Conspectus Among many outstanding findings associated with the quantum size effect, one of the most exciting is the discovery of the antigalvanic reaction (AGR), which is the opposite of the classic ...galvanic reaction (GR) that has a history of nearly 240 years. The GR, named after Italian scientist Luigi Galvani, involves the spontaneous reduction of a noble-metal cation by a less noble metal in solution driven by the difference in electrochemical potentials. Classic galvanic reduction has been widely applied and has recently received particular interest in nanoscience and nanotechnology. However, the opposite of GR, that is, reduction of metal ions by less reactive (or more noble) metals, has long been regarded as a virtual impossibility until the recent surprising findings regarding atomically precise ultrasmall metal nanoparticles (nanoclusters), which bridge the gap between metal atoms (complexes) and metal nanocrystals and provide opportunities for novel scientific findings due to their well-defined compositions and structures. The AGR is significant not only because it is the opposite of the classic galvanic theory but also because it opens extensive applications in a large range of fields, such as sensing and tuning the compositions, structures, and properties of nanostructures that are otherwise difficult to obtain. Starting with the proposal of the general AGR concept in 2012 by Wu, a new era began, in which AGR received widespread attention and was extensively studied. After years of effort, great advances have been achieved in the research on AGR, which will be reviewed below. In this Account, we first provide a short introduction to the AGR concept and then discuss the driving force of the AGR together with the effecting factors, including the ligand, particle size, solvent, metal ion precursor, and ion dose. Subsequently, the application of the AGR in engineering atomically precise alloy (bimetallic and trimetallic) and monometallic nanoclusters is described, and tuning the properties of the parent nanoclusters is also included. In particular, four alloying modes (namely, (i) addition, (ii) replacement, (iii) replacement and structural transformation, and (iv) nonreplacement and structural transformation) associated with the AGR are discussed. After that, the applications of the AGR in metal ion sensing and antioxidation are reviewed. Finally, future prospects are discussed, and some challenging issues are presented at the end of this Account. It is expected that this Account will stimulate more scientific and technological interests in the AGR, and exciting progress in the understanding and application of the AGR will be made in the coming years.
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IJS, KILJ, NUK, PNG, UL, UM
Abstract
This article is an examination of the extent to which traditional medical knowledge in China can be protected by intellectual property laws. The analysis begins by providing a global picture ...with regard to the historic origin of intellectual property, exploring the reasons why China does not have indigenous counterparts to the western system of intellectual property rights protecting its traditional knowledge (including traditional medical knowledge) and stating the problems of transplanting western intellectual property standards in China. A discussion follows on how China, under foreign pressure, has made efforts to comply with the changing standards mandated by various international, regional, and bilateral arrangements related to intellectual property, with examples of the development of China’s patent law. China’s approach towards the protection of traditional medical knowledge in various international fora related to intellectual property is explored. Finally, there is a specific examination of the compatibilities between the western system of intellectual property rights and traditional medical knowledge in China, at the national and community levels. This article argues that the system of intellectual property rights does not easily fit with China’s traditional medical knowledge because of China’s unique cultural traits, distinctive historical context and wide ethnic, religious, and local community diversity.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
A photothermal bacterium (PTB) is reported for tumor‐targeted photothermal therapy (PTT) by using facultative anaerobic bacterium Shewanella oneidensis MR‐1 (S. oneidensis MR‐1) to biomineralize ...palladium nanoparticles (Pd NPs) on its surface without affecting bacterial activity. It is found that PTB possesses superior photothermal property in near infrared (NIR) regions, as well as preferential tumor‐targeting capacity. Zeolitic imidazole frameworks‐90 (ZIF‐90) encapsulating photosensitizer methylene blue (MB) are hybridized on the surface of living PTB to further enhance PTT efficacy. MB‐encapsulated ZIF‐90 (ZIF‐90/MB) can selectively release MB at mitochondria and cause mitochondrial dysfunction by producing singlet oxygen (1O2) under light illumination. Mitochondrial dysfunction further contributes to adenosine triphosphate (ATP) synthesis inhibition and heat shock proteins (HSPs) down‐regulated expression. The PTB‐based therapeutic platform of PTB@ZIF‐90/MB demonstrated here will find great potential to overcome the challenges of tumor targeting and tumor heat tolerance in PTT.
A bacteria‐based photothermal therapeutic platform comprising PTB@ZIF‐90/MB is developed, which reveals great potential to augment photothermal therapy efficacy by tackling the challenges of tumor targeting and heat resistance.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
By leveraging the ability of Shewanella oneidensis MR‐1 (S. oneidensis MR‐1) to anaerobically catabolize lactate through the transfer of electrons to metal minerals for respiration, a lactate‐fueled ...biohybrid (Bac@MnO2) was constructed by modifying manganese dioxide (MnO2) nanoflowers on the S. oneidensis MR‐1 surface. The biohybrid Bac@MnO2 uses decorated MnO2 nanoflowers as electron receptor and the tumor metabolite lactate as electron donor to make a complete bacterial respiration pathway at the tumor sites, which results in the continuous catabolism of intercellular lactate. Additionally, decorated MnO2 nanoflowers can also catalyze the conversion of endogenous hydrogen peroxide (H2O2) into generate oxygen (O2), which could prevent lactate production by downregulating hypoxia‐inducible factor‐1α (HIF‐1α) expression. As lactate plays a critical role in tumor development, the biohybrid Bac@MnO2 could significantly inhibit tumor progression by coupling bacteria respiration with tumor metabolism.
