Influence of Film Composition on the Morphology, Mechanical Properties, and Surfactant Recovery of Phase-Separated Phospholipid-Perfluorinated Fatty Acid Mixed Monolayers

Monolayer surfactant films composed of a mixture of phospholipids and perfluorinated (or partially fluorinated) surfactants are of potential utility for applications in pulmonary lung surfactant-based therapies. As a simple, minimal model of such a lung surfactant system, binary mixed monolayer films composed of 1,2-dipalmitoyl-<i>sn</i>-glycero-3-phosphocholine (DPPC) and perfluorooctadecanoic acid (C18F) prepared on a simplified lung fluid mimic subphase (pH 7.4, 150 mM NaCl) have been characterized in terms of mixing thermodynamics and compressibility (measured through π–<i>A</i> compression isotherms), film morphology (via atomic force, fluorescence, and Brewster angle microscopy), as well as spreading rate and hysteresis response to repeated expansion–contraction cycles for a variety of compositions of mixed films. Under all mixing conditions, films and their components were found to be completely immiscible and phase-separated, though there were significant changes in the aforementioned film properties as a function of composition. Of particular note was the existence of a maximum in the extent of immiscibility (characterized by Δ<i>G</i>_ex^π values) and enhanced surfactant recovery during hysteresis experiments at χ_C18F ≥ 0.30. The latter was attributed to the relatively rapid respreading rate of the perfluorinated amphiphile in comparison with DPPC alone at the air–water interface, which enhances the performance of this mixture as a potential pulmonary lung surfactant. Further, monolayer film structure could be tracked dynamically as a function of compression at the air–water interface via Brewster angle microscopy, with the C18F component being preferentially squeezed out of the film with compression, but returning rapidly upon re-expansion. In general, addition of C18F to DPPC monolayers resulted in improvements to mechanical, structural, and respreading properties of the film, indicating the potential value of these compounds as additives to pulmonary lung surfactant formulations

Influence of Film Composition on the Morphology, Mechanical Properties, and Surfactant Recovery of Phase-Separated Phospholipid-Perfluorinated Fatty Acid Mixed Monolayers

Monolayer surfactant films composed of a mixture of phospholipids and perfluorinated (or partially fluorinated) surfactants are of potential utility for applications in pulmonary lung surfactant-based therapies. As a simple, minimal model of such a lung surfactant system, binary mixed monolayer films composed of 1,2-dipalmitoyl-<i>sn</i>-glycero-3-phosphocholine (DPPC) and perfluorooctadecanoic acid (C18F) prepared on a simplified lung fluid mimic subphase (pH 7.4, 150 mM NaCl) have been characterized in terms of mixing thermodynamics and compressibility (measured through π–<i>A</i> compression isotherms), film morphology (via atomic force, fluorescence, and Brewster angle microscopy), as well as spreading rate and hysteresis response to repeated expansion–contraction cycles for a variety of compositions of mixed films. Under all mixing conditions, films and their components were found to be completely immiscible and phase-separated, though there were significant changes in the aforementioned film properties as a function of composition. Of particular note was the existence of a maximum in the extent of immiscibility (characterized by Δ<i>G</i>_ex^π values) and enhanced surfactant recovery during hysteresis experiments at χ_C18F ≥ 0.30. The latter was attributed to the relatively rapid respreading rate of the perfluorinated amphiphile in comparison with DPPC alone at the air–water interface, which enhances the performance of this mixture as a potential pulmonary lung surfactant. Further, monolayer film structure could be tracked dynamically as a function of compression at the air–water interface via Brewster angle microscopy, with the C18F component being preferentially squeezed out of the film with compression, but returning rapidly upon re-expansion. In general, addition of C18F to DPPC monolayers resulted in improvements to mechanical, structural, and respreading properties of the film, indicating the potential value of these compounds as additives to pulmonary lung surfactant formulations

Morphology and Composition of Structured, Phase-Separated Behenic Acid–Perfluorotetradecanoic Acid Monolayer Films

The phase separation of immiscible surfactants in mixed monolayer films provides an approach to physically manipulate important properties of thin films, including surface morphology, microscale composition, and mechanical properties. In this work, we predict, based upon existing miscibility studies and their thermodynamic underpinnings described in the literature, the miscibility and film morphology of mixed monolayers comprised of behenic acid (C₂₁H₄₃COOH) and perfluorotetradecanoic acid (C₁₃F₂₇COOH) in various molar ratios. Predictions are tested using a combination of experimental surface characterization methods for probing miscibility and film morphology at the solid/air and air/water interfaces. Film components were immiscible and phase-separated into chemically well-defined domains under a variety of experimental conditions, with monolayer morphology consistent with initial predictions. The extensibility of these basic predictions to other systems is discussed in the context of using these works for different perfluorinated surfactant molecules

