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Piezo‐catalytic self‐Fenton (PSF) system has been emerging as a promising technique for wastewater treatment, while the competing O2 reductive hydrogen peroxide (H2O2) production and FeIII reduction seriously limited the reaction kinetics. Here, we develop a two‐electron water oxidative H2O2 production (WOR−H2O2) coupled with FeIII reduction over a FeIII/BiOIO3 piezo‐catalyst for highly efficient PSF. It is found that the presence of FeIII can simultaneously initiate the WOR−H2O2 and reduction of FeIII to FeII, thereby enabling a rapid reaction kinetics towards subsequent Fenton reaction of H2O2/FeII. The FeIII initiating PSF system offers exceptional self‐recyclable degradation of pollutants with a degradation rate constant for sulfamethoxazole (SMZ) over 3.5 times as that of the classic FeII‐PSF system. This study offers a new perspective for constructing efficient PSF systems and shatters the preconceived notion of FeIII in the Fenton reaction. [ABSTRACT FROM AUTHOR]

Reducible oxide‐supported noble metal nanoparticles exhibit high activity in catalyzing many important oxidation reactions. However, atom migration under harsh reaction conditions leads to deactivation of the catalyst. Meanwhile, single‐atom catalysts demonstrate enhanced stability, but often suffer from poor catalytic activity owing to the ionized surface states. In this work, we simultaneously address the poor activity and stability issues by synthesizing highly active and durable rhodium (Rh) single‐atom catalysts through a "wrap‐bake‐peel" process. The pre‐coated SiO2 layer during synthesis of catalyst plays a crucial role in not only protecting CeO2 support against sintering, but also donating electron to weaken the Ce−O bond, producing highly loaded Rh single atoms on the CeO2 support exposed with high‐index {210} facets. Benefiting from the unique electronic structure of CeO2 {210} facets, more oxygen vacancies are generated along with the deposition of more electropositive Rh single atoms, leading to remarkably improved catalytic performance in CO oxidation. [ABSTRACT FROM AUTHOR]

Exploring high‐efficiency and stable halide perovskite‐based photocatalysts for the selective reduction of CO2 to methane is a challenge because of the intrinsic photo‐ and chemical instability of halide perovskites. In this study, halide perovskites (Cs3Bi2Br9 and Cs2AgBiBr6) were grown in situ in mesoporous TiO2 frameworks for an efficient CO2 reduction. Benchmarked CH4 production rates of 32.9 and 24.2 μmol g−1 h−1 with selectivities of 88.7 % and 84.2 %, were achieved, respectively, which are better than most reported halide perovskite photocatalysts. Focused ion‐beam sliced‐imaging techniques were used to directly image the hyperdispersed perovskite nanodots confined in mesopores with tunable sizes ranging from 3.8 to 9.9 nm. In situ X‐ray photoelectronic spectroscopy and Kelvin probe force microscopy showed that the built‐in electric field between the perovskite nanodots and mesoporous titania channels efficiently promoted photo‐induced charge transfer. Density functional theory calculations indicate that the high methane selectivity was attributed to the Bi‐adsorption‐mediated hydrogenation of *CO to *HCO that dominates CO desorption. [ABSTRACT FROM AUTHOR]

Heat‐induced blueshift (HIB) observed in many luminescent materials is a puzzling phenomenon that has remained unexplained for decades. By using the high‐throughput first‐principles calculations and energy‐screening techniques, we generated a number of model structures for five phosphors, RbLi[Li3SiO4]2:Eu2+, Na[Li3SiO4]:Eu2+, K[Li3SiO4]:Eu2+, Sr[LiAl3N4]:Eu2+, and Ca[LiAl3N4]:Eu2+. Our analyses suggest, to a first approximation, a logarithmic energy dependence on the nearest distance between the dopant and the metal‐cation vacancy. By identifying the 5d→4f transition energies from the electronic structures calculated for the screened model structures, we show that the vibration of the Eu2+ ion lying in an asymmetric and anharmonic potential well couples with the electronic states, leading to their HIB phenomena. [ABSTRACT FROM AUTHOR]

Precise control of in vivo transport of anticancer drugs in normal and cancerous tissues with engineered nanoparticles is key to the future success of cancer nanomedicines in clinics. This requires a fundamental understanding of how engineered nanoparticles impact the targeting‐clearance and permeation‐retention paradoxes in the anticancer‐drug delivery. Herein, we systematically investigated how renal‐clearable gold nanoparticles (AuNPs) affect the permeation, distribution, and retention of the anticancer drug doxorubicin in both cancerous and normal tissues. Renal‐clearable AuNPs retain the advantages of the free drug, including rapid tumor targeting and high tumor vascular permeability. The renal‐clearable AuNPs also accelerated body clearance of off‐target drug via renal elimination. These results clearly indicate that diverse in vivo transport behaviors of engineered nanoparticles can be used to reconcile long‐standing paradoxes in the anticancer drug delivery. [ABSTRACT FROM AUTHOR]

