Gai L, Cui D, Dang F
… +3 more, Wang Q, Yu H, Lian G
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42360002
·
Publisher ↗
Lithium-oxygen batteries (LOBs) represent a promising next-generation energy storage technology due to their ultrahigh theoretical energy density. However, their practical application is hindered by critical challenges i...Lithium-oxygen batteries (LOBs) represent a promising next-generation energy storage technology due to their ultrahigh theoretical energy density. However, their practical application is hindered by critical challenges including electrolyte volatility and decomposition, lithium anode degradation, and the incomplete reversibility of LiO discharge products. Herein, we design a novel fluorinated ether co-solvent, 1,1'-[oxybis[(1,1,2,2-tetrafluoro-2,1-ethanediyl)-oxy(2,2-difluoro-2,1-etha-nediyl)]]bis(1,1,1-trifluoromethanesulfonate) (FTE), which features a high boiling point that effectively suppresses electrolyte evaporation. More importantly, its incorporation promotes the formation of a fluorine-rich solid electrolyte interphase (SEI) on the lithium metal anode, significantly enhancing interfacial stability. Simultaneously, FTE modulates the Li solvation structure, steering the growth of LiO away from the conventional toroidal morphology toward a highly decomposable three-dimensional porous network. These synergistic effects collectively contribute to a substantial improved cycling performance, enabling LOBs with FTE-modified tetraethylene glycol dimethyl ether based (FTE/TEG-based) electrolyte to deliver high discharge specific capacities, excellent rate capabilities, and remarkable cycling stability. This study highlights a multifunctional electrolyte design strategy that prioritizes long-term reversibility, paving the way for practical high-energy-density LOBs.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42359991
·
Publisher ↗
Nanofiltration technology shows promise for lithium extraction from salt lakes, yet the fixed nanochannel size of conventional membranes proves insufficient for the complex demands of multi-stage separation processes, es...Nanofiltration technology shows promise for lithium extraction from salt lakes, yet the fixed nanochannel size of conventional membranes proves insufficient for the complex demands of multi-stage separation processes, especially given the drastic variations in Mg/Li ratios. To address this issue, 4'-Aminobenzo 15-crown-5-ether (AB-15C5) macrocycles were grafted onto the surface of polyamide (PA) membranes to fabricate adaptive Mg-gating membranes (PA-15C5 membranes). The adaptive Mg-gating effect enables responsive dimensional switching of nanochannels through spatial rearrangement of crown ether under varying Mg concentrations, as evidenced by experimental confirmation achieved through molecular weight cutoff (MWCO) testing and Zeta potential analyses under ionic modulation conditions. Systematic theoretical validation from density functional theory (DFT) calculations and molecular dynamics (MD) simulations further elaborates on this gating effect. This gating effect converts competing Mg ions into a separation advantage and extends applicability to ultralow Mg concentrations, achieving a Li/Mg separation factor of 214.9 at a Mg/Li molar ratio of 0.01. The three-stage nanofiltration process effectively reduced the Mg/Li ratio in brine to 4.0 * 10 , while achieving the extraction of battery-grade lithium with a purity of 99.97%. This performance surpasses most reported state-of-the-art, thereby establishing a novel paradigm for deploying adaptive gating membranes in lithium extraction from salt-lake brines.
