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Water clarity serves as both an indicator and a regulator of biological function in aquatic systems. Large-scale, consistent water clarity monitoring is needed for informed decision-making. Inland freshwater ponds and lakes across Cape Cod, a 100-km peninsula in Massachusetts, are of particular interest for water clarity monitoring. Secchi disk depth (SDD), a common measure of water clarity, has been measured intermittently for over 200 Cape Cod ponds since 2001. Field-measured SDD data were used to estimate SDD from satellite data, leveraging the NASA/USGS Landsat Program and Copernicus Sentinel-2 mission, spanning 1984 to 2022. Random forest machine learning models were generated to estimate SDD from satellite reflectance data and maximum pond depth. Spearman rank correlations (r s ) were "strong" for Landsat 5 and 7 (r s  = 0.78 and 0.79), and "very strong" for Landsat 8, 9, and Sentinel-2 (r s  = 0.83, 0.86, and 0.80). Mean absolute error also indicated strong predictive capacity, ranging from 0.65 to 1.05 m, while average bias ranged from -0.20 to 0.06 m. Long- and recent short-term changes in satellite-estimated SDD were assessed for 193 ponds, selected based on surface area and the availability of maximum pond depth data. Long-term changes between 1984 and 2022 established a retrospective baseline using the Mann-Kendall test for trend and Theil-Sen slope. Generally, long-term water clarity improved across the Cape; 149 ponds indicated increasing water clarity, and 8 indicated deteriorating water clarity. Recent short-term changes between 2021 and 2022 identified ponds that may benefit from targeted management efforts using the Mann-Whitney U test. Between 2021 and 2022, 96 ponds indicated deteriorations in water clarity, and no ponds improved in water clarity. While the 193 ponds analyzed here constitute only one quarter of Cape Cod ponds, they represent 85% of its freshwater surface area, providing the most spatially and temporally comprehensive assessment of Cape Cod ponds to date. Efforts are focused on Cape Cod, but can be applied to other areas given the availability of local field data. This study defines a framework for monitoring and assessing change in satellite-estimated SDD, which is important for both local and regional management and resource prioritization., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Covalent assemblies of conjugated organic chromophores provide the opportunity to engineer new excited states with novel properties. In this work, a newly developed triple-stranded cage architecture, in which meta-substituted aromatic caps serve as covalent linking groups that attach to both top and bottom of the conjugated molecule walls, is used to tune the properties of thiophene oligomer assemblies. Benzene-capped and triazine-capped 5,5'-(2,2-bithiophene)-containing arylene cages are synthesized and characterized using steady-state and time-resolved spectroscopic methods. The conformational freedom and electronic states are analyzed using time-dependent density functional theory. The benzene cap acts as a passive spacer whose electronic states do not mix with those of the chromophore walls. The excited state properties are dominated by through-space interactions between the chromophore subunits, generating a neutral Frenkel H-type exciton state. This excitonic state undergoes intersystem crossing on a 200 ps time scale while the fluorescence output is suppressed by a factor of 2 due to a decreased radiative rate. Switching to a triazine cap enables electron transfer from the chromophore-linker after the initial excitation to the exciton state, leading to the formation of a charge-transfer state within 10 ps. This state can avoid intersystem crossing and exhibits red-shifted fluorescence with enhanced quantum yield. The ability to interchange structural modules with different electronic properties while retaining the overall cage morphology provides a new approach for tuning the properties of discrete chromophore assemblies.

Aluminum monochloride (AlCl) has been proposed as a promising candidate for laser cooling to ultracold temperatures, and recent spectroscopy results support this prediction. It is challenging to produce large numbers of AlCl molecules because it is a highly reactive open-shell molecule and must be generated in situ . Here we show that pulsed-laser ablation of stable, non-toxic mixtures of Al with alkali or alkaline earth chlorides, denoted XCl n , can provide a robust and reliable source of cold AlCl molecules. Both the chemical identity of XCl n and the Al : XCl n molar ratio are varied, and the yield of AlCl is monitored using absorption spectroscopy in a cryogenic gas. For KCl, the production of Al and K atoms was also monitored. We model the AlCl production in the limits of nonequilibrium recombination dominated by first-encounter events. The non-equilibrium model is in agreement with the data and also reproduces the observed trend with different XCl n precursors. We find that AlCl production is limited by the solid-state densities of Al and Cl atoms and the recondensation of Al atoms in the ablation plume. We suggest future directions for optimizing the production of cold AlCl molecules using laser ablation.

Ruthenium-catalyzed butadiene-mediated benzannulation enabled the first synthesis of 3,10-(di-tert-butyl)rubicene and its N-doped derivatives as well as preliminary studies on their photophysical properties. Unlike the parent rubicene and 3,10-(di-tert-butyl)rubicene, which adopt classical herringbone-type packing motifs in the solid state, the N-doped congener 7 b displayed columnar packing with an alternating co-facial arrangement of aromatic and heteroaromatic substructures., (© 2021 Wiley-VCH GmbH.)

