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Calendar aging occurring during high-temperature storage has long plagued practical realization of long-life, high-safety lithium-ion batteries (LIBs). Generally, the aging process is ascribed to the hydrolysis reaction of fluorine-containing electrolyte salt that generates hydrofluoric acid and chemically corrodes the anode surface. Nevertheless, the underlying mechanism about electrolyte degradation, HF generation and surface corrosion remains concealed for various electrolytes. In this work, we employed in situ liquid time-of-flight secondary ion mass spectroscopy to resolve the chemical evolution during high-temperature calendar aging in the bulk of the electrolyte and at the anode/electrolyte interface. Two conventional salts, LiPF6 and Li bis(fluorosulfonyl)imide (LiFSI), were employed for comparison. We identify that the high-temperature hydrolysis of LiPF6 preferentially occurs when the anion aggregates ([PF6+LiPF6]-) are attacked by trace H2O. HPO2F2, HF and LiF are generated and assist formation of an inorganics-rich solid electrolyte interphase (SEI), improving anode stability against parasitic reactions. The LiFSI-based electrolyte does not involve hydrolysis, which facilities the formation of an organics-rich SEI. Nevertheless, the SEI does not passivate the anode surface and could induce severe corrosions via electron tunneling at a high temperature. Our work offers original insights into rational design of electrolyte and interface for high-energy, long-calendar-life LIBs., (© 2025 Wiley‐VCH GmbH.)

Thermally induced tensile strain that remains in perovskite films after annealing is one of the key reasons for diminishing the performance and operational stability of perovskite solar cells (PSCs). Herein, a glass transition temperature (T g ) regulation (TR) strategy is developed by introducing two polymerizable monomers, 2-(N-3-Sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate (SBMA) and 2-Hydroxyethyl acrylate (HEA), into the perovskite layer. SBMA and HEA undergo in situ polymerization, which regulates the nucleation and crystal growth of the perovskite film. In addition, adjusting the ratio of SBMA and HEA to lower the T g of the resulting polymer effectively releases the strain in the perovskite film. The modified film exhibits significantly reduced tensile strain, decreased trap density and improved stability. As a result, the optimized PSCs achieve a champion power conversion efficiency (PCE) of 26.15% (certified as 25.59%). Furthermore, the encapsulated device demonstrates prominent enhanced operation stability, maintaining 90.3% of its initial efficiency after 500 h of continuous sunlight exposure., (© 2025 Wiley‐VCH GmbH.)

Trap-assisted non-radiative recombination losses and moisture-induced degradation significantly impede the development of highly efficient and stable inverted (p-i-n) perovskite solar cells (PSCs), which require high-quality perovskite bulk. In this research, we mitigate these challenges by integrating thermally stable perovskite layers with Lewis base covalent organic frameworks (COFs). The ordered pore structure and surface binding groups of COFs facilitate cyclic, multi-site chelation with undercoordinated lead ions, enhancing the perovskite quality across both its bulk and grain boundaries. This process not only reduces defects but also promotes improved energy alignment through n-type doping at the surface. The inclusion of COF dopants in p-i-n devices achieves power conversion efficiencies (PCEs) of 25.64 % (certified 24.94 %) for a 0.0748-cm 2 device and 23.49 % for a 1-cm 2 device. Remarkably, these devices retain 81 % of their initial PCE after 978 hours of accelerated aging at 85°C, demonstrating remarkable durability. Additionally, COF-doped devices demonstrate excellent stability under illumination and in moist conditions, even without encapsulation., (© 2024 Wiley-VCH GmbH.)

Biomolecular piezoelectric materials show great potential in the field of wearable and implantable biomedical devices. Here, a self-assemble approach is developed to fabricating flexible β-glycine piezoelectric nanofibers with interfacial polarization locked aligned crystal domains induced by Nb 2 CT x nanosheets. Acted as an effective nucleating agent, Nb 2 CT x nanosheets can induce glycine to crystallize from edges toward flat surfaces on its 2D crystal plane and form a distinctive eutectic structure within the nanoconfined space. The interfacial polarization locking formed between O atom on glycine and Nb atom on Nb 2 CT x is essential to align the β-glycine crystal domains with (001) crystal plane intensity extremely improved. This β-phase glycine/Nb 2 CT x nanofibers (Gly-Nb 2 C-NFs) exhibit fabulous mechanical flexibility with Young's modulus of 10 MPa, and an enhanced piezoelectric coefficient of 5.0 pC N -1 or piezoelectric voltage coefficient of 129 × 10 -3 Vm N -1 . The interface polarization locking greatly improves the thermostability of β-glycine before melting (≈210°C). A piezoelectric sensor based on this Gly-Nb 2 C-NFs is used for micro-vibration sensing in vivo in mice and exhibits excellent sensing ability. This strategy provides an effective approach for the regular crystallization modulation for glycine crystals, opening a new avenue toward the design of piezoelectric biomolecular materials induced by 2D materials., (© 2024 Wiley‐VCH GmbH.)

