A Cages-on-Cluster Structure Constructed by Post-Clustering Covalent Modifications and Guest-Enabled Stimuli-Responsive Luminescence.

A novel gold(I)-cluster-based twin-cage is constructed by post-clustering covalent modification of a hexa-aldehyde cluster precursor with triaminotriethylamines. The cages-on-cluster structure have double cavities and four binding sites, showing site discriminative binding for silver(I) and copper(I) guests. The guests in the tripodal hats affect the luminescence of the cluster: tetra-silver(I) host-guest complex is weak red emissive, while bis-copper(I)-bis-silver(I) one is non-emissive but a stimuli-responsive supramolecule. The copper(I) ion inside the tri-imine cavity is oxidation sensitive, which enable the release of the bright emissive precursor cluster triggered by H2O2 solution. The hybridization of a cluster with cavities to construct a cluster-based cage presents an innovative concept for functional cluster design, and the post-clustering covalent modification opens up new avenues of finely tuning the properties of clusters.

Chiroptical Activity Amplification of Chiral Metal Nanoclusters via Surface/Interface Solidification.

It remains a grand challenge to amplify the chiroptical activity of chiral metal nanoclusters (NCs) although it is desirable for fundamental research and practical application. Herein, we report a strategy of surface/interface solidification (SIS) for enhancing the chiroptical activity of gold NCs. Structural analysis of [Au19(2R,4R/2S,4S-BDPP)6Cl2]3+ (BDPP is 2,4-bis(diphenylphosphino)pentane) clusters reveals that one of the interfacial gold atoms is flexible between two sites and large space is present on the surface, thus hampering chirality transfer from surface chiral ligands to metal core and leading to low chiroptical activity. Following SIS by filling the flexible sites and replacing chlorides with thiolate ligands affords another pair of [Au20(2R,4R/2S,4S-BDPP)6(4-F-C6H4S)2]4+, which shows a more compact and organized structure and thus an almost 40-fold enhancement of chiroptical activity. This work not only provides an efficient approach for amplifying the chiroptical activity of metal nanoclusters but also highlights the significance of achiral components in shaping chiral nanostructures.

Research on the key technology of high-precision waveform synchronization identification and measurement.

High-precision waveform identification and measurement are effective for waveform detection and evaluation in signal processing. The accuracy of waveform identification, precision of measurement, and speed of response are important indicators of waveform measurement instruments. To detect the waveform accurately, a hold and attenuation circuit divided into two is designed, and the STM32F4 microcontroller is used to accurately capture and perform spectrum analysis using a high-precision analog-to-digital converter based on fast Fourier transform technology to identify key parameters, such as waveform type, frequency, peak-to-peak value, and duty cycle. To improve the recognition accuracy and response speed, technical solutions, such as high-frequency sampling and over-zero detection, are used to improve the system efficiency. Algorithm simulation, circuit simulation, and physical testing show that the high-precision waveform synchronization recognition circuit and algorithm can accurately recognize various essential waveforms in the voltage and frequency ranges of 50 mV ≤ VPP ≤ 10 V and 1 Hz ≤ f ≤ 50 kHz, respectively, and simultaneously measure important parameters, such as frequency, peak-to-peak value, and duty cycle with an accuracy within ±1%. Intelligent linkage, no intermediate parameter setting, and a response speed of approximately 0.3 s make it suitable for such applications as fast and high-precision waveform intelligent detection and display. The method is highly integrated, simple to operate, cost-effective, and practical.

A bowl-shaped phosphangulene-protected cubic Cu58 nanocluster.

A bowl-shaped phosphangulene-protected cubic Cu58 nanocluster has been synthesized. The structure was determined by X-ray crystallography and further analyzed by multiple techniques. The phosphangulenes not only enable ligand substitutions with triphenylphosphines in a cluster-to-cluster transformation way, but also facilitate inter-cluster interactions with fullerenes. These interactions further influence the entirety's photocurrent response and ability to liberate hydrogen when stimulated by light.

Near-unity NIR phosphorescent quantum yield from a room-temperature solvated metal nanocluster.