With more and more engineered nanoparticles (NPs) being translated to the clinic, the United States Food and Drug Administration (FDA) has recently issued the latest draft guidance on nanomaterial‐containing drug products with an emphasis on understanding their in vivo transport and nano–bio interactions. Following these guidelines, NPs can be designed to target and treat diseases more efficiently than small molecules, have minimum accumulation in normal tissues, and induce minimum toxicity. In this Minireview, we integrate this guidance with our ten‐year studies on developing renal clearable luminescent gold NPs. These gold NPs resist serum protein adsorption, escape liver uptake, target cancerous tissues, and report kidney dysfunction at early stages. At the same time, off‐target gold NPs can be eliminated by the kidneys with minimum accumulation in the body. Additionally, we identify challenges to the translation of renal clearable gold NPs from the bench to the clinic. NPs get clearance: Animal studies of renal clearable gold nanoparticles from the Zheng group in the past decade are revisited from the viewpoint of in vivo transport of nanoparticles and nano–bio interactions in tissues/organs. Additionally, these results are integrated with the latest FDA guidance on nanomedicines. [ABSTRACT FROM AUTHOR]

While dose dependencies in pharmacokinetics and clearance are often observed in clinically used small molecules, very few studies have been dedicated to the understandings of potential dose-dependent in vivo transport of nanomedicines. Here we report that the pharmacokinetics and clearance of renal clearable gold nanoparticles (GS-AuNPs) are strongly dose-dependent once injection doses are above 15 mg kg−1: high dose expedited the renal excretion and shortened the blood retention. As a result, the no-observed-adverse-effect-level (NOAEL) of GS-AuNPs was >1000 mg kg−1 in CD-1 mice. The efficient renal clearance and high compatibility can be translated to the non-human primates: no adverse effects were observed within 90 days after intravenous injection of 250 mg kg−1 GS-AuNPs. These fundamental understandings of dose effect on the in vivo transport of ultrasmall AuNPs open up a pathway to maximize their biomedical potentials and minimize their toxicity in the future clinical translation. [ABSTRACT FROM AUTHOR]

With more and more engineered nanoparticles (NPs) being designed renal clearable for clinical translation, fundamental understanding of their transport in the different compartments of kidneys becomes increasingly important. Here, we report noninvasive X-ray imaging of renal clearable gold NPs (AuNPs) in normal and nephropathic kidneys. By quantifying the transport kinetics of the AuNPs in cortex, medulla and pelvis of the normal and injured kidneys, we found that ureteral obstruction not just blocked the NP elimination through the ureter but also slowed down their transport from the medulla to pelvis and enhanced the cellular uptake. Moreover, the transport kinetics of the NPs and renal anatomic details can be precisely correlated with local pathological lesion. These findings not only advance our understandings of the nano-bio interactions in kidneys but also offer a new pathway to noninvasively image kidney dysfunction and local injuries at the anatomical level. [ABSTRACT FROM AUTHOR]

Sessile organisms have undergone long-term evolution to develop the unique ability by positioning themselves on wet solid surface through secreting adhesive proteins. The present study reveals that natural amino acid monomers can also exhibit similar adhesion capacity. This kind of biomimetic adhesives were created by the one-step aqueous assembly of basic amino acids with assistance of anionic polyoxometalates. The polyoxometalates not only serve as multivalent scaffold to initiate the supramolecular cross-linking of amino acid molecules, but also function as a redox component, bestowing the wet adhesives with electrochromic features. [ABSTRACT FROM AUTHOR]

Neurodegenerative diseases and spinal cord injury affect approximately 50 million people worldwide, bringing the total healthcare cost to over 600 billion dollars per year. Nervous system growth factors, that is, neurotrophins, are a potential solution to these disorders, since they could promote nerve regeneration. An average of 500 publications per year attests to the significance of neurotrophins in biomedical sciences and underlines their potential for therapeutic applications. Nonetheless, the poor pharmacokinetic profile of neurotrophins severely restricts their clinical use. On the other hand, small molecules that modulate neurotrophic activity offer a promising therapeutic approach against neurological disorders. Nature has provided an impressive array of natural products that have potent neurotrophic activities. This Review highlights the current synthetic strategies toward these compounds and summarizes their ability to induce neuronal growth and rehabilitation. It is anticipated that neurotrophic natural products could be used not only as starting points in drug design but also as tools to study the next frontier in biomedical sciences: the brain activity map project. [ABSTRACT FROM AUTHOR]