Twisted bilayer graphene (TBG) generates significant attention in the fundamental research of 2D materials due to its distinct twist-angle-dependent properties. Exploring the efficient production of TBG with a wide range of twist angles stands as one of the major frontiers in moiré materials. Here, the local space-confined chemical vapor deposition growth technique for high-quality single-crystal TBG with twist angles ranging from 0° to 30° on liquid copper substrates is reported. The clean surface, pristine interface, high crystallinity, and thermal stability of TBG are verified by using comprehensive characterization techniques including optical microscopy, electron microscopy, and secondary-ion mass spectrometry. The proportion of TBG in bilayer graphene reaches as high as 89%. In addition, the stacking structure and growth mechanism of TBG are investigated, revealing that the second graphene layer develops beneath the first one. A series of comparative experiments illustrates that the liquid copper surface, with its excellent fluidity, promotes the growth of TBG. Electrical measurements show the twist-angle-dependent electronic properties of as-grown TBG, achieving a room-temperature carrier mobility of 26640 cm 2 V -1 s -1 . This work provides an approach for the in situ preparation of 2D twisted materials and facilitates the application of TBG in the fields of electronics., (© 2023 Wiley-VCH GmbH.)

Solid-state lithium-sulfur batteries have shown prospects as safe, high-energy electrochemical storage technology for powering regional electrified transportation. Owing to limited ion mobility in crystalline polymer electrolytes, the battery is incapable of operating at subzero temperature. Addition of liquid plasticizer into the polymer electrolyte improves the Li-ion conductivity yet sacrifices the mechanical strength and interfacial stability with both electrodes. In this work, we showed that by introducing a spherical hyperbranched solid polymer plasticizer into a Li + -conductive linear polymer matrix, an integrated dynamic cross-linked polymer network was built to maintain fully amorphous in a wide temperature range down to subzero. A quasi-solid polymer electrolyte with a solid mass content >90 % was prepared from the cross-linked polymer network, and demonstrated fast Li + conduction at a low temperature, high mechanical strength, and stable interfacial chemistry. As a result, solid-state lithium-sulfur batteries employing the new electrolyte delivered high reversible capacity and long cycle life at 25 °C, 0 °C and -10 °C to serve energy storage at complex environmental conditions., (© 2023 Wiley-VCH GmbH.)

Engineered nanomaterials hold great promise to improve the specificity of disease treatment. Herein, a fully protein-based material is obtained from nonpathogenic Escherichia coli (E. coli), which is capable of morphological transformation from globular to fibrous in situ for inducing tumor cell apoptosis. The protein-based material P1 is comprised of a β-sheet-forming peptide KLVFF, pro-apoptotic protein BAK, and GFP along with targeting moieties. The self-assembled nanoparticles of P1 transform into nanofibers in situ in the presence of cathepsin B, and the generated nanofibrils favor the dimerization of functional BH3 domain of BAK on the mitochondrial outer membrane, leading to efficient anticancer activity both in vitro and in vivo via mitochondria-dependent apoptosis through Bcl-2 pathway. To precisely manipulate the morphological transformation of biosynthetic molecules in living cells, a spatiotemporally controllable anticancer system is constructed by coating P1-expressing E. coli with cationic conjugated polyelectrolytes to release the peptides in situ under light irradiation. The biosynthetic peptide-based enzyme-catalytic transformation strategy in vivo would offer a novel perspective for targeted delivery and shows great potential in precision disease therapeutics., (© 2023 Wiley-VCH GmbH.)

Passivating the interfaces between the perovskite and charge transport layers is crucial for enhancing the power conversion efficiency (PCE) and stability in perovskite solar cells (PSCs). Here we report a dual-interface engineering approach to improving the performance of FA 0.85 MA 0.15 Pb(I 0.95 Br 0.05 ) 3 -based PSCs by incorporating Ti 3 C 2 Cl x Nano-MXene and o-TB-GDY nanographdiyne (NanoGDY) into the electron transport layer (ETL)/perovskite and perovskite/ hole transport layer (HTL) interfaces, respectively. The dual-interface passivation simultaneously suppresses non-radiative recombination and promotes carrier extraction by forming the Pb-Cl chemical bond and strong coordination of π-electron conjugation with undercoordinated Pb defects. The resulting perovskite film has an ultralong carrier lifetime exceeding 10 μs and an enlarged crystal size exceeding 2.5 μm. A maximum PCE of 24.86 % is realized, with an open-circuit voltage of 1.20 V. Unencapsulated cells retain 92 % of their initial efficiency after 1464 hours in ambient air and 80 % after 1002 hours of thermal stability test at 85 °C., (© 2023 Wiley-VCH GmbH.)

