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Squids: Sophisticated skin

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Squids: Sophisticated skin

Squids have long been a source of fascination for humans, providing the stuff of legend, superstition and myth. And it’s no wonder — their odd appearances and strange intelligence, their mastery of the open ocean can inspire awe in those who see them.

Legends aside, squids continue to intrigue people today — people like UC Santa Barbara professor Daniel Morse — for much the same, albeit more scientific, reasons. Having evolved for hundreds of millions of years to hunt, communicate, evade predators and mate in the vast, often featureless expanses of open water, squids have developed some of the most sophisticated skin in the animal kingdom.

“For centuries, people have been amazed at the ability of squids to change the color and patterns of their skin — which they do beautifully — for camoflage and underwater communication, signaling to one another and to other species to keep away, or as attraction for mating and other kinds of signaling,” said Morse, a Distinguished Professor Emeritus of Biochemistry and Molecular Genetics.

Like their cephalopod cousins the octopus and cuttlefish, squids have specialized pigment-filled cells called chromatophores that expand to expose them to light, resulting in various shades of pigmentary color. Of particular interest to Morse, however, is the squids’ ability to shimmer and flicker, reflecting different colors and breaking light over their skin. It’s an effect that is thought to mimic the dappled light of the upper ocean — the only feature in an otherwise stark seascape. By understanding how squids manage to fade themselves into even the plainest of backgrounds — or stand out — it may be possible to produce materials with the same, light tuning properties for a variety of applications.

Morse has been working to unlock the secret of squid skin for the last decade, and with support from the Army Research Office and research published in the journal Applied Physics Letters, he and co-author Esther Taxon come even closer to unraveling the complex mechanisms that underlie squid skin.

An Elegant Mechanism

“What we’ve discovered is that not only is the squid able to tune the color of the light that’s reflected, but also its brightness,” Morse said. Research had thus far has established that certain proteins called reflectins were responsible for iridescence, but the squid’s ability to tune the brightness of the reflected light was still something of a mystery, he said.


Previous research by Morse had uncovered structures and mechanisms by which iridocytes — light-reflecting cells — in the opalescent inshore squid’s (Doryteuthis opalescens) skin can take on virtually every color of the rainbow. It happens with the cell membrane, where it folds into nanoscale accordion-like structures called lamellae, forming tiny, subwavelength-wide exterior grooves.

“Those tiny groove structures are like the ones we see on the engraved side of a compact disc,” Morse said. The color reflected depends on the width of the groove, which corresponds to certain light wavelengths (colors). In the squid’s iridocytes, these lamellae have the added feature of being able to shapeshift, widening and narrowing those grooves through the actions of a remarkably finely tuned “osmotic motor” driven by reflectin proteins condensing or spreading apart inside the lamellae.

While materials systems containing reflectin proteins were able to approximate the iridescent color changes squid were capable of, attempts to replicate the ability to intensify brightness of these reflections always came up short, according to the researchers, who reasoned that something had to be coupled to the reflectins in squid skin, amplifying their effect.

That something turned out to be the very membrane enclosing the reflectins — the lamellae, the same structures responsible for the grooves that split light into its constituent colors.

“Evolution has so exquisitely optimized not only the color tuning, but the tuning of the brightness using the same material, the same protein and the same mechanism,” Morse said.


Light at the Speed of Thought

It all starts with a signal, a neuronal pulse from the squid’s brain.

“Reflectins are normally very strongly positively charged,” Morse said of the iridescent proteins, which, when not activated, look like a string of beads. Their same charge means they repel each other.

But that can change when a neural signal causes the reflectins to bind negatively charged phosphate groups that neutralize the positive charge. Without the repulsion keeping the proteins in their disordered state they fold and attract each other, accumulating into fewer, larger aggregations in the lamellae.

These aggregations exert osmotic pressure on the lamellae, a semipermeable membrane built to withstand only so much pressure created by the clumping reflectins before releasing water outside the cell.