Zhang W, Zhao D, Kang B
… +6 more, Zhang HJ, Park Y, Jung YM, Kim W, Lin J, Kim D
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42359987
·
Publisher ↗
Structural distortion is widely recognized to suppress emissions in organic chromophores; however, the mechanistic origin of the associated enhancement in nonradiative decay remains unresolved. Here, we employ a series o...Structural distortion is widely recognized to suppress emissions in organic chromophores; however, the mechanistic origin of the associated enhancement in nonradiative decay remains unresolved. Here, we employ a series of perylene bisimide derivatives with systematically controlled bending to directly elucidate the structural origin of distortion-enhanced nonradiative relaxation. A pronounced transition is observed from near-unity emission to strongly enhanced nonradiative decay within the singlet manifold, while intersystem crossing remains negligible. Time-resolved electronic spectroscopy excludes triplet-mediated pathways and establishes internal conversion as the dominant decay channel. Crucially, time-resolved Raman measurements provide direct insight into the underlying structural dynamics, revealing that bending suppresses the electronically coupled aromatic skeletal mode, reorganizes the low-frequency vibrational manifold, and accelerates vibrational dephasing. The results herein demonstrate that bending enhances internal conversion not primarily through energy-gap reduction, but by transforming the excited-state vibrational landscape into a more dissipative environment that facilitates efficient energy relaxation. More broadly, this work identifies vibrational dissipation and coherence loss as key determinants of nonradiative decay and establishes a general structure-vibrational dynamics framework for controlling excited-state energy flow in π-conjugated systems.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42359979
·
Publisher ↗
Efficient alcohol electrosynthesis from CO relies on ion-conductive polymers to mediate ion transport and maintain product separation. However, alcohol-induced instability of ion channels within these polymers compromise...Efficient alcohol electrosynthesis from CO relies on ion-conductive polymers to mediate ion transport and maintain product separation. However, alcohol-induced instability of ion channels within these polymers compromises electrolysis durability. Here we report a nonpolar cross-linked polymer architecture that stabilizes ion channels in alcohol-rich environments, enabling robust CO-to-alcohol conversion. Covalent integration of ion-conductive poly(arylene) piperidinium into a nonpolar poly(styrene) network creates a hydrophobic scaffold that confines ion channels, locking them against alcohol-induced swelling. The resulting structure retains over 97% of mechanical integrity after 1000 h of alcohol exposure, dramatically outperforming conventional poly(arylene) piperidinium that retains only 17% within 1 h. This excellent structural stability minimizes alcohol crossover and maintains efficient ion transport during electrolysis, sustaining continuous ethanol production with over 99% product retention and stable cell performance, whereas poly(arylene) piperidinium exhibits rapid failure. This work establishes nonpolar cross-linking as a general strategy for constructing stable ion channels within ion-conductive polymers, offering a molecular design approach for durable CO-to-alcohol electrolysis.
Zhou X, Han F, Zhang Y
… +4 more, Du J, Sun W, Fan J, Peng X
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42359975
·
Publisher ↗
The emergence of photochemical technology has revolutionized the fields of biology and medicine. Among them, photodynamic therapy represents a highly precise oncological treatment method. However, its therapeutic efficie...The emergence of photochemical technology has revolutionized the fields of biology and medicine. Among them, photodynamic therapy represents a highly precise oncological treatment method. However, its therapeutic efficiency is severely hindered by inherent bottlenecks of traditional photosensitizers. While cyanine dyes have become the preferred molecular framework for overcoming these challenges. Over the past 8 years, our research team has made pioneering contributions in this field, which has catalyzed sustained interdisciplinary interest, spurring the rational design of a broad spectrum of photosensitizers. However, due to the fragmentation of internal communication within this field and the ambiguity of some key technologies, inconsistencies have emerged in some important application aspects. Given the significant contributions and professional expertise of our research team, we have conducted this review to provide a comprehensive introduction. We will examine the evolving biomedical applications of it through multiple perspectives, including photosensitization efficiency, hypoxic microenvironments, tissue penetration limitations, control of photosensitization activity, reactivation of the immune system, and transformation of molecular design paradigms. The aim is to provide both experts and non-experts with a clear and understandable resource, promoting a deeper understanding of modern cyanine dye-based photosensitizers and proposing actionable principles for the design and innovation of next-generation cyanine photosensitizers.
