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.

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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; however, upon opening of the lactone ring by the formation of the ethyl ester derivative, the fluorophore absorbs at 920 nm and emits at 1092 nm, which are both in the NIR II region. In addition, 4-cyanophenyl- (CNRhIndz) and 4-methoxyphenyl-substituted rhodindolizine (MeORhIndz) could also be prepared by the C–H activation reaction.

The design of visible light absorbing organic dyes as strong photoinduced oxidants is needed for many potential applications in energy production and storage. To access more positive potentials, the electron deficient thienopyrroledione building block is promising as a π-bridge combined with weak aryl-ether donor groups and the phenyl-cyanoacetic acid acceptor group. The thienopyrroledione (TPD) building block is compared to the ubiquitous benzothiadiazole (BTD) building block, which was recently used in a dye-sensitized solar cell (DSC) device with >1.4 V photovoltage output. The variation in dye donor group is studied through UV−vis absorption spectroscopy and electrochemical methods both in solution and on TiO 2 films. The TPD building block resulted in a more positive ground state and excited state oxidation potential, a higher photocurrent (up to 3.5 mA/ cm 2 ), and a higher power conversion efficiency (up to 2.9%) than a BTD analogue while retaining comparable photovoltages (∼1.3 versus ∼1.4 V). Computational analysis was used to better understand the optical properties of the thienopyrroledionebased dyes showing overlap of orbitals at the TPD bridge in the S 0 and S 1 states. The dyes were analyzed in high voltage-DSC devices with a challenging to oxidize redox shuttle, Fe(bpy) 3 2+ , at 1.37 V versus NHE.

Interfacial properties of cellulose nanocrystals (CNC) and surfactants were studied in high ionic strength (I) brines and correlated to the stability of dodecane/brine Pickering emulsions. Bis-(2-hydroxyethyl) cocoalkylamine (CAA), dodecyltrimethylammonium bromide (DTAB), and octyl-β-d-glucopyranoside (OGP) were adsorbed onto CNC in American Petroleum Institute (API) brine (I = 1.9 M) and synthetic seawater (SSW), with I = 0.65 M. Raman spectroscopy indicated that hydroxyl groups on the CNC surface interact with all three surfactants in high ionic strength media. Ionic interactions still play a role at the very large ionic strengths studied herein. Despite all surfactants adsorbing onto CNC, only the surface tension of CAA solutions in both brines was increased by the addition of 0.5 wt % CNC. The effect was much more prominent in API than in SSW. Contact angle measurements indicated that CAA increased the wettability of CNC by both brines in dodecane; DTAB, on the other hand, decreased wettability. Emulsion stability studies revealed that ionic strength, wettability, adsorption energy, and oil content strongly affect emulsion stability, more so than surfactant adsorption. In API, CNC aggregates alone stabilized the emulsions better compared to samples with additional emulsifiers; the same was true in SSW for oil contents below 50% v/v. For oil contents above 50% v/v in SSW, CAA was either detrimental or failed to improve emulsion stability. On the other hand, DTAB increased the stability of dodecane in SSW emulsions. Emulsions stable for over 21 months were prepared with oil contents of 75% v/v. The adsorption of CAA onto CNC limits the migration of both CNC and CAA to the dodecane/brine interface, while DTAB adsorption has the opposite effect.