Particle replication in nonwetting templates (PRINT) is a continuous, roll-to-roll, high-resolution molding technology which allows the design and synthesis of precisely defined micro- and nanoparticles. This technology adapts the lithographic techniques from the microelectronics industry and marries these with the roll-to-roll processes from the photographic film industry to enable researchers to have unprecedented control over particle size, shape, chemical composition, cargo, modulus, and surface properties. In addition, PRINT is a GMP-compliant (GMP=good manufacturing practice) platform amenable for particle fabrication on a large scale. Herein, we describe some of our most recent work involving the PRINT technology for application in the biomedical and material sciences. [ABSTRACT FROM AUTHOR]

We report here a tumor‐pretargted theranostic approach for multimodality imaging‐guided synergistic cancer PDT by cascade alkaline phosphatase (ALP)‐mediated in situ self‐assembly and bioorthogonal inverse electron demand Diels–Alder (IEDDA) reaction. Using the enzymatic catalysis of ALP that continuously catalyses the dephosphorylation and self‐assembly of trans‐cyclooctene (TCO)‐bearing P‐FFGd‐TCO, a high density of fluorescent and magnetic TCO‐containing nanoparticles (FMNPs‐TCO) can be synthesized and retained on the membrane of tumor cells. They can act as 'artificial antigens' amenable to concurrently capture lately administrated tetrazine (Tz)‐decorated PS (775NP‐Tz) and carbonic anhydrase (CA) inhibitor (SA‐Tz) via the fast IEDDA reaction. This two‐step pretargeting process can further induce FMNPs‐TCO regrowth into microparticles (FMNPs‐775/SA) directly on tumor cell membranes, which is analyzed by bio‐SEM and fluorescence imaging. Thus, efficient enrichment of both SA‐Tz and 775NP‐Tz in tumors can be achieved, allowing to alleviate hypoxia by continuously inhibiting CA activity and improving PDT of tumors. Findings show that subcutaneous HeLa tumors could be completely eradicated and no tumor recurred after irradiation with an 808 nm laser (0.33 W cm−2, 10 min). This pretargeted approach may be applied to enrich other therapeutic agents in tumors to improve targeted therapy. [ABSTRACT FROM AUTHOR]

The transport behavior of ions in the nanopores has an important impact on the performance of the electrochemical devices. Although the classical Transmission‐Line (TL) model has long been used to describe ion transport in pores, the boundary conditions for the applicability of the TL model remain controversial. Here, we investigated the transport kinetics of different ions, within nanochannels of different lengths, by using transient single‐particle imaging with temporal resolution up to microseconds. We found that the ion transport kinetics within short nanochannels may deviate significantly from the TL model. The reason is that the ion transport under nanoconfinement is composed of multi basic stages, and the kinetics differ much under different stage domination. With the shortening of nanochannels, the electrical double layer (EDL) formation would become the "rate‐determining step" and dominate the apparent ion kinetics. Our results imply that using the TL model directly and treating the in‐pore mobility as an unchanged parameter to estimate the ion transport kinetics in short nanopores/nanochannels may lead to orders of magnitude bias. These findings may advance the understanding of the nanoconfined ion transport and promote the related applications. [ABSTRACT FROM AUTHOR]

High‐resolution in vivo optical multiplexing in second near‐infrared window (NIR‐II, 1000–1700 nm) is vital to biomedical research. Presently, limited by bio‐tissue scattering, only luminescent probes located at NIR‐IIb (1500–1700 nm) window can provide high‐resolution in vivo multiplexed imaging. However, the number of available luminescent probes in this narrow NIR‐IIb region is limited, which hampers the available multiplexed channels of in vivo imaging. To overcome the above challenges, through theoretical simulation we expanded the conventional NIR‐IIb window to NIR‐II long‐wavelength (NIR‐II‐L, 1500–1900 nm) window on the basis of photon‐scattering and water‐absorption. We developed a series of novel lanthanide luminescent nanoprobes with emission wavelengths from 1852 nm to 2842 nm. NIR‐II‐L nanoprobes enabled high‐resolution in vivo dynamic multiplexed imaging on blood vessels and intestines, and provided multi‐channels imaging on lymph tubes, tumors and intestines. The proposed NIR‐II‐L probes without mutual interference are powerful tools for high‐contrast in vivo multiplexed detection, which holds promise for revealing physiological process in living body. [ABSTRACT FROM AUTHOR]

