Search

Recently, open tubular capillary electrochromatography (OT-CEC) has captured considerable interest; its efficient separation capability hinges on the interactions between analytes and polymer coatings. However, in situ growth of stimuli-responsive polymers as coatings has been rarely studied and is crucial for expanding the OT-CEC technique and its application. Herein, following poly(styrene-maleicanhydride) (PSM) chemically bonded onto the inner surface of the capillary, a dual pH/temperature stimuli-responsive block copolymer, P(SMN-COOH), was prepared by in situ polymerizing poly(N-isopropylacrylamide) carboxylic acid terminated [P(N-COOH)] in PSM. An OT-CEC protocol was first explored using the coated capillary for epimedins separation. As a proof of concept, the developed OT-CEC system facilitated hydrogen bonding and tuning the hydrophilic/hydrophobic interactions between the test analytes and the P(SMN-COOH) coating by varying buffer pH and environmental temperature. Four epimedins with similar chemical structures were baseline separated under 40 °C at pH 10.0, exhibiting dramatical improvement in separation efficiency in comparison to its performance under 25 °C at pH 4.0. In addition, the coated capillary showed good repeatability and reusability with relative standard deviations for migration time and peak area between 0.7 and 1.7% and between 2.9 and 4.6%, respectively, and no significant changes after six runs. This work introduces a paradigm for efficient OT-CEC separation of herbal medicines through adjusting the interactions between analytes and smart polymer coatings, addressing polymer coating design and OT-CEC challenges. [ABSTRACT FROM AUTHOR]

We aimed to explore the anti-obesity mechanism from the microbiome, metabolome, and transcriptome viewpoints, focusing on the sulfated polysaccharides found in the cooking liquid of Apostichopus japonicus (CLSPAJ) to explore the potential mediators of the anti-obesity effects in mice fed a high-fat diet (HFD). The mice treated with CLSPAJ showed a decrease in obesity and blood lipid levels. Gut microbiome dysbiosis caused by the HFD was reversed after CLSPAJ supplementation, along with increased levels of indole-3-ethanol, N-2-succinyl-L-glutamic acid 5-semialdehyde, and urocanic acid. These increases were positively related to the increased Akkermansia, Lactobacillus, Roseburia, and Phascolarctobacterium. Transcriptome analysis showed that B cell receptor signaling and cytochrome P450 xenobiotic metabolism were the main contributors to the improvement in obesity. Metabolome–transcriptome analysis revealed that CLSPAJ reversal of obesity was mainly due to amino acid metabolism. These findings suggest that CLSPAJ could be a valuable prebiotic preparation for preventing obesity-related diseases. [ABSTRACT FROM AUTHOR]

Trichostatin A (TSA), a histone deacetylase (HDAC) inhibitor, promotes the cytotoxicity of the genotoxic anticancer drug cisplatin, yet the underlying mechanism remains poorly understood. Herein, we revealed that TSA at a low concentration (1 μM) promoted the cisplatin-induced activation of caspase-3/6, which, in turn, increased the level of cleaved PARP1 and degraded lamin A&C, leading to more cisplatin-induced apoptosis and G2/M phase arrest of A549 cancer cells. Both ICP-MS and ToF-SIMS measurements demonstrated a significant increase in DNA-bound platinum in A549 cells in the presence of TSA, which was attributable to TSA-induced increase in the accessibility of genomic DNA to cisplatin attacking. The global quantitative proteomics results further showed that in the presence of TSA, cisplatin activated INF signaling to upregulate STAT1 and SAMHD1 to increase cisplatin sensitivity and downregulated ICAM1 and CD44 to reduce cell migration, synergistically promoting cisplatin cytotoxicity. Furthermore, in the presence of TSA, cisplatin downregulated TFAM and SLC3A2 to enhance cisplatin-induced ferroptosis, also contributing to the promotion of cisplatin cytotoxicity. Importantly, our posttranslational modification data indicated that acetylation at H4K8 played a dominant role in promoting cisplatin cytotoxicity. These findings provide novel insights into better understanding the principle of combining chemotherapy of genotoxic drugs and HDAC inhibitors for the treatment of cancers. [ABSTRACT FROM AUTHOR]

