Nanoarchitectonics of Vesicle Microreactors for Oscillating ATP Synthesis and HydrolysisWang, Tonghui; Fei, Jinbo; Yu, Fanchen; Xu, Xia; Cui, Yue; Li, Junbai
doi: 10.1002/anie.202411981pmid: 39041718
We construct a compartmentalized nanoarchitecture to regulate bioenergy level. Glucose dehydrogenase, urease and nicotinamide adenine dinucleotide are encapsulated inside through liquid‐liquid phase separation. ATPase and glucose transporter embedded in hybrid liposomes are attached at the surface. Glucose is transported and converted to gluconic acid catalyzed by glucose dehydrogenase, resulting in an outward proton gradient to drive ATPase for ATP synthesis. In parallel, urease catalyzes hydrolysis of urea to generate ammonia, which leads to an inward proton gradient to drive ATPase for ATP hydrolysis. These processes lead to a change of the direction of proton gradient, thus achieving artificial ATP oscillation. Importantly, the frequency and the amplitude of the oscillation can be programmed. The work explores nanoarchitectonics integrating multiple components to realize artificial and precise oscillation of bioenergy level.
Helicene Covalent Organic Frameworks for Robust Light Harvesting and Efficient Energy TransfersYin, Cong; Ye, Xingyao; Tao, Shanshan; Zhao, Dan; Zhi, Yongfeng; Jiang, Donglin
doi: 10.1002/anie.202411558pmid: 39024117
Helicenes represent a class of fascinating π compounds with fused yet folded backbones. Despite their broad structural diversity, harnessing helicenes to develop well‐defined materials is still a formidable challenge. Here we report the synthesis of crystalline porous helicene materials by exploring helicenes to synthesize covalent 2D lattices and layered π frameworks. Topology‐directed polymerization of [6]helicenes and porphyrin creates 2D covalent networks with alternate helicene‐porphyrin alignment along the x and y directions at a 1.5‐nm interval and develops [6]helicene frameworks through reversed anti‐AA stack along the z direction to form segregated [6]helicene and porphyrin columnar π arrays. Notably, this π configuration enables the frameworks to be highly red luminescent with benchmark quantum yields. The [6]helicene frameworks trigger effieicnt intra‐framework singlet‐to‐singlet state energy transfer from [6]helicene to porphyrin and facilitate intermolecular triplet‐to‐triplet state energy transfer from frameworks to molecular oxygen to produce reactive oxygen species, harvesting a wide range of photons from ultraviolet to near‐infrared regions for light emitting and photo‐to‐chemical conversion. This study introduces a new family of extended frameworks, laying the groundwork for exploring well‐defined helicene materials with unprecedented structures and functions.
A Rhodamine‐Spiropyran Conjugate Empowering Tunable Mechanochromism in Polymers under Multiple StimuliSun, Ze‐Ying; Li, Yiran; Wu, Mengjiao; He, Weiye; Yuan, Yuan; Cao, Yi; Chen, Yulan
doi: 10.1002/anie.202411629pmid: 38966872
Mechanochromic functionality realized via the force‐responsive mechanophores in polymers has great potential for damage sensing and information storage. Mechanophores with the ability to recognize multiple stimuli for tunable chromic characteristics are highly sought after for versatile sensing ability and color programmability. Nevertheless, the majority of mechanophores are based on single‐component chromophores with limited sensitivity, or require additional fabrication technology for multi‐modal chromism. Here, we report a novel multifunctional mechanophore capable of vividly detectable and tunable mechanochromism in polymers. This synergistic optical coupling relies on strategically fusing rhodamine and spiropyran (Rh−SP), and tethering polymer chains on both subunits. The mechanochromic behaviors of the Rh−SP‐linked polymers under sonication and compression are thoroughly evaluated in response to changes in force and the light‐controlled relaxation process. Non‐sequential ring‐opening of the two subunits under force is identified, endowing high‐contrast mechanochromism. Light‐induced differential ring‐closing reactions of the two subunits, together with the acidichromism of the SP moiety, are employed to engineer elastomers with programmable and wide‐spectrum colors. Our work presents an effective strategy for highly appreciable and regulable mechanochromic functionality, and also provides new insights into the rupture mechanisms of π‐fused mechanophores, as well as how the stimuli history controls stress accumulation in polymers.
Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated AlkenesVaishanv, Narendra K.; Eghbarieh, Nadim; Jagtap, Rahul A.; Gose, Anthony E.; Haines, Brandon E.; Masarwa, Ahmad
doi: 10.1002/anie.202412167pmid: 38980310
Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis are difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ and stereoselectivity, enabling the predictable and efficient synthesis of stereodefined alkenes. In fact, an appealing alternative approach for accessing challenging stereodefined alkene molecular frameworks could involve the sequential selective activation and cross‐coupling of strong bonds instead of conventional C−C bond formation. In this study, we introduce a series of programmed site‐ and stereoselective strategies that capitalizes on the versatile reactivity of readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through a tandem cross‐coupling reaction, which is catalyzed by an organometallic Rh‐complex to produce complex molecular scaffolds. By merging selective C−B and remote C−H bond functionalization, we achieve the in situ generation of polyfunctional C(sp2)‐nucleophilic intermediates. These species can be further modified by selective coupling reactions with various C‐based electrophiles, enabling the formation of C(sp2)−C(sp3) bond for the generation of even more complex molecular architectures using the readily available starting polyborylated‐alkenes. Mechanistic and computational studies provide insight into the origins of the stereoselectivities and C−H activation via a 1,4‐Rh migration process.