Single‐cell epigenetics is envisioned to decipher manifold epigenetic phenomena and to contribute to our accurate knowledge about basic epigenetic mechanisms. Engineered nanopipette technology has gained momentum in single‐cell studies; however, solutions to epigenetic questions remain unachieved. This study addresses the challenge by exploring N6‐methyladenine (m6A)‐bearing deoxyribozyme (DNAzyme) confined within a nanopipette for profiling a representative m6A‐modifying enzyme, fat mass and obesity‐associated protein (FTO). Electroosmotic intracellular extraction of FTO could remove the m6A and cause DNAzyme cleavage, leading to the altered ionic current signal. Because the cleavage can release a DNA sequence, we simultaneously program it as an antisense strand against FTO‐mRNA, intracellular injection of which has been shown to induce early stage apoptosis. This nanotool thus features the dual functions of studying single‐cell epigenetics and programmable gene regulation. [ABSTRACT FROM AUTHOR]

Cuproptosis is a new form of programmed cell death and exhibits enormous potential in cancer treatment. However, reducing the undesirable Cu ion release in normal tissue and maximizing the copper‐induced therapeutic effect in cancer sites are two main challenges. In this study, we constructed a photothermally triggered nanoplatform (Au@MSN‐Cu/PEG/DSF) to realize on‐demand delivery for synergistic therapy. The released disulfiram (DSF) chelated with Cu2+ in situ to generate highly cytotoxic bis(diethyldithiocarbamate)copper (CuET), causing cell apoptosis, and the formed Cu+ species promoted toxic mitochondrial protein aggregation, leading to cell cuproptosis. Synergistic with photothermal therapy, Au@MSN‐Cu/PEG/DSF could effectively kill tumor cells and inhibit tumor growth (inhibition rate up to 80.1 %). These results provide a promising perspective for potential cancer treatment based on cuproptosis, and may also inspire the design of advanced nano‐therapeutic platforms. [ABSTRACT FROM AUTHOR]

Single‐cell protein therapeutics is expected to promote our in‐depth understanding of how a specific protein with a therapeutic dosage treats the cell without population averaging. However, it has not yet been tackled by current single‐cell nanotools. We address this challenge by the use of a double‐barrel nanopipette, in which one lumen was used for electroosmotic cytosolic protein delivery and the other was customized for ionic evaluation of the consequence. Upon injection of protein DJ‐1 through the delivery lumen, upregulation of the antioxidant protein could protect neural PC‐12 cells against oxidative stress from phorbol myristate acetate exposure, as deduced by targeting of the cytosolic hydrogen peroxide by the detecting lumen. The nanotool developed in this study for single‐cell protein therapeutics provides a perspective for future single‐cell therapeutics involving different therapeutic modalities, such as peptides, enzymes and nucleic acids. [ABSTRACT FROM AUTHOR]

Abstract: The site‐selective functionalization of unactivated C(sp3)−H bonds remains one of the greatest challenges in organic synthesis. Herein, we report on the site‐selective δ‐C(sp3)−H alkylation of amino acids and peptides with maleimides via a kinetically less favored six‐membered palladacycle in the presence of more accessible γ‐C(sp3)−H bonds. Experimental studies revealed that C−H bond cleavage occurs reversibly and preferentially at γ‐methyl over δ‐methyl C−H bonds while the subsequent alkylation proceeds exclusively at the six‐membered palladacycle that is generated by δ‐C−H activation. The selectivity can be explained by the Curtin–Hammett principle. The exceptional compatibility of this alkylation with various oligopeptides renders this procedure valuable for late‐stage peptide modifications. Notably, this process is also the first palladium(II)‐catalyzed Michael‐type alkylation reaction that proceeds through C(sp3)−H activation. [ABSTRACT FROM AUTHOR]

Rational utilization of the rich light‐bio‐matter interplay taking place in single‐cell analysis represents a new technological direction in the field. The light‐fueled operation is expected to achieve advanced photoelectrochemical (PEC) single‐cell analysis with unknown possibilities. Here, a PEC nanoreactor capable of single‐cell sampling and near zero‐background Faradaic detection of intracellular microRNA (miR) is devised by the construction of a small reaction chamber accommodating the target‐triggered hybridization chain reaction for binding the metallointercalator of [Ru(bpy)2(dppz)]2+ as the signal reporter. Light stimulation of the dsDNA/metallointercalator adduct will induce the generation of photocurrents, underpinning a zero‐biased and near zero‐background PEC method toward Faradaic detection of non‐electrogenic miR at the single‐cell level. Using this nanotool, lower miR concentration in the near‐nucleus region than that in the main cytosol was revealed. [ABSTRACT FROM AUTHOR]