Experimental work has shown that spatial experiences influence spatiotemporal metaphor use. In these studies, participants are asked a question that yields different responses depending on the metaphor participants use. It has been claimed that English speakers are equally likely to respond with either variant in the absence of priming. Related studies testing non-spatial experiences demonstrate varied results with a wide range of primes. Here, the effects of eye movement and stimuli presentation modality on comprehension of this question are investigated in different formats. In addition, the results of prior reported controls are re-analyzed in a meta-analysis to verify reliable ambiguity of the test question. Results suggest that English speakers have a baseline preference for the Moving Ego metaphor variant, with a stronger preference in verbal rather than written presentation. The findings have implications both for (re)interpretation of prior studies' results and future study designs., (Copyright © 2017 Cognitive Science Society, Inc.)

Purpose: To determine the dependence on acoustic parameters of molecular uptake and viability of cells exposed to low-frequency ultrasound., Methods: DU145 prostate cancer cells bathed in a solution of calcein were exposed to ultrasound at 24 kHz over a range of different acoustic pressures. exposure times, pulse lengths, and duty cycles. Flow cytometry was employed to quantify the number of calcein molecules delivered into each cell and levels of cell viability., Results: Both molecular uptake and cell viability showed a strong dependence on acoustic pressure and exposure time, weak dependence on pulse length, and no significant dependence on duty cycle. When all of the data were pooled together, they exhibited good correlation with acoustic energy exposure. Although molecular uptake showed large cell-to-cell heterogeneity, up to approximately 15% of cells achieved an intracellular calcein concentration approximately equal to its extracellular concentration., Conclusions: Large numbers of molecules can be delivered intracellularly using low-frequency ultrasound. Both uptake and viability correlate with acoustic energy, which is useful for design and control of ultrasound protocols.

Objectives: We studied enhancement of local gene delivery to the arterial wall by using an endovascular catheter ultrasound (US)., Background: Ultrasound exposure is standard for enhancement of in vitro gene delivery. We postulate that in vivo endovascular applications can be safely developed., Methods: We used a rabbit model of arterial mechanical overdilation injury. After arterial overdilation, US catheters were introduced in bilateral rabbit femoral arteries and perfused with plasmidor adenovirus-expressing blue fluorescent protein (BFP) or phosphate buffered saline. One side received endovascular US (2 MHz, 50 W/cm2, 16 min), and the contralateral artery did not., Results: Relative to controls, US exposure enhanced BFP expression measured via fluorescence 12-fold for plasmid (1,502.1+/-927.3 vs. 18,053.9+/-11,612 microm2, p < 0.05) and 19-fold for adenovirus (877.1+/-577.7 vs. 17,213.15+/-3,892 microm2, p < 0.05) while increasing cell death for the adenovirus group only (26+/-5.78% vs. 13+/-2.55%, p < 0.012)., Conclusions: Endovascular US enhanced vascular gene delivery and increased the efficiency of nonviral platforms to levels previously attained only by adenoviral strategies.

Purpose: Ultrasound has been shown to transiently permeabilize biological membranes, thereby facilitating delivery of large compounds such as proteins and DNA into cells and across tissues such as skin. In this study, we sought to quantitatively determine the dependence of cell membrane permeabilization on ultrasound parameters and to identify acoustic signals which correlate with observed membrane permeabilization., Methods: Bovine red blood cells were exposed to ultrasound at 24 kHz over a range of controlled conditions. The degree of membrane permeabilization was measured by release of hemoglobin and was determined as a function of ultrasound parameters and measured acoustic signals., Results: These studies showed that permeabilization increased with incident ultrasound pressure, increased with total exposure time above a threshold of approximately 100 msec, showed a weak dependence on pulse length with a small maximum at 3 msec, and did not depend on duty cycle under the conditions examined. Using measured acoustic spectra we found that red blood cell membrane permeabilization correlated best with the pressure measured at half the driving frequency (f/ 2 = 12 kHz) and its ultraharmonics, less strongly with the broadband noise pressure measured between peaks, and least strongly with pressure measured at the driving frequency and its higher harmonics. Permeabilization caused by ultrasound applied at any set of conditions tested in this study could be well predicted by the parameter tau x Pf/2, which characterizes the total cavitational exposure., Conclusions: This study provides a quantitative guide to designing ultrasound protocols useful for drug delivery. The acoustic measurements support the hypothesis that ultrasonic cavitation is the mechanism by which membranes are permeabilized. They also suggest that measurable acoustic signals can provide noninvasive, real-time feedback about membrane permeabilization and drug delivery.