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.

An inexpensive platform has been developed for automated measurements of air quality. Low-cost sensors for aerosol optical thickness, ozone, temperature, relative humidity, and pressure were combined with a low-cost computer (Raspberry Pi) for automated monitoring. The Raspberry Pi is well-suited to automated measurements because of: (1) its low cost, (2) its low power consumption, (3) its ability to communicate over Ethernet or wireless networks and (4) its ability to interface with many sensors through analog-to-digital converters or directly through Universal Serial Bus (USB), serial port, Inter-Integrated Circuit (I2C), and Serial Peripheral Interface (SPI). This setup is appropriate for use in, e.g., undergraduate atmospheric research groups, where the cost of typical automated sensors is prohibitively expensive. We report measurements taken over a two-month period which includes evidence of high nighttime ozone due to being downwind of a forest fire. This platform can be expanded to enable other atmospheric measurements from a number of sensors.

Fast and programmable transport of liquid droplets on a solid substrate is desirable in microfluidic, thermal, biomedical, and energy devices. Past research has focused on designing substrates with asymmetric structures or gradient wettability where droplet behaviors are passively controlled, or by applying external electric, thermal, magnetic, or acoustic stimuli that either require the fabrication of electrodes or a strong applied field. In this work, we demonstrate tunable and programmable droplet motion on liquid-infused surfaces (LIS) and inside solid-surface capillary channels using low-intensity light and photo-responsive surfactants. When illuminated by the light of appropriate wavelengths, the surfactants can reversibly change their molecular conformation thereby tuning interfacial tensions in a multi-phase fluid system. This generates a Marangoni flow that drives droplet motions. With two novel surfactants that we synthesized, we demonstrate fast linear and complex 2D movements of droplets on liquid surfaces, on LIS, and inside microchannels. We also visualized the internal flow pattern using tracer particles and developed simple scaling arguments to explain droplet-size-dependent velocity. The method demonstrated in this study serves as a simple and exciting new approach for the dynamic manipulation of droplets for microfluidic, thermal, and water harvesting devices.

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.

A fluidic assembly of III-nitride micro-light-emitting diodes (μLEDs) is demonstrated by applying external forces. This work introduces a solution-based mass transfer approach for inorganic semiconductor devices with the advantages in being material- and dimensional-agnostic. This method offers precise control in device alignment and orientation. The alignment of μLEDs in solution is controlled by acoustic focusing and the induced pressure forces, and the device orientation is modulated using magnetic field. The detailed mechanisms of the use of acoustic focusing and magnetic field are discussed. This fluidic assembly technique allows high throughput rate and roll-to-roll manufacturing, which is critical to the mass transfer of μLEDs for display and functional fabric applications.

Many variations of the canonical nucleobases, such as different derivatives and analogues, would likely have been present in a primordial soup. Alternative combinations of molecular building blocks would conceivably have been possible to form self-replicating RNA-like structures. The nucleobases that are involved in replication selectively exhibit short excited-state lifetimes which provide high intrinsic stability against otherwise harmful UV photo-damage. The stark difference in response to UV irradiation between these structures and many of the alternative bases suggests the possibility of a photochemical selection of the molecular building blocks of life long before the advent of biological selection. It is thus conceivable that the molecular photo-properties of nucleobases are molecular fossils of the prebiotic chemistry that occurred 4 billion years ago. This chapter considers the excited-state dynamics of the purine bases by comparing a full set of canonical and alternative nucleobases formed by oxo- and amino- substitutions of purine.

Abstract Interstellar carbon has been detected in both gas-phase molecules and solid particles. The goal of this study is to identify the link between these two phases of cosmic carbon. Here we report preliminary results on the low temperature formation of carbonaceous dust grains from gas-phase aromatic hydrocarbon precursors. This is done using the supersonic expansion of an argon jet seeded with aromatic molecules and exposed to an electrical discharge. We report experimental evidence of efficient carbon dust condensation from aromatic molecules including benzene and naphthalene. The molecular content of the solid grains is probed with laser desorption mass spectrometry. The mass spectra reveal a rich molecular composition including fragments of the parent molecule but also growth into larger molecular species.

