Correction: Ion pair extractant selective for LiCl and LiBr.

[This corrects the article DOI: 10.1039/D4SC03760J.].

Making an inverted Keggin ion lacunary.

The century-old inverted Keggin ion has been revisited in an effort to unleash its potential in the structural engineering and functional development of polyoxomolybdates (POMos). Over the past hundred years, attempts to program the metal-oxo scaffold of inverted Keggins have been conducted continually but without any success. In this work, a structurally inert, inverted Keggin-type POMo could finally be altered by means of a binary heterogroup-templated approach, resulting in the successful isolation of two lacunary species.

Stabilized four-electron aqueous zinc-iodine batteries by quaternary ammonium complexation.

Four-electron aqueous zinc-iodine batteries (4eZIBs) leveraging the I/I/I redox couple have garnered attention for their potential high voltage, capacity, and energy density. However, the electrophilic I species is highly susceptible to hydrolysis due to the nucleophilic attack by water. Previous endeavors to develop 4eZIBs primarily relied on highly concentrated aqueous electrolytes to mitigate the hydrolysis issue, nonetheless, it introduced challenges associated with dissolution, high electrolyte viscosity, and sluggish electrode kinetics.

Xanthene-based near-infrared chromophores for high-contrast fluorescence and photoacoustic imaging of dipeptidyl peptidase 4.

Near-infrared (NIR) chromophores with analyte tunable emission and absorption properties are highly desirable for developing activatable fluorescence and photoacoustic (PA) probes for bioimaging and disease diagnosis. Here we engineer a class of new chromophores by extending the π-conjugation system of a xanthene scaffold at position 7 with different electron withdrawing groups. It is demonstrated that these chromophores exhibit pH-dependent transition from a spirocyclic "closed" form to a xanthene "open" form with remarkable changes in spectral properties.

A collagen-immobilized nanodevice for ratiometric imaging of cancer biomarkers in the tumor microenvironment.

Monitoring the spatiotemporal dynamics of cancer biomarkers within the tumor microenvironment (TME) is critical to understanding their roles in tumorigenesis. Here, we reported a multifunctional fusion protein (collagen-binding domain and duck circovirus tag fused to mCherry, CBD-mCherry-DCV) capable of binding collagen with high affinity and covalently binding specific nucleic acids with exceptional efficiency. We then constructed a chimeric protein-nucleic acid nanodevice (CPNN) using CBD-mCherry-DCV and an aptamer-based sensing module to enable spatially controlled ratiometric imaging of cancer biomarkers in the TME.

Engineering fluorescent protein chromophores with an internal reference for high-fidelity ratiometric G4 imaging in living cells.

G-quadruplexes (G4s) are significant nucleic acid secondary structures formed by guanine-rich sequences. Many single-emission G4 fluorescent probes that are lit up by inhibiting intramolecular rotation have been reported. However, they are non-fluorescent unless structurally rigidified, making them sensitive to other intracellular crowding and confinement environments in the cell, like viscosity.

Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction.

We report here a novel family of boraolympicenes, structurally featuring boron-doping at the concave 11a-position of their π-skeletons and synthetically prepared a facile one-pot triply borylation-based double-fold borocyclization reaction. Despite having no bulky protecting groups, these boraolympicenes exhibit excellent chemical stability against air and moisture, ascribed to the significant π-electron delocalization over the vacant p orbitals of boron atoms as evidenced by both single-crystallographic and theoretical analyses. More importantly, the modular synthesis of these boraolympicenes allows the fine-tuning of their physicochemical properties, endowing them with intriguing electronic features, such as intense visible-to-NIR absorption and low-lying LUMO energy levels (∼-3.

Bond modulation of MoSe driving combined intercalation and conversion reactions for high-performance K cathodes.

The urgent demand for large-scale global energy storage systems and portable electronic devices is driving the need for considerable energy density and stable batteries. Here, Se atoms are introduced between MoSe layers (denoted as MoSe ) by bond modulation to produce a high-performance cathode for potassium-ion batteries. The introduced Se atoms form covalent Se-Se bonds with the Se in MoSe, and the advantages of bond modulation are as follows: (i) the interlayer spacing is enlarged which increases the storage space of K; (ii) the system possesses a dual reaction mechanism, and the introduced Se can provide an additional conversion reaction when discharged to 0.

Membrane-tethered activation design of a photosensitizer boosts systemic antitumor immunity pyroptosis.

