ChemistryEurope

Vighnesh, Kunnathodi; Rogach, Andrey L.

doi: 10.1002/ceur.70298pmid: N/A

Heterostructures have driven the commercialization of classical quantum dots by substantially enhancing their optoelectronic performance and stability. Lead halide perovskite nanocrystals demonstrate excellent optoelectronic properties while suffering from structural degradation under stresses like moisture, heat, oxygen, and light. Consequently, the implementation of heterostructure design strategies in perovskite nanocrystals remains an active area of research. This review provides a comprehensive overview of recent advances in perovskite‐based nanoheterostructures, focusing on synthetic strategies, growth mechanisms, crystallographic relationships, optical properties, and their implementation in various optoelectronic devices. We emphasize the concept of epitaxial interfaces and the challenges associated with epitaxial growth in perovskite nanocrystals. Nanoheterostructures formed by integrating perovskite nanocrystals with metal chalcogenides, lead chalcohalides, metal halides, oxides, perovskite derivatives, and metallic nanoparticles are considered. The interfacial band alignment, facet‐selective growth, and their influence on charge carrier dynamics, photoluminescence properties and environmental stability in epitaxial perovskite nanoheterostructures are discussed. These advances have enabled demonstrations of perovskite nanoheterostructures in devices including solar cells, light‐emitting diodes, photodetectors, and photocatalytic systems. Finally, the Review explores the possibilities for expanding the library of perovskite‐based nanoheterostructures, including strategies to enable multifacet heteronucleation, utilization of common sublattices for epitaxial coupling, and the development of anisotropic architectures, such as nanorod heterostructures.

Homölle, Simon L.; Bauch, Tristan; Hamad, Aboubakr; Zhang, Bo‐Sheng; Ackermann, Lutz

doi: 10.1002/ceur.70305pmid: N/A

Molecular editing and atom insertion are powerful tools for the late‐stage construction of complex molecular architectures, especially in medicinal chemistry. However, up to now, such transformations rely on harsh conditions and superstoichiometric chemical oxidants. Although electrochemical strategies for skeletal editing strongly mitigate some of these constraints, the substrate scope remains narrow. Moreover, the use of hazardous reagents in high concentrations severely limits the applicability of these strategies for scale‐up and subsequent industrial application. To overcome these bottlenecks, we herein present a manganaelectro‐catalyzed nitrogen atom insertion furnishing isoquinolines with broad functional group tolerance. Furthermore, our approach also proved suitable for recirculation flow electrolysis, including scale‐up, reflecting its potential for industrial application.

Hum, Gavin; Phang, Si Jia Isabel; Ong, How Chee; Li, Yongxin; León, Felix; Ng, Zheng Jie Glenn; Clegg, Jack K.; García, Felipe

doi: 10.1002/ceur.202500480pmid: N/A

The integration of main‐group elements into anion receptor design has recently garnered attention due to their redox flexibility and structural diversity. Among these, aminocyclodiphosphazanes (PIII2N2 and PV2N2) have emerged as promising alternatives to classical organic motifs such as ureas and squaramides, offering modularity and postsynthetic tunability. Herein, we report the synthesis of iridium‐ and palladium‐chelated, NH‐bridged acyclic dimeric PIII2N2 receptors exhibiting a fixed trifurcated geometry and a novel PNP coordination motif. These conformationally preorganized metal–phosphazane hybrids demonstrate significantly enhanced hydrogen‐bonding affinity toward both monoatomic and weakly coordinating polyatomic anions—including PF6−— surpassing previously reported PV2N2 analogs. Notably, these systems allow further tuning of electronic and structural properties via ligand substitution or additional metal coordination to its uncoordinated P(III) sites. These features render the systems chemically robust and readily adaptable, positioning them as versatile scaffolds for the development of advanced supramolecular architectures with potential utility in molecular recognition, sensing, and ion capture technologies.

Adlbert, Lukas; Zimmermann, Lisa; Riesinger, Christoph; Scheer, Manfred

doi: 10.1002/ceur.70303pmid: N/A

Despite their structural similarity, the controlled conversion of elemental arsenic remains significantly less investigated than that of its lighter congener phosphorus. Exploring how As4 responds to low‐valent main‐group compounds is therefore essential to understand differences in bonding and reactivity across the heavier pnictogens. The reactivity of N,N‐bis(silylenyl)aniline ((LSi)2NPh) (L = PhC(NtBu)2) toward yellow arsenic (As4) has been explored, revealing unprecedented arsasila‐cycles. Under strict light‐excluding conditions, a selective conversion of As4 with (LSi)2NPh into the first 2,5‐disila‐3,4‐diarsapyrrole, [(LSi)2(NPh)As2] (1), featuring two SiAs double bonds is observed. Irradiation of 1 induces dimerization and ring contraction to [(LSi)(NPh)AsSi]2L2 (L2 = [PhC(NtBu)2]2) (2), accompanied by the formation of gray arsenic. Compound 2 reacts with untreated glass surfaces to give [(LSi)(NPh)As(LHSi)] (LH = PhCH(NtBu)2) (3), retaining the four‐membered heterocycle. Variation of stoichiometry between 1 and As4 affords the six‐membered heterocycle [(LSi)2(NPh)As2(LSi)] (4) and the four‐membered heterocycle [(LSiH)2(NPh)2] (5). The product distribution can be directed by controlling light exposure, stoichiometry, temperature, and vessel surface, highlighting the distinctive structural rearrangements and enhanced reactivity of arsenic compared to phosphorus.