Bioethics provides a new perspective for the comparative study of Christianity and Chinese Buddhism. This paper provides a comprehensive comparison of the sources, states of existence, and fundamental principles and purposes of the Christian and Chinese Buddhist perspectives on human life, focusing specifically on the realm of bioethics. It places special emphasis on teachings about God's creation and dependent origination, original sin and Buddhist causality, as well as love and compassion. Despite the significant geographic distance between Christianity and Chinese Buddhism, the dialogue highlights potential cultural differences and interpretations. It also demonstrates mutual acceptance and the process of redefining one's own identity. Religious bioethics greatly benefits from a comprehensive study of various religions from around the world. It aims to encourage cross-cultural and interdisciplinary research on different religions globally. It promotes religious bioethics as a relevant field of study. [ABSTRACT FROM AUTHOR]

Unconventional fermions in the immensely studied topological semimetals are the source for rich exotic topological properties. Here, using symmetry analysis and first-principles calculations, we propose the coexistence of multiple topological nodal structure in LaSb2, including topological nodal surfaces, nodal lines and in particular eightfold degenerate nodal points, which have been scarcely observed in a single material. Further, utilizing angle-resolved photoemission spectroscopy, we confirm the existence of nodal surfaces and eightfold degenerate nodal points in LaSb2. The intriguing multiple topological nodal structure might play a crucial role in giving rise to the large linear magnetoresistance. Our work renews the insights into the exotic topological phenomena in LaSb2. [ABSTRACT FROM AUTHOR]

Strophanthidin (SPTD), one of the cardiac glycosides, is refined from traditional Chinese medicines such as Semen Lepidii and Antiaris toxicaria, and was initially used for the treatment of heart failure disease in clinic. Recently, SPTD has been shown to be a potential anticancer agent, but the underlying mechanism of action is poorly understood. Herein, we explored the molecular mechanism by which SPTD exerts anticancer effects in A549 human lung adenocarcinoma cells by means of mass spectrometry-based quantitative proteomics in combination with bioinformatics analysis. We revealed that SPTD promoted the expression of tumor necrosis factor (TNF)-related apoptosis-inducing ligand receptor 2 (TRAIL-R2, or DR5) in A549 cells to activate caspase 3/6/8, in particular caspase 3. Consequently, the activated caspases elevated the expression level of apoptotic chromatin condensation inducer in the nucleus (ACIN1) and prelamin-A/C (LMNA), ultimately inducing apoptosis via cooperation with the SPTD-induced overexpressed barrier-to-autointegration factor 1 (Banf1). Moreover, the SPTD-induced DEPs interacted with each other to downregulate the p38 MAPK/ERK signaling, contributing to the SPTD inhibition of the growth of A549 cells. Additionally, the downregulation of collagen COL1A5 by SPTD was another anticancer benefit of SPTD through the modulation of the cell microenvironment. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Four trinucleotides 5′-ATA-3′ (I), 5′-ATC-3′ (II), 5′-CTA-3′ (III) and 5′-CTC-3′ (IV) were introduced to interact with a diazido-based photoactivatable anticancer prodrug trans,trans,trans-[PtIV(N3)2(OH)2(py)2] (py = pyridine; 1) upon light irradiation. Using electrospray ionization mass spectrometry (ESI-MS), we aimed to investigate the possibility of 1,3-intrastrand crosslinks at adenine and/or cytosine in the trinucleotides via the bi-functional trans-[PtII(py)2]2+ species generated by photodecomposition of complex 1. The primary mass spectrometry results showed that although mono- and di-platinated trinucleotides bound by mono-functional trans-[PtII(N3)(py)2]+ species were the major platinated adducts, comparable amounts of bifunctional trans-[PtII(py)2]2+-bound trinucleotides were also observed. Further tandem mass spectrometry of the trans-[PtII(py)2]2+-bound trinucleotides showed the formation of 1,3-crosslinks between adenine–adenine, adenine–cytosine and cytosine–cytosine bases in the trinucleotides. The formation of such unique structures is not only distinct from the action modes of cisplatin with DNA but also an important complement to the acknowledged 1,3-GNG intrastrand crosslink by trans-Pt species, which may support the promising and distinct anticancer activities of such photoactivatable diazido Pt(IV) anticancer prodrugs and deserve further studies. [ABSTRACT FROM AUTHOR]