Pyroptotic immunogenic cell death presents an emerging targeting pathway for cancer immunotherapy. We report a novel membrane-tethered activation design of a photosensitizer (PS) that boosts systemic anti-tumor immunity to primary and distant tumors pyroptosis induction. The membrane-tethered PS is designed by installing a new phenylbenzopyrylium PS with zwitterionic lipid anchors and a target-cleavable caging moiety.

DTBP-mediated cross-dehydrogenative coupling of 3-aryl benzofuran-2(3)-ones with toluenes/phenols for all-carbon quaternary centers.

We have developed a transition-metal free protocol for efficient cross-dehydrogenative coupling of 3-aryl benzofuran-2(3)-ones and toluenes/phenols using DTBP as an oxidant. A diverse range of 3-aryl benzofuran-2(3)-ones, toluenes, and phenols undergo C-H bond cleavage to generate all-carbon quaternary centers in good yields, making this protocol useful for the synthesis of complex molecules. A gram scale experiment was performed in good yield.

Multifunctional stimuli-responsive chemogenetic platform for conditional multicolor cell-selective labeling.

Multicolor conditional labeling is a powerful tool that can simultaneously and selectively visualize multiple targets for bioimaging analysis of complex biological processes and cellular features. We herein report a multifunctional stimuli-responsive Fluorescence-Activating and absorption-Shifting Tag (srFAST) chemogenetic platform for multicolor cell-selective labeling. This platform comprises stimuli-responsive fluorogenic ligands and the organelle-localizable FAST.

Benzothiazole appended 2,2'-(1,4-phenylene)diacetonitrile for the colorimetric and fluorescence detection of cyanide ions.

A benzothiazole appended 2,2'-(1,4-phenylene)diacetonitrile derivative (2,2')-2,2'-(1,4-phenylene)bis(3-(3-(benzo[]thiazol-2-yl)-4-hydroxyphenyl)acrylonitrile) (PDBT) has been synthesized and investigated as a novel sensor, capable of showing high selectivity and sensitivity towards CN over a wide range of other interfering anions. After reaction with CN, PDBT shows a new absorption peak at 451 nm with a color transformation from colorless to reddish-brown. When yellow fluorescent PDBT is exposed to CN, it displays a significant increase in fluorescence at 445 nm, resulting in strong sky-blue fluorescence emission.

Multi-scale hybrid spherical graphite composites: a light weight thermal interface material with high thermal conductivity and simple processing technology.

In consideration of low density and high intrinsic thermal conductivity, spherical graphite powders can act as promising fillers for light weight thermal interface materials. Herein, spherical artificial graphite derived composites exhibit a similar thermal conductivity and significantly reduced bulk density compared with traditional AlO-derived composites. Further, based on the particle packing theory, an innovatively optimized calculation method has been proposed by introducing the quadratic programming method into the traditional calculation method to acquire the optimum formulation of multi-scale spherical graphite particles.

A stable and high-energy aqueous aluminum based battery.

Aqueous aluminum ion batteries (AAIBs) have received growing attention because of their low cost, safe operation, eco-friendliness, and high theoretical capacity. However, one of the biggest challenges for AAIBs is the poor reversibility due to the presence of an oxide layer and the accompanying hydrogen evolution reaction. Herein, we develop a strongly hydrolyzed/polymerized aluminum-iron hybrid electrolyte to improve the electrochemical behavior of AAIBs.

Covalent organic framework with sulfonic acid functional groups for visible light-driven CO reduction.

In this study, a covalent organic framework (TpPa-SOH) photocatalyst with sulfonic acid function groups was synthesized using a solvothermal method. The morphologies and structural properties of the as-prepared composites were characterized by X-ray diffraction, infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, N adsorption-desorption measurements, and field emission scanning electron microscopy. An electrochemical workstation was used to test the photoelectric performance of the materials.

Iron porphyrin-catalyzed -trifluoroethylation of anilines with 2,2,2-trifluoroethylamine hydrochloride in aqueous solution.

An iron porphyrin-catalyzed -trifluoroethylation of anilines has been developed with 2,2,2-trifluoroethylamine hydrochloride as the fluorine source. This one-pot N-H insertion reaction is conducted cascade diazotization/-trifluoroethylation reactions. The developed transformation can afford a wide range of -trifluoroethylated anilines in good yields using readily available primary amines and secondary anilines as starting materials.