The multiple quantum wells (QWs) distribution in low-dimensional perovskite films hinders charge transport due to the fundamental difficulty of controlling crystal growth from precursor solutions, yielding poorly homogeneous low-dimensional perovskite solar cells (PSCs), especially in upscaling fabrication. Here, efficient low-dimensional PSCs are realized by modulating the colloidal assembly behavior in the precursor solution to induce intermediate structures. In combination with in situ liquid time-of-flight secondary ion mass spectrometry, the assembly behavior of organic cations involved lead iodide-dominated colloidal soft framework is visualized by investigating the precursor species differences under hydrogen bonding interactions. Subsequently, solid-state reactions emerge and the formamidine (FA)-based perovskite films exhibit significantly suppressed multiple QWs distribution. Encouragingly, the FA device (n=9, by meniscus-assisted coating) achieves a power conversion efficiency (PCE) of 20.28 % for a size of 0.04 cm 2 and a PCE of 15.35 % for a mini-module of 16.94 cm 2 with superior stability., (© 2023 Wiley-VCH GmbH.)

Surface trap as intrinsic defects-mediated non-radiative charge recombination is a major obstacle to achieving the reliable fabrication of high-efficiency and large-area perovskite photovoltaics. Here a CS 2 vapor-assisted passivation strategy is proposed for perovskite solar module, aiming to passivate the iodine vacancy and uncoordinated Pb 2+ caused by ion migration. Significantly, this method can avoid the disadvantages of inhomogeneity film caused by spin-coating-assisted passivation and reconstruction of perovskite surface from solvent. The CS 2 vapor passivated perovskite device presents a higher defect formation energy (0.54 eV) of iodine vacancy than the pristine (0.37 eV), while uncoordinated Pb 2+ is bonded with CS 2 . The shallow level defect passivation of iodine vacancy and uncoordinated Pb 2+ has obviously enhanced the device efficiencies (25.20% for 0.08 cm 2 and 20.66% for 40.6 cm 2 ) and the stability, exhibiting an average T 80 -lifetime of 1040 h working at the maximum power point, and maintaining over 90% of initial efficiency after 2000 h at RH = 30% and 30 °C., (© 2023 Wiley-VCH GmbH.)

The uncontrollable dendrite growth and unstable solid electrolyte interphase have long plagued the practical application of Li metal batteries. Herein, a dual-layered artificial interphase LiF/LiBO-Ag is demonstrated that is simultaneously reconfigured via an electrochemical process to stabilize the lithium anode. This dual-layered interphase consists of a heterogeneous LiF/LiBO glassy top layer with ultrafast Li-ion conductivity and lithiophilic Li-Ag alloy bottom layer, which synergistically regulates the dendrite-free Li deposition, even at high current densities. As a result, Li||Li symmetric cells with LiF/LiBO-Ag interphase achieve an ultralong lifespan (4500 h) at an ultrahigh current density and area capacity (20 mA cm -2 , 20 mAh cm -2 ). LiF/LiBO-Ag@Li anodes are successfully applied in quasi-solid-state batteries, showing excellent cycling performances in symmetric cells (8 mA cm -2 , 8 mAh cm -2 , 5000 h) and full cells. Furthermore, a practical quasi-solid-state pouch cell coupling with a high-nickel cathode exhibits stable cycling with a capacity retention of over 91% after 60 cycles at 0.5 C, which is comparable or even better than that in liquid-state pouch cells. Additionally, a high-energy-density quasi-solid-state pouch cell (10.75 Ah, 448.7 Wh kg -1 ) is successfully accomplished. This well-orchestrated interphase design provides new guidance in engineering highly stable interphase toward practical high-energy-density lithium metal batteries., (© 2023 Wiley-VCH GmbH.)

In overcoming the Li + desolvation barrier for low-temperature battery operation, a weakly-solvated electrolyte based on carboxylate solvent has shown promises. In case of an organic-anion-enriched primary solvation sheath (PSS), we found that the electrolyte tends to form a highly swollen, unstable solid electrolyte interphase (SEI) that shows a high permeability to the electrolyte components, accounting for quickly declined electrochemical performance of graphite-based anode. Here we proposed a facile strategy to tune the swelling property of SEI by introducing an inorganic anion switch into the PSS, via LiDFP co-solute method. By forming a low-swelling, Li 3 PO 4 -rich SEI, the electrolyte-consuming parasitic reactions and solvent co-intercalation at graphite-electrolyte interface are suppressed, which contributes to efficient Li + transport, reversible Li + (de)intercalation and stable structural evolution of graphite anode in high-energy Li-ion batteries at a low temperature of -20 °C., (© 2023 Wiley-VCH GmbH.)

