Unravelling photoisomerization dynamics in a metastable-state photoacid.

Direct access to trans-cis photoisomerization in a metastable state photoacid (mPAH) remains challenging owing to the presence of competing excited-state relaxation pathways and multiple transient isomers with overlapping spectra. Here, we reveal the photoisomerization dynamics in an indazole mPAH using time-resolved fluorescence (TRF) spectroscopy by exploiting a unique property of this mPAH having fluorescence only from the trans isomer. The combination of these experimental results with time-dependent density function theory (TDDFT) calculations enables us to gain mechanistic insight into this key dynamical process.

Photoacid for releasing carbon dioxide from sorbent.

Carbon dioxide (CO2) is the most important greenhouse gas that causes global warming. Different sorbents, e.g. amines have been applied to capture CO2. Sorbent regeneration, which is currently conducted by thermal processes, is the most energy consuming step. In this work, we studied a photoacid, which can reversibly increase the acidity of a solution under light, and consequently lead to CO2 release. The photoactivity, acidity and solubility of the photoacid was tuned for CO2 release by structural design. The photoacid was mixed with morpholine, which is a well-studied amine for CO2 capture. Results showed that an aqueous solution containing the mixture can repeatedly capture and release CO2 under moderate irradiation of visible light. The CO2 released was nearly the same to that was captured, which indicates the high efficiency of this method.

Photochemically-Driven CO2 Release Using a Metastable-State Photoacid for Energy Efficient Direct Air Capture.

One of the grand challenges underlying current direct air capture (DAC) technologies relates to the intensive energy cost for sorbent regeneration and CO2 release, making the massive scale (GtCO2 /year) deployment required to have a positive impact on climate change economically unfeasible. This challenge underscores the critical need to develop new DAC processes with substantially reduced regeneration energies. Here, we report a photochemically-driven approach for CO2 release by exploiting the unique properties of an indazole metastable-state photoacid (mPAH). Our measurements on simulated and amino acid-based DAC systems revealed the potential of mPAH to be used for CO2 release cycles by regulating pH changes and associated isomers driven by light. Upon irradiating with moderate intensity light, a ≈55 % and ≈68 % to ≈78 % conversion of total inorganic carbon to CO2 was found for the simulated and amino acid-based DAC systems, respectively. Our results confirm the feasibility of on-demand CO2 release under ambient conditions using light instead of heat, thereby providing an energy efficient pathway for the regeneration of DAC sorbents.

Poly(butyl cyanoacrylate) nanoparticle containing an organic photoCORM.

Carbon monoxide (CO) is a gasotransmitter, which has shown therapeutic effects in recent studies. Photo carbon monoxide releasing molecules (PhotoCORMs) allow the delivery of CO to be controlled by light. In this work, a new organic photoCORM DK4 is studied. DK4 is a diketone type photoCORM, which releases two CO molecules under visible light and simultaneously generates a fluorescent anthracene derivative. However, this type of CORM suffers from a deactivating hydration reaction and often needs to be incorporated in polymers or micelles. The two highly hydrophobic tert-butyl groups of DK4 protect it from the hydration reaction. DK4 functions in 1% DMSO aqueous solution, in which other DKs are deactivated. DK4 was incorporated in a poly(butyl cyanoacrylate) (PBCA) nanoparticle. PBCA has been used as a tissue adhesive and has been extensively studied for delivery of drugs to the brain. The PBCA/DK4 nanoparticle showed good photoactivity and low cytotoxicity, and thus is a promising material for studying the biomedical effects of CO.

Carbon monoxide release from ultrasound-sensitive microbubbles improves endothelial cell growth.

Carbon monoxide is a gasotransmitter that may be beneficial for vascular tissue engineering and regenerative medicine strategies because it can promote endothelial cell (EC) proliferation and migration by binding to heme-containing compounds within cells. For example, CO may be beneficial for vascular cognitive impairment and dementia because many patients' disrupted blood-brain barriers do not heal naturally. However, control of the CO dose is critical, and new controlled delivery methods need to be developed. This study developed ultrasound-sensitive microbubbles with a carefully controlled precipitation technique, loaded them with CO, and assessed their ability to promote EC proliferation and function. Microbubbles fabricated with perfluoropentane exhibited good stability at room temperature, but they could still be ruptured and release CO in culture with application of ultrasound. Microbubbles synthesized from the higher boiling point compound, perfluorohexane, were too stable at physiological temperature. The lower-boiling point perfluoropentane microbubbles had good biocompatibility and appeared to improve VE-cadherin expression when CO was loaded in the bubbles. Finally, tissue phantoms were used to show that an imaging ultrasound probe can efficiently rupture the microbubbles and that the CO-loaded microbubbles can improve EC spreading and proliferation compared to control conditions without microbubbles as well as microbubbles without application of ultrasound. Overall, this study demonstrated the potential for use of these ultrasound-sensitive microbubbles for improving blood vessel endothelialization.

Localized pH Pulses in PBS Buffer Repeatedly Induced by Visible Light.

The pH of biological systems is important for the activity of enzymes, and abnormal cellular pH is related to many diseases. Spatial and temporal modulation of pH with light will be useful for studying the pH effects on enzymatic functions and disease mechanisms and may lead to new drug delivery and therapeutic methods. However, the pH of biological systems is maintained by pH buffers, which implies that only temporary pH change (pH pulse) can be induced in an open system. A key fundamental problem is whether a photoinduced pH pulse can be strong and long enough to generate a significant effect. In this work, a photoinduced pH pulse in a micrometer hydrophilic film in PBS buffer has been demonstrated. The thin film was made of an metastable-state photoacid (mPAH) polymer. It is an open system that allows exchange of protons. A quick release of the protons from the mPAHs and the proton exchange between the film and PBS resulted in a pH pulse generated by moderate visible-light irradiation. The magnitude of the pulse is 1.4-1.9 units with maximum pH change occurring after ∼18 s of the irradiation. Since the mPAH is a reversible photoacid, the pH pulse could be repeatedly generated after the photoacid recovered in the dark. This work shows that photochemical modulation of pH is possible even in buffered solutions.