| 1. |
- Baggi, Nicolò, et al.
(author)
-
Flow-Integrated Preparation of Norbornadiene Precursors for Solar Thermal Energy Storage
- 2024
-
In: ChemSusChem. - 1864-5631 .- 1864-564X. ; 17:2
-
Journal article (peer-reviewed)abstract
- Molecular solar thermal (MOST) energy storage systems are getting increased attention related to renewable energy storage applications. Particularly, 2,3-difunctionalized norbornadiene-quadricyclane (NBD-QC) switches bearing a nitrile (CN) group as one of the two substituents are investigated as promising MOST candidates thanks to their high energy storage densities and their red-shifted absorbance. Moreover, such NBD systems can be prepared in large quantities (a requirement for MOST-device applications) in flow through Diels-Alder reaction between cyclopentadiene and appropriately functionalized propynenitriles. However, these acetylene precursors are traditionally prepared in batch from their corresponding acetophenones using reactive chemicals potentially leading to health and physical hazards, especially when working on a several-grams scale. Here, we develop a multistep flow-chemistry route to enhance the production of these crucial precursors. Furthermore, we assess the atom economy (AE) and the E-factor showing improved green metrics compared to classical batch methods. Our results pave the way for a complete flow synthesis of NBDs with a positive impact on green chemistry aspects.
|
|
| 2. |
- Ghasemi, Shima, 1993, et al.
(author)
-
Pyrene Functionalized Norbornadiene-Quadricyclane Fluorescent Photoswitches: Characterization of their Spectral Properties and Application in Imaging of Amyloid Beta Plaques
- 2024
-
In: Chemistry - A European Journal. - 1521-3765 .- 0947-6539. ; 30:34
-
Journal article (peer-reviewed)abstract
- This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aβ) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization, aligning with what has been previously reported, for the first time we observed luminescence after irradiation of the quadricyclane (QC) isomer. We deduce how the observed emission is induced by photoisomerization to the excited state of the parent isomer (NBD) which is then the emitting species. Thorough characterizations including NMR, UV-Vis, fluorescence, X-ray structural analysis and density functional theory (DFT) calculations provide a comprehensive understanding of these systems. Notably, one NBD-QC system exhibits exceptional durability. Additionally, these molecules serve as effective fluorescent stains targeting Aβ plaques in situ, with observed NBD/QC switching within the plaques. Molecular docking simulations explore NBD interactions with amyloid, unveiling novel binding modes. These insights mark a crucial advancement in the comprehension and design of future photochromic NBDs for bioimaging applications and beyond, emphasizing their potential in studying and addressing protein aggregates.
|
|
| 3. |
- Gimenez-Gomez, Alberto, et al.
(author)
-
Cover Feature: Unveiling the Potential of Heterogeneous Catalysts for Molecular Solar Thermal Systems (Chem. Eur. J. 1/2024)
- 2024
-
In: Chemistry - A European Journal. - 1521-3765 .- 0947-6539. ; 30:1
-
Journal article (other academic/artistic)abstract
- Trapping sunlight energy into chemical bonds has become an important method for storing renewable energy and releasing it on demand. To illustrate the new catalyst-testing protocol, a cyclic road shows the photoisomerization process trapping sunlight (top) and the back-conversion catalytic reaction releasing heat. The bottom wheel indicates that up to 27 different catalysts were studied. More information can be found in the Research Article by I. Funes-Ardoiz, D. Sampedro and co-workers (DOI: 10.1002/chem.202303230).
|
|
| 4. |
- Gimenez-Gomez, Alberto, et al.
(author)
-
Unveiling the Potential of Heterogeneous Catalysts for Molecular Solar Thermal Systems
- 2024
-
In: Chemistry - A European Journal. - 1521-3765 .- 0947-6539. ; 30:1
-
Journal article (peer-reviewed)abstract
- Solar energy utilization has gained considerable attention due to its abundance and renewability. However, its intermittent nature presents a challenge in harnessing its full potential. The development of energy storing compounds capable of capturing and releasing solar energy on demand has emerged as a potential solution. These compounds undergo a photochemical transformation that results in a high-energy metastable photoisomer, which stores solar energy in the form of chemical bonds and can release it as heat when required. Such systems are referred to as MOlecular Solar Thermal (MOST)-systems. Although the photoisomerization of MOST systems has been vastly studied, its back-conversion, particularly using heterogeneous catalysts, is still underexplored and the development of effective catalysts for releasing stored energy is crucial. Herein we compare the performance of 27 heterogeneous catalysts releasing the stored energy in an efficient Norbornadiene/Quadricyclane (NBD/QC) MOST system. We report the first benchmarking of heterogeneous catalysts for a MOST system using a robust comparison method of the catalysts’ activity and monitoring the conversion using UV-Visible (UV-Vis) spectroscopy. Our findings provide insights into the development of effective catalysts for MOST systems. We anticipate that our assay will reveal the necessity of further investigation on heterogeneous catalysis.
|
|
| 5. |
- Magson, Lucien, et al.
(author)
-
Synthesis and Characterization of Carbon-Based Heterogeneous Catalysts for Energy Release of Molecular Solar Thermal Energy Storage Materials
- 2024
-
In: ACS Applied Materials & Interfaces. - 1944-8252 .- 1944-8244. ; 16:6, s. 7211-7218
-
Journal article (peer-reviewed)abstract
- Molecular solar thermal energy storage (MOST) systems are rapidly becoming a feasible alternative to energy storage and net-zero carbon emission heating. MOST systems involve a single photoisomerization pair that incorporates light absorption, storage, and heat release processes in one recurring cycle. Despite significant recent advancements in the field, the catalytic back-reaction from MOST systems remains relatively unexplored. A wide range of applications is possible, contingent on the energy densities of the specific photoisomers. Here, we report platinum-, copper-, and nickel-based heterogeneous catalysts screened in batch conditions for the back-conversion reaction on the cyano-3-(4-methoxyphenyl)-norbornadiene/quadricyclane pair. Catalyst reactivities are investigated using structural characterization, imaging techniques, and spectroscopic analysis. Finally, the thermal stability is also explored for our best-performing catalysts.
|
|
