Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution.

Nitroaromatic compounds are major constituents of the brown carbon aerosol particles in the troposphere that absorb near-ultraviolet (UV) and visible solar radiation and have a profound effect on the Earth's climate. The primary sources of brown carbon include biomass burning, forest fires, and residential burning of biofuels, and an important secondary source is photochemistry in aqueous cloud and fog droplets. Nitrobenzene is the smallest nitroaromatic molecule and a model for the photochemical behavior of larger nitroaromatic compounds. Despite the obvious importance of its droplet photochemistry to the atmospheric environment, there have not been any detailed studies of the ultrafast photochemical dynamics of nitrobenzene in aqueous solution. Here, we combine femtosecond transient absorption spectroscopy, time-resolved infrared spectroscopy, and quantum chemistry calculations to investigate the primary steps following the near-UV (λ ≥ 340 nm) photoexcitation of aqueous nitrobenzene. To understand the role of the surrounding water molecules in the photochemical dynamics of nitrobenzene, we compare the results of these investigations with analogous measurements in solutions of methanol, acetonitrile, and cyclohexane. We find that vibrational energy transfer to the aqueous environment quenches internal excitation, and therefore, unlike the gas phase, we do not observe any evidence for formation of photoproducts on timescales up to 500 ns. We also find that hydrogen bonding between nitrobenzene and surrounding water molecules slows the S1/S0 internal conversion process.

Loss of cardiac myosin light chain kinase contributes to contractile dysfunction in right ventricular pressure overload.

Nearly 1 in every 100 children born have a congenital heart defect. Many of these defects primarily affect the right heart causing pressure overload of the right ventricle (RV). The RV maintains function by adapting to the increased pressure; however, many of these adaptations eventually lead to RV hypertrophy and failure. In this study, we aim to identify the cellular and molecular mechanisms of these adaptions. We utilized a surgical animal model of pulmonary artery banding (PAB) in juvenile rats that has been shown to accurately recapitulate the physiology of right ventricular pressure overload in young hearts. Using this model, we examined changes in cardiac myocyte protein expression as a result of pressure overload with mass spectrometry 4 weeks post-banding. We found pressure overload of the RV induced significant downregulation of cardiac myosin light chain kinase (cMLCK). Single myocyte calcium and contractility recordings showed impaired contraction and relaxation in PAB RV myocytes, consistent with the loss of cMLCK. In the PAB myocytes, calcium transients were of smaller amplitude and decayed at a slower rate compared to controls. We also identified miR-200c, which has been shown to regulate cMLCK expression, as upregulated in the RV in response to pressure overload. These results indicate the loss of cMLCK is a critical maladaptation of the RV to pressure overload and represents a novel target for therapeutic approaches to treat RV hypertrophy and failure associated with congenital heart defects.

Infrared Organic Photodetectors Employing Ultralow Bandgap Polymer and Non-Fullerene Acceptors for Biometric Monitoring.

Recent efforts in the field of organic photodetectors (OPD) have been focused on extending broadband detection into the near-infrared (NIR) region. Here, two blends of an ultralow bandgap push-pull polymer TQ-T combined with state-of-the-art non-fullerene acceptors, IEICO-4F and Y6, are compared to obtain OPDs for sensing in the NIR beyond 1100 nm, which is the cut off for benchmark Si photodiodes. It is observed that the TQ-T:IEICO-4F device has a superior IR responsivity (0.03 AW-1 at 1200 nm and -2 V bias) and can detect infrared light up to 1800 nm, while the TQ-T:Y6 blend shows a lower responsivity of 0.01 AW-1 . Device physics analyses are tied with spectroscopic and morphological studies to link the superior performance of TQ-T:IEICO-4F OPD to its faster charge separation as well as more favorable donor-acceptor domains mixing. In the polymer blend with Y6, the formation of large agglomerates that exceed the exciton diffusion length, which leads to high charge recombination, is observed. An application of these devices as biometric sensors for real-time heart rate monitoring via photoplethysmography, utilizing infrared light, is demonstrated.