A review of shape memory polymers based on the intrinsic structures of their responsive switches.

Shape memory polymers (SMPs), as stimuli-responsive materials, have attracted worldwide attention. Based on the history and development of SMPs, a variety of reports about SMPs in recent years are summarized in this paper. The responsive switches are analyzed and divided into two kinds according to their intrinsic structures: physical switch and chemical one.

A benzothiazole-based new fluorogenic chemosensor for the detection of CN and its real-time application in environmental water samples and living cells.

Since the cyanide ion is used in a wide range of industries and is harmful to both human health and the environment, a number of research efforts are dedicated to creating fluorescence sensors for the detection of cyanide (CN). Herein, for the fluorescence detection of CN, a new highly selective and sensitive sensor 2-(3-(benzo[]thiazol-2-yl)-4-hydroxybenzylidene)-1-indene-1,3(2)-dione (BID) was created by conjugating a benzothiazole moiety with 1-indene-1,3(2)-dione. The donor and acceptor components of this hybrid receptor were covalently connected through a double bond.

Highly sensitive naphthalimide based Schiff base for the fluorimetric detection of Fe.

A simple 1,8-naphthalimide based Schiff base probe ()-6-((4-(diethylamino)-2-hydroxybenzylidene)amino)-2-(2-morpholinoethyl)-1-benzo[de]isoquinoline-1,3(2)-dione (NDSM) has been designed and synthesized for the specific detection of Fe based on a fluorimetric mode. The absorbance of NDSM at 360 nm increased significantly in acetonitrile : water (7 : 3, v/v) medium only in the presence of Fe ions with a visible colour change from yellow to golden yellow. Likewise, fluorescence emission intensity at 531 nm was almost wholly quenched in the presence of Fe.

PAM-less conditional DNA substrates leverage trans-cleavage of CRISPR-Cas12a for versatile live-cell biosensing.

The CRISPR-Cas system has been repurposed as a powerful live-cell imaging tool, but its utility is limited to genomic loci and mRNA imaging in living cells. Here, we demonstrated the potential of the CRISPR-Cas system as a generalizable live-cell biosensing tool by extending its applicability to monitor diverse intracellular biomolecules. In this work, we engineered a CRISPR-Cas12a system with a generalized stimulus-responsive switch mechanism based on PAM-less conditional DNA substrates (pcDNAs).

Trimacrocyclic hexasubstituted benzene linked by labile octahedral [X(CHCl)] clusters.

Crystalline supramolecular architectures mediated by cations, anions, ion pairs or neutral guest species are well established. However, the robust crystallization of a well-designed receptor mediated by labile anionic solvate clusters remains unexplored. Herein, we describe the synthesis and crystalline behaviors of a trimacrocyclic hexasubstituted benzene in the presence of guanidium halide salts and chloroform.

Multiplexed droplet loop-mediated isothermal amplification with scorpion-shaped probes and fluorescence microscopic counting for digital quantification of virus RNAs.

Highly sensitive digital nucleic acid techniques are of great significance for the prevention and control of epidemic diseases. Here we report the development of multiplexed droplet loop-mediated isothermal amplification (multiplexed dLAMP) with scorpion-shaped probes (SPs) and fluorescence microscopic counting for simultaneous quantification of multiple targets. A set of target-specific fluorescence-activable SPs are designed, which allows establishment of a novel multiplexed LAMP strategy for simultaneous detection of multiple cDNA targets.

Controlled dimerization of artificial membrane receptors for transmembrane signal transduction.

In biology, membrane-spanning proteins are responsible for the transmission of chemical signals across membranes, including the signal recognition-mediated conformational change of transmembrane receptors at the cell surface, and a trigger of an intracellular phosphorylation cascade. The ability to reproduce such biological processes in artificial systems has potential applications in smart sensing, drug delivery, and synthetic biology. Here, an artificial transmembrane receptors signaling system was designed and constructed based on modular DNA scaffolds.

A DNA-mediated crosslinking strategy to enhance cellular delivery and sensor performance of protein spherical nucleic acids.

Intracellular delivery of enzymes is essential for protein-based diagnostic and therapeutic applications. Protein-spherical nucleic acids (ProSNAs) defined by protein core and dense shell of oligonucleotides have been demonstrated as a promising vehicle-free enzyme delivery platform. In this work, we reported a crosslinking strategy to vastly improve both delivery efficiency and intracellular sensor performance of ProSNA.