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We identify unique features of a highly-absorbing negatively photochromic molecular switch, donor acceptor Stenhouse adduct (DASA), that enable its use for self-regulating light-activated control of fluid flow. Leveraging features of DASA’s chemical properties and solvent-dependent reaction kinetics, we demonstrate its use for photo-controlled Rayleigh-Bénard convection to generate dynamic, self-regulating flows with unparalleled fluid velocities (~mm s −1 ) simply by illuminating the fluid with visible light. The exceptional absorbance of DASAs in solution, uniquely controllable reaction kinetics and resulting spatially-confined photothermal flows demonstrate the ways in which photoswitches present exciting opportunities for their use in optofluidics applications requiring tunable flow behavior. Autonomous control of liquid motion is vital to the development of new actuators and pumps in fluid systems but autonomous control of fluid motion is inaccessible in current systems. Here, the authors identify unique features of a photochromic molecular switch that enables its use for self-regulating light activated control of fluid flow.

An enantioselective aza-Piancatelli rearrangement has been developed using a chiral Brønsted acid based on pentacarboxycyclopentadiene (PCCP). This reaction provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available starting material and is operationally simple.

Cationic conjugated oligoelectrolytes (COEs) are a class of compounds that can be tailored to achieve relevant in vitro antimicrobial properties with relatively low cytotoxicity against mammalian cells. Three distyrylbenzene‐based COEs were designed containing amide functional groups on the side chains. Their properties were compared to two representative COEs with only quaternary ammonium groups. The optimal compound, COE2−3C−C3‐Apropyl, has an antimicrobial efficacy against Escherichia coli with an MIC=2 μg mL−1, even in the presence of human serum albumin low cytotoxicity (IC50=740 μg mL−1) and minimal hemolytic activity. Moreover, we find that amide groups increase interactions between COEs and a bacterial lipid mimic based on calcein leakage assay and allow COEs to readily permeabilize the cytoplasmic membrane of E. coli. These findings suggest that hydrogen bond forming moieties can be further applied in the molecular design of antimicrobial COEs to further improve their selectivity towards bacteria. Distyrylbenzene‐based conjugated oligoelectrolytes were designed as a framework for antimicrobial agents. It is shown that hydrogen bond forming moieties can modulate membrane‐active properties of the compounds and increase interactions with bacteria. In addition, they facilitate cytoplasmic membrane permeabilization of Gram‐negative bacteria. This work highlights the importance of hydrogen bonds in designing membrane‐active antimicrobial compounds.

The development of noninvasive and robust strategies for manipulation of droplets and bubbles is crucial in applications such as boiling and condensation, electrocatalysis, and microfluidics. In this work, we realize the swift departure of droplets and bubbles from solid substrates by introducing photoresponsive surfactants and applying asymmetric illumination, thereby inducing a “photo-Marangoni” lift force. Experiments show that a pinned toluene droplet can depart the substrate in only 0.38 s upon illumination, and the volume of an air bubble at departure is reduced by 20%, indicating significantly faster departure. These benefits can be achieved with moderate light intensities and dilute surfactant concentrations, without specially fabricated substrates, which greatly facilitates practical applications. Simulations suggest that the net departure force includes contributions from viscous stresses directly caused by the Marangoni flow, as well as from pressure buildup due to flow stagnation at the contact line. The manipulation scheme proposed here shows potential for applications requiring droplet and bubble removal from working surfaces.

Fast and programmable transport of droplets on a substrate is desirable in microfluidic, thermal, biomedical, and energy devices. Photoresponsive surfactants are promising candidates to manipulate droplet motion due to their ability to modify interfacial tension and generate “photo-Marangoni” flow under light stimuli. Previous works have demonstrated photo-Marangoni droplet migration in liquid media; however, migration on other substrates, including solid and liquid-infused surfaces (LIS), remains an outstanding challenge. Moreover, models of photo-Marangoni migration are still needed to identify optimal photoswitches and assess the feasibility of new applications. In this work, we demonstrate 2D droplet motion on liquid surfaces and on LIS, as well as rectilinear motion in solid capillary tubes. We synthesize photoswitches based on spiropyran and merocyanine, capable of tension changes of up to 5.5 mN/m across time scales as short as 1.7 s. A millimeter-sized droplet migrates at up to 5.5 mm/s on a liquid, and 0.25 mm/s on LIS. We observe an optimal droplet size for fast migration, which we explain by developing a scaling model. The model also predicts that faster migration is enabled by surfactants that maximize the ratio between the tension change and the photoswitching time. To better understand migration on LIS, we visualize the droplet flow using tracer particles, and we develop corresponding numerical simulations, finding reasonable agreement. The methods and insights demonstrated in this study enable advances for manipulation of droplets for microfluidic, thermal and water harvesting devices.