“Water gets squished out of the accordion-like structure, and that collapses the accordion so the thickness in spacing between the folds gets reduced, and that’s like bringing the grooves of a compact disc closer together,” Morse explained. “So the light that’s reflected can shift progressively from red to green to blue.”

At the same time, the membrane’s collapse concentrates the reflectins, causing an increase in their refractive index, amplifying brightness. Osmotic pressure, the motor that drives these tunings of optical properties, couples the lamellae tightly to the reflectins in a highly calibrated relationship that optimizes the output (color and brightness) to the input (neural signal). Wipe away the neural signal and the physics reverses, Morse said.

“It’s a very clever, indirect way of changing color and brightness by controlling the physical behavior of what’s called a colligative property — the osmotic pressure, something that’s not immediately obvious, but it reveals the intricacy of the evolutionary process, the millennia of mutation and natural selections that have honed and optimized these processes together.”

Tunable-Brightness Thin-Films

The presence of a membrane may be the vital link for the development of bioinspired thin films with the optical tuning capacity of the opalescent inshore squid.

“This discovery of the key role the membrane plays in tuning the brightness of reflectance has intriguing implications for the design of future buihybrid materials and coatings with tunable optical properties that could protect soldiers and their equipment,” said Stephanie McElhinny, a program manager at the the Army Research Office, an element of the U.S. Army Combat Capabilities Development Command’s Army Research Laboratory.

According to the researchers, “This evolutionarily honed, efficient coupling of reflectin of its osmotic amplifier is closely analogous to the impedance matched coupling of activator-transducer-amplifier networks in well-engineered electronic, magnetic, mechanical and acoustic systems.” In this case the activator would be the neuronal signal, while the reflectins acts as transducers and the osmotically controlled membranes serve as the amplifiers.

“Without that membrane surrounding the reflectins, there’s no change in the brightness for these artificial thin-films,” said Morse, who is collaborating with engineering colleagues to investigate the potential for a more squid skin-like thin-film. “If we want to capture the power of the biological, we have to include some kind of membrane-like enclosure to allow reversible tuning of the brightness.”

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Early dark energy could resolve cosmology’s two biggest puzzles

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A new study by MIT physicists proposes that a mysterious force known as early dark energy could solve two of the biggest puzzles in cosmology and fill in some major gaps in our understanding of how the early universe evolved.

One puzzle in question is the “Hubble tension,” which refers to a mismatch in measurements of how fast the universe is expanding. The other involves observations of numerous early, bright galaxies that existed at a time when the early universe should have been much less populated.

Now, the MIT team has found that both puzzles could be resolved if the early universe had one extra, fleeting ingredient: early dark energy. Dark energy is an unknown form of energy that physicists suspect is driving the expansion of the universe today. Early dark energy is a similar, hypothetical phenomenon that may have made only a brief appearance, influencing the expansion of the universe in its first moments before disappearing entirely.

Some physicists have suspected that early dark energy could be the key to solving the Hubble tension, as the mysterious force could accelerate the early expansion of the universe by an amount that would resolve the measurement mismatch.

The MIT researchers have now found that early dark energy could also explain the baffling number of bright galaxies that astronomers have observed in the early universe. In their new study, reported in the Monthly Notices of the Royal Astronomical Society, the team modeled the formation of galaxies in the universe’s first few hundred million years. When they incorporated a dark energy component only in that earliest sliver of time, they found the number of galaxies that arose from the primordial environment bloomed to fit astronomers’ observations.

You have these two looming open-ended puzzles,” says study co-author Rohan Naidu, a postdoc in MIT’s Kavli Institute for Astrophysics and Space Research. “We find that in fact, early dark energy is a very elegant and sparse solution to two of the most pressing problems in cosmology.”

The study’s co-authors include lead author and Kavli postdoc Xuejian (Jacob) Shen, and MIT professor of physics Mark Vogelsberger, along with Michael Boylan-Kolchin at the University of Texas at Austin, and Sandro Tacchella at the University of Cambridge.

Big city lights

Based on standard cosmological and galaxy formation models, the universe should have taken its time spinning up the first galaxies. It would have taken billions of years for primordial gas to coalesce into galaxies as large and bright as the Milky Way.