MnO2 nanoflowers were modified on the cell surface of electrochemically active bacteria, S. oneidensis MR‐1. The biohybrids, which couple bacterial respiration with tumor metabolism, can catabolize intercellular lactate and prevent intracellular lactate production in the tumor, thereby inducing significant tumor inhibition.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Synthetic biology based on bacteria has been displayed in antitumor therapy and shown good performance. In this study, an engineered bacterium Escherichia coli MG1655 is designed with NDH‐2 enzyme ...(respiratory chain enzyme II) overexpression (Ec‐pE), which can colonize in tumor regions and increase localized H2O2 generation. Following from this, magnetic Fe3O4 nanoparticles are covalently linked to bacteria to act as a catalyst for a Fenton‐like reaction, which converts H2O2 to toxic hydroxyl radicals (•OH) for tumor therapy. In this constructed bioreactor, the Fenton‐like reaction occurs with sustainably synthesized H2O2 produced by engineered bacteria, and severe tumor apoptosis is induced via the produced toxic •OH. These results show that this bioreactor can achieve effective tumor colonization, and realize a self‐supplied therapeutic Fenton‐like reaction without additional H2O2 provision.
A Fenton‐like bioreactor based on bacteria is reported for tumor therapy without exogenous H2O2 provision. It is found that this bioreactor can achieve effective tumor colonization, and realize a self‐supplied therapeutic Fenton‐like reaction without additional H2O2 provision.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Synthetic biology based on bacteria has been displayed in antitumor therapy and shown good performance. In this study, an engineered bacterium Escherichia coli MG1655 is designed with NDH-2 enzyme ...(respiratory chain enzyme II) overexpression (Ec-pE), which can colonize in tumor regions and increase localized H
O
generation. Following from this, magnetic Fe
O
nanoparticles are covalently linked to bacteria to act as a catalyst for a Fenton-like reaction, which converts H
O
to toxic hydroxyl radicals (•OH) for tumor therapy. In this constructed bioreactor, the Fenton-like reaction occurs with sustainably synthesized H
O
produced by engineered bacteria, and severe tumor apoptosis is induced via the produced toxic •OH. These results show that this bioreactor can achieve effective tumor colonization, and realize a self-supplied therapeutic Fenton-like reaction without additional H
O
provision.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
•Carbon cloth is treated with a moderate electrochemical activation strategy to enrich its surface functional groups.•Ni-incorporated into activated carbon cloth can synergistically deliver efficient ...and robust alkaline water oxidation activity.•A η10 of 245 mV is maintained after a long-term durability test for as long as 24 h.•Carbon cloth is treated with a moderate electrochemical activation strategy to enrich its surface functional groups. Ni-incorporated into activated carbon cloth can synergistically deliver efficient and robust alkaline water oxidation activity
Carbon cloth is treated with a moderate electrochemical activation strategy to enrich its surface functional groups. In result, the hydrophilicity and intrinsic activity of carbon cloth (CC) can be enhanced. Furthermore, the activated carbon cloth (ACC) can adsorb massive transition-metal like nickel ions with a wet chemistry method. Combined with a low temperature thermal reduction under the atmosphere of Ar/H2, nickel-incorporated activated carbon cloth (Ni-ACC) can be obtained. In comparison with bare CC and nickel-incorporated carbon cloth (Ni-CC), the Ni-ACC displays more superior activity and durability of water oxidation in alkaline environment. The overpotential at the current density of 10 mA cm−2 (η10) is maintained at 245 mV after chronopotentiometry (CP) test for 24 h. The electrochemical activated method can serve as a simple approach for fabricating various metal-incorporated ACC.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Cyclic GMP-AMP synthase (cGAS) senses double-strand (ds) DNA in the cytosol and then catalyzes synthesis of the second messenger cGAMP, which activates the adaptor MITA/STING to initiate innate ...antiviral response. How cGAS activity is regulated remains enigmatic. Here, we identify ZCCHC3, a CCHC-type zinc-finger protein, as a positive regulator of cytosolic dsDNA- and DNA virus-triggered signaling. We show that ZCCHC3-deficiency inhibits dsDNA- and DNA virus-triggered induction of downstream effector genes, and that ZCCHC3-deficient mice are more susceptible to lethal herpes simplex virus type 1 or vaccinia virus infection. ZCCHC3 directly binds to dsDNA, enhances the binding of cGAS to dsDNA, and is important for cGAS activation following viral infection. Our results suggest that ZCCHC3 is a co-sensor for recognition of dsDNA by cGAS, which is important for efficient innate immune response to cytosolic dsDNA and DNA virus.
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