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1. Synthesis of model bacteriochlorophylls containing substituents of native rings A, C and E

   https://doi.org/10.1039/d1nj02469h  

   Chung, Duy T.; Tran, Phuong Vy; Chau Nguyen, Khiem; Wang, Pengzhi; Lindsey, Jonathan S. (August 2021, New Journal of Chemistry)

   null (Ed.)

   A route under development for the synthesis of bacteriochlorophyll a and analogues relies on joining an AD-dihydrodipyrrin (bearing a D-ring carboxaldehyde) and a BC-dihydrodipyrrin (bearing a C-ring β-ketoester group and a B-ring dimethoxymethyl group) via Knoevenagel condensation followed by double-ring closure (Nazarov cyclization, electrophilic aromatic substitution, and elimination of methanol). Prior synthetic studies afforded the bacteriochlorophyll skeleton containing a gem-dimethyl group in ring B, a trans -dialkyl group in ring D, and a carboethoxy group at the 3-position of ring A. To explore the incorporation of native substituents, the synthesis of two bacteriochlorophyll analogues thereof was pursued, one with 12-methyl and 3-carboethoxy groups and the other with 2,12-dimethyl and 3-acetyl groups. The 12-methyl group resulted in half the yield ( versus the unsubstituted analogue) in the Knoevenagel reaction, but insignificant effects in all other steps including the rate and yield of double-ring closure despite the known effects of alkyl groups to facilitate electrophilic substitution of pyrroles. The 2-methyl-3-acetyl group, however, resulted in diminished yields in several steps, including the Knoevenagel reaction, but not the double-ring closure. The results point to obstacles and openings on the path to total syntheses of the native pigments. 

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2. Study of conditions for streamlined assembly of a model bacteriochlorophyll from two dihydrodipyrrin halves

   https://doi.org/10.1039/d0nj04855k  

   Nguyen, Khiem Chau; Wang, Pengzhi; Lindsey, Jonathan S. (January 2021, New Journal of Chemistry)

   null (Ed.)

   A long-term goal is to gain synthetic access to native photosynthetic bacteriochlorophylls. A recently developed route entails Knoevenagel condensation of an AD dihydrodipyrrin ( I , bearing a carboxaldehyde attached to pyrroline ring D) and a BC dihydrodipyrrin ( II , bearing a β-ketoester attached to pyrrole ring C) to form the Z / E -enone. Acid-mediated double-ring closure of the E -enone III-E (Nazarov cyclization, electrophilic aromatic substitution, and elimination of methanol) affords the bacteriochlorophyll skeleton BC-1 containing the isocyclic ring (ring E), a trans -dialkyl group in ring D, and a gem-dimethyl group in ring B. Prior work established the synthesis and the integrity of the resulting trans -dialkyl groups and bacteriochlorin chromophore. The counterpart report here concerns an in-depth study of conditions for the double-ring closure: catalyst/solvent surveys; grid search including time courses of [ III-E ] versus [acid] concentrations emphasizing equimolar, inverse molar, and variable acid lines of inquiry; and chlorin byproduct quantitation. Key findings are that (1) the double-ring closure can be carried out in 4 h ( t 1/2 ∼ 40 min) instead of 20 h, affording ∼1/5th the chlorin byproduct (0.16%) while maintaining the yield of BC-1 (up to 77%); (2) the separate Z / E -enones of III have comparable reactivity; (3) sub-stoichiometric quantities of acid are ineffective; (4) the Knoevenagel condensation (40 mM, room temperature, piperidine/acetic acid in acetonitrile) and the acid-mediated double-ring closure (0.20 mM, 80 °C, Yb(OTf) 3 in acetonitrile) can be carried out in a two-step process; and (5) zinc insertion to form ZnBC-1 is straightforward. Together, the results enable streamlined conversion of dihydrodipyrrin reactants to the bacteriochlorophyll model compounds. 

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3. Phenalenannulations: Three‐Point Double Annulation Reactions that Convert Benzenes into Pyrenes

   https://doi.org/10.1002/anie.202006087  

   Kawade, Rahul Kisan; Hu, Chaowei; Dos Santos, Nikolas R.; Watson, Noelle; Lin, Xinsong; Hanson, Kenneth; Alabugin, Igor V. (July 2020, Angewandte Chemie International Edition)

   Abstract 3‐Point annulations, or phenalenannulations, transform a benzene ring directly into a substituted pyrene by “wrapping” two new cycles around the perimeter of the central ring at three consecutive carbon atoms. This efficient, modular, and general method for π‐extension opens access to non‐symmetric pyrenes and their expanded analogues. Potentially, this approach can convert any aromatic ring bearing a ‐CH₂Br or a ‐CHO group into a pyrene moiety. Depending upon the workup choices, the process can be directed towards either tin‐ or iodo‐substituted product formation, giving complementary choices for further various cross‐coupling reactions. The two‐directional bis‐double annulation adds two new polyaromatic extensions with a total of six new aromatic rings at a central core. 

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4. Trapping of Small Molecules within Single or Double Cyclo[18]carbon Rings

   https://doi.org/10.3390/molecules28052157  

   Trzęsowska, Natasza; Wysokiński, Rafał; Michalczyk, Mariusz; Zierkiewicz, Wiktor; Scheiner, Steve (March 2023, Molecules)

   The encapsulation of a set of small molecules, H2, CO, CO2, SO2, and SO3, by a circular C18 ring is investigated by quantum calculations. These ligands lie near the center of the ring but, with the exception of H2, are disposed roughly perpendicular to the ring plane. Their binding energies with the C18 vary from 1.5 kcal/mol for H2 up to 5.7 kcal/mol for SO2, and the bonding is dominated by dispersive interactions spread over the entire ring. The binding of these ligands on the outside of the ring is weaker but allows the opportunity for each to bond covalently with the ring. A pair of C18 units lie parallel to one another. This pair can bind each of these ligands in the area between them with only small perturbations of the double ring geometry. The binding energies of these ligands to this double ring configuration are amplified by some 50% compared to the single ring systems. The presented data concerning the trapping of small molecules may have larger implications regarding hydrogen storage or air pollution reduction. 

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5. Acceleration-induced transport of quantum vortices in joined atomtronic circuits

   https://doi.org/10.21468/SciPostPhys.19.1.005  

   Chaika, Andrii; Oliinyk, A O; Yatsuta, I V; Proukakis, Nikolaos; Edwards, Mark; Yakimenko, Alexander; Bland, Thomas (July 2025, SciPost Physics)

   Persistent currents–inviscid quantized flow around an atomic circuit–are a crucial building block of atomtronic devices. We investigate how acceleration influences the transfer of persistent currents between two density-connected, ring-shaped atomic Bose-Einstein condensates, joined by a tunable weak link that controls system topology. We find that the acceleration of this system modifies both the density and phase dynamics between the rings, leading to a bias in the periodic vortex oscillations studied in T. Bland et al., Phys. Rev. Research 4, 043171 (2022). Accounting for dissipation suppressing such vortex oscillations, the acceleration facilitates a unilateral vortex transfer to the leading ring. We analyze how this transfer depends on the weak-link amplitude, the initial persistent current configuration, and the acceleration strength and direction. Characterization of the sensitivity to these parameters paves the way for a new platform for acceleration measurements, for which we outline a proof-of-concept ultracold double-ring accelerometer. 

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