But in 2023, NASA’s James Webb Space Telescope (JWST) made a startling observation. With an ability to peer farther back in time than any observatory to date, the telescope uncovered a surprising number of bright galaxies as large as the modern Milky Way within the first 500 million years, when the universe was just 3 percent of its current age.

“The bright galaxies that JWST saw would be like seeing a clustering of lights around big cities, whereas theory predicts something like the light around more rural settings like Yellowstone National Park,” Shen says. “And we don’t expect that clustering of light so early on.”

For physicists, the observations imply that there is either something fundamentally wrong with the physics underlying the models or a missing ingredient in the early universe that scientists have not accounted for. The MIT team explored the possibility of the latter, and whether the missing ingredient might be early dark energy.

Physicists have proposed that early dark energy is a sort of antigravitational force that is turned on only at very early times. This force would counteract gravity’s inward pull and accelerate the early expansion of the universe, in a way that would resolve the mismatch in measurements. Early dark energy, therefore, is considered the most likely solution to the Hubble tension.

Galaxy skeleton

The MIT team explored whether early dark energy could also be the key to explaining the unexpected population of large, bright galaxies detected by JWST. In their new study, the physicists considered how early dark energy might affect the early structure of the universe that gave rise to the first galaxies. They focused on the formation of dark matter halos — regions of space where gravity happens to be stronger, and where matter begins to accumulate.

“We believe that dark matter halos are the invisible skeleton of the universe,” Shen explains. “Dark matter structures form first, and then galaxies form within these structures. So, we expect the number of bright galaxies should be proportional to the number of big dark matter halos.”

The team developed an empirical framework for early galaxy formation, which predicts the number, luminosity, and size of galaxies that should form in the early universe, given some measures of “cosmological parameters.” Cosmological parameters are the basic ingredients, or mathematical terms, that describe the evolution of the universe.

Physicists have determined that there are at least six main cosmological parameters, one of which is the Hubble constant — a term that describes the universe’s rate of expansion. Other parameters describe density fluctuations in the primordial soup, immediately after the Big Bang, from which dark matter halos eventually form.

The MIT team reasoned that if early dark energy affects the universe’s early expansion rate, in a way that resolves the Hubble tension, then it could affect the balance of the other cosmological parameters, in a way that might increase the number of bright galaxies that appear at early times. To test their theory, they incorporated a model of early dark energy (the same one that happens to resolve the Hubble tension) into an empirical galaxy formation framework to see how the earliest dark matter structures evolve and give rise to the first galaxies.

“What we show is, the skeletal structure of the early universe is altered in a subtle way where the amplitude of fluctuations goes up, and you get bigger halos, and brighter galaxies that are in place at earlier times, more so than in our more vanilla models,” Naidu says. “It means things were more abundant, and more clustered in the early universe.”

“A priori, I would not have expected the abundance of JWST’s early bright galaxies to have anything to do with early dark energy, but their observation that EDE pushes cosmological parameters in a direction that boosts the early-galaxy abundance is interesting,” says Marc Kamionkowski, professor of theoretical physics at Johns Hopkins University, who was not involved with the study. “I think more work will need to be done to establish a link between early galaxies and EDE, but regardless of how things turn out, it’s a clever — and hopefully ultimately fruitful — thing to try.”

We demonstrated the potential of early dark energy as a unified solution to the two major issues faced by cosmology. This might be an evidence for its existence if the observational findings of JWST get further consolidated,” Vogelsberger concludes. “In the future, we can incorporate this into large cosmological simulations to see what detailed predictions we get.”

This research was supported, in part, by NASA and the National Science Foundation.



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Plant-derived secondary organic aerosols can act as mediators of plant-plant interactions

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A new study published in Science reveals that plant-derived secondary organic aerosols (SOAs) can act as mediators of plant-plant interactions. This research was conducted through the cooperation of chemical ecologists, plant ecophysiologists and atmospheric physicists at the University of Eastern Finland.

