By combining photochemical reactions with molecular self-assembly, scientists have achieved the impossible: using light to create molecular fits that defy thermodynamic equilibrium.
This groundbreaking approach could revolutionize technology and medicine by leveraging sunlight to develop innovative materials, smart drugs, and dynamic systems mimicking the non-equilibrium processes in living organisms.
Harnessing Light for Molecular Manipulation
Using a creative combination of light-driven (photochemical) reactions and molecular self-assembly, a research team led by Prof. Alberto Credi at the University of Bologna has achieved a groundbreaking feat. They successfully inserted a thread-like molecule into the cavity of a ring-shaped molecule, forming a high-energy structure that would normally be impossible under thermodynamic equilibrium. In essence, light enables the creation of molecular configurations that nature cannot achieve on its own.
“We have shown that by administering light energy to an aqueous solution, a molecular self-assembly reaction can be prevented from reaching a thermodynamic minimum, resulting in a product distribution that does not correspond to that observed at equilibrium,” says Alberto Credi. “Such a behavior, which is at the root of many functions in living organisms, is poorly explored in artificial molecules because it is very difficult to plan and observe. The simplicity and versatility of our approach, together with the fact that visible light – i.e., sunlight – is a clean and sustainable energy source, allow us to foresee developments in various areas of technology and medicine.”
Self-Assembly: The Core of Nanotechnology
The self-assembly of molecular components to obtain systems and materials with structures on the nanometer scale (1 nanometer = 1 billionth of a meter) is one of the basic processes of nanotechnology. It takes advantage of the tendency of molecules to evolve to reach a state of thermodynamic equilibrium, that is, of minimum energy.
However, living things function by chemical transformations that occur away from thermodynamic equilibrium and can only occur by providing external energy. Reproducing such mechanisms with artificial systems is a complex and ambitious challenge that, if met, could enable the creation of new substances, capable of responding to stimuli and interacting with the environment, which could be used to develop, for example, smart drugs and active materials.
The Molecular Fit: Cyclodextrins and Azobenzene
The interlocking components are cyclodextrins, hollow water-soluble molecules with a truncated cone shape, and azobenzene derivatives, molecules that change shape under the effect of light. In water, interactions between these components lead to the formation of supramolecular complexes in which the filiform azobenzene species is inserted into the cyclodextrin cavity.
Light-Induced Control of Molecular Orientation
In this study, the filiform compound possesses two different ends; since the two rims of the cyclodextrin are also different, insertion of the former into the latter generates two distinct complexes, which differ in the relative orientation of the two components (see figure above).
Complex A is more stable than complex B, but the latter forms more rapidly than the former. In the absence of light, only the thermodynamically favored complex, namely A, is observed at equilibrium. By irradiating the solution with visible light, the azobenzene changes from an extended configuration akin to cyclodextrin to a bent one incompatible with the cavity; as a result, the complex dissociates.
However, the same light can convert the azobenzene back from the bent to the extended form, and the dissociated components can reassemble. Because complex B forms much faster than A, under continuous illumination a steady state is reached in which complex B is the dominant product. Once the light is turned off, the azobenzene slowly reverts to the extended form, and after some time only the A complex is observed.
Dynamic Systems Beyond Thermodynamic Equilibrium
This self-assembly mechanism coupled with a photochemical reaction makes it possible to harness the energy of light to accumulate unstable products, thus paving the way for new methodologies of chemical synthesis and the development of dynamic molecular materials and devices (e.g., nanomotors) that operate under non-equilibrium conditions, similar to living beings.
Reference: “Light-driven ratcheted formation of diastereomeric host-guest systems” by Iago Neira, Chiara Taticchi, Federico Nicoli, Massimiliano Curcio, Marcos D. Garcia, Carlos Peinador, Serena Silvi, Massimo Baroncini and Alberto Credi, 27 December 2024, Chem.
DOI: 10.1016/j.chempr.2024.11.013
The study was published in the prestigious scientific journal Chem and is the result of a collaboration between the Departments of Industrial Chemistry “Toso Montanari,” Chemistry “Ciamician” and Agricultural and Food Science and Technology of the Alma Mater, the University of Coruña in Spain and the Isof-Cnr institute in Bologna. The team coordinated by Alberto Credi includes researchers Neira, Chiara Taticchi, Federico Nicoli, and Massimiliano Curcio, and professors Marcos Garcia, Carlos Peinador, Massimo Baroncin,i and Serena Silvi.
Funded by the Ministry of University and Research, the project is aimed at the realization of next-generation molecular devices and machines and is being developed in the Center for Light Activated Nanostructures (Clan; https://centri.unibo.it/clan/en), a joint laboratory between the University of Bologna and CNR recognized as an international leader in the field. The lab had already attracted public attention by developing molecular pumps (Nature Nanotechnology 2015, 2022), sponges (Nature Chemistry 2015), and other devices (Chem 2021, 2024).