Oxygen-induced degradation in AgBiS2 nanocrystal solar cells.

AgBiS2 nanocrystal solar cells are among the most sustainable emerging photovoltaic technologies. Their environmentally-friendly composition and low energy consumption during fabrication make them particularly attractive for future applications. However, much remains unknown about the stability of these devices, in particular under operational conditions. In this study, we explore the effects of oxygen and light on the stability of AgBiS2 nanocrystal solar cells and identify its dependence on the charge extraction layers. Normally, the rate of oxygen-induced degradation of nanocrystals is related to their ligands, which determine the access sites by steric hindrance. We demonstrate that the ligands, commonly used in AgBiS2 solar cells, also play a crucial chemical role in the oxidation process. Specifically, we show that the tetramethylammonium iodide ligands enable their oxidation, leading to the formation of bismuth oxide and silver sulphide. Additionally, the rate of oxidation is impacted by the presence of water, often present at the surface of the ZnO electron extraction layer. Moreover, the degradation of the organic hole extraction layer also impacts the overall device stability and the materials' photophysics. The understanding of these degradation processes is necessary for the development of mitigation strategies for future generations of more stable AgBiS2 nanocrystal solar cells.

Selenium-Substituted Non-Fullerene Acceptors: A Route to Superior Operational Stability for Organic Bulk Heterojunction Solar Cells.

Non-fullerene acceptors (NFAs) for organic solar cells (OSCs) have significantly developed over the past five years with continuous improvements in efficiency now over 18%. However, a key challenge still remains in order to fully realize their commercialization potential: the need to extend device lifetime and to control degradation mechanisms. Herein, we investigate the effect of two different molecular engineering routes on the widely utilized ITIC NFA, to tune its optoelectronic properties and interactions with the donor polymer in photoactive blends. Heavier selenium (Se) atoms substitute sulfur (S) atoms in the NFA core in either outer or inner positions, and methyl chains are attached to the end groups. By investigating the effects of these structural modifications on the long-term operational stability of bulk-heterojunction OSC devices, we identify outer selenation as a powerful strategy to significantly increase device lifetime compared to ITIC. Combining outer selenation and methylation results in an impressive 95% of the initial OSC efficiency being retained after 450 h under operating conditions, with an exceptionally long projected half-lifetime of 5600 h compared to 400 h for ITIC. We find that the heavier and larger Se atoms at outer-core positions rigidify the molecular structure to form highly crystalline films with low conformational energetic disorder. It further enhances charge delocalization over the molecule, promoting strong intermolecular interactions among acceptor molecules. Upon methylation, this strong intermolecular interaction stabilizes acceptor domains in blends to be resilient to light-induced morphological changes, thereby leading to superior device stability. Our results highlight the crucial role of NFA molecular structure for OSC operational stability and provide important NFA design rules via heteroatom position and end-group control.

Exploring ultraviolet photoinduced charge-transfer dynamics in a model dinucleotide of guanine and thymine.

An understanding of the initial photoexcited states of DNA is essential to unravelling deleterious photoinduced chemical reactions and the intrinsic ultrafast photoprotection of the genetic code for all life. In our combined experimental and theoretical study, we have elucidated the primary non-radiative relaxation dynamics of a model nucleotide of guanine and thymine (2'-deoxyguanosine 3'-monophosphate 5'-thymidine, d(GpT)) in buffered aqueous solution. Experimentally, we unequivocally demonstrate that the Franck-Condon excited states of d(GpT) are significantly delocalised across both nucleobases, and mediate d(G+pT-) exciplex product formation on an ultrafast (<350 fs) timescale. Theoretical studies show that the nature of the vertical excited states is very dependent on the specific geometry of the dinucleotide, and dictate the degree of delocalised, charge-transfer or localised character. Our mechanism for prompt exciplex formation involves a rapid change in electronic structure and includes a diabatic surface crossing very close to the Franck-Condon region mediating fast d(G+pT-) formation. Exciplexes are quickly converted back to neutral ground state molecules on a ∼10 ps timescale with a high quantum yield, ensuring the photostability of the nucleotide sequence.