Li K, Li Y, Wang Y
… +16 more, Wang Y, Zhang X, Shen L, Zhou L, Luo Y, Zhao Z, Bu Z, Yue B, Chen G, Ruan M, Kang B, Liu X, Feng X, Yu P, Li Q, Li Q
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42345520
·
Publisher ↗
Anionic redox reaction (ARR) has emerged as a pivotal mechanism to support next-generation of high-energy-density batteries. While extensive efforts have focused on elucidating the origin of ARR-induced additional capaci...Anionic redox reaction (ARR) has emerged as a pivotal mechanism to support next-generation of high-energy-density batteries. While extensive efforts have focused on elucidating the origin of ARR-induced additional capacity, ARR operating voltage constitutes the limiting factor for its practical applications. Particularly, voltage hysteresis between charge-discharge brings poor energy efficiency. This work investigates key factors determining ARR operating voltage in LiTiNiO (LTNO), a unique model system enabled by its well-isolated ARR plateau around 2.0 V. By combining in situ XRD, TEM, sXAS, and RIXS, the kinetic regulation of both transition metal redox and ARR voltages is validated. For the very first time, depth-resolved Li 1s XPS and Li-K sXAS are combined to trace Li distribution profile and occupation sites. A metastable over-lithiated shell forms on the LTNO surface, where the extra surface Li-ions occupy tetrahedral coordination. Such a surface shell exerts a large energy barrier for Li-ion transfer and leads to an extremely low ARR plateau. Furthermore, the kinetics-regulated ARR voltage may work in other cathodes, where voltage decay in Li-rich layered cathode can be kinetically dominated in long-term cycle. These findings provide new insights into understanding the ARR operating mechanism, and guidelines for optimizing ARR performance can be proposed via facilitating Li transfer kinetics.
Bhattacharyya P, Singuru MMR, Banerjee R
… +3 more, Le PTN, Tian Q, You M
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340164
·
Publisher ↗
Mechanical forces at cell-cell junctions play essential roles in tissue organization, morphogenesis, and disease progression, yet their transient and low-intensity nature makes detection challenging. Here, we introduce f...Mechanical forces at cell-cell junctions play essential roles in tissue organization, morphogenesis, and disease progression, yet their transient and low-intensity nature makes detection challenging. Here, we introduce force-locking integrator probe (FLIP)-a DNA-based system that records cumulative molecular tension events over time. FLIP employs membrane-anchored DNA hairpins as force sensors and fluorophore-labeled locking strands that selectively hybridize upon hairpin unfolding, forming stable duplexes that preserve force history at the single-cell level. By leveraging endocytosis-driven uptake, FLIP converts membrane tension signals into whole-cell fluorescence, extending detection beyond the short surface lifetime of lipid-DNA probes. We demonstrate long-term and high-throughput measurement of integrin- and E-cadherin-mediated intercellular forces using fluorescence microscopy and flow cytometry across thousands of cells. FLIP reveals force-dependent changes under cytoskeletal perturbation and supports ratiometric imaging for precise analysis. This platform enables robust mapping of cumulative intercellular forces, offering new opportunities to study mechanotransduction in collective cell behaviors and to accelerate the development of mechano-active therapeutics.
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340151
·
Publisher ↗
Hypercrosslinked polymers, a class of porous organic polymers (POPs), are constructed by crosslinking linear polymers or knitting small aromatic molecules with a molecular crosslinker, typically via Friedel-Crafts alkyla...Hypercrosslinked polymers, a class of porous organic polymers (POPs), are constructed by crosslinking linear polymers or knitting small aromatic molecules with a molecular crosslinker, typically via Friedel-Crafts alkylation. In this study, we report a new approach for the synthesis of POPs via the crosslinking of linear polyimines with m‑phenylenediamine through nucleophilic addition of amines to imines, forming aminal linkages. The resulting aminal-linked POPs, with an estimated low cost of 16 USD/kg, exhibited high surface areas up to 650 m/g and abundant microporosity, in contrast to the ∼100 m/g observed for the linear polyimine. This method demonstrated good generality: four linear polyimines with different structures were successfully crosslinked into POPs with high porosity. Both experimental results and theoretical calculations indicate that the use of diamines at the meta-position is critical for efficient crosslinking, whereas para-diamines did not initiate crosslinking. With their high surface area and rich microporosity, these POPs displayed high adsorption capacities for C hydrocarbons and CO, but significantly lower capacity for CH. Dynamic breakthrough experiments confirmed excellent separation performance for C hydrocarbons/CH mixtures, highlighting their potential for hydrocarbon separation. This study provides a new strategy for the synthesis of cost-effective POPs and demonstrates their promising applications in gas separation.