Micron-sized Si anode promises a much higher theoretical capacity than the traditional graphite anode and more attractive application prospect compared to its nanoscale counterpart. However, its severe volume expansion during lithiation requires solid electrolyte interphase (SEI) with reinforced mechanical stability. Here, we propose a solvent-induced selective dissolution strategy to in situ regulate the mechanical properties of SEI. By introducing a high-donor-number solvent, gamma-butyrolactone, into conventional electrolytes, low-modulus components of the SEI, such as Li alkyl carbonates, can be selectively dissolved upon cycling, leaving a robust SEI mainly consisting of lithium fluoride and polycarbonates. With this strategy, raw micron-sized Si anode retains 87.5% capacity after 100 cycles at 0.5 C (1500 mA g−1, 25°C), which can be improved to >300 cycles with carbon-coated micron-sized Si anode. Furthermore, the Si||LiNi0.8Co0.1Mn0.1O2 battery using the raw micron-sized Si anode with the selectively dissolved SEI retains 83.7% capacity after 150 cycles at 0.5 C (90 mA g−1). The selective dissolution effect for tailoring the SEI, as well as the corresponding cycling life of the Si anodes, is positively related to the donor number of the solvents, which highlights designing high-donor-number electrolytes as a guideline to tailor the SEI for stabilizing volume-changing alloying-type anodes in high-energy rechargeable batteries. The severe volume expansion during the lithiation of micron-sized Si in Li-ion batteries requires a solid electrolyte interphase with reinforced mechanical stability. Here, the authors propose a solvent-induced selective dissolution strategy to regulate the mechanical properties of the interphase. [ABSTRACT FROM AUTHOR]

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 FA0.85MA0.15Pb(I0.95Br0.05)3‐based PSCs by incorporating Ti3C2Clx 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. [ABSTRACT FROM AUTHOR]

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 FA0.85MA0.15Pb(I0.95Br0.05)3‐based PSCs by incorporating Ti3C2Clx 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. [ABSTRACT FROM AUTHOR]

Ruthenium(II) polypyridyl complexes have drawn growing attention due to their photophysical properties and anticancer activity. Herein we report four ruthenium(II) polypyridyl complexes [(N^N)2RuII(L)]2+ (1–4, L = 4-anilinoquinazoline derivatives, N^N = bidentate ligands with bis-nitrogen donors) as multi-functional anticancer agents. The epidermal growth factor receptor (EGFR) is overexpressed in a broad range of cancer cells and related to many kinds of malignance. EGFR inhibitors, such as gefitinib and erlotinib, have been approved as clinical anticancer drugs. The EGFR-inhibiting 4-anilinoquinazoline ligands greatly enhanced the in vitro anticancer activity of these ruthenium(II) polypyridyl complexes against a series of human cancer cell lines compared to [Ru(bpy)2(phen)], but interestingly, these complexes were actually not potent EGFR inhibitors. Further mechanism studies revealed that upon irradiation with visible light, complexes 3 and 4 generated a high level of singlet oxygen (1O2), and their in vitro anticancer activities against human non-small-cell lung (A549), cervical (HeLa) and squamous (A431) cancer cells were significantly improved. Specifically, complex 3 displayed potent phototoxicity upon irradiation with blue light, of which the photo-toxicity indexes (PIs) against HeLa and A431 cells were 11 and 8.3, respectively. These complexes exhibited strong fluorescence emission at ca. 600 nm upon excitation at about 450 nm. A subcellular distribution study by fluorescence microscopy imaging and secondary ion mass spectrometry imaging (ToF-SIMS) demonstrated that complex 3 mainly localized at the cytoplasm and complex 4 mainly localized in the nuclei of cells. Competitive binding with ctDNA showed that complex 4 was more favorable to bind to the DNA minor groove than complex 3. These differences support that complex 3 possibly exerts its anticancer activities majorly by photo-induced 1O2 generation and complex 4 by binding to DNA. [ABSTRACT FROM AUTHOR]