Identifying key factors that govern the in vivo behavior of nanomaterials is critical to the clinical translation of nanomedicines. Overshadowed by size-, shape-, and surface-chemistry effects, the impact of the particle core density on clearance and tumor targeting of inorganic nanoparticles (NPs) remains largely unknown. By utilizing a class of ultrasmall metal NPs with the same size and surface chemistry but different densities, we found that the renal-clearance efficiency exponentially increased in the early elimination phase while passive tumor targeting linearly decreased with a decrease in particle density. Moreover, lower-density NPs are more easily distributed in the body and have shorter retention times in highly permeable organs than higher-density NPs. The density-dependent in vivo behavior of metal NPs likely results from their distinct margination in laminar blood flow, which opens up a new path for precise control of nanomedicines in vivo. [ABSTRACT FROM AUTHOR]

Electrochemical splitting of water to produce hydrogen and oxygen is an important process for many energy storage and conversion devices. Developing efficient, durable, low-cost, and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is of great urgency. To achieve the rapid synthesis of transition-metal nitride nanostructures and improve their electrocatalytic performance, a new strategy has been developed to convert cobalt oxide precursors into cobalt nitride nanowires through N2 radio frequency plasma treatment. This method requires significantly shorter reaction times (about 1 min) at room temperature compared to conventional high-temperature NH3 annealing which requires a few hours. The plasma treatment significantly enhances the OER activity, as evidenced by a low overpotential of 290 mV to reach a current density of 10 mA cm−2, a small Tafel slope, and long-term durability in an alkaline electrolyte. [ABSTRACT FROM AUTHOR]

The human brain is an incredibly complex network of neurons that controls life, thoughts, and emotion. Age‐ or disease‐related neural degeneration leads to breakdown of this network, incapacitating the affected individual. Certain natural products can induce outgrowth of neurites, the bridges that allow cell–cell communication in the brain, and so restore the neuronal web. E. A. Theodorakis et al. summarize in their Review on page 956 ff. recent advances in the synthesis of these molecules and highlight their potential as tools for studying neuronal web structure and function. [ABSTRACT FROM AUTHOR]

We report a photodynamic therapy driven by electrochemiluminescence (ECL). The luminescence generated by Ru(bpy)32+ and co‐reactant tripropylamine (TPA) pair acts as both optical readout for ECL imaging, and light source for the excitation of photosensitizer to produce reactive oxygen species (ROS) in photodynamic therapy (PDT) system. The ECL‐driven PDT (ECL‐PDT) relies on the effective energy transfer from ECL emission to photosensitizer chlorin e6 (Ce6), which sensitizes the surrounding O2 into ROS. The dynamic process of gradual morphological changes, the variation of cell‐matrix adhesions, as well as the increase of cell membrane permeability in the process of ECL‐PDT were monitored under ECL microscopy (ECLM) with good spatiotemporal resolution. Combining real‐time imaging with ECL‐PDT, this new strategy provides not only new insights into dynamic cellular processes, but also promising potential of ECL in clinical applications. [ABSTRACT FROM AUTHOR]

Single‐nanoparticle electrochemistry offers electrochemical behaviors of individual entities beyond the ensemble system. An electric double layer (EDL) exists on any charged particle–liquid interface because of counter‐ion accumulation, while direct measuring of the interfacial ion migration remains a challenge. Herein, a plasmonic‐based transient microscopic method, with a temporal resolution of 1–2 μs, was demonstrated to directly track the ion migration dynamics on single charged nanoparticles. We found that the dynamics of EDL formation might deviate significantly from the prediction made by using the classical resistance–capacitance (RC) model under nanoscale and transient conditions. Under ultrafast charging, due to the limit migration rate of ions in the solution, the actual time scale of the EDL formation could be up to 5 times slower than the predicted value from the RC model. We then proposed a new theoretical model to describe the transient dynamics of EDL formation. These results may expand our current knowledge about nano‐electrochemistry and transient electrochemistry. [ABSTRACT FROM AUTHOR]

An efficient method for the diastereo- and enantioselective construction of vicinal all-carbon quaternary stereocenters through palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with activated Michael acceptors was developed. By using a palladium complex generated in situ from [Pd2(dab)3]⋅CHCl3 and a phosphoramidite ligand as a catalyst under mild reaction conditions, the process provides multifunctionalized tetrahydrofurans bearing vicinal all-carbon quaternary stereocenters in high yields with a high level of absolute and relative stereocontrol. [ABSTRACT FROM AUTHOR]

With reduced background and high sensitivity, photoelectrochemistry (PEC) may be applied as an intracellular nanotool and open a new technological direction of single‐cell study. Nevertheless, the present palette of single‐cell tools lacks such a PEC‐oriented solution. Here a dual‐functional photocathodic single‐cell nanotool capable of direct electroosmotic intracellular drug delivery and evaluation of oxidative stress is devised by engineering a target‐specific organic molecule/NiO/Ni film at the tip of a nanopipette. Specifically, the organic molecule probe serves simultaneously as the biorecognition element and sensitizer to synergize with p‐type NiO. Upon intracellular delivery at picoliter level, the oxidative stress effect will cause structural change of the organic probe, switching its optical absorption and altering the cathodic response. This work has revealed the potential of PEC single‐cell nanotool and extended the boundary of current single‐cell electroanalysis. [ABSTRACT FROM AUTHOR]