Wang S, Zhu Q, Tian Y
… +7 more, Cui P, Ji Q, Xie T, Wang H, Zhou D, Wang G, Huang W
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340150
·
Publisher ↗
Achieving quasi-solid-state electrolytes (QSSEs) that simultaneously deliver fast ion transport and intrinsic thermal safety remains a central challenge for lithium batteries, as improvements in ionic conductivity are of...Achieving quasi-solid-state electrolytes (QSSEs) that simultaneously deliver fast ion transport and intrinsic thermal safety remains a central challenge for lithium batteries, as improvements in ionic conductivity are often coupled with increased flammability and interfacial instability. Here, we present a spray-assisted in situ assembly strategy to construct azolate hybrid frameworks (AHFs) directly on glass fiber substrates, followed by thermal polymerization to yield a chemically integrated QSSE. The heterocyclic AHF provides ordered lithium-philic coordination sites and continuous ion-transport pathways, enabling efficient Li migration while maintaining high thermal robustness. As a result, the resulting LiFePO|FP10v-GF|Li cell sustains stable cycling for over 500 cycles at 25°C and 100 cycles at 60°C. Notably, the framework architecture enables molecular level confinement of triethyl phosphate (TEP) as a flame-retardant component, establishing a nitrogen phosphorus synergistic flame-retardant mechanism without compromising electrochemical compatibility. Consequently, high-loading Li||LiFePO cells exhibit stable cycling under practical conditions (E/C = 0.56 g Ah, N/p = 3.27) and successfully withstand accelerated rate calorimetry tests from 25°C to 300°C without thermal runaway. This work demonstrates how framework chemistry and molecular confinement can be synergistically integrated to decouple ionic conductivity from flammability, providing a general design principle for intrinsically safe, high-energy quasi-solid-state lithium batteries.
Zeng X, Chen J, Xu X
… +9 more, Kuang W, Shi X, Zhang X, Wan Y, Zhou Z, Zhou X, Kumar A, Chou SL, Li L
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340149
·
Publisher ↗
Sodium-ion batteries (SIBs) capable of stable operation under fast-charging conditions across a wide temperature range are of great significance for the efficient utilization of intermittent renewable clean energy. Herei...Sodium-ion batteries (SIBs) capable of stable operation under fast-charging conditions across a wide temperature range are of great significance for the efficient utilization of intermittent renewable clean energy. Herein, a multifunctional electrolyte additive containing tetrabutylammonium (TBA) cation and perchlorate (ClO ) anion is employed to construct an environmentally friendly fluorine-free electrolyte system, significantly enhancing the temperature tolerance and fast-charging performance of SIBs. Specifically, the TBA cations, due to their low reduction potential, induce an electrostatic shielding effect that guides the uniform distribution of Na flux on the electrode surface. Meanwhile, the introduced ClO anions facilitate the formation of the anion-reinforced solvation structure. This structure effectively reduces the desolvation energy barrier of Na and promotes the formation of a stable electrode-electrolyte interface with high ionic conductivity. This synergistic mechanism effectively suppresses Na plating during fast charging and mitigates continuous electrolyte decomposition and transition metal dissolution. Consequently, the assembled Prussian blue||hard carbon (PB||HC) full cell demonstrates excellent fast-charging performance across a wide temperature range (10-100°C). More importantly, the PB||HC 18650 cylindrical cell exhibits a superior cycling stability and outstanding rate performance at an elevated temperature of 55°C, demonstrating the great potential of this electrolyte system for practical applications.
Hsieh CM, Schoonover KG, Ahmed N
… +10 more, Ahn JB, Qian S, Hore MJA, Xia W, Hsiao K, Yuan Y, Sengoden M, Darensbourg DJ, Pentzer E, Wei P
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340146
·
Publisher ↗
Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curi...Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO-based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m). These results establish clear structure-processing-property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.