The interaction of a photoactivatable diazidodihydroxido Pt(IV) prodrug, trans,trans,trans-[Pt(N3)2(OH)2(py)2] (py = pyridine; 1), with a hexamer straight human telomeric DNA unit sequence (5′-T1T2A3G4G5G6-3′, I) upon light irradiation was investigated by electrospray ionization mass spectroscopy (ESI-MS). In the primary mass spectrum, two major mono-platinated I adducts with the bound Pt moieties, trans-[PtII(N3)(py)2]+ (1′) and trans-[PtII(py)2]2+ (1′′), respectively, were detected. It is rare to observe such high abundance and nearly equal intensity platinated DNA adducts formed by these two PtII species because 1′ is usually the only major reduced Pt(II) species produced by the photodecomposition of complex 1 in the presence of DNA while 1′′ was rarely detected as the major reduced PtII species reported previously. Subsequent tandem mass spectrometric analysis by collision-induced dissociation (CID) showed that in the former adduct {I + 1′}2+, G6 and A3 were the platination sites. While in the latter adduct {I + 1′′}2+, a potential intrastrand crosslink was speculated after G4 and G6 sites were identified. Additionally, other minor platinated adducts like di-platinated I adduct by 1′ with platination sites at G4 and G6 and mono-platinated I adducts containing base oxidation were also detected by mass spectrometry. Due to the rich guanines and their sensitivity to oxidation, the oxidation induced by 1 most probably occurred at guanine. The oxidation adducts were proposed as 8-hydroxyl guanine, spiroiminodihydantoin (Sp), 2,6-diamino-4-hydroxy-5-formamidopyrimidine (FapyG), 5-guanidinohydantoin (Gh), and/or dehydroguanidinohydantoin (DGh) referring to previous reports. The obtained results provide useful chemical information about the photoreaction between photoactivatable Pt(IV) anticancer prodrugs and human telomeric DNA. Such special damages of Pt(IV) prodrugs on human telomeric DNA implicate its active role in the mechanism of Pt(IV) prodrugs and further support the unique sequence-dependent photointeraction profile of complex 1 reacting with DNA. [ABSTRACT FROM AUTHOR]

Using liquid secondary ion mass spectrometry, we in situ unraveled that the single walled carbon nanotubes-modified gold electrode surface is free of a dense adsorption phase and abundant in water molecules, which facilitated the electro-oxidation reaction of ascorbate. Such an understanding will expedite the knowledge-based development of electrochemical interfaces. [ABSTRACT FROM AUTHOR]

Electrical stimulation (ES) is widely used in physiological and medical sciences, while its application to treat inflammatory skin diseases (ISDs) remains a challenge owing to their natural pathological cuticle barrier and lack of an effective combination with chemotherapy to achieve specific immunomodulation. Here, a wearable, battery‐free, multi‐component drug‐loaded electronic microneedle (mD‐eMN) system is developed by integrating remodeled metal microneedles loaded with multi‐component chemical drugs and flexible triboelectric nanogenerators (TENGs). The system can rapidly release drugs into the site of ISDs and then realize an efficient penetration into cell body and specific immunomodulation under the synergism of pulsed electrons originating from the TENG. Also, the pulsed electrons can promote skin tissue homeostasis reconstruction to alleviate the inflammatory process of ISDs. Sufficient evidence shows that a significant skin inflammation regression of psoriasis (a typical ISDs model) is achieved using the mD‐eMN system compared to traditional ES or chemotherapy alone. This innovative wearable mD‐eMN system provides an effective flexible electronic and chemical drug joint technological platform for the treatment of ISDs, which is not only suitable for the treatment of psoriasis in this study but also maybe for other ISDs such as diabetic ulcers and skin tumors. [ABSTRACT FROM AUTHOR]

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 cm2 and a PCE of 15.35 % for a mini‐module of 16.94 cm2 with superior stability. [ABSTRACT FROM AUTHOR]

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 cm2 and a PCE of 15.35 % for a mini‐module of 16.94 cm2 with superior stability. [ABSTRACT FROM AUTHOR]

High‐energy lithium‐ion batteries built with silicon‐based anode materials are usually associated with short cycle lives due to mechanical failure at an anode level and more importantly, due to electrochemical failure at a cell level as a result of irreversible consumption of cathode Li during initial charge. (Electro)chemical prelithiation has shown promises to compensate initial Li loss and improve cycling performance of the battery. However, previous strategies applied directly at anode or cathode could raise concerns on safety and degraded electrode structure, and are less compatible with industrial manufacture of batteries. Here, a new concept of prelithiation by lithiation agents supported functional separator, which is highly adaptive to electrode preparation, battery manufacture and formation, and is capable of, by simply adjusting cell voltage, not only replenishing cathode Li loss but re‐uptaking anode Li to inhibit local over‐lithiation and dendrite formation, is shown. By employing the functional separator, a 3‐Ah Li‐ion pouch cell that pairs a silicon‐based anode and a high‐nickel layered oxide cathode demonstrates stable energy output of >330 Wh kg−1 and much improved cycling performance. [ABSTRACT FROM AUTHOR]

