Spectroscopy and dynamics of the hydrated electron at the water/air interface.

The hydrated electron, e-(aq), has attracted much attention as a central species in radiation chemistry. However, much less is known about e-(aq) at the water/air surface, despite its fundamental role in electron transfer processes at interfaces. Using time-resolved electronic sum-frequency generation spectroscopy, the electronic spectrum of e-(aq) at the water/air interface and its dynamics are measured here, following photo-oxidation of the phenoxide anion. The spectral maximum agrees with that for bulk e-(aq) and shows that the orbital density resides predominantly within the aqueous phase, in agreement with supporting calculations. In contrast, the chemistry of the interfacial hydrated electron differs from that in bulk water, with e-(aq) diffusing into the bulk and leaving the phenoxyl radical at the surface. Our work resolves long-standing questions about e-(aq) at the water/air interface and highlights its potential role in chemistry at the ubiquitous aqueous interface.

Allophycocyanin A is a carbon dioxide receptor in the cyanobacterial phycobilisome.

Light harvesting is fundamental for production of ATP and reducing equivalents for CO2 fixation during photosynthesis. However, electronic energy transfer (EET) through a photosystem can harm the photosynthetic apparatus when not balanced with CO2. Here, we show that CO2 binding to the light-harvesting complex modulates EET in photosynthetic cyanobacteria. More specifically, CO2 binding to the allophycocyanin alpha subunit of the light-harvesting complex regulates EET and its fluorescence quantum yield in the cyanobacterium Synechocystis sp. PCC 6803. CO2 binding decreases the inter-chromophore distance in the allophycocyanin trimer. The result is enhanced EET in vitro and in live cells. Our work identifies a direct target for CO2 in the cyanobacterial light-harvesting apparatus and provides insights into photosynthesis regulation.

Photooxidation of the Phenolate Anion is Accelerated at the Water/Air Interface.

Molecular photodynamics can be dramatically affected at the water/air interface. Probing such dynamics is challenging, with product formation often probed indirectly through its interaction with interfacial water molecules using time-resolved and phase-sensitive vibrational sum-frequency generation (SFG). Here, the photoproduct formation of the phenolate anion at the water/air interface is probed directly using time-resolved electronic SFG and compared to transient absorption spectra in bulk water. The mechanisms are broadly similar, but 2 to 4 times faster at the surface. An additional decay is observed at the surface which can be assigned to either diffusion of hydrated electrons from the surface into the bulk or due to increased geminate recombination at the surface. These overall results are in stark contrast to phenol, where dynamics were observed to be 104 times faster and for which the hydrated electron was also a photoproduct. Our attempt to probe phenol showed no electron signal at the interface.

Transcranial magnetic stimulation (TMS) for geriatric depression.

BACKGROUND: The prevalence of treatment-resistant geriatric depression (GD) highlights the need for treatments that preserve cognitive functions and recognize polypharmacy in elderly, yet effectively reduce symptom burden. Transcranial magnetic stimulation (TMS) is a proven intervention for treatment-resistant depression in younger adults but the efficacy of TMS to treat depressed older adults is still unclear. This review provides an updated view on the efficacy of TMS treatment for GD, discusses methodological differences between trials in TMS application, and explores avenues for optimization of TMS treatment in the context of the ageing brain. METHODS: A systematic review was conducted to identify published literature on the antidepressant efficacy of TMS for GD. Databases PubMed, Embase, and PsycINFO were searched for English language articles in peer-reviewed journals in March 2021. RESULTS: Seven randomized controlled trials (RCTs) (total n = 260, active n = 148, control n = 112) and seven uncontrolled trials (total n = 160) were included. Overall, we found substantial variability in the clinical response, ranging from 6.7% to 54.3%. CONCLUSIONS: The reviewed literature highlights large heterogeneity among studies both in terms of the employed TMS dosage and the observed clinical efficacy. This highlights the need for optimizing TMS dosage by recognizing the unique clinical features of GD. We showcase a set of novel approaches for the optimization of the TMS protocol for depression and discuss the possibility for a standardized TMS protocol tailored for the treatment of GD.

Time-resolved electronic sum-frequency generation spectroscopy with fluorescence suppression using optical Kerr gating.

Excited state dynamics of molecules at interfaces can be studied using second-order non-linear spectroscopic methods such as time-resolved electronic sum-frequency generation (SFG). However, as such measurements inherently generate very small signals, they are often overwhelmed by signals originating from fluorescence. Here, this limitation is overcome by optical Kerr gating of the SFG signal to discriminate against fluorescence. The new approach is demonstrated on the excited state dynamics of malachite green at the water/air interface, in the presence of a highly fluorescent coumarin dye, and on the photo-oxidation of the phenolate anion at the water/air interface. The generality of the use of optical Kerr gating to SFG measurements is discussed.

Safety and Feasibility of Tele-Supervised Home-Based Transcranial Direct Current Stimulation for Major Depressive Disorder.

Major depressive disorder (MDD) is a worldwide cause of disability in older age, especially during the covid pandemic. Transcranial direct current stimulation (tDCS) is a non-invasive neuromodulation technique that has shown encouraging efficacy for treatment of depression. Here, we investigate the feasibility of an innovative protocol where tDCS is administered within the homes of older adults with MDD (patient participants) with the help of a study companion (i.e. caregiver). We further analyze the feasibility of a remotely-hosted training program that provides the knowledge and skills to administer tDCS at home, without requiring them to visit the lab. We also employed a newly developed multi-channel tDCS system with real-time monitoring designed to guarantee the safety and efficacy of home-based tDCS. Patient participants underwent a total of 37 home-based tDCS sessions distributed over 12 weeks. The protocol consisted of three phases each lasting four weeks: an acute phase, containing 28 home-based tDCS sessions, a taper phase containing nine home-based tDCS sessions, and a follow up phase, with no stimulation sessions. We found that the home-based, remotely-supervised, study companion administered, multi-channel tDCS protocol for older adults with MDD was feasible and safe. Further, the study introduces a novel training program for remote instruction of study companions in the administration of tDCS. Future research is required to determine the translatability of these findings to a larger sample. Clinical Trial Registration: https://clinicaltrials.gov/ct2/show/NCT04799405?term=NCT04799405&draw=2&rank=1, identifier NCT04799405.