Qiao F, Jia F, Cao Y
… +7 more, Liu XC, Li ZJ, Liu Q, Zhang JJ, Wu LM, Song KP, Xia SQ
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340112
·
Publisher ↗
La Te materials are ideal candidates for next-generation radioisotope thermoelectric generators due to their excellent thermoelectric performance and high-temperature stability. For decades, researchers have used substit...La Te materials are ideal candidates for next-generation radioisotope thermoelectric generators due to their excellent thermoelectric performance and high-temperature stability. For decades, researchers have used substitutional doping or vacancy modulation to tune carrier concentration, but these methods can only tune it without optimizing the conduction band structure or suppressing lattice thermal conductivity. Interstitial doping strategy breaks this deadlock by enabling simultaneous electronic and thermal regulation without mutual interference. Herein, a series of Cu-doped LaCuTe (x = 0, 0.01, 0.05, 0.1, 0.15) samples were synthesized. Cu incorporation elevates the Seebeck coefficient without degrading significantly the power factor, while simultaneously suppressing lattice thermal conductivity via anharmonic vibrational behavior that strengthens low-frequency acoustic phonon modes and intensifies phonon-phonon scattering. Among the synthesized compositions, LaCuTe achieves a peak thermoelectric figure of merit of 1.58 at 1073 K, representing a 34% improvement over the undoped LaTe. Furthermore, the material exhibits a notable average zT value of 1.5 within the operational temperature range of 873-1073 K. When compared to the previously reported state-of-the-art lanthanum telluride-based thermoelectrics, this represents a significant improvement of 71.3% in the average zT value.
Zhang J, Feng Y, Sun H
… +12 more, Zhang W, Zhang T, Jia Z, Zhang Z, Yang W, Li H, Shen F, Xie W, Li Y, Yan Z, Zhang K, Chen J
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340105
·
Publisher ↗
Li-rich Mn-based layered oxides (LRMOs) are considered promising cathode candidates for next-generation high-energy-density lithium batteries, owing to their high capacity and low cost. However, they are plagued by latti...Li-rich Mn-based layered oxides (LRMOs) are considered promising cathode candidates for next-generation high-energy-density lithium batteries, owing to their high capacity and low cost. However, they are plagued by lattice-oxygen release and surface-driven structural degradation, which lead to low initial coulombic efficiency and poor cycling stability. Here, a B-heterogeneous coordination structure is incorporated into the Li-rich materials, forming a ≈4 nm surface layer enriched in BO units while retaining BO units within the bulk. Both of tetrahedral BO and trigonal BO display stronger bonding interaction than those of transition metal (TM)─O bonds (i.e., Mn─O, Ni─O, and Co─O), while surface BO further strengthens the B─O bonds compared with bulk BO, thus robustly anchoring lattice oxygen to suppress irreversible oxygen loss. Benefiting from this synergistic heterogeneous coordination, the modified LRMOs deliver a high reversible capacity of ∼300 mAh g at 0.1C, an enhanced initial Coulombic efficiency of 93.5% and excellent capacity retention of 85.8% after 300 cycles at 1C. This work demonstrates the surface BO structure as an effective paradigm to reconcile oxygen-redox activity with long-term stability in high-energy-density lithium batteries.
Lee EG, Yun J, Kang HW
… +4 more, Jung D, Kwon SR, Jung JH, Jung SH
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340101
·
Publisher ↗
Stimuli-responsive supramolecular polymerization with high precision is essential for developing adaptive materials with programmable kinetics and functions. Here, we present a redox-responsive strategy that integrates c...Stimuli-responsive supramolecular polymerization with high precision is essential for developing adaptive materials with programmable kinetics and functions. Here, we present a redox-responsive strategy that integrates chemical redox reactions and electrochemical potential to direct the self-assembly of a perylene diimide-histidine (PDI-His). A chemical redox process with sodium dithionite (SDT) rapidly converts kinetically trapped dimeric aggregates (Agg-I) of PDI-His stabilized by intramolecular hydrogen bonding into thermodynamically favored helical nanofibers (Agg-II), enabling the preparation of seeds with tunable lengths. Electrochemical potential application also induces reorganization of Agg-I into Agg-II, accompanied by morphological evolution, and improved conductivity via enhanced π-π stacking. Importantly, the redox-cycle-driven supramolecular reorganization was achieved not only on electrode surfaces through electrochemical stimuli but also through seeded-living supramolecular polymerization using seeds generated via both chemical and electrochemical kinetic pathways, yielding nanofibers with predictable lengths. This combined chemical- and electrochemical-redox approach provides an adaptable platform for controlling pathways in supramolecular polymerization, advancing the design of stimuli-responsive materials for applications in electronics, sensing, catalysis, and bioinspired systems.