The aging of precursor solutions is the major stumbling block for the commercialization of perovskite solar cells (PSCs). Herein, for the first time we used the state-of-the-art in situ liquid time-of-flight secondary ion mass spectrometry to molecularly explore the perovskite precursor solution chemistry. We identified that the methylammonium and formamidinium cations and the I - anion are the motivators of the aging chemistry. Further, we introduced two kinds of Lewis bases, triethyl phosphate (TP) and ethyl ethanesulfonate (EE), as new additives in the solution and unraveled that both of them can protect the reactive cations from aging through weak interactions. Significantly, TP is superior to EE in enhancing long-term solution stability as it can well-maintain the internal interaction structures within the solution phase. The PSC derived from a fresh TP-doped solution delivered a high power conversion efficiency of 23.06 %, 92.23 % of which remained in that from a 21-day-old solution., (© 2022 Wiley-VCH GmbH.)

The interfacial stability is highly responsible for the longevity and safety of sodium ion batteries (SIBs). However, the continuous solid-electrolyte interphase(SEI) growth would deteriorate its stability. Essentially, the SEI growth is associated with the electron leakage behavior, yet few efforts have tried to suppress the SEI growth, from the perspective of mitigating electron leakage. Herein, we built two kinds of SEI layers with distinct growth behaviors, via the additive strategy. The SEI physicochemical features (morphology and componential information) and SEI electronic properties (LUMO level, band gap, electron work function) were investigated elaborately. Experimental and calculational analyses showed that, the SEI layer with suppressed growth delivers both the low electron driving force and the high electron insulation ability. Thus, the electron leakage is mitigated, which restrains the continuous SEI growth, and favors the interface stability with enhanced electrochemical performance., (© 2022 Wiley-VCH GmbH.)

Lithium-sulfur batteries are promising candidates of energy storage devices. Both adjusting salt/solvent ratio and applying quasi-solid-state electrolytes are regarded as effective strategies to improve the lithium (Li) anode performance. However, reaction mechanisms and interfacial properties in quasi-solid-state lithium-sulfur (QSSLS) batteries with high salt concentration are not clear. Here we utilize in-situ characterizations and molecular dynamics simulations to unravel aforesaid mysteries, and construct relationships of electrolyte structure, interfacial behaviour and performance. The generation mechanism, formation process, and mechanical/chemical/electrochemical properties of the anion-derived solid electrolyte interphase (SEI) are deeply explored. Li deposition uniformity and dissolution reversibility are further tuned by the sustainable SEI. These straightforward evidences and deepgoing studies would guide the electrolyte design and interfacial engineering of QSSLS batteries., (© 2022 Wiley-VCH GmbH.)

We report here the development of clickable and highly near-infrared (NIR) fluorescent lanthanide (Ln) complexes for bioorthogonal labeling of biomolecules. These azide- or alkyne-functionalized Ln complexes are hydrophilic and fluorogenic, exhibiting a strong increase of NIR fluorescence upon conjugation with biomolecules. Metabolic labeling of biomolecules with azide or alkyne, followed by click labeling with the Ln complexes, enables NIR fluorescence (NIRF) imaging of DNA, RNA, proteins, and glycans in cells. Furthermore, multicolor imaging is performed by combining click-labeling with the Ln complexes and immunostaining. In addition, the Ln complexes is compatible with click-expansion microscopy (click-ExM), which enables high-resolution NIRF imaging of cellular glycoproteins. Finally, the Ln complexes can be used for time-of-flight secondary-ion mass spectrometry (ToF-SIMS) imaging, thus achieving the first example of dual-modal imaging combining NIRF and SIMS microscopies., (© 2022 Wiley-VCH GmbH.)

The inhomogeneity, poor interfacial contact, and pinholes caused by the coffee-ring effect severely affect the printing reliability of flexible perovskite solar cells (PSCs). Herein, inspired by the bio-glue of barnacles, a bionic interface layer (Bio-IL) of NiO x /levodopa is introduced to suppress the coffee-ring effect during printing perovskite modules. The coordination effect of the sticky functional groups in Bio-IL can pin the three-phase contact line and restrain the transport of perovskite colloidal particles during the printing and evaporation process. Moreover, the sedimentation rate of perovskite precursor is accelerated due to the electrostatic attraction and rapid volatilization from an extraordinary wettability. The superhydrophilic Bio-IL affords an even spread over a large-area substrate, which boosts a complete and uniform liquid film for heterogeneous nucleation as well as crystallization. Perovskite films on different large-area substrates with negligible coffee-ring effect are printed. Consequently, inverted flexible PSCs and perovskite solar modules achieve a high efficiency of 21.08% and 16.87%, respectively. This strategy ensures a highly reliable reproducibility of printing PSCs with a near 90% yield rate., (© 2022 Wiley-VCH GmbH.)