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4 Comments
B note 2412280249 source 1. Analyzing_【】
1.
Scientists have made it possible for molecules to do the impossible with light. Using light, researchers have opened up a new realm of nanotechnology by guiding molecules to self-assemble in a way that nature does not allow. This method may inspire future solutions in medicine and dynamic devices.
Scientists have accomplished the impossible task of combining photochemical reactions and molecular self-assembly to create a molecular fit that rejects thermodynamic equilibrium. This groundbreaking approach can revolutionize technology and medicine by using sunlight to develop dynamic systems that mimic the non-equilibrium processes of innovative materials, smart drugs, and living things.
1-1. Utilization of light for molecular manipulation
Using a creative combination of light-induced (photochemical) reactions and molecular self-assembly, the research team achieved the breakthrough.
They successfully inserted a thread-like molecule into the [1-1]-shaped cavity of molecules, forming a high-energy structure that is generally impossible under thermodynamic equilibrium. Essentially, light allows nature to produce molecular configurations that it cannot achieve on its own.
[1′]We showed that by supplying light energy to the aqueous solution, it is possible to prevent the molecular self-assembly reaction from reaching a thermodynamic minimum, resulting in a product distribution inconsistent with that observed in equilibrium.
_[1,1′] Assuming that the aqueous solution is msbase and the method of preventing the minimum value of thermal equilibrium inside the mcell is oser or qvixer. The role of light energy in the mcell compared to the aqueous solution is shown to be oser (oss) and qvixer quantum entanglement in the mcell. The oser must newly construct the thermal equilibrium of os, and the qvixer indicates that qms is a single photon energy, so it is possible to construct dna.rna, the real number of molecules in the msbase aqueous solution as much as possible. Huh.
Since qpeoms mediators are formed between mcells, making atomic nuclei with quark combinations, whether their qp is a compatible molecule of atoms, is infinite proliferation between scalable mcells that is independent of the thermal equilibrium magnetum. In other words, various geometric linear.po=pl shapes are possible even for numbers that freely deviate from squares in the shape of msbase. Huh.
Maybe it’s because my parents passed away, but our three brothers lost their balance and moved away from each other’s core. This is like the diffusion of molecules and atomic nuclei, which broke thermal equilibrium. There, rings and threads always edit the world like threads in the eyes of a needle. Uh-huh.
2.
This behavior, which is the source of many functions of life, is not well explored in artificial molecules because it is very difficult to plan and observe. The simplicity and diversity of our approach, and the fact that visible light (i.e., sunlight) is a clean and sustainable energy source, allow us to predict advances in various fields of technology and medicine.
Self-assembly: Key to Nanotechnology
Self-assembly of molecular components to obtain materials and systems with nanometer-scale structures (1 nanometer = one-billionth of a meter) is one of the basic processes of nanotechnology. It takes advantage of the tendency of molecules to evolve to reach thermodynamic equilibrium, or minimum energy.
[2]However, life can only occur if it functions by chemical transformations that occur out of thermodynamic equilibrium and provides external energy.
_[2] The externally provided energy is qms.point and qpeoms.plane. This creates an infinite dna.msbase free.fiber of po=pl.n. Inside the optical fiber, light travels *in total reflection.
*Total reflection refers to 100% reflection of light on a specific surface. For example, if the angle of incidence of light hitting the glass is greater than the critical angle, the light cannot pass through the glass and is 100% reflected. This phenomenon is called total reflection. Applications of total reflection include optical cables and pentaprism of a camera. Of course, msbase is also total reflection, so all light is collected at the exit of nk2. Haha.
4. Dynamic systems beyond thermodynamic equilibrium
This [4] self-assembly mechanism, combined with photochemical reactions, allows the use of photovoltaic energy] to accumulate unstable products, paving the way for the development of novel chemical synthesis methodologies and dynamic molecular materials and devices (e.g., nanomotors) that operate under non-equilibrium conditions. It is similar to life.
_[4] The total point energy of the msbase in which the total reflection of the line of the incident light energy of the optical fiber reaches the value of the output light is nk2. The total biological energy is distributed in several forms in which the position nk2 is distributed. It represents the biological structure, shape, and function that distributes energy to show the balance of overall thermodynamics. The overall msbase is maintained with nk2 biological output energy in order to increase the natural adaptability of partial free evolution where legs and arms, head and body are different. So the molecular chambers of non-equilibrium parts.nk2 with degrees of freedom enable the living organism to naturally evolve. Huh.
Thank you! That was helpful for an old person even if I don’t understand all of it! And you’re funny!
Thank heavens that light is helping progress with forming new materials such as super conductors. If the light originates from concentrated sunlight the Solar Collector design will soon become an essential part of materials processing and the patent will be valuable. I am not planning to be part of the manufacturing personally but will collect royalties for having thought of how to avail the energy.
If they had done it, then it was quite clearly not impossible.