems is put forward. A series of receptors (five pyridine-based and one triazine-based) are evaluated as CO2 binders in terms of number of hydrogen bonding sites, strength of hydrogen bond donors, and number of nucleophilic sites. The binding of CO2 to the receptors was probed by computational models, absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and 1H NMR studies. Multiple solvents with varying ionic strength additives are probed to analyze the effects on CO2-bound intermediates. The receptors were screened progressively down-selecting through the different analytical techniques arriving at a promising pyridine receptor, which shows evidence of CO2 binding with each of the analytical techniques. The diaminopyridine motif demonstrates reversible CO2 binding and has convenient substitution sites for derivatization to incorporate into functional sensor systems.

Organic dyes that absorb and emit in the near-infrared (NIR) region are potentially noninvasive, high-resolution, and rapid biological imaging materials. Indolizine donor-based cyanine and squaraine dyes with water-solubilizing sulfonate groups were targeted in this study due to strong absorptions and emissions in the NIR region. As previously observed for nonwater-soluble derivatives, the indolizine group with water-solubilizing groups retains a substantial shift toward longer wavelengths for both absorption and emission with squaraines and cyanines relative to classically researched indoline donor analogues. Very high quantum yields (as much as 58%) have been observed with absorption and emission >700 nm in fetal bovine serum. Photostability studies, cell culture cytotoxicity, and cell uptake specificity profiles were all studied for these dyes, demonstrating exceptional biological imaging suitability.

Molecular engineering strategies designed to red-shift cyanine dye absorptions and emissions further into the near-infrared (NIR) spectral region are explored. Through the use of a novel donor group, indolizine, with varying cyanine bridge lengths, dye absorptions and emissions, were shifted deeper into the NIR region than common indoline-cyanines. Stokes shifts resulting from intramolecular steric interactions of up to ∼60 nm in many cases were observed and explained computationally. Molecular brightnesses of up to 5800 deep into the NIR region were observed. Structure-property relationships are explored for the six indolizine-cyanine dyes with varying cyanine bridge length and indolizine substituents showing broad absorption and emission tunability. The dyes are characterized by crystallography, and the photophysical properties are probed by varying solvent for absorption and emission studies. Computational data show involvement of the entire indolizine π-system during light absorption, which suggests these systems can be tunable even further into the NIR region through select derivatizations.

The development of deep red and near infrared emissive materials with high quantum yields is an important challenge. Several classes of squaraine dyes have demonstrated high quantum yields, but require significantly red-shifted absorptions to access the NIR window. Additionally, squaraine dyes have typically shown narrow Stokes shifts, which limits their use in living biological imaging applications due to dye emission interference with the light source. Through the incorporation of indolizine heterocycles we have synthesized novel indolizine squaraine dyes with increased Stokes shifts (up to >0.119 eV, >50 nm increase) and absorptions substantially further into the NIR region than an indoline squaraine benchmark (726 nm versus 659 nm absorption maxima). These materials have shown significantly enhanced water solubility, which is unique for squaraine dyes without water-solubilizing substituents. Absorption, electrochemical, computational, and fluorescence studies were undertaken and exceptional fluorescence quantum yields of up 12 % were observed with emission curves extending beyond 850 nm.

Near-infrared emissive materials with tunable Stokes shifts and solid-state emissions are needed for several active research areas and applications. To aid in addressing this need, a series of indolizine-cyanine compounds varying only the anions based on size, dipole, and hydrophilicity were prepared. The effect of the non-covalently bound anions on the absorption and emission properties of identical &pi, system indolizine-cyanine compounds were measured in solution and as thin films. Interestingly, the anion choice has a significant influence on the Stokes shift and molar absorptivities of the dyes in solution. In the solid-state, the anion choice was found to have an effect on the formation of aggregate states with higher energy absorptions than the parent monomer compound. The dyes were found to be emissive in the NIR region, with emissions peaking at near 900 nm for specific solvent and anion selections.