Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers

Definitions

• An electronically active coacervate based on CPE of the present disclosure may be used in a variety of applications such as electronically conducting underwater adhesives and waterbased, photoactive, viscoelastic pastes. This could be useful for environmentally benign soldering materials, sensing, col or- sensitive coatings and to enhance rates of photochemically driven chemical reactions.
• Implementations of the above embodiment may include one or more of the following features.
• the plurality of monomers may be selected from the group consisting of fluorene, phenylene, thiophene, benzothiadi azole, bithiophene, benzodi thiophene, thienothiophene, and carbazole.
• the plurality of monomers may include at least two of fluorene, phenylene, thiophene, benzothiadiazole, bithiophene, benzodithiophene, thienothiophene, or carbazole.
• Each of the polar nonionic sidechains may include at least one oligo(ethylene glycol) branch extending from a monomer of the plurality of monomers.
• the conjugated polyelectrolyte may be configured to form a liquid coacervate phase in the aqueous solution.
• a coacervate composition includes an aqueous solution of a salt and a first conjugated polyelectrolyte including: a conjugated polymer backbone having a plurality of monomers; ionic sidechains; and polar nonionic sidechains. Each of the ionic sidechains and each the polar nonionic sidechains extends from each monomer of the plurality of monomers in an alternating manner.
• the composition also includes a second conjugated polyelectrolyte having an opposite charge from the first conjugated polyelectrolyte.
• Implementations of the above embodiment may include one or more of the following features.
• the second conjugated polyelectrolyte is anionic poly(cyclopentadithieno-alt-phenylene).
• FIG. 1 shows chemical structures of CPEs according to an embodiment of the present disclosure
• FIG. 2 shows a schematic diagram of synthesis for forming coacervates via liquid/liquid phase separation according to an embodiment of the present disclosure
• FIG. 3 shows a chemical structure of an oppositely charged CPE according to an embodiment of the present disclosure
• FIG. 4 includes images of CPE-based coacervate droplets in which frame (A) is a wide- field transmitted light differential interference contrast (TL-DIC) image of the phase coexistence; frame (B) is a photoluminescence (PL) image with excitation between 340-380 nm and collecting emission between 450-490 nm; frame (C) is a PL image excitation between 450-490 nm and collecting emission between 500-550 nm; frame (D) is a merged PL image; and frame (E) is a bar graph comparing the number of coacervate droplets vs. droplet diameter between 2.5 M and 5.0 M KBr samples;
• TL-DIC transmitted light differential interference contrast
• FIG. 6 shows a cryogenic-transmission electron microscopy (cryo-TEM) images of coacervate droplets in frames (A) and (B);
• suitable salts may include K + and/or Mg 2+ cations.
• suitable salts may include Ca 2+ , Mg 2+ , Fe 2+ , Fe 3+ cations.
• Salts may include any suitable anion, such as, chloride (Cl-), iodide (F), fluoride (F‘), bromide (Bf). Salt may be present in the solution at a concentration from about 3 M to about 5
• the appropriate CPEs are dissolved in water without added salt and then combined each polymer or with appropriate amounts of aqueous salt solution to form the final desired salt and polymer concentration.
• the solution may be heated to a temperature of from about 60 °C to about 80 °C from about 1 hour to about 8 hours to form liquid coacervates.
• a more detailed synthesis is described below in the Examples.
• the coacervate phase may be mechanically isolated from the dilute solution, e.g., filtering and exhibit strong adhesive properties while being electronically active as shown in the Examples below.
• the coacervates according to the present disclosure may be used as electronically active underwater adhesives.
• the liquid CPE coacervates may be electronically doped to convert the liquid CPE coacervate from a semiconducting to a conducting viscoelastic liquid.
• reaction contents were added to 16 mL of cold DI H2O, followed by extraction of the product with dichloromethane (DCM) (4 x 10 mL).
• DCM dichloromethane
• the organic layer was washed with DI H2O (2 x 10 mL), brine (1 x 10 mL), and subsequently dried over Na2SC>4.
• the anhydrous organic layer was decanted away from the drying agent and concentrated under reduced pressure to provide the product TG9 as a colorless oil (99% yield, 4.06 g).