Metal nanoclusters have emerged as promising near-infrared (NIR)-emissive materials, but their room-temperature photoluminescence quantum yield (PLQY), especially in solution, is often low (<10%). We studied the photophysics of Au22(tBuPhC≡C)18 (Au22) and its alloy counterpart Au16Cu6(tBuPhC≡C)18 (Au16Cu6) (where tBu is tert-butyl and Ph is phenyl) and found that copper (Cu) doping suppressed the nonradiative decay (~60-fold less) and promoted intersystem crossing rate (~300-fold higher). The Au16Cu6 nanocluster exhibited >99% PLQY in deaerated solution at room temperature with an emission maximum at 720 nanometers tailing to 950 nanometers and 61% PLQY in the oxygen-saturated solution. The approach to achieve near-unity PLQY could enable the development of highly emissive metal cluster materials.

Heterometallic AuI 6 AgI 6 Macrocyclic Cluster Templated by a Supramolecular Melamine Dimer.

The application of supramolecular templates in aligning atomically precise heterometal arrays is important for pursuing functional materials. Herein, we report that a bilayered supramolecular tri-deprotonated melamine dimer functions as an effective template in the construction of a heterometallic gold(I)-silver(I) macrocyclic cluster [µ6 -(C3 N6 H3 )3- ]2 -AuI 6 AgI 6 . X-ray single crystal structural analysis showed that a crown-like AuI 6 AgI 6 macrocycle is aligned around two parallelly stacked µ6 -(C3 N6 H3 )3- moieties hold together with π-π interactions. Theoretical calculations revealed that the [µ6 -(C3 N6 H3 )3- ]2 motif dominantly contributes to the near-occupied orbitals in the electronic structure, which is closely related to its luminescence properties. This work demonstrates that the supramolecular templates containing multiple symmetric binding sites may present a facile approach in the construction of functional metal clusters.

One-step preparation of Pt/Ag nanoclusters for CO2 transformation.

Structurally precise metal nanoclusters with a facile synthetic process and high catalytic performance have been long pursued. These atomically precise nanocatalysts are regarded as model systems to study structure-performance relationships, surface coordination chemistry, and the reaction mechanism of heterogeneous metal catalysts. Nevertheless, the research on silver-based nanoclusters for driving chemical transformations is sluggish in comparison to gold counterparts. Herein, we report the one-step synthesis of Pt/Ag alloy nanoclusters of [PtAg9(C18H12Br3P)7Cl3](C18H12Br3P), which are highly active in catalysing cycloaddition reactions of CO2 and epoxides. The cluster was obtained in a rather simple way with the reduction of silver and platinum salts in the presence of ligands in one pot. The molecular structure of the titled cluster describes the protection of the Pt-centred Ag9 crown by the shell of phosphine ligands and halides. Its electronic structure, as revealed by density function theoretical calculations, adopts a superatomic geometry with 1S21P6 configuration. Interestingly, the cluster displays high activity in the formation of cyclic carbonates from CO2 under mind conditions.

PtAg18 superatoms costabilized by phosphines and halides: synthesis, structure, and catalysis.

Reported herein is the facial synthesis, molecular structure, and catalysis of a Pt/Ag nanocluster costabilized by organic ligands of phosphines and inorganic ligands of chlorides. The nanocluster with molecular formula of [PtAg18(dppp)6Cl8](SbF6)2 has been obtained facilely by the one pot method. The structure of the cluster could be anatomized as the stabilizaiton of PtAg12-centered icosahedral core by the metalloligand of dppp-Ag-Cl, in which Cl- not only caps the surface Ag atoms but also binds the core and surface motifs. Featuring eight free electrons in its structure, the cluster exhibits high stability. More interestingly, the exposure of surface metal sites endows the cluster with counterintutively  high catalytic activity in hydrogenation reactions.

Barley TAPETAL DEVELOPMENT and FUNCTION1 (HvTDF1) gene reveals conserved and unique roles in controlling anther tapetum development in dicot and monocot plants.