Zeng D, Gu H, Li J
… +10 more, Zhao C, Yang L, Peng B, Zheng T, Cui S, Du A, Ju D, Zhao-Karger Z, Fichtner M, Li Z
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42340090
·
Publisher ↗
The practical implementation of calcium metal anodes in rechargeable batteries is persistently hindered by surface passivation, which impedes Ca transport and induces inhomogeneous Ca deposition. Herein, we demonstrate t...The practical implementation of calcium metal anodes in rechargeable batteries is persistently hindered by surface passivation, which impedes Ca transport and induces inhomogeneous Ca deposition. Herein, we demonstrate that introducing a tailored trace amount of water (∼139 ppm) fundamentally modifies the interfacial chemistry in a state-of-the-art Ca[B(hfip)]/DME electrolyte. Mechanistic investigations reveal that instead of triggering deleterious bulk side reactions, the trace water stably enters Ca solvation sheath, directing a controlled electrochemical hydrolysis pathway during cycling. This process generates a thin, uniform bilayer solid electrolyte interphase (SEI) comprising an outer hybrid organic-inorganic layer and an inner inorganic layer rich in CaH, CaO, and CaF, while concurrent H evolution effectively eliminates the passivating native oxide layer. Consequently, this tailored SEI enables highly stable Ca plating/stripping for over 400 h at 0.2 mA cm and over 300 h at 1 mA cm. Furthermore, the high anodic stability of the electrolyte enables reliable operation of various high-voltage cathodes within a wide voltage window (up to 4.5 V) for up to 70 cycles. These results highlight the critical role of a stable SEI for Ca metal anodes, but also illustrate how subtle electrolyte modification can profoundly regulate the interfacial chemistry toward high-performance multivalent batteries.
Zhang XD, Wang W, Li P
… +9 more, Wang Y, Zhang G, Hou Y, Zhang Y, Sun X, Kang X, Qian Q, Zhu Q, Han B
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42338071
·
Publisher ↗
Electroreduction of nitrate (NO ) to ammonia (NH) provides a sustainable method for waste valorization. However, low nitrate levels and the coexistence of interfering ions in real wastewater severely affect catalytic sel...Electroreduction of nitrate (NO ) to ammonia (NH) provides a sustainable method for waste valorization. However, low nitrate levels and the coexistence of interfering ions in real wastewater severely affect catalytic selectivity and stability. Herein, we report for the first time that pulsed design enables efficient NH synthesis from dilute NO in real wastewater. Using diluted wastewater from a graphene production plant (∼5 mM NO with various interfering ions), the periodic application of anodic and cathodic pulses (E = 0.8 V, t = 0.5 s, E = -0.4 V, and t = 5 s) over a Ru@Cu catalyst achieved a high NH Faradaic efficiency (FE) of 90.2% and an NH yield rate of 1.48 mg·h cm, significantly surpassing the FE(NH) of 45.0% obtained under potentiostatic conditions. Notably, the catalyst stability improved significantly under pulsed conditions, with FE(NH) remaining above 86.3% after six cycles (3 h), compared to a sharp drop to 11.4% under potentiostatic conditions. Mechanistic studies reveal that the intermittent application of a positive potential generates a localized electric field that enriches NO and repels interfering cations near the cathode, thereby mitigating hydroxide precipitation and enhancing NO availability. This work establishes a sustainable and economically viable strategy for real wastewater treatment.