One of the most pressing challenges in single‐atom catalysis is the manipulation of the coordination environment of central metals to maximize the catalyst performance. Herein, we fabricated a high‐performance catalyst (Co‐SNC) by introducing S into the neighboring position of the Co‐N4 coordination. The developed ball‐milling method enabled large‐scale synthesis, that over 4.7 g of Co‐SNC can be produced in one pot. In benzylamine coupling reaction, Co‐SNC exhibited the highest conversion of 97.5 % with 99 % selectivity toward N‐benzylidenebenzylamine in 10 h among various Co catalysts. Density functional theory calculations revealed the crucial role of S atoms, which serve as the active sites for O2 activation, leaving the Co atoms free to adsorb benzylamine. Consequently, the adsorption energies of O2 and benzylamine were significantly increased. Our strategy suggests a feasible approach to enhance catalytic performance by delicately integrating dual active sites into a single catalyst unit. [ABSTRACT FROM AUTHOR]

A novel mass spectrometric method for probing the flash chemistry of electrogenerated reactive intermediates was developed based on rapid collision mixing of electrosprayed microdroplets by using a theta‐glass capillary. The two individual microchannels of the theta‐glass capillary are asymmetrically or symmetrically fabricated with a carbon bipolar electrode to produce intermediates in situ. Microdroplets containing the newly formed intermediates collide with those of the invoked reactants at sub‐10 microsecond level, making it a powerful tool for exploring their ultrafast initial transformations. As a proof‐of‐concept, we present the identification of the key radical cation intermediate in the oxidative dimerization of 8‐methyl‐1,2,3,4‐tetrahydroquinoline and also the first disclosure of previously hidden nitrenium ion involved reaction pathway in the C−H/N−H cross‐coupling between N,N′‐dimethylaniline and phenothiazine. [ABSTRACT FROM AUTHOR]

New tools for single‐cell interrogation enable deeper understanding of cellular heterogeneity and associated cellular behaviors and functions. Information of RNA expression in single cell could contribute to our knowledge of the genetic regulatory circuits and molecular mechanism of disease development. Although significant progresses have been made for intracellular RNA analysis, existing methods have a trade‐off between operational complexity and practical feasibility. We address this challenge by combining the ionic current rectification property of nanopipette reactor with duplex‐specific nuclease‐assisted hybridization chain reaction for signal amplification to realize a simple and practical intracellular nanosensor with minimal invasiveness, which enables single‐cell collection and electrochemical detection of intracellular RNA with cell‐context preservation. Systematic studies on differentiation of oncogenic miR‐10b expression levels in non‐malignant breast cells, metastatic breast cancer cells as well as non‐metastatic breast cancer cells were then realized by this nanotool accompanied by assessment of different drugs effects. This work has unveiled the ability of electrochemistry to probe intracellular RNA and opened new opportunities to study the gene expression and heterogeneous complexity under physiological conditions down to single‐cell level. [ABSTRACT FROM AUTHOR]

We report a new mass spectrometric method for detecting electrogenerated intermediates. This approach is based on simultaneous activation of electrospray ionization and redox reaction on a wireless bipolar ultramicroelectrode, which is fabricated in the tip of a quartz nanopipette. The hollow structure of the ultramicroelectrode permits rapid transferring the transient species from electrode–electrolyte interfaces into the gas phase for mass spectrometric identification on the time scale of microseconds. The long‐sought fleeting intermediates including TPrA.+, whose lifetime in solution is only 200 μs, and catecholamine o‐semiquinone radicals, the second‐order rate constant of which is typically 109 m−1 s−1, were successfully identified, helping clarify the previously hidden reaction pathways. Accordingly, our method may have wide applicability in exploring the dynamics of many electrochemical reactions, especially their ultrafast initial steps. [ABSTRACT FROM AUTHOR]

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine] from ring‐opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co−O bond, allowing for in situ transformation of the ROCOP active species (Salen)CoIII‐OR into the OMRP photoinitiator (Salen)CoIII‐CO2R. The proposed mechanism, which involves CO coordination to (Salen)CoIII‐OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on‐demand sequence control can be achieved for the one‐pot synthesis of polyester‐b‐polyacrylate diblock copolymers (Đ<1.15). [ABSTRACT FROM AUTHOR]