The anther tapetum helps control microspore release and essential components for pollen wall formation. TAPETAL DEVELOPMENT and FUNCTION1 (TDF1) is an essential R2R3 MYB tapetum transcription factor in Arabidopsis thaliana; however, little is known about pollen development in the temperate monocot barley. Here, we characterize the barley (Hordeum vulgare L.) TDF1 ortholog using reverse genetics and transcriptomics. Spatial/temporal expression analysis indicates HvTDF1 has tapetum-specific expression during anther stage 7/8. Homozygous barley hvtdf1 mutants exhibit male sterility with retarded tapetum development, delayed tapetum endomitosis and cell wall degeneration, resulting in enlarged, vacuolated tapetum surrounding collapsing microspores. Transient protein expression and dual-luciferase assays show TDF1 is a nuclear-localized, transcription activator, that directly activates osmotin proteins. Comparison of hvtdf1 transcriptome data revealed several pathways were delayed, endorsing the observed retarded anther morphology. Arabidopsis tdf1 mutant fertility was recovered by HvTDF1, supporting a conserved role for TDF1 in monocots and dicots. This indicates that tapetum development shares similarity between monocot and dicots; however, barley HvTDF1 appears to uniquely act as a modifier to activate tapetum gene expression pathways, which are subsequently also induced by other factors. Therefore, the absence of HvTDF1 results in delayed developmental progression rather than pathway failure, although inevitably still results in pollen degeneration.

Alkynyl-Protected Bimetallic Nanoclusters with a Hybrid Mackay Icosahedral Ag42 Cu12 Cl Kernel and an Octahedral Ag22 Cu12 Kernel.

A facile strategy that directly reduces alkynyl-silver precursors and copper salts for the synthesis of bimetallic nanoclusters using the weak reducing agent Ph2 SiH2 is demonstrated. Two alkynyl-protected concentric-shell nanoclusters, (Ph4 P)2 [Ag22 Cu12 (C≡CR)28 ] and (Ph4 P)3 [Ag42 Cu12 Cl(C≡CR)36 ] (Ag22 Cu12 and Ag42 Cu12 Cl, R=bis(trifluoromethyl)phenyl), were successfully obtained and characterized by single-crystal X-ray diffraction and electro-spray ionization mass spectrometry. For the first time, a hybrid 55-atom two-shell Mackay icosahedron was found in Ag42 Cu12 Cl, which is icosahedral M54 Cl instead of M55 . The incorporation of a chloride in the metal icosahedron contributes to the stability of the cluster from both electronic and geometric aspects. Alkynyl ligands show various binding-modes including linear "RC≡C-Cu-C≡CR" staple motifs.

A cage-on-MOF strategy to coordinatively functionalize mesoporous MOFs for manipulating selectivity in adsorption and catalysis.

Functionalizing porous materials with capping agents generates hybrid materials with enhanced properties, while the challenge is how to improve the selectivity and maintain the porosity of the parent framework. Herein, we developed a "Cage-on-MOF" strategy to tune the recognition and catalytic properties of MOFs without impairing their porosity. Two types of porous coordination cages (PCCs) of opposite charges containing secondary binding groups were developed to coordinatively functionalize two distinct porous MOFs, namely MOF@PCC nanocomposites. We demonstrated that the surface-capped PCCs can act as "modulators" to effectively tune the surface charge, stability, and adsorption behavior of different host MOF particles. More importantly, the MOF@PCCs can serve as selective heterogeneous catalysts for condensation reactions to achieve reversed product selectivity and excellent recyclability. This work sets the foundation for using molecular cages as porous surface-capping agents to functionalize and manipulate another porous material, without affecting the intrinsic properties of the parent framework.

Recent advances in porous molecular cages for photocatalytic organic conversions.

Photocatalytic organic conversion is considered an efficient, environmentally friendly, and energy-saving strategy for organic synthesis. In recent decades, the molecular cage has emerged as a creative functional material with broad applications in host-guest recognition, drug delivery, catalysis, intelligent materials and other fields. Based on the unique properties of porous molecular cage materials, they provide an ideal platform for leveraging pre-structuring in catalytic reactions and show great potential in various photocatalytic organic reactions. As a result, they have emerged as promising alternatives to conventional molecules or inorganic photocatalysts in redox processes. In this Review, the synthesis strategies based on coordination cages and organic cages, as well as their recent progress in photocatalytic organic conversion, are comprehensively summarized. Finally, we deliver the persistent challenges associated with porous molecular cage compounds that need to be overcome for further development in this field.

Ultralow-quantum-defect single-frequency fiber laser.

A single-frequency distributed-Bragg-reflector fiber laser at 980 nm with a quantum defect of less than 0.6% was developed with a 1.5-cm 12 wt% ytterbium-doped phosphate fiber pumped by a 974.5-nm laser diode. Linearly polarized single-longitude-mode laser with a polarization extinction ratio (PER) of nearly 30 dB and spectral linewidth of less than 1.8 kHz was obtained. A maximum output power of 275 mW was measured at a launched pump power of 620 mW. The performance of the single-frequency fiber laser pumped at 909 nm and 976 nm was also characterized. This research demonstrated an approach to high-power single-frequency fiber laser oscillators with mitigated thermal effects.