The ruthenium polypyridine complex [Ru(dppa)2(pytp)] (PF6)2 (termed as ZQX-1), where dppa = 4,7-diphenyl-1,10-phenanthroline and pytp = 4′-pyrene-2,2′:6′,2′′-terpyridine, has been shown a high and selective cytotoxicity to hypoxic and cisplatin-resistant cancer cells either under irradiation with blue light or upon two-photon excitation. The IC50 values of ZQX-1 towards A549 cancer cells and HEK293 health cells are 0.16 ± 0.09 µM and >100 µM under irradiation at 420 nm, respectively. However, the mechanism of action of ZQX-1 remains unclear. In this work, using the quantitative proteomics method we identified 84 differentially expressed proteins (DEPs) with |fold-change| ≥ 1.2 in A549 cancer cells exposed to ZQX-1 under irradiation at 420 nm. Bioinformatics analysis of the DEPs revealed that photoactivated ZQX-1 generated reactive oxygen species (ROS) to activate oxidative phosphorylation signaling to overproduce ATP; it also released ROS and pyrene derivative to damage DNA and arrest A549 cells at S-phase, which synergistically led to oncotic necrosis and apoptosis of A549 cells to deplete excess ATP, evidenced by the elevated level of PRAP1 and cleaved capase-3. Moreover, the DNA damage inhibited the expression of DNA repair-related proteins, such as RBX1 and GPS1, enhancing photocytotoxicity of ZQX-1, which was reflected in the inhibition of integrin signaling and disruption of ribosome assembly. Importantly, the photoactivated ZQX-1 was shown to activate hypoxia-inducible factor 1A (HIF1A) survival signaling, implying that combining use of ZQX-1 with HIF1A signaling inhibitors may further promote the photocytotoxicity of the prodrug. [ABSTRACT FROM AUTHOR]

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, Li3PO4‐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. [ABSTRACT FROM AUTHOR]

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, Li3PO4‐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. [ABSTRACT FROM AUTHOR]

CpG and its cytosine-methylated counterpart (5mCpG) are a unique reversible pair of sequences in regulating the expression of genes epigenetically. As DNA is the potential target of Pt-based anticancer metallodrugs, herein, we comparatively investigate the interactions of 5′-CpG and 5′-5mCpG with a photoactivatable anticancer Pt(IV) prodrug, trans,trans,trans-[PtIV(N3)2(OH)2(py)2] (1; py = pyridine), to explore the effects of methylation on the platination and ROS-induced oxidation of the CpG motif. Mono-platinated dinucleotides were demonstrated by ESI-MS to be the main products for both 5′-CpG and 5′-5mCpG with the bound Pt moiety as [PtII(N3)(py)2] generated by the photodecomposition of complex 1 under irradiation with blue light, accompanied by the formation of less abundant di-platinated adducts. G-N7 and C-N3/5mC-N3 were shown to be the major and minor platination sites, respectively, with G-N1 as the third and weakest platination site, in particular, in di-platinated products. Moreover, platinated dinucleotides associated with guanine and/or cytosine oxidation were also observed. Apart from 8-oxo-guanine (oxG) and N-formylamidoiminohydantoin (RedSp) reported previously, novel oxidation adducts 5-guanidinohydantoin (Gh) derived from guanine and 1-carbamoyl-4,5-dihydroxy-2-oxoimidazolidine (ImidCyt) derived from cytosine in CpG, and diimino imidazole (DIz) and 2,5-diaminoimidazol-4-one (imidazolone, Iz) derived from guanine and Imid5mCyt derived from 5mC in 5mCpG were proposed according to MS information. These results showed that methylation exerted little effects on the platination modes of CpG, but triggered distinct oxidation pathways of CpG, perhaps causing discriminated DNA damage to CpG-rich genes. This work provides novel insights into the role of the anticancer photoactivatable Pt(IV) prodrug through damaging the epigenetically modified DNA sequences. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In order to effectively mine the structural features in time series and simplify the complexity of time series analysis, equiprobable symbolization pattern entropy (EPSPE) is proposed in this paper. The original time series are implemented through symbolic processing according to an equal probability distribution. Then, the sliding window technique is used to obtain a finite number of different symbolic patterns, and the pattern pairs are determined by calculating the conversion between the symbolic patterns. Next, the conversion frequency between symbolized patterns is counted to calculate the probability of the pattern pairs, thus estimating the complexity measurement of complex signals. Finally, we conduct extensive experiments based on the Logistic system under different parameters and the natural wind field. The experimental results show our EPSPE of the Logistic system increases from 5 to 7.5 as the parameters increase, which makes the distinction of periodic and complex time series with varying degrees intuitive. Meanwhile, it can more concisely reflect the structural characteristics and interrelationships between time series from the natural wind field (8.8–10 for outdoor and 7.8–8.3 for indoor). In contrast, the results of several state-of-the-art schemes are irregular and cannot distinguish the complexity of periodic time series as well as accurately predict the spatial deployment relationship of nine 2D ultrasonic anemometers. [ABSTRACT FROM AUTHOR]