The commercial high‐temperature water‐gas shift (HT‐WGS) catalyst consists of CuO‐Cr2O3‐Fe2O3, where Cu functions as a chemical promoter to increase the catalytic activity, but its promotion mechanism is poorly understood. In this work, a series of iron‐based model catalysts were investigated with in situ or pseudo in situ characterization, steady‐state WGS reaction, and density function theory (DFT) calculations. For the first time, a strong metal‐support interaction (SMSI) between Cu and FeOx was directly observed. During the WGS reaction, a thin FeOx overlayer migrates onto the metallic Cu particles, creating a hybrid surface structure with Cu‐FeOx interfaces. The synergistic interaction between Cu and FeOx not only stabilizes the Cu clusters, but also provides new catalytic active sites that facilitate CO adsorption, H2O dissociation, and WGS reaction. These new fundamental insights can potentially guide the rational design of improved iron‐based HT‐WGS catalysts. [ABSTRACT FROM AUTHOR]

The commercial high‐temperature water‐gas shift (HT‐WGS) catalyst consists of CuO‐Cr2O3‐Fe2O3, where Cu functions as a chemical promoter to increase the catalytic activity, but its promotion mechanism is poorly understood. In this work, a series of iron‐based model catalysts were investigated with in situ or pseudo in situ characterization, steady‐state WGS reaction, and density function theory (DFT) calculations. For the first time, a strong metal‐support interaction (SMSI) between Cu and FeOx was directly observed. During the WGS reaction, a thin FeOx overlayer migrates onto the metallic Cu particles, creating a hybrid surface structure with Cu‐FeOx interfaces. The synergistic interaction between Cu and FeOx not only stabilizes the Cu clusters, but also provides new catalytic active sites that facilitate CO adsorption, H2O dissociation, and WGS reaction. These new fundamental insights can potentially guide the rational design of improved iron‐based HT‐WGS catalysts. [ABSTRACT FROM AUTHOR]

The daphniphyllum alkaloids are a structurally fascinating and remarkably diverse family of natural products. General strategies for the chemical synthesis of their challenging architectures are highly desirable for efficiently accessing these intriguing alkaloids and addressing their pharmaceutical potential. Herein, a concise strategy designed to provide general and diversifiable access to various daphniphyllum alkaloids is described and utilized in the asymmetric synthesis of (−)‐himalensine A, which was accomplished in 14 steps. Key features of this strategy include a Cu‐catalyzed nitrile hydration, a Heck reaction to construct the challenging 2‐azabicyclo[3.3.1]nonane motif, a Meinwald rearrangement reaction, six, pot‐economic reactions, and the minimal use of protecting groups, which significantly improved the overall synthetic efficiency. [ABSTRACT FROM AUTHOR]

Molecular complexes with inexpensive transition‐metal centers have drawn extensive attention, as they show a high selectivity in the electrochemical conversion of CO2 to CO. In this work, we propose a new strategy to covalently graft cobalt porphyrin onto the surface of a carbon nanotube by a substitution reaction at the metal center. Material characterization and electrochemical studies reveal that the porphyrin molecules are well dispersed at a high loading of 10 wt. %. As a result, the turnover frequency for CO formation is improved by a factor of three compared to traditional physically‐mixed catalysts with the same cobalt content. This leads to an outstanding overall current density of 25.1 mA cm−2 and a Faradaic efficiency of 98.3 % at 490 mV overpotential with excellent long‐term stability. This work provides an effective pathway for the improvement of the performance of electrocatalysts that could inspire rational design of molecular catalysts in the future. [ABSTRACT FROM AUTHOR]

The aggregation‐induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane‐free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds show a reductive–oxidative mechanism in contrast to other organic materials that show oxidative–reductive mechanisms. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications. Carborane‐based AIEgens: The reductive–oxidative aggregation‐induced electrochemiluminescence (AIECL) of carboranyl carbazoles in air‐saturated aqueous media was investigated. Mechanistic studies indicate that the carboranyl motif plays vital role in the high ECL intensity and stability of the aggregates. [ABSTRACT FROM AUTHOR]

Abstract: Ionic current rectification (ICR) based nanopipettes allow accurate monitoring of cellular behavior in single living cells. Herein, we proposed a 30 nm nanopipette functionalized with G‐quadruplex DNAzyme as an efficient biomimetic recognizer for ROS generation at subcellular level via the changes of current–voltage relationship. Taking advantages of the ultra‐small tip, the nanopipette could penetrate into a single living cell repeatedly or keep measuring for a long time without compromising the cellular functions. Coupled with precision nanopositioning system, generation of ROS in mitochondria in response to cell inflammation was determined with high spatial resolution. Meanwhile, the changes of aerobic metabolism in different cell lines under drug‐induced oxidative stress were monitored continuously. We believe that the ICR‐nanopipette could be developed as a powerful approach for the study of cellular activities via electrochemical imaging in living cells. [ABSTRACT FROM AUTHOR]