Schulz J, Chinoy ZS, Khalaf T
… +5 more, Li Y, Ma P, Svatunek D, Houk KN, Friscourt F
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42338061
·
Publisher ↗
Bioorthogonal reactions have revolutionized our way of performing chemistry in a highly complex biological environment. In particular, strain-promoted 1,3-dipolar cycloadditions, employing cyclooctyne probes in conjuncti...Bioorthogonal reactions have revolutionized our way of performing chemistry in a highly complex biological environment. In particular, strain-promoted 1,3-dipolar cycloadditions, employing cyclooctyne probes in conjunction with azido-reporters (strain-promoted alkyne-azide cycloaddition, SPAAC), have permitted the labeling and visualization of bio-macromolecules in vitro, in living cells, as well as in animals. However, SPAAC's slow kinetics (< 1 Ms), in combination with the necessity to eliminate the excess of the used fluorescent probes, have hampered its widespread application, especially for the real-time imaging of low concentration targets. Here we describe two novel thiophene-based cycloalkynes that not only exhibit very high kinetics toward a variety of 1,3-dipoles (up to 1528 Ms), but are also efficiently turned-on (up to 150-fold increase in brightness) upon reaction with their target. We demonstrated their fast and fluorogenic capabilities by monitoring the labeling overtime of a glycoprotein in physiological and no-wash conditions, using as little as 5 µM of the probes and reaching full labeling in less than 15 min. These fluorogenic cycloalkynes significantly expand our chemical biology toolbox, and we anticipate them to open new avenues for the fast and real-time imaging of biomolecules in complex environments.
Solomon NSD, Huang X, Richardson C
… +1 more, Keaveney ST
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42338058
·
Publisher ↗
Nickel-catalyzed cross-coupling reactions are of increasing importance in chemical synthesis. However, rate data for transmetalation at Ni is limited due to the difficulty of analyzing this step, hindering a priori react...Nickel-catalyzed cross-coupling reactions are of increasing importance in chemical synthesis. However, rate data for transmetalation at Ni is limited due to the difficulty of analyzing this step, hindering a priori reaction design. To address this limitation, a user-friendly method for analyzing transmetalation at Ni using NMR spectroscopy is reported. This approach is underpinned by the generation of an unsaturated coupling product that coordinates to Ni, preventing comproportionation with remaining Ni and the generation of problematic Ni side products. This methodology was used to obtain rate data for transmetalation at 18 Ni complexes. Significant variation in the rate constant (k) was observed, spanning at least 5 orders of magnitude. The most important factor in influencing k was ligand choice, with weakly coordinating, monodentate ligands generally affording larger rate constants. The choice of halide (Cl, Br, I) had comparatively little effect, though the use of OTs and OTf resulted in modest rate enhancements. The mechanism of transmetalation at two representative complexes was examined through kinetic and computational studies, revealing differences in the rate-determining step. The foundational insight on transmetalation at Ni provided through the kinetic studies allowed guiding principles for reaction design to be developed.
Abad-Montero D, Bosch M, Garcés-Castellanos R
… +9 more, Schottenhamel MQ, Pedraza-Arevalo S, Ibáñez-Costa A, Castaño JP, García-Becerra T, Rebollo E, Alberto ME, Francés-Monerris A, Marchán V
Angew Chem Int Ed Engl
· 2026 Jun · PMID 42334843
·
Publisher ↗
Fluorescent probes operating in the near-infrared (NIR) region offer deep-tissue visualization with minimal background interference, reduced phototoxicity, and enhanced signal-to-noise ratios. However, most conventional...Fluorescent probes operating in the near-infrared (NIR) region offer deep-tissue visualization with minimal background interference, reduced phototoxicity, and enhanced signal-to-noise ratios. However, most conventional NIR fluorophores exhibit poor photostability, low fluorescence quantum yields, and limited chemical versatility, which constrain their use in demanding biological environments. Here, we report a new family of π-extended COUPY dyes (3-7), rationally engineered to deliver efficient far-red/NIR performance through vinylogation of the exocyclic double bond of the coumarin scaffold. This single structural modification induces a bathochromic shift exceeding 100 nm in both absorption and emission spectra while preserving the compact architecture and synthetic accessibility of the parent coumarin. The resulting dyes combine high molar absorptivity, moderate-to-high quantum yields, and exceptional photostability under biologically-relevant conditions. Their performance was validated in live-cell imaging using both intensity-based and fluorescence lifetime imaging microscopy (FLIM), demonstrating compatibility with advanced imaging techniques. Furthermore, site-specific bioconjugation to a clinically relevant peptide confirmed their suitability for targeted imaging. Collectively, π-extended COUPY dyes represent a promising class of synthetically modular, chemically robust, and biologically compatible far-red/NIR fluorophores for high-resolution imaging, targeted strategies, and advanced bioimaging modalities, and provide a foundation for future studies aimed at evaluating their performance in more complex biological models.