Bioelectricity plays a significant role in major biological processes and electrical stimulation is an effective and non-invasive way to promote cellular growth, differentiation and tissue regeneration. In tissue engineering, piezoelectric materials not only act as modulators to regulate behaviors and functions of cells and tissues, but are also used as scaffolds to regulate and guide cell growth and matrix synthesis, thus promoting the formation of new tissue. Piezoelectronic electrons are produced from piezoelectric materials upon mechanical stimuli and have similar effects on cells as an external electrical field. Devices based on piezoelectronics have been widely applied in bioelectronics and biomedical fields. In this review, the effects of piezoelectronic electrons on cells and their possible mechanisms are briefly introduced. Then, we overview the applications of piezoelectronic electrons in cell regulation and tissue regeneration according to the type of cells and tissues. Finally, future perspectives and challenges are also provided. [ABSTRACT FROM AUTHOR]

Correction for 'Open-flow microperfusion combined with mass spectrometry for in vivo liver lipidomic analysis' by Tuo Li et al., Analyst, 2021, 146, 1915–1923, https://doi.org/10.1039/D0AN02189J. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Invasive electrical stimulation (iES) is prone to cause neural stimulus-inertia owing to its excessive accumulation of exogenous charges, thereby resulting in many side effects and even failure of nerve regeneration and functional recovery. Here, a wearable neural iES system is well designed and built for bionic and long-lasting neural modulation. It can automatically yield biomimetic pulsed electrical signals under the driven of respiratory motion. These electrical signals are full of unique physiological synchronization can give biofeedback to respiratory behaviors, self-adjusting with different physiological states of the living body, and thus realizing a dynamic and biological self-matched modulation of voltage-gated calcium channels on the cell membrane. Abundant cellular and animal experimental evidence confirm an effective elimination of neural stimulus-inertia by these bioelectrical signals. An unprecedented nerve regeneration and motor functional reconstruction are achieved in long-segmental peripheral nerve defects, which is equal to the gold standard of nerve repair -- autograft. The wearable neural iES system provides an advanced platform to overcome the common neural stimulus-inertia and gives a broad avenue for personalized iES therapy of nerve injury and neurodegenerative diseases. Designing wereable neural invasive electrical stimulation system remains a challenge. Here, researchers provide an effective technology platform for the elimination of tricky neural stimulus-inertia using bionic electronic modulation, which is a significant step forward for long-lasting treatment of nervous system diseases. [ABSTRACT FROM AUTHOR]

Photoactivatable Pt(IV) anticancer prodrug trans,trans,trans-[Pt(N3)2(OH)2(pyridine)2] (1) has been shown to bind to and induce oxidation of all four DNA nucleobases. Herein, to further render the binding spectrum of complex 1 to nucleic acids, the interaction between complex 1 and uridine, an exclusive RNA component, was investigated by electrospray ionization mass spectrometry (ESI-MS) and NMR spectroscopy. The results showed that complex 1 can bind to uridine through the N3 (major) and O4 (minor) sites upon light irradiation to form the major mono-platinated uridine adduct and the minor di-platinated uridine adduct. Moreover, mono-platinated uridine associated with the oxidation of uridine to 5-hydroxyuridine and 6-hydroxyuridine was also observed. This is the first report that the photoactivatable Pt(IV) prodrug binds to and induces the oxidation of uridine, and also the last piece of the puzzle for the interactions of complex 1 with nucleobases. Combined with our previous results about the interactions between complex 1 and DNA bases, these data showed a wide interaction spectrum of this kind of photoactivatable diazido Pt(IV) prodrugs with nucleobases through such dual-action modes, strongly suggesting that RNA may be a potential target of Pt(IV) prodrugs. [ABSTRACT FROM AUTHOR]