Collin Steen opened discussion of Tomas Polivka's paper: It would be very interesting to study the excited state dynamics of this E-FCP protein in the context of the whole organism. Dynamics and behavior are frequently altered in an in vivo sample compared to an isolated one. As an example, I'd

Nadia Korovina opened discussion of the paper by David N. Beratan: Does the excited state energy of the bridge affect the coupling between the donor and the acceptor? How does the rate of energy transfer through the bridge scale with respect to the bridge energy? David N. Beratan

Isoguanine is an alternative nucleobase that has been proposed as a component of expanded genetic codes. It has also been considered as a molecule with potential relevance to primordial informational polymers. Here, we scrutinize the photodynamics of isoguanine, because photostability has been proposed as a critical criterion for the prebiotic selection of biomolecular building blocks on an early Earth. We discuss resonance-enhanced multiphoton ionization, IR-UV double resonance spectroscopy and pump-probe measurements performed for this molecule to track the excited-state behaviour of its different tautomeric forms in the gas phase. These experiments, when confronted with highly accurate quantum chemical calculations and nonadiabatic dynamics simulations provide a complete mechanistic picture of the tautomer-specific photodynamics of isoguanine. Our results indicate that UV-excited enol tautomers of isoguanine are relatively short lived and therefore photostable. In contrast, the biologically more relevant keto forms are trapped in dark nπ* states which are sufficiently long lived to participate in destructive photochemistry. The resulting lower photostability compared to canonical nucleobases may have been one of the reasons why isoguanine was not incorporated into DNA and RNA.

Compositionally similar organic red colorants in the anthraquinone family, whose photodegradation can cause irreversible color and stability changes, have long been used in works of art. Different organic reds, and their multiple chromophores, suffer degradation disparately. Understanding the details of these molecules' degradation therefore provides a window into their behavior in works of art and may assist the development of improved conservation methods. According to one proposed model of photodegradation dynamics, intramolecular proton transfer provides a kinetically favored decay pathway in some photoexcited chromophores, preventing degradation-promoting electron transfer (ET). To further test this model, we measured excited state lifetimes of substituted gas-phase anthraquinones using high-level theory to explain the experimental results. The data show a general structural trend: Anthraquinones with 1,4-OH substitution are long-lived and prone to damaging ET, while excited state intramolecular proton transfers promote efficient quenching for hydroxyanthraquinones that lack this motif.

Indigo is a blue dye molecule that has been used since antiquity, although it is better known today for its use in blue jeans. Indigo has previously been shown to exhibit remarkable photostability due to fast excited state dynamics mediated by an excited state intramolecular proton transfer. Study of this process is complicated by the fact that the photophysics of indigo is very sensitive to the environment. In order to disentangle the intrinsic photodynamics of indigo from the effects contributed by the environment, we studied indigo in a molecular beam using resonance enhanced multiphoton ionization. We obtained excited state lifetimes of individual vibronic bands with pump-probe spectroscopy ranging from 60 ps to 24 ns. We have mapped a barrier to relaxation at about 700 cm(-1), beyond which fast excited state dynamics dominate. Below this barrier two decay processes compete and mode-specific relaxation occurs with certain vibronic bands near the origin relaxing faster than others, or exhibiting different partitioning between the two relaxation channels. Computational studies at the ADC(2)/MP2/cc-pVDZ level indicate that two low-barrier reaction paths exist in the S-1 state of indigo, one corresponding to proton transfer, the other to hydrogen transfer. In both cases the charge distribution changes drastically upon de-excitation. These data provide a sensitive probe of the potential energy landscape, responsible for the response to absorption of light. The results may help in understanding the photostability that preserves the blue color of indigo dyes.

We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump-probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson-Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of ∼1010 s-1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.