Discovery and Characterization of a Myxobacterial Lanthipeptide with Unique Biosynthetic Features and Anti-inflammatory Activity.

The genomes of myxobacteria harbor a variety of biosynthetic gene clusters encoding numerous secondary metabolites, including ribosomally synthesized and post-translationally modified peptides (RiPPs) with diverse chemical structures and biological activities. However, the biosynthetic potential of RiPPs from myxobacteria remains barely explored. Herein, we report a novel myxobacteria lanthipeptide myxococin identified from Myxococcus fulvus. Myxococins represent the first example of lanthipeptides, of which the characteristic multiple thioether rings are installed by employing a Class II lanthipeptide synthetase MfuM and a Class I lanthipeptide cyclase MfuC in a cascaded way. Unprecedentedly, we biochemically characterized the first M61 family aminopeptidase MfuP involved in RiPP biosynthesis, demonstrating that MfuP showed the activity of an endopeptidase activity. MfuP is leader-independent but strictly selective for the multibridge structure of myxococin A and responsible for unwrapping two rings via amide bond hydrolysis, yielding myxococin B. Furthermore, the X-ray crystal structure of MfuP and structural analysis, including active-site mutations, are reported. Finally, myxococins are evaluated to exhibit anti-inflammatory activity in lipopolysaccharide-induced macrophages without detectable cytotoxicity.

Modeling the Enzyme Specificity by Molecular Cages through Regulating Reactive Oxygen Species Evolution.

Mimicking the active site and the substrate binding cavity of the enzyme to achieve specificity in catalytic reactions is an essential challenge. Herein, porous coordination cages (PCCs) with intrinsic cavities and tunable metal centers have proved the regulation of reactive oxygen species (ROS) generating pathways as evidenced by multiple photo-induced oxidations. Remarkably, in the presence of the Zn4 -µ4 -O center, PCC converted dioxygen molecules from triplet to singlet excitons, whereas the Ni4 -µ4 -O center promoted the efficient dissociation of electrons and holes to conduct electron transfer towards substrates. Accordingly, the distinct ROS generation behavior of PCC-6-Zn and PCC-6-Ni enables the conversion of O2 to 1 O2 and O2 ⋅- , respectively. In contrast, the Co4 -µ4 -O center combined the 1 O2 and O2 ⋅- together to generate carbonyl radicals, which in turn reacted with the oxygen molecules. Harnessing the three oxygen activation pathways, PCC-6-M (M=Zn/Ni/Co) display specific catalytic activities in thioanisole oxidation (PCC-6-Zn), benzylamine coupling (PCC-6-Ni), and aldehyde autoxidation (PCC-6-Co). This work not only provides fundamental insights into the regulation of ROS generation by a supramolecular catalyst but also demonstrates a rare example of achieving reaction specificity through mimicking natural enzymes by PCCs.

Bridging the Gap between Charge Storage Site and Transportation Pathway in Molecular-Cage-Based Flexible Electrodes.

Porous materials have been widely applied for supercapacitors; however, the relationship between the electrochemical behaviors and the spatial structures has rarely been discussed before. Herein, we report a series of porous coordination cage (PCC) flexible supercapacitors with tunable three-dimensional (3D) cavities and redox centers. PCCs exhibit excellent capacitor performances with a superior molecular capacitance of 2510 F mmol-1, high areal capacitances of 250 mF cm-2, and unique cycle stability. The electrochemical behavior of PCCs is dictated by the size, type, and open-close state of the cavities. Both the charge binding site and the charge transportation pathway are unambiguously elucidated for PCC supercapacitors. These findings provide central theoretical support for the "structure-property relationship" for designing powerful electrode materials for flexible energy storage devices.

Disc-Like Silver Nanocluster Ag93 Built with Bicapped Hexagonal Prismatic Ag15 and Ino Decahedral Ag13 Units.