Rationale: The identification and evaluation of novel biomarkers are essential to clinical diagnosis and prognosis of colorectal cancer (CRC). Serum phosphopeptides have been recognized as a potential signature pool for cancers; therefore, we aim to profile the expression of serum phosphopeptides and to evaluate their feasibility in CRC diagnosis. Methods: We conducted the characterization and absolute quantification of endogenous phosphopeptides in sera using liquid chromatography–mass spectrometry analysis in combination with enrichment of phosphopeptides by ZrAs‐Fe3O4@SiO2nanoparticles and use of deuterium‐labeled standards. Differentially expressed analysis of four phosphopeptides was performed, generating a two‐phosphopeptide‐based biomarker, LF3–4, by logistic regression analysis, where LF3–4 is equal to (5.85 − 5.13 × [F3] − 3.57 × [F4]), and [F3] and [F4] are the concentration of phosphopeptides DpSGEGDFLAEGGGVR and ADpSGEGDFLAEGGGVR in sera, respectively. Results: The LF3–4 values showed significant difference in CRC cases compared with controls, and yielded a specificity of 100%, leading to correct classification of 56 (93%) out of 60 CRC patients, including 12 (92.3%) of 13 CRC cases in stage I. Double‐blind validation showed that 97.5% of CRC cases were discriminated accurately. Conclusions: The LF3–4 value was firstly verified to be a potential biomarker for CRC diagnosis, and may expand our view in underlying mechanisms for CRC. [ABSTRACT FROM AUTHOR]

Manganese-enhanced MRI (MEMRI) is a powerful tool to study neuronal activity and microarchitecture in vivo. Yet the influence of exogenous manganese on the brain of the Parkinson's disease (PD) model mouse is poorly understood. Laser ablation connected to inductively coupled plasma mass spectrometry (LA-ICP-MS) imaging for tissue section is an ideal tool to simultaneously analyze the metabolism of endogenous metal ions. In this study, DJ-1 knockout PD model mice were subjected to an MnCl2 saline treatment and the distribution of Mn and several other endogenous metal ions in brain regions was assessed by MEMRI and LA-ICP-MS imaging. The results demonstrated that Mn mainly deposited in subcortical regions, such as ventricles, hippocampus (HC), medial preoptic nucleus (MPO), lateral septal nucleus (LS), and ventromedial hypothalamic nucleus (VMH). The enhanced signal-to-noise ratio (S/N) determined by MEMRI for Mn is closely related to the signal in LA-ICP-MS imaging. Significantly, the treatment of MnCl2 disturbs the homeostasis of iron, zinc, copper, and calcium in the DJ-1 mouse, which could result in more severe symptoms of PD. Therefore, the application of MEMRI in the study of neurological disease must be made with caution. [ABSTRACT FROM AUTHOR]

Halide perovskites are highly promising semiconductors for photovoltaics due to their high efficiency and simple solution processing. However, their halide-terminated surface is unstable due to the low binding energy of the Pb–I bond in the perovskites, which allows for surface defect formation and ion migration under external stresses, deteriorating the performance of perovskite solar cells (PSCs). Here, phenethylammonium fluoride (PEAF) is deposited on a perovskite film with controlled thickness via a fast thermal evaporation method at low temperatures and normal pressure, passivating the commonly existing surface halide vacancies without destabilizing the underlying perovskite and sacrificing charge transport in the PSC. Moreover, the fluoride anion in PEAF could undergo a strong interaction with the perovskites due to its high electronegativity, effectively reinforcing the structural stability of the perovskite film. The PEAF-treated PSCs exhibit high power conversion efficiency (PCE) of 23.2% with significantly enhanced stability. [ABSTRACT FROM AUTHOR]