It is well known that plants release volatile organic compounds (VOCs) into the atmosphere when damaged by herbivores. These VOCs play a crucial role in plant-plant interactions, whereby undamaged plants may detect warning signals from their damaged neighbours and prepare their defences. “Reactive plant VOCs undergo oxidative chemical reactions, resulting in the formation of secondary organic aerosols (SOAs). We wondered whether the ecological functions mediated by VOCs persist after they are oxidated to form SOAs,” said Dr. Hao Yu, formerly a PhD student at UEF, but now at the University of Bern.

The study showed that Scots pine seedlings, when damaged by large pine weevils, release VOCs that activate defences in nearby plants of the same species. Interestingly, the biological activity persisted after VOCs were oxidized to form SOAs. The results indicated that the elemental composition and quantity of SOAs likely determines their biological functions.

“A key novelty of the study is the finding that plants adopt subtly different defence strategies when receiving signals as VOCs or as SOAs, yet they exhibit similar degrees of resistance to herbivore feeding,” said Professor James Blande, head of the Environmental Ecology Research Group. This observation opens up the possibility that plants have sophisticated sensing systems that enable them to tailor their defences to information derived from different types of chemical cue.

“Considering the formation rate of SOAs from their precursor VOCs, their longer lifetime compared to VOCs, and the atmospheric air mass transport, we expect that the ecologically effective distance for interactions mediated by SOAs is longer than that for plant interactions mediated by VOCs,” said Professor Annele Virtanen, head of the Aerosol Physics Research Group. This could be interpreted as plants being able to detect cues representing close versus distant threats from herbivores.

The study is expected to open up a whole new complex research area to environmental ecologists and their collaborators, which could lead to new insights on the chemical cues structuring interactions between plants.



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Folded or cut, this lithium-sulfur battery keeps going

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Most rechargeable batteries that power portable devices, such as toys, handheld vacuums and e-bikes, use lithium-ion technology. But these batteries can have short lifetimes and may catch fire when damaged. To address stability and safety issues, researchers reporting in ACS Energy Letters have designed a lithium-sulfur (Li-S) battery that features an improved iron sulfide cathode. One prototype remains highly stable over 300 charge-discharge cycles, and another provides power even after being folded or cut.

Sulfur has been suggested as a material for lithium-ion batteries because of its low cost and potential to hold more energy than lithium-metal oxides and other materials used in traditional ion-based versions. To make Li-S batteries stable at high temperatures, researchers have previously proposed using a carbonate-based electrolyte to separate the two electrodes (an iron sulfide cathode and a lithium metal-containing anode). However, as the sulfide in the cathode dissolves into the electrolyte, it forms an impenetrable precipitate, causing the cell to quickly lose capacity. Liping Wang and colleagues wondered if they could add a layer between the cathode and electrolyte to reduce this corrosion without reducing functionality and rechargeability.

The team coated iron sulfide cathodes in different polymers and found in initial electrochemical performance tests that polyacrylic acid (PAA) performed best, retaining the electrode’s discharge capacity after 300 charge-discharge cycles. Next, the researchers incorporated a PAA-coated iron sulfide cathode into a prototype battery design, which also included a carbonate-based electrolyte, a lithium metal foil as an ion source, and a graphite-based anode. They produced and then tested both pouch cell and coin cell battery prototypes.

After more than 100 charge-discharge cycles, Wang and colleagues observed no substantial capacity decay in the pouch cell. Additional experiments showed that the pouch cell still worked after being folded and cut in half. The coin cell retained 72% of its capacity after 300 charge-discharge cycles. They next applied the polymer coating to cathodes made from other metals, creating lithium-molybdenum and lithium-vanadium batteries. These cells also had stable capacity over 300 charge-discharge cycles. Overall, the results indicate that coated cathodes could produce not only safer Li-S batteries with long lifespans, but also efficient batteries with other metal sulfides, according to Wang’s team.

The authors acknowledge funding from the National Natural Science Foundation of China; the Natural Science Foundation of Sichuan, China; and the Beijing National Laboratory for Condensed Matter Physics.



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