Lima, Carlos D. L.; Abrantes, Rafaela; Lorrain, Victor; Gomes, Joana; Núñez‐Franco, Reyes; António, João P. M.; Gomes, Catarina; Gimeno, Ana; Pinheiro, Benedita A.; Palma, Angelina S.; Jiménez‐Barbero, Jesús; Gois, Pedro M. P.; Jiménez‐Osés, Gonzalo; van Vliet, Sandra J.; Reis, Celso A.; Marcelo, Filipa

doi: 10.1002/ceur.70288pmid: N/A

Cancer remains a major cause of mortality, especially in advanced stages where current therapies are less effective. Antibody‐drug conjugates offer targeted treatment, but their efficacy is limited by on‐target/off‐tumor toxicity since most protein receptors are also present in healthy tissues. Abnormal glycosylation is a hallmark of cancer, with Thomsen‐nouveau (Tn) and Sialyl‐Tn (STn) antigens driving tumor progression. The human macrophage galactose‐type lectin (MGL) binds αGalNAc within these antigens through its carbohydrate recognition domain (CRD), distinguishing Tn/STn‐expressing cancer cells from healthy ones. This specificity positions the MGL‐CRD as a promising vehicle for safer drug delivery. Herein, an MGL‐based drug conjugate was engineered by introducing an exposed cysteine (mMGL) to allow chemical linkage to monomethyl auristatin E derivative (vcMMAE). The resulting conjugate (mMGL‐vcMMAE) is stable and preserves the thermal stability, the αGalNAc binding profile and, the affinity of the native MGL‐CRD, including its selectivity toward glycoengineered cancer models expressing Tn/STn antigens. Tissue validation confirmed selective binding to colorectal cancer (CRC) tissues. Metabolism and apoptosis analysis demonstrated that mMGL‐vcMMAE impacts glycoengineered cancer cells expressing Tn/STn O‐glycans compared to free vcMMAE, improving targeting precision. This strategy offers a novel glycan‐guided approach to potentially minimize off‐target effects, advancing in safer and more effective cancer therapies.

Valencia, Esteban A.; Escobar, Luis; Aragay, Gemma; Hunter, Christopher A.; Ballester, Pablo

doi: 10.1002/ceur.70286pmid: N/A

We quantify the free‐energy penalty for burying a carboxylate group in the upper aromatic cavity of a super aryl‐extended calix[4]pyrrole in water using chemical double mutant cycles. We perform isothermal titration calorimetry and pairwise competitive experiments, monitored by proton nuclear magnetic resonance spectroscopy, to thermodynamically characterize the 1:1 complexes formed between the pyridine N‐oxide guests and the calix[4]pyrrole receptors. Complexation‐induced chemical shift changes and density functional theory (DFT) calculations were used to assign guest binding geometries in the complexes. Replacing a terminal methyl group on the guest with a carboxylate yields significant repulsive interactions (from +1.3 to +3.0 kcal·mol−1), which depend on the location of the charged group within the hydrophobic aromatic pocket. However, these repulsive interactions are much weaker than the estimate for complete desolvation of a carboxylate in water (>8 kcal·mol−1), suggesting that the carboxylate remains substantially hydrated when bound. Calculations indicated that water molecules can penetrate the cracks in the aromatic walls and the open portal at the top of the binding pocket, creating a surprisingly polar microenvironment. The use of synthetic calix[4]pyrrole receptors provides a simplified model for evaluating the cost of burying charged and polar groups within wet, hydrophobic, protein‐like binding pockets.

Papp, Florian; Sukowski, Verena; Verboom, Jos; Johansson, Magnus J.; Fernández‐Ibáñez, M. Ángeles

doi: 10.1002/ceur.70299pmid: N/A

The introduction of methyl groups into drug candidates is a widely used strategy in medicinal chemistry to improve pharmaceutical properties. However, the introduction of methyl groups to the meta‐position of electron‐rich arenes is a key challenge, since it is complementary to the natural reactivity in electrophilic aromatic substitutions and therefore mostly relies on prefunctionalized substrates or directing groups. Herein, we disclose a selective meta‐CH methylation of anilines and anisole derivatives that eliminates the need for less step‐economical prefunctionalization strategies, enabled by a Pd/S, O‐ligand/norbornene cooperative catalytic system with the potential for modification and isotope labeling of drug candidates and natural products.

Pollastri, Sara; Delaunay, Clara; Antonini, Giulia; Froment, Carine; Thépaut, Michel; Pasquali, Davide; Mazzotta, Sarah; Belvisi, Laura; Marcoux, Julien; Fieschi, Franck; Dal Corso, Alberto; Bernardi, Anna

doi: 10.1002/ceur.202500485pmid: N/A

The derivatization of small molecule ligands with salicylaldehyde (SA) tags is being increasingly pursued to form imine adducts with protein lysine residues, aiming at strong and selective inhibition of a wide range of protein targets. In this work, we describe SA‐tagged, glycomimetic ligands specific for the human C‐type lectin DC‐SIGN. Covalent docking studies guided the SA installation at the anomeric position of mannose scaffolds, enabling imine bond formation with a Lys residue in the vicinity of the ligand binding site. Compared to control compounds, the synthesized SA‐bearing glycomimetics showed improved binding to DC‐SIGN and exquisite selectivity for this lectin over the closely‐related L‐SIGN, where the relevant Lys are replaced by different residues. Mass spectrometry data confirmed the formation of a covalent adduct between the SA‐tagged ligand and DC‐SIGN, ultimately confirming the potential of SA‐tagged glycomimetics as drug candidates against viral infections.

Sterk, Ellen B.; Kappé, Bram T.; Monai, Matteo; Louwen, Jaap N.; Vogt, Eelco T. C.; Filot, Ivo A. W.; Weckhuysen, Bert M.

doi: 10.1002/ceur.70309pmid: N/A