• the product (FN) was extracted from the wet DMSO layer with diethyl ether (Et2O, 8 x 25 mL), and washed with a 10 wt. % aqueous NaOH (10 wt. % aq. NaOH, 2 x 50 mL).
• the organic layer was washed with DI H2O (3 x 50 mL), followed by a brine wash (1 x 50 mL), and then dried over anhydrous sodium sulfate (Na2SO4).
• the contents of the reaction were stirred and heated at 80 °C for 24 hours. Reaction progress was monitored by TLC. Upon completion, the reaction was concentrated to dryness, and the crude solid was extracted with hot HPLC-grade hexanes (7 x 100 mL). The combined hexanes layer was filtered, concentrated to dryness, reextracted with hot hexanes, and re-concentrated to dryness. Acetone was used to extract the product from the redried hexanes layer and was allowed to crystallize out of the solution as an off-white solid. The FNB crystals were collected via filtration and washed with a minimal amount of cold acetone to obtain FNB (55% yield, 0.6647 mg).
• the anhydrous organic layer was decanted away from the drying agent. While stirring, a mixture consisting of 95% DCM with 5% Methanol (MeOH) was used to wash the product from the Na2SC>4 slurry.
• the DCM: MeOH solution was decanted from the Na2SO4 and combined with the organic layer.
• the organic layer was concentrated under reduced pressure to provide a semi-crude solid which was purified further via a silica gel column (Ethyl Acetate: MeOH, 90: 10). Since the percentage of MeOH in the solvent used to elute the aggregated fraction of FG9 was 10%, FG9 was dissolved in chloroform (CHCh) to help precipitate out the once dissolved silica gel.
• CHCI3 solution was then filtered to remove the precipitate and concentrated under reduced pressure to obtain FG9 (30.0% yield, 0.710 g).
• Potassium bromide (KBr, 99.99 % purity) was obtained from Sigma-Aldrich. Tetraethylammonium bromide (> 98.0 % purity) (TEAB) from TCI Chemicals, and calcium bromide (CaBn, extra pure) from Fisher Scientific. All chemicals were used as received.
• Stock solutions of 11 mg/mL PFNG9, 5.0 M KBr, 7.0 M LiBr, and 7.0 M TEAB were prepared using degassed (argon) high-performance liquid chromatography (HPLC) grade water (Sigma- Aldrich). The PFNG9 stock was stirred at 70 °C for 6 hrs in a light protected vial. The salt stocks were stirred and heated at 70 °C for 15 min to guarantee all salt crystals were fully dissolved.
• PFNG9 concentration was fixed at 4.624 mg/mL for all solutions.
• Samples containing 5.0 M KBr were made with solid KBr; samples at 0.5 M and 2.5 M KBr were made using degassed KBr stock. The order of addition was as follows: KBr, HPLC water, PFNG9. Samples were stirred at 250 rpm at 70 °C for 6 hrs. Samples were allowed to cool to room temperature before any analysis was performed and care was taken to limit ambient light exposure. All other samples containing TEAB or CaBn were made using degassed salt stocks in using the same prep described above.
• the A4 filter was chosen to select for the emission of the dilute phase and a GFP filter was used to select for the emission of the coacervate phase. Samples were also imaged using transmitted light DIC when using a 40x objective.
• a Leica SP5 Confocal Microscope was used to collect PL spectra from regions of interest in an image after performing a xyX scan, in which the excitation wavelength was fixed, and the detected emission wavelength was scanned in 5-nm increments. Images were collected using a 20x/0.75 objective at 16-bit resolution. xyk scans were taken while exciting with 405, 458, 476, and 496 nm laser lines, and emission was detected out to 750 nm.
• FIG. 7 shows a room -temperature phase diagram of the PFNG12 simple coacervate in the presence of aqueous KBr.
• the y-axis is the KBr concentration
• the x-axis is the PFNG12 concentration.
• Hashed regions correspond to unexplored (PFNG12 concentration > 50 mg/mL) or metastable regions (KBr concentration > 5 M).
