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Heterografted molecular bottlebrushes (MBBs) with side chains composed of poly(n-butyl acrylate) (PnBA) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA, pKa = 7.4) have been shown to be efficient, robust, and responsive emulsifiers. However, it remains unknown how they respond to external stimuli at interfaces. In this work, the shape-changing behavior of six hetero- and homografted MBBs at air–water interfaces in response to pH changes and lateral compression was investigated using a Langmuir–Blodgett trough and atomic force microscopy. At a surface pressure of 0.5 mN m−1, PDEAEMA-containing MBBs showed no worm-globule transitions when the pH was increased from 4.0 to 10.0, at which PDEAEMA becomes insoluble in water. Upon lateral compression at pH 4.0, MBBs with a mole fraction of PDEAEMA side chains (xPDEAEMA) < 0.50 underwent pronounced worm-globule shape transitions; there was an increasing tendency for bottlebrushes to become connected with increasing xPDEAEMA. At xPDEAEMA = 0.76, the molecules remained wormlike even at high compression. These observations were presumably caused by the increased electrostatic repulsion between protonated PDEAEMA side chains in the subphase with increasing xPDEAEMA, hindering the shape change. At pH 10.0, MBBs with xPDEAEMA < 0.50 showed a lower tendency to change their wormlike morphologies upon compression than at pH 4.0. No shape transition was observed when xPDEAEMA > 0.50, attributed to the relatively high affinity toward water and the rigidity of PDEAEMA. This study revealed the shape-changing behavior of amphiphilic pH-responsive MBBs at air–water interfaces, which could be useful for future design of multicomponent MBBs for potential applications. 

A key challenge in millimeter-wave and terahertz wireless networks is blockage of the line-of-sight path between a base station and a user. User and environmental mobility can lead to blockage of highly directional beams by intervening people or objects, yielding link disruptions and poor quality of service. Here, we propose a solution to this problem which leverages the fact that, in such scenarios, users are likely to be located within the electromagnetic near field of the base station, which opens the possibility to engineer wave fronts for link maintenance. We show that curved beams, carrying data at high bit rates, can realize a link by curving around an intervening obstacle. We develop a model to analyze and experimentally evaluate the bandwidth limitations imposed by the use of self accelerating beams. We also demonstrate that such links employ the full aperture of the transmitter, even those portions which have no direct line of sight to the receiver, emphasizing that ray optics fails to capture the behavior of these near-field wave fronts. This approach, which is ideally suited for use at millimeter-wave and terahertz frequencies, opens vast new possibilities for wave front management in directional wireless networks.

 

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed^1,2. Although new particle formation (NPF) mechanisms have been described at specific sites^3–6, in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes^1,7. Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO₃probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10–80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols.

 

Abstract. This study describes a modeling framework, model evaluation, and source apportionment to understand the causes of Los Angeles (LA) air pollution. A few major updates are applied to the Community Multiscale Air Quality (CMAQ) model with a high spatial resolution (1 km × 1 km). The updates include dynamic traffic emissions based on real-time, on-road information and recent emission factors and secondary organic aerosol (SOA) schemes to represent volatile chemical products (VCPs). Meteorology is well predicted compared to ground-based observations, and the emission rates from multiple sources (i.e., on-road, volatile chemical products, area, point, biogenic, and sea spray) are quantified. Evaluation of the CMAQ model shows that ozone is well predicted despite inaccuracies in nitrogen oxide (NOx) predictions. Particle matter (PM) is underpredicted compared to concurrent measurements made with an aerosol mass spectrometer (AMS) in Pasadena. Inorganic aerosol is well predicted, while SOA is underpredicted. Modeled SOA consists of mostly organic nitrates and products from oxidation of alkane-like intermediate volatility organic compounds (IVOCs) and has missing components that behave like less-oxidized oxygenated organic aerosol (LO-OOA). Source apportionment demonstrates that the urban areas of the LA Basin and vicinity are NOx-saturated (VOC-sensitive), with the largest sensitivity of O3 to changes in VOCs in the urban core. Differing oxidative capacities in different regions impact the nonlinear chemistry leading to PM and SOA formation, which is quantified in this study.