Ulrichdelgado1418

Secondary organic aerosol formation in the atmospheric aqueous/particulate phase by photosensitized reactions is currently subject to uncertainties. To understand the impact of photosensitized reactions, photophysical and -chemical properties of photosensitizers, kinetic data, and reaction mechanisms of these processes are required. The photophysical properties of acetophenones, benzaldehydes, benzophenones, and naphthalenes were investigated in aqueous solution using laser flash excitation. Quantum yields of excited photosensitizers were determined giving values between 0.06-0.80 at 298 K and pH = 5. Molar absorption coefficients (εmax(3PS*) = (0.8-13) × 104 L mol-1 cm-1), decay rate constants in water (k1st = (9.4 ± 0.5) × 102 to (2.2 ± 0.1) × 105 s-1), and quenching rate constants with oxygen (kq(O2) = (1.7 ± 0.1-4.4 ± 0.4) × 109 L mol-1 s-1) of the excited triplet states were determined at 298 K and pH = 5. Photosensitized reactions of carboxylic acids and alkenes show second-order rate constants in the range of (37 ± 7.0-0.55 ± 0.1) × 104 and (27 ± 5.0-0.04 ± 0.01) × 108 L mol-1 s-1. The results show that different compound classes act differently as a photosensitizer and can be a sink for certain organic compounds in the atmospheric aqueous phase.Accurate estimation of black carbon (BC) emissions is essential for assessing the health and climate impact of this pollutant. Smad inhibitor Past emission inventories were associated with high uncertainty due to data limitations, and recent information has provided a unique updating opportunity. Moreover, understanding the drivers that cause temporal emission changes is of research value. Here, we update the global BC emission estimates using new data on the activities and emission factors (EFs). The new inventory covers 73 detailed sources at 0.1° × 0.1° spatial resolution and monthly temporal resolution from 1960 to 2017. The estimated annual emissions were 32% higher than the average of several previous inventories, which was primarily due to field-measured EFs for residential stoves and differentiated EFs for motor vehicles. In addition, the updated emissions show an inverse U-shaped temporal trend, which was mainly driven by the interaction between the positive effects of population growth, per capita energy consumption, and vehicle fleet and the negative effects of residential energy switching, stove upgrading, phasing out of beehive coke ovens, and reduced EFs for vehicles and industrial processes. Urbanization caused a significant increase in urban emissions accompanied by a more significant decline in rural emissions.The transport of molecules through nanoscale confined space is relevant in biology, biosensing, and industrial filtration. Microscopically modeling transport through nanopores is required for a fundamental understanding and guiding engineering, but the short duration and low replica number of existing simulation approaches limit statistically relevant insight. Here we explore protein transport in nanopores with a high-throughput computational method that realistically simulates hundreds of up to seconds-long protein trajectories by combining Brownian dynamics and continuum simulation and integrating both driving forces of electroosmosis and electrophoresis. Ionic current traces are computed to enable experimental comparison. By examining three biological and synthetic nanopores, our study answers questions about the kinetics and mechanism of protein transport and additionally reveals insight that is inaccessible from experiments yet relevant for pore design. The discovery of extremely frequent unhindered passage can guide the improvement of biosensor pores to enhance desired biomolecular recognition by pore-tethered receptors. Similarly, experimentally invisible nontarget adsorption to pore walls highlights how to improve recently developed DNA nanopores. Our work can be expanded to pressure-driven flow to model industrial nanofiltration processes.The measurement of ion concentrations and fluxes inside living cells is key to understanding cellular physiology. Fluorescent indicators that can infiltrate and provide intel on the cellular environment are critical tools for biological research. Developing these molecular informants began with the seminal work of Racker and colleagues ( Biochemistry (1979) 18, 2210), who demonstrated the passive loading of fluorescein in living cells to measure changes in intracellular pH. This work continues, employing a mix of old and new tradecraft to create innovative agents for monitoring ions inside living systems.The random Lorentz gas (RLG) is a minimal model of both percolation and glassiness, which leads to a paradox in the infinite-dimensional, d → ∞ limit the localization transition is then expected to be continuous for the former and discontinuous for the latter. As a putative resolution, we have recently suggested that, as d increases, the behavior of the RLG converges to the glassy description and that percolation physics is recovered thanks to finite-d perturbative and nonperturbative (instantonic) corrections [Biroli et al. Phys. Rev. E 2021, 103, L030104]. Here, we expand on the d → ∞ physics by considering a simpler static solution as well as the dynamical solution of the RLG. Comparing the 1/d correction of this solution with numerical results reveals that even perturbative corrections fall out of reach of existing theoretical descriptions. Comparing the dynamical solution with the mode-coupling theory (MCT) results further reveals that, although key quantitative features of MCT are far off the mark, it does properly capture the discontinuous nature of the d → ∞ RLG. These insights help chart a path toward a complete description of finite-dimensional glasses.The abnormal tumor vasculature in solid tumors creates hypoxia and leads to compromising the delivery and anticancer efficiency of nanomedicine. Nanomaterials with intrinsic antiangiogenesis ability might normalize tumor vessels and improve the therapeutic effect of O2-related treatment like PDT. Herein, we designed and prepared ROS-responsive side-chain selenium-grafted polymers, which had potential antiangiogenic activity, as vehicles to load photodynamic therapeutic agent Ce6 and chemotherapeutic drug oridonin. Under NIR irradiation, the C-Se bonds on the side chain of polymers could be cleaved in the presence of 1O2 produced by Ce6 and further formed organic selenic acid through selenoxide elimination reaction. The generated seleninic acid could downregulate the expression of vascular endothelial growth factor (VEGF) and matrix metalloproteinase-2 (MMP-2) to inhibit angiogenesis and further relieve hypoxia. The released oridonin could significantly increase the intracellular ROS concentration. Both could modulate cancer cells' microenvironment to reinforce PDT.