Efficiency of Noncoherent Photon Upconversion by Triplet–Triplet Annihilation: The C60 Plus Anthanthrene System and the Importance of Tuning the Triplet Energies

As part of a continuing effort to find noncoherent photon upconversion (NCPU) systems with improved energy conversion efficiencies, the photophysics of the blue emitter, anthanthrene (An), and the fullerene absorber–sensitizer, C₆₀, have been examined by both steady-state and pulsed laser techniques. An is a promising candidate for NCPU by homomolecular triplet–triplet annihilation (TTA) because its triplet state lies ∼800 cm^–1 below the triplet energy of the C₆₀ donor (thereby improving efficiency by reducing back triplet energy transfer), and its fluorescent singlet state lies in near resonance with double its triplet energy (thus minimizing thermal energy losses in the annihilation process). In fluid solution, efficient triplet–triplet donor–acceptor energy transfer is observed, and rate constants for homomolecular TTA in the An acceptor are estimated to approach the diffusion limit. NCPU is also observed in An + C₆₀ in poly­(methylmethacrylate) thin films

Photophysics of Zinc Porphyrin Aggregates in Dilute Water–Ethanol Solutions

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S₂ with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S₁ state is the only significant product of the radiationless decay of the S₂ state of the excited monomer, and the aggregates also produce substantial quantum yields of S₁ fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet–triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed

Mixing Behavior in Binary Anionic Gemini Surfactant–Perfluorinated Fatty Acid Langmuir Monolayers

The miscibility and film structure of mixed Langmuir monolayer films composed of an anionic gemini <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-dialkyl-<i>N</i>,<i>N</i>′-diacetate ethylenediamine surfactant (Ace(12)-2-Ace(12)) with perfluoro­tetradecanoic acid (C₁₃F₂₇COOH; PF) have been investigated using a variety of thermodynamic and structural characterization methods. The two film components were found to be miscible in monolayers at the air–water interface over a range of compositions and at all but the lowest surface pressures, with attractive interactions occurring between the two components. While pure PF monolayers formed crystalline lattices with hexagonal symmetry and with the surfactant tails oriented normal to the underlying water subphase, the pure gemini surfactant formed amorphous films with little tendency to orient at the subphase. In mixed films with mole ratios of PF:Ace(12)-2-Ace(12) < 2.5, the miscibility of the two components resulted in a nearly complete loss of crystallinity of the PF, though films at higher mole fractions of PF showed some residual crystallinity, albeit with lattice structures that were significantly different from that of pure PF. Miscibility and film structure in this mixed system are discussed in comparison with other mixed gemini surfactant systems in the literature as well as binary mixtures of phospholipids or monomeric fatty acids with PF

Spectroscopic and Structural Studies of a Surface Active Porphyrin in Solution and in Langmuir–Blodgett Films

Controlling aggregation of the dual sensitizer–emitter (S-E) zinc tetraphenylporphyrin (ZnTPP) is an important consideration in solid state noncoherent photon upconversion (NCPU) applications. The Langmuir–Blodgett (LB) technique is a facile means of preparing ordered assemblies in thin films to study distance-dependent energy transfer processes in S-E systems and was used in this report to control the aggregation of a functionalized ZnTPP on solid substrates. This was achieved by synthetic addition of a short polar tail to one of the pendant phenyl rings in ZnTPP in order to make it surface active. The surface active ZnTPP derivative formed rigid films at the air–water interface and exhibited mean molecular areas consistent with approximately vertically oriented molecules under appropriate film compression. A red shift in the UV–vis spectra as well as unquenched fluorescence emission of the LB films indicated formation of well-ordered aggregates. However, NCPU, present in the solution phase, was not observed in the LB films, suggesting that NCPU from ZnTPP as a dual S-E required not just a controlled aggregation but a specific orientation of the molecules with respect to each other

Photophysics of Soret-Excited Tin(IV) Porphyrins in Solution

The photophysics of low-chlorin tin­(IV) tetraphenylporphyrin dihydroxide, a core building block for axially substituted supramolecular tin porphyrin constructs, has been studied in a variety of hydrogen-bonding, nonpolar, and aprotic polar solvents using steady-state, nanosecond, and femtosecond time-resolved emission, and femtosecond time-resolved absorption methods. In hydrogen-bonding solvents the metalloporphyrin exists as solvated monomers, and its Soret-excited S₂ state in these solvents exhibits the expected linear energy gap law relationship with first-order population decay times in the 0.8 to 1.7 ps range. Evidence is presented that this metalloporphyrin aggregates in other solvents at the concentrations typically used for these ultrafast measurements and yields species-averaged time-resolved data. Cw laser excitation in the Q-band under deaerated conditions produces weak S₂–S₀ fluorescence (photon upconversion) as a result of triplet–triplet annihilation