Abstract: Noble metal nanoparticles are promising catalysts in electrochemical reactions, while understanding the relationship between the structure and reactivity of the particles is important to achieve higher efficiency of electrocatalysis, and promote the development of single‐molecule electrochemistry. Electrogenerated chemiluminescence (ECL) was employed to image the catalytic oxidation of luminophore at single Au, Pt, and Au‐Pt Janus nanoparticles. Compared to the monometal nanoparticles, the Janus particle structure exhibited enhanced ECL intensity and stability, indicating better catalytic efficiency. On the basis of the experimental results and digital simulation, it was concluded that a concentration difference arose at the asymmetric bimetallic interface according to different heterogeneous electron‐transfer rate constants at Au and Pt. The fluid slip around the Janus particle enhanced local redox reactions and protected the particle surface from passivation. [ABSTRACT FROM AUTHOR]

Abstract: A nearly‐30‐year‐old unanswered synthetic puzzle, astellatol, has been solved in an enantiospecific manner. The highly congested pentacyclic skeleton of this rare sesterterpenoid, which possesses a unique bicyclo[4.1.1]octane motif, ten stereocenters, a cyclobutane that contains two quaternary centers, an exo‐methylene group, and a sterically encumbered isopropyl trans‐hydrindane motif, makes astellatol arguably one of the most challenging targets for sesterterpenoid synthesis. An intramolecular Pauson–Khand reaction was exploited to construct the right‐hand side scaffold of this sesterterpenoid. An unprecedented reductive radical 1,6‐addition, mediated by SmI2, forged the cyclobutane motif. Last, a strategic oxidation/reduction step provided not only the decisive solution for the remarkably challenging late‐stage transformations, but also a highly valuable unravelling of the notorious issue of trans‐hydrindane synthesis. Importantly, the synthesis of astellatol showcases a rapid, scalable strategy to access diverse complex isopropyl trans‐hydrindane sesterterpenoids. [ABSTRACT FROM AUTHOR]

A crack-free sub-nanometer composite structure for the study of ion transfer was constructed by in situ growth of ZIF-90 [Zn(ICA)2, ICA=Imidazole-2-carboxaldehyde] on the tip of a glass nanopipette. The potential-driven ion transfer through the sub-nanometer channels in ZIF-90 is strongly influenced by the pH of the solution. A rectification ratio over 500 is observed in 1 m KCl solution under alkaline conditions (pH 11.58), which is the highest value reported under such a high salt concentration. Fluorescence experiments show the super-high rectification ratio under alkaline conditions results from the strong electrostatic interaction between ions and the sub-nanometer channels of ZIF-90. In addition to providing a general pathway for further study of mass-transfer process through sub-nanometer channels, the approach enable all kinds of metal-organic frameworks (MOFs) to be used as ionic permselectivity materials in nanopore-based analysis. [ABSTRACT FROM AUTHOR]

A correction to the article "Palladium-Catalyzed Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Michael Acceptors: Construction of Vicinal Quaternary Stereocenters" that was published in the 2014 issue is presented.

The selective generation of covalent bonds between and within proteins would provide new avenues for studying protein function and engineering proteins with new properties. New covalent bonds were genetically introduced into proteins by enabling an unnatural amino acid (Uaa) to selectively react with a proximal natural residue. This proximity-enabled bioreactivity was expanded to a series of haloalkane Uaas. Orthogonal tRNA/synthetase pairs were evolved to incorporate these Uaas, which only form a covalent thioether bond with cysteine when positioned in close proximity. By using the Uaa and cysteine, spontaneous covalent bond formation was demonstrated between an affibody and its substrate Z protein, thereby leading to irreversible binding, and within the affibody to increase its thermostability. This strategy of proximity-enabled protein crosslinking (PEPC) may be generally expanded to target different natural amino acids, thus providing diversity and flexibility in covalent bond formation for protein research and protein engineering. [ABSTRACT FROM AUTHOR]

Electrochemistry, Hybridization Chain Reaction, Nanopipette, RNA, Single Cell Analysis Keywords: Electrochemistry; Hybridization Chain Reaction; Nanopipette; RNA; Single Cell Analysis EN Electrochemistry Hybridization Chain Reaction Nanopipette RNA Single Cell Analysis 1 1 1 06/05/21 20210607 NES 210607 B Single-Cell Analysis b A duplex-specific nuclease-assisted nanopipette was fabricated in the Research Article on page 13244 by Wei-Wei Zhao, Jing-Juan Xu et al. for tracking the drug-induced variation of miR-10b levels at single-cell level. [Extracted from the article]