As two stable hydrogen isotopes, protium and deuterium show magnified isotope effects in physicochemical properties due to the significantly varied atomic masses. In this work, aqueous electrolytes based on heavy water (D 2 O) and light water (H 2 O) were prepared to reveal the electrochemical isotope effects between the hydrogen isotopes. The covalent hydrogen-oxygen bond and intermolecular hydrogen bond in D 2 O are much stronger than those in H 2 O, making them thermodynamically more stable. Compared with the H 2 O-based electrolyte, the D 2 O-based electrolyte shows a broader electrochemical window, a higher percentage of coordinated water and a longer lifetime of hydrogen bond. Because of the above electrochemical isotope effects, the D 2 O-based electrolyte shows high anodic stability against operation of high-voltage layered oxide cathode materials including LiCoO 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 , which enables long cycle life and favorable rate performance of aqueous Li-ion batteries., (© 2022 Wiley-VCH GmbH.)

High-nickel (Ni ≥ 90%) cathodes with high specific capacity hold great potential for next-generation lithium-ion batteries (LIBs). However, their practical application is restricted by the high interfacial reactivity under continuous air erosion and electrolyte assault. Herein, a stable high-nickel cathode is rationally designed via in situ induction of a dense amorphous Li 2 CO 3 on the particle surface by a preemptive atmosphere control. Among the residual lithium compounds, Li 2 CO 3 is the most thermodynamically stable one, so a dense Li 2 CO 3 coating layer can serve as a physical protection layer to isolate the cathode from contact with moist air. Furthermore, amorphous Li 2 CO 3 can be transformed into a robust F-rich cathode electrolyte interphase (CEI) during cycling, which reinforces the cathode's interfacial stability and improves the electrochemical performance. The assembled coin cell with this modified cathode delivers a high discharge capacity of 232.4 mAh g -1 with a superior initial Coulombic efficiency (CE) of 95.1%, and considerable capacity retention of 90.4% after 100 cycles. Furthermore, no slurry gelation occurs during the large-scale electrode fabrication process. This work opens a valuable perspective on the evolution of amorphous Li 2 CO 3 in LIBs and provides guidance on protecting unstable high-capacity cathodes for energy-storage devices., (© 2022 Wiley-VCH GmbH.)

Synthesis of large-scale single-crystalline graphene monolayers without multilayers involves the fabrication of proper single-crystalline substrates and the ubiquitous formation of multilayered graphene islands during chemical vapor deposition. Here, a method of cyclic electrochemical polishing combined with thermal annealing, which allows the conversion of commercial polycrystalline Cu foils to single-crystal Cu(111) with an almost 100% yield, is presented. A global "bottom-up-etching" method that is capable of fabricating large-area pure single-crystalline graphene monolayers without multilayers through selectively etching bottom multilayered graphene underneath large area as-grown graphene monolayer on Cu(111) surface is demonstrated. Terahertz time-domain spectroscopy (THz-TDS) measurement of the pure monolayer graphene film shows a high average sheet conductivity of 2.8 mS and mean carrier mobility of 6903 cm 2 V -1 s -1 over a large area. Density functional theory (DFT) calculations show that the selective etching is induced by the much easier diffusion of hydrogen atoms than hydrocarbon radicals across the edges of the top graphene layer, and the simulated selective etching processes based on phase field modeling are well consistent with experimental observations. This work provides new ways toward the production of single-crystal Cu(111) and the synthesis of pure monolayer graphene with high electronic quality., (© 2021 Wiley-VCH GmbH.)

Suppressing the irreversible interfacial reactions is an important scientific bottleneck in the development of stable high-energy-density lithium-ion battery. The interfacial chemistry of graphdiyne (GDY) on the high-voltage cathode of LiNi 0.5 Mn 1.5 O 4 (LNMO) shows a very interesting process, in which the sp-hybridization carbon atoms chemically scavenge the hydrofluoric acid (HF) and in situ form the fluorinated GDY interface. It first turns the harmful HF into profit, and greatly enhances the interfacial stability and restrains the side reaction on the cathode under high working voltage. The GDY-coated LNMO cathode obviously alleviates the electrolyte degradation, achieves high Coulombic efficiency and reliability. Due to atomic-level selectivity and chemical trapping of HF by GDY, it effectively suppresses the dissolution of Mn, Ni elements. These results highlight the unparalleled advantages of GDY in the formation of high stable interfaces and protection of high-energy-density electrodes., (© 2021 Wiley-VCH GmbH.)

