Nanoengineering Multilength-Scale Porous Hierarchy in Mesoporous Metal-Organic Framework Single Crystals.

Developing a reliable method for constructing mesoporous metal-organic frameworks (MOFs) with single-crystalline forms remains a challenging task despite numerous efforts. This study presents a solvent-mediated assembly method for fabricating zeolitic imidazolate framework (ZIF) single-crystal nanoparticles with a well-defined micro-mesoporous structure using polystyrene-block-poly(ethylene oxide) diblock copolymer micelles as a soft-template. The precise control of particle sizes, ranging from 85 to 1200 nm, is achieved by regulating nucleation and crystal growth rates while maintaining consistent pore diameters in mesoporous nanoparticles and a rhombohedral dodecahedron morphology. Furthermore, this study presents a robust platform for nanoarchitecturing to prepare hierarchically porous materials (e.g., core-shell and hollow structures), including microporous ZIF@mesoporous ZIF, hollow mesoporous ZIF, and mesoporous ZIF@mesoporous ZIF. Such a multimodal pore design, ranging from microporous to microporous/mesoporous and further micro-/meso-/macroporous, provides significant evidence for the future possibility of the structural design of MOFs.

Mesoporous amorphous non-noble metals as versatile substrates for high loading and uniform dispersion of Pt-group single atoms.

Atomically dispersed Pt-group metals are promising as nanocatalysts because of their unique geometric structures and ultrahigh atomic utilization. However, loading isolated Pt-group metals in single-atom alloys (SAAs) with distinctive bimetallic sites is challenging. In this study, we present amorphous mesoporous Ni boride (Ni-B) as an ideal substrate to uniformly disperse Pt atoms with tunable loadings (1.7 to 12.2 wt %). The effect of the morphology, composition, and crystal phase of the Ni-B host on the growth and dispersion of Pt atoms is discussed. The resulting amorphous Pt-Ni-B mesoporous nanospheres exhibit superior electrocatalytic H2 evolution performance in acidic media. This strategy holds the potential to synthesize a diverse library of mesoporous amorphous Pt-group SAAs, by leveraging functional amorphous nanostructured 3d transition-metal borides as substrates, thereby proposing a comprehensive strategy to control atomically dispersed