• the bottom region corresponds to a homogeneous solution, i.e., no phase separation.
• the middle region corresponds to a coexistence of a dilute solution with solid-like particles.
• the top region corresponds to a three-phase coexistence of the dilute solution, solid particles and liquid droplets.
• the blue region corresponds to a coexistence between the dilute solution and liquid droplets (see FIG. 4).
• the sample was blotted for 2.5 s using a Vitrobot Mark IV (FEI Company) at 22 °C and -100% humidity and sequentially fast-plunged into liquid ethane.
• the images were acquired using 1-s exposure on a 4k x 4k CETA CCD Camera coupled to a ThermoFischer Glacios cryo-TEM operating at 200 kV. Images were collected at a nominal 2A pixel size, 73,000 x magnification, and -3.5 pM defocus. Fiji - Imagel was used for data analysis.
• TRPL photoluminescence
• PL lifetimes were determined using forward convolution with the measured instrument response function taken using a scattering Ludox sample. This was done using least-squares minimization via the DecayFit MATLAB package developed by Soren Preus (Fluorescence Decay Analysis Software 1.3, FluorTools, www.fluortools.com). A sum-of-exponentials model was used for the decay.
• Frame A of FIG. 8 shows absorption or optical density (OD) spectra of dilute and concentrated phases, which were acquired by carefully separating the phases.
• OD optical density
• the coacervate g-band is likely primarily composed of interchain exciton states.
• the fact that only one new, relatively narrow absorption band appears within the coacervate but that two putative emissive species include the g-band PL spectrum is consistent with a coexistence of excimers and H-aggregate excitons within a coacervate droplet.
• Evidence for H-aggregate formation is provided by the appearance of a new redshifted absorption band in the OD spectrum of the coacervate compared to the dilute phase (frame A of FIG. 4). Fluorenone defects also contribute to the coacervate emission spectrum.
• the PL spectra support the finding that the CPE coacervate of Example 3 is an intrinsically excitonically coupled viscoelastic liquid as shown in
• Regions corresponding to excimer and H-aggregate exciton states are labeled as magenta domains with few or extended interchain contacts, respectively. Illustrations of the corresponding potential energy curves as a function of the (average) inter-chromophore separation R are shown in the side panels.
• FLIM fluorescence lifetime imaging
• FLIM measurements were carried out using a Zeiss LSM 980 NLO confocal microscope (Becker-Hickl TCSPC FLIM). Samples were excited using a 445-nm laser line, and PL was collected using a 590/50 nm filter cube. Images were collected using a 512 x 512 pixel resolution and a 50-s collection time. Fluorescence lifetime averages and distributions were determined using the SPCImage 8.5 NG software via the maximum likelihood estimation method.
• the FLIM heat map shows that T is a function of position within the droplet, demonstrating that (T) is a fluctuating variable within the coacervate. This observation is consistent with the viscous liquid macrostate.
• the extracted image grey value as a function of position for the different linecuts shows that relatively small fluctuations in ( ) occur on the ⁇ 1 pm scale, while larger fluctuations are also seen on the ⁇ 10 pm scale. Differences in (T) must reflect differences in local structure.
• the PL lifetime was somewhat longer near the edge of the droplets than in the center. This is shown in frame C of FIG. 14, which compares decays collected in the middle of the droplet to that of the near-surface region (indicated by squares in the image of the frame A of FIG. 14).
• the lifetime of the short component increased from 255 ps to 298 ps, while the lifetime of the long component increased from 1367 ps to 1693 ps.
• the difference between bulk and surface lifetimes increased closer to the edge of the droplet, as seen from the lifetime histogram and the corresponding FLIM image.
• Frame (D) shows an overlay of all fluorescence images of frames (A)-(C) with the same optical filters for the PFNG9:NaPCPT complex
• frame (E) shows an overlay for the PFNG6:NaPCPT complex
• (F) shows an overlay for the PFNG12:NaPCPT complex.

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• 2023
  • 2023-09-14 EP EP23866456.9A patent/EP4587500A2/de active Pending
  • 2023-09-14 WO PCT/US2023/074134 patent/WO2024059678A2/en not_active Ceased

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