Inorganic cesium lead halide perovskites offer a pathway towards thermally stable photovoltaics. However, moisture-induced phase degradation restricts the application of hole transport layers (HTLs) with hygroscopic dopants. Dopant-free HTLs fail to realize efficient photovoltaics due to severe electrical loss. Herein, we developed an electrical loss management strategy by manipulating poly(3-hexylthiophene) with a small molecule, i.e., SMe-TATPyr. The developed P3HT/SMe-TATPyr HTL shows a three-time increase of carrier mobility owing to breaking the long-range ordering of "edge-on" P3HT and inducing the formation of "face-on" clusters, over 50 % decrease of the perovskite surface defect density, and a reduced voltage loss at the perovskite/HTL interface because of favorable energy level alignment. The CsPbI 2 Br perovskite solar cell demonstrates a record-high efficiency of 16.93 % for dopant-free HTL, and superior moisture and thermal stability by maintaining 96 % efficiency at low-humidity condition (10-25 % R. H.) for 1500 hours and over 95 % efficiency after annealing at 85 °C for 1000 hours., (© 2021 Wiley-VCH GmbH.)

Novel all-inorganic Sn-Pb alloyed perovskites are developed aiming for low toxicity, low bandgap, and long-term stability. Among them, CsPb 1- x Sn x I 2 Br is predicted as an ideal perovskite with favorable band gap, but previously is demonstrated unable to convert to perovskite phase by thermal annealing. In this report, a series of CsPb 1- x Sn x I 2 Br perovskites with tunable bandgaps from 1.92 to 1.38 eV are successfully prepared for the first time via low annealing temperature (60 °C). Compared to the pure CsPbI 2 Br, these Sn-Pb alloyed perovskites show superior stability. Furthermore, a novel α-phase-stabilization mechanism of the inorganic Sn-Pb alloyed perovskite by reconfiguring the perovskite crystallization process with chloride doping is provided. Simultaneously, a dense protection layer is formed by the coordination reaction between the surface lead dangling bonds and sulfate ion to retard the permeation of external oxygen and moisture, leading to less oxidation of Sn 2+ in perovskite film. As a result, the fabricated all-inorganic Sn-Pb perovskite solar cells (PSCs) show a champion power conversion efficiency of 10.39% with improved phase stability and long-term ambient stability against light, heat, and humidity. This work provides a viable strategy in fabricating high-performance narrow-bandgap all-inorganic PSCs., (© 2021 Wiley-VCH GmbH.)

The low toxicity, narrow bandgaps, and high charge-carrier mobilities make tin perovskites the most promising light absorbers for low-cost perovskite solar cells (PSCs). However, the development of the Sn-based PSCs is seriously hampered by the critical issues of poor stability and low power conversion efficiency (PCE) due to the facile oxidation of Sn 2+ to Sn 4+ and poor film formability of the perovskite films. Herein, a synthetic strategy is developed for the fabrication of methylammonium tin iodide (MASnI 3 ) film via ion exchange/insertion reactions between solid-state SnF 2 and gaseous methylammonium iodide. In this way, the nucleation and crystallization of MASnI 3 can be well controlled, and a highly uniform pinhole-free MASnI 3 perovskite film is obtained. More importantly, the detrimental oxidation can be effectively suppressed in the resulting MASnI 3 film due to the presence of a large amount of remaining SnF 2 . This high-quality perovskite film enables the realization of a PCE of 7.78%, which is among the highest values reported for the MASnI 3 -based solar cells. Moreover, the MASnI 3 solar cells exhibit high reproducibility and good stability. This method provides new opportunities for the fabrication of low-cost and lead-free tin-based halide perovskite solar cells., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

While tremendous advancements in Ag nanoparticle (AgNP)-based materials have been made, the development of a facile protocol for preparing sub-10 nm AgNPs with controllable size and ultrahigh performance remains a formidable challenge. It is shown that AgNPs/graphene oxide (AgNPs/GO) bearing 2.5, 4.3, and 6.2 nm AgNPs (2.5-AgNPs/GO, 4.3-AgNPs/GO, and 6.2-AgNPs/GO, respectively) could be fabricated via light-induced synthesis. Their catalytic activity toward 4-nitrophenol (4-NP) reduction, which is a "gold standard" for evaluating the performance of noble metal-based catalysts, is studied. When normalized by mole and area, the activity exhibits an order of 4.3-AgNPs/GO > 6.2-AgNPs/GO > 2.5-AgNPs/GO and 6.2-AgNPs/GO > 4.3-AgNPs/GO > 2.5-AgNPs/GO, respectively. This trend is a result of GO-induced electron concentration reduction with decreasing AgNP size. Significantly, under similar conditions, the activity of 4.3-AgNPs/GO is substantially superior to that of numerous state-of-the-art noble metal-based catalysts. The ultrafine size of the AgNPs and their surface accommodation on the unobstructed 2D GO scaffolds without capping reagents/covers, which make the abundantly exposed catalytically active sites highly accessible to substrate molecules, play an important role in their extremely ultrahigh performance. This work paves a new avenue for high-performance AgNP-based materials, and by taking 4-NP reduction as a proof-of-concept, provides new scientific insights into the rational design of surface-based advanced materials., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