The circadian rhythm generates out-of-equilibrium metabolite oscillations that are controlled by feedback loops under light/dark cycles. Here we describe a non-equilibrium nanosystem comprising a binary population of enzyme-containing polymersomes capable of light-gated chemical communication, controllable feedback and coupling to macroscopic oscillations. The populations consist of esterase-containing polymersomes functionalized with photo-responsive donor–acceptor Stenhouse adducts (DASA) and light-insensitive semipermeable urease-loaded polymersomes. The DASA–polymersome membrane becomes permeable under green light, switching on esterase activity and decreasing the pH, which in turn initiates the production of alkali in the urease-containing population. A pH-sensitive pigment that absorbs green light when protonated provides a negative feedback loop for deactivating the DASA–polymersomes. Simultaneously, increased alkali production deprotonates the pigment, reactivating esterase activity by opening the membrane gate. We utilize light-mediated fluctuations of pH to perform non-equilibrium communication between the nanoreactors and use the feedback loops to induce work as chemomechanical swelling/deswelling oscillations in a crosslinked hydrogel. We envision possible applications in artificial organelles, protocells and soft robotics.The circadian rhythm generates out-of-equilibrium metabolite oscillations controlled by feedback loops under light/dark cycles. Now, it has been shown that these life-like properties can emerge from a non-equilibrium nanosystem comprising a binary population of enzyme-containing polymersomes capable of light-gated chemical communication, controllable feedback and coupling to macroscopic oscillations.

The ability of molecular photoswitches to convert on/off responses into large macroscale property change is fundamental to light-responsive materials. However, moving beyond simple binary responses necessitates the introduction of new elements that control the chemistry of the photoswitching process at the molecular scale. To achieve this goal, we designed, synthesized and developed a single photochrome, based on a modified donor–acceptor Stenhouse adduct (DASA), capable of independently addressing multiple molecular states. The multi-stage photoswitch enables complex switching phenomena. To demonstrate this, we show spatial control of the transformation of a three-stage photoswitch by tuning the population of intermediates along the multi-step reaction pathway of the DASAs without interfering with either the first or final stage. This allows for a photonic three-stage logic gate where the secondary wavelength solely negates the input of the primary wavelength. These results provide a new strategy to move beyond traditional on/off binary photochromic systems and enable the design of future molecular logic systems. Moving beyond binary responses in photoswitches necessitates the introduction of new elements along their switching pathway. Now, a modified donor–acceptor Stenhouse adduct (DASA) capable of independently addressing multiple molecular states has been developed. This enables the transformation of a three-stage photoswitch to be controlled by regulating intermediates along the DASA reaction pathway.

The development of automated experimental facilities and the digitization of experimental data have introduced numerous opportunities to radically advance chemical laboratories. As many laboratory tasks involve predicting and understanding previously unknown chemical relationships, machine learning (ML) approaches trained on experimental data can substantially accelerate the conventional design-build-test-learn process. This outlook article aims to help chemists understand and begin to adopt ML predictive models for a variety of laboratory tasks, including experimental design, synthesis optimization, and materials characterization. Furthermore, this article introduces how artificial intelligence (AI) agents based on large language models can help researchers acquire background knowledge in chemical or data science and accelerate various aspects of the discovery process. We present three case studies in distinct areas to illustrate how ML models and AI agents can be leveraged to reduce time-consuming experiments and manual data analysis. Finally, we highlight existing challenges that require continued synergistic effort from both experimental and computational communities to address.

The ability of cells to reorganize in response to external stimuli is important in areas ranging from morphogenesis to tissue engineering. Elongated cells can co-align due to steric effects, forming states with local order. We show that molecular-scale substrate anisotropy can direct cell organization, resulting in the emergence of nematic order on tissue scales. To quantitatively examine the disorder-order transition, we developed a high-throughput imaging platform to analyze velocity and orientational correlations for several thousand cells over days. The establishment of global, seemingly long-ranged order is facilitated by enhanced cell division along the substrate's nematic axis, and associated extensile stresses that restructure the cells' actomyosin networks. Our work, which connects to a class of systems known as active dry nematics, provides a new understanding of the dynamics of cellular remodeling and organization in weakly interacting cell collectives. This enables data-driven discovery of cell-cell interactions and points to strategies for tissue engineering.