Leap‐Type Response of Redox/Photo‐Active Lanthanide‐Based Metal–Organic Frameworks for Early and Accurate Screening of Prostate CancerGe, Kaiming; Chen, Guoli; Zhang, Dapeng; Hao, Ji‐Na; Li, Yongsheng
doi: 10.1002/anie.202411956pmid: 39031278
The development of high‐accuracy technologies to distinguish the quite tiny concentration change of tumor markers between negative and positive is of vital significance for early screening and diagnosis of cancers, but is still a great challenge for the conventional biosensors because of their “gradual” detection mode. Herein, a unique “leap‐type” responsive lanthanide MOF‐based biosensor (designated as Tb‐CeMOF‐X) with defect‐mediated redox‐/photo‐activities is developed for precisely identifying acid phosphatase (ACP), an early pathological marker of prostate cancer (PCa) in serum. The engineered Tb‐CeMOF‐X probe achieves a bursting switch‐on luminescence at the critical concentration of ACP (9 U ⋅ L−1), while keeping silent below this threshold, undergoing a qualitative signal change from “zero” to “one” between negative and positive indicators and thus significantly improving the identification precision. Significantly, such “leap‐type” response performance can be further edited and amplified by rational defect engineering in the crystal structure to improve the accessibility of active centers, consequently maximizing the detection sensitivity toward ACP in the complex biological media. This study proposes the first paradigm for the development of “leap‐type” biosensors with ultra‐sensitive differentiation capability between negative and positive, and provides a potentially valuable tool for early and accurate screening of PCa.
Solvent Attenuation of London Dispersion in Polycyclic Aromatic StackingElmi, Alex; Bąk, Krzysztof M.; Cockroft, Scott L.
doi: 10.1002/anie.202412056pmid: 39041859
Solvent competition for London dispersion attenuates its energetic significance in molecular recognition processes. By varying both the stacked contact area and the solvent, here we experimentally deconvolute solvent attenuation using molecular balances. Experimental stacking energies (phenyl to pyrene) correlated strongly with calculations only when dispersion was considered. Such calculations favoured stacking by up to −27 kJ mol−1 in the gas phase, but it was weakly disfavoured in our solution‐phase experiments (+0.5 to +4.6 kJ mol−1). Nonetheless, the propensity for stacking increased with contact area and in solvents with lower bulk polarisabilities that compete less for dispersion. Experimental stacking energies per unit change in solvent accessible area ranged from −0.02 kJ mol−1 Å−2 in CS2, to −0.05 kJ mol−1 Å−2 in CD2Cl2, but were dwarfed by the calculated gas‐phase energy of −0.6 kJ mol−1 Å−2. The results underscore the challenge facing the exploitation of dispersion in solution. Solvent competition strongly but imperfectly cancels dispersion at molecular recognition interfaces, making the energetic benefits difficult to realise.
Leveraging Ion Pairing and Transport in Localized High‐Concentration Electrolytes for Reversible Lithium Metal Anodes at Low TemperaturesZhao, Zhengfei; Wang, Aoxuan; Chen, Aosai; Zhao, Yumeng; Hu, Zhenglin; Wu, Kai; Luo, Jiayan
doi: 10.1002/anie.202412239pmid: 39032142
Coulombic efficiency of over 99 % is rarely achieved for Li metal anode below −40 °C, hindering the practical application of high‐energy‐density Li metal batteries under extreme conditions. Herein, limiting factors for Li metal reversibility are investigated utilizing ether‐based localized high‐concentration electrolytes of different solvent‐diluent combinations. We find that along with the desolvation barrier, bulk ion transport properties including ionic conductivity, transference number, and diffusivity are also crucial factors for low‐temperature Li deposition behavior. Superior Li metal reversibility was observed within the combination of the solvent with moderately weak solvating power and the diluent with minimal viscosity, highlighting the role of ion transport and the necessity for a trade‐off with desolvation. The optimized electrolyte composed of lithium bis(fluorosulfonyl)imide, methyl n‐propyl ether, and 1,1,2,2‐tetrafluoroethyl methyl ether delivers exceptional Coulombic efficiency of 99.34 % at −40 °C and 98.96 % at −60 °C under a current density of 0.5 mA cm−2. Furthermore, Li||LiCoO2 (2.7 mAh cm−2) cells demonstrate impressive reversible capacity and cycling stability at these temperatures. This work sheds light on the less‐recognized relevance of bulk ion transport to low‐temperature performance and provides guidelines for the electrolyte design of Li metal batteries operating in cold environments.