G-quadruplex (G4)-forming sequences are prevalent in the genome and are considered to play important roles in gene regulation, and hence have been viewed as potential therapeutic targets in oncology. However, the structures and functions of most G4s in the genome are poorly understood. Therefore, the development of fluorescent probes and ligands for G4s is important for G4 research and drug discovery. Herein, we report a new G4 ligand, 2,9-bis[4-(4-methylpiperazin-1-yl)styryl]-1,10-phenanthroline (BMSP), which was synthesized by a simple process. BMSP exhibits almost no fluorescence in aqueous buffer. The interaction of BMSP with G4s greatly enhances its fluorescence with a large Stokes' shift of 160 nm. Antiparallel human telomeric G4s exhibit the strongest binding affinity (Kd ≈0.13 μm) to BMSP and induce a fluorescence enhancement of up to 150-fold. BMSP binds to G4s through π-π stacking on the terminal G-quartets. BMSP can enter live cells, and it strongly inhibits the growth of cancer cells rather than causing cell death. Our results suggest that BMSP has the potential to serve both as a fluorescent probe for some G4s and as a chemotherapeutic agent for cancer treatment., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Novel porous polymer monoliths grafted with poly{oligo[(ethylene glycol) methacrylate]-co-glycidyl methacrylate} brushes were fabricated via two-step atom-transfer radical polymerization and used as a trypsin-based reactor in a continuous flow system. This is the first time that atom-transfer radical polymerization technique was utilized to design and construct polymer monolith bioreactor. The prepared monoliths possessed excellent permeability, providing fast mass transfer for enzymatic reaction. More importantly, surface properties, which were modulated via surface-initiated atom-transfer radical polymerization, were found to have a great effect on bioreactor activities based on Michaelis-Menten studies. Furthermore, three model proteins were digested by the monolith bioreactor to a larger degree within dramatically reduced time (50 s), about 900 times faster than that by free trypsin (12 h). The proposed method provided a platform to prepare porous monoliths with desired surface properties for immobilizing various enzymes., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Worth the excitement: Highly reactive oxygen and nitrogen species are generated by photoactivation of the anticancer platinum(IV) complex trans,trans,trans-[Pt(N3 )2 (OH)2 (MA)(Py)] (MA=methylamine, Py=pyridine). Singlet oxygen is formed from the hydroxido ligands and not from dissolved oxygen, and ammine ligands are products from the conversion of azido ligands to nitrenes. Both processes can induce oxidation of guanine., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel and simple method for the separation of major vitamin B analytes, such as thiamine, riboflavin, nicotinamide, vitamin B4, pyridoxine, has been developed by CEC using the monolithic column. It has been found that the baseline separation of the five analytes could be achieved with 5.0 mM phosphate buffer at pH 4.0. Compared with the open-tubular capillary and the bared capillary columns, the poly(butylmethacrylate-co-ethylene glycol dimethacrylate) monolithic capillary could exhibit the best resolution in the analysis. Then the method was validated and the linear calibration ranges were obtained with correlation coefficients more than 0.997. The precision and the recovery were also investigated and showed a good result. Furthermore, the proposed method was successfully applied to assay the concentration of vitamin B analytes and the metabolic situation in human urine samples.

A novel kind of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate)-based monolithic column was developed for LC by directing supramolecular self-assembly of high internal phase emulsion. Mercury intrusion porosimetry characterization and scanning electron microscope pictures showed that these monoliths presented micrometer-sized throughpores, unique sub-micron skeletons and relatively large specific surface area. Additionally, porosity of monoliths could be adjusted while skeletons remained in the size range of 100.0-1000.0 nm. The new monoliths demonstrated not only better column efficiency, but also larger binding capacity. Dynamic binding capacity for protein (BSA) was evaluated to be 42.5 mg/mL, above two times higher than that of the general monoliths (19.1 mg/mL) and higher than that of commercial "Convective Interaction Media" monolithic columns (30.0 mg/mL). Moreover, their chromatographic behaviors were also evaluated in detail by chemical stability and swelling characterization of the monolithic column. Separation of proteins mixture (cytochrome c, myoglobin, ribonuclease A, lysozyme and BSA) on the monolith was achieved within 4 min at velocity of 1440.0 cm/h. Those unique properties made the novel monolithic column a promising alternative to commercially available monolithic supports in LC applications.