The reduction of alkynyl-silver and phosphine-silver precursors with a weak reducing reagent Ph2 SiH2 led to the formation of a novel silver nanocluster [Ag93 (PPh3 )6 (C≡CR)50 ]3+ (R=4-CH3 OC6 H4 ), which is the largest structurally characterized cluster of clusters. This disc-shaped cluster has a Ag69 kernel consisting of a bicapped hexagonal prismatic Ag15 unit wrapped by six Ino decahedra through edge-sharing. This is the first time that Ino decahedra are used as a building block to assemble a cluster of clusters. Moreover, the central silver atom has a coordination number of 14, which is the highest in metal nanoclusters. This work provides a diverse metal packing pattern in metal nanoclusters, which is helpful for understanding metal cluster assembling mechanisms.

Eight-Electron Superatomic Cu31 Nanocluster with Chiral Kernel and NIR-II Emission.

Owing to the inherent instability caused by the low Cu(I)/Cu(0) half-cell reduction potential, Cu(0)-containing copper nanoclusters are quite uncommon in comparison to their Ag and Au congeners. Here, a novel eight-electron superatomic copper nanocluster [Cu31(4-MeO-PhC≡C)21(dppe)3](ClO4)2 (Cu31, dppe = 1,2-bis(diphenylphosphino)ethane) is presented with total structural characterization. The structural determination reveals that Cu31 features an inherent chiral metal core arising from the helical arrangement of two sets of three Cu2 units encircling the icosahedral Cu13 core, which is further shielded by 4-MeO-PhC≡C- and dppe ligands. Cu31 is the first copper nanocluster carrying eight free electrons, which is further corroborated by electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and density functional theory calculations. Interestingly, Cu31 demonstrates the first near-infrared (750-950 nm, NIR-I) window absorption and the second near-infrared (1000-1700 nm, NIR-II) window emission, which is exceptional in the copper nanocluster family and endows it with great potential in biological applications. Of note, the 4-methoxy groups providing close contacts with neighboring clusters are crucial for the cluster formation and crystallization, while 2-methoxyphenylacetylene leads only to copper hydride clusters, Cu6H or Cu32H14. This research not only showcases a new member of copper superatoms but also exemplifies that copper nanoclusters, which are nonluminous in the visible range may emit luminescence in the deep NIR region.

Recent Advances in Discovery, Bioengineering, and Bioactivity-Evaluation of Ribosomally Synthesized and Post-translationally Modified Peptides.

Ribosomally synthesized and post-translationally modified peptides (RiPPs) are of increasing interest in natural products as well as drug discovery. This empowers not only the unique chemical structures and topologies in natural products but also the excellent bioactivities such as antibacteria, antifungi, antiviruses, and so on. Advances in genomics, bioinformatics, and chemical analytics have promoted the exponential increase of RiPPs as well as the evaluation of biological activities thereof. Furthermore, benefiting from their relatively simple and conserved biosynthetic logic, RiPPs are prone to be engineered to obtain diverse analogues that exhibit distinct physiological activities and are difficult to synthesize. This Review aims to systematically address the variety of biological activities and/or the mode of mechanisms of novel RiPPs discovered in the past decade, albeit the characteristics of selective structures and biosynthetic mechanisms are briefly covered as well. Almost one-half of the cases are involved in anti-Gram-positive bacteria. Meanwhile, an increasing number of RiPPs related to anti-Gram-negative bacteria, antitumor, antivirus, etc., are also discussed in detail. Last but not least, we sum up some disciplines of the RiPPs' biological activities to guide genome mining as well as drug discovery and optimization in the future.

Numerical simulation of a mechanical flocculation process with multi-chambers in series.

A mechanical flocculation system with multi-chambers in series is commonly used as the advanced phosphorus removal technology for wastewater treatment. This work aims to numerically investigate the inner states and overall performance of industrial-scale mechanical flocculators in series. This is based on our previously developed computational fluid dynamics (CFD) flocculation model which is extended to consider the key chemical reactions of phosphorus removal. The effects of the number of flocculation chambers, locations, and sizes of the flocculation chamber connection as well as operational combinations of impeller speeds are investigated. With a decreasing number of flocculation chambers, the main vortexes and chemical reactions are weakened, while the small flocs form. Both the phosphorus removal efficiency η and the average floc size dp reduce as the number of flocculation chambers decreases. The connection location of flocculation chambers directly determines the turbulent flow, thus influencing the key performance indicators. However, the phosphorus removal efficiency η and average particle size dp are little affected by the size of the flocculation chamber connection. As the impeller speeds in series gradually increase, the gradient of floc size distribution in each chamber is enlarged and the chemical reaction is enhanced over the working volume.