Cationic aryl triazole oligomers have been synthesized through "click chemistry". The results show that cationic aryl triazole oligomers adopt a helical conformation in water or in a mixture of water and methanol, but prevail as a random-coiled conformation in methanol. Importantly, circular dichroism spectroscopy and dynamic light scattering experiments revealed that cationic oligomers aggregated intermolecularly to form higher order architectures with a helical sense opposite to that of the individual helix, which eventually led to the formation of aggregates with sizes in the range 100-500 nm. The aggregation of cationic oligomers was governed by the concentration and polarity of the environment. More interestingly, cationic foldamers were able to recognize chloride and fluoride anions in aqueous solution. The recognition consequently destabilized intermolecular aggregation.

Interactions of organometallic ruthenium anticancer complexes [Ru(eta6-arene)Cl(en)][PF6] (arene=p-cymene (1) or biphenyl (2), en=ethylenediamine) with human serum albumin were investigated by means of mass spectrometry combined with trypsin digestion, specific sidechain modifications and computational modelling. Both complexes were shown to bind to surface histidine (His128, His247, His510) and methionine (Met298) residues in human albumin, but only the p-cymene complex can gain entry to the crevice containing the free cysteine thiolate (Cys34) and induce oxidation to sulfinate. The two complexes exhibit a similar coordination preference for histidine and methionine residues on the protein surface. His128 binding is favoured both kinetically and thermodynamically. At 310 K, six days of incubation of recombinant human albumin (rHA) with complex 1 (rHA:Ru 50:250 microM) led to about 18 % ruthenation of His128 in the protein. However, the extent of ruthenation of albumin by complex 2 was less than that by 1, due to the steric hindrance from the biphenyl ligand. These results imply that the arene ligand in the organometallic ruthenium anticancer complexes plays a crucial role in interactions with proteins.

We have studied the interaction of the organometallic anticancer ruthenium(II) complexes [(eta(6)-p-cymene)Ru(en)Cl][PF(6)] (1) and [(eta(6)-biphenyl)Ru(en)Cl][PF(6)] (2) (en=ethylenediamine) with the single-stranded (ss) DNA hexamer d(CGGCCG) (I) and the duplex d(CGGCCG)(2) (II) by HPLC, ESI-MS, and one- and two-dimensional (1)H and (15)N NMR spectroscopy. For ss-DNA, all three G's are readily ruthenated with [(eta(6)-arene)Ru(en)](2+), but for duplex DNA there is preferential ruthenation of G3 and G6, and no binding to G2 was detected. For monoruthenated duplexes, N7 ruthenation of G is accompanied by strong hydrogen bonding between G-O6 and en-NH for the p-cymene adducts. Intercalation of the non-coordinated phenyl ring between G3 and C4 or G6 and C5 was detected in the biphenyl adducts of mono- and diruthenated duplexes, together with weakening of the G-O6NH-en hydrogen bonding. The arene ligand plays a major role in distorting the duplex either through steric interactions (p-cymene) or through intercalation (biphenyl).

The aqua adducts of the anticancer complexes [(eta(6)-X)Ru(en)Cl][PF(6)] (X=biphenyl (Bip) 1, X=5,8,9,10-tetrahydroanthracene (THA) 2, X=9,10-dihydroanthracene (DHA) 3; en=ethylenediamime) were separated by HPLC and characterised by mass spectrometry as the products of hydrolysis in water. The X-ray structures of the aqua complexes [(eta(6)-X)Ru(en)Y][PF(6)](n), X=Bip, Y=0.5 H(2)O/0.5 OH, n=1.5 (4), X=THA, Y=0.5 H(2)O/0.5 OH, n=1.5 (5 A), X=THA, Y=H(2)O, n=2 (5 B), and X=DHA, Y=H(2)O, n=2 (6), are reported. In complex 4 there is a large propeller twist of 45 degrees of the pendant phenyl ring with respect to the coordinated phenyl ring. Although the THA ligand in 5 A and 5 B is relatively flat, the DHA ring system in 6 is markedly bent (hinge bend ca. 35 degrees ) as in the chloro complex 3 (41 degrees ). The rates of aquation of 1-3 determined by UV/Vis spectroscopy at various ionic strengths and temperatures (1.23-2.59x10(-3) s(-1) at 298 K, I=0.1 M) are >20x faster than that of cisplatin. The reverse, anation reactions were very rapid on addition of 100 mM NaCl (a similar concentration to that in blood plasma). The aquation and anation reactions were about two times faster for the DHA and THA complexes compared to the biphenyl complex. The hydrolysis reactions appear to occur by an associative pathway. The pK(a) values of the aqua adducts were determined by (1)H NMR spectroscopy as 7.71 for 4, 8.01 for 5 and 7.89 for 6. At physiologically-relevant concentrations (0.5-5 microM) and temperature (310 K), the complexes will exist in blood plasma as >89 % chloro complex, whereas in the cell nucleus significant amounts (45-65 %) of the more reactive aqua adducts would be formed together with smaller amounts of the hydroxo complexes (9-25 %, pH 7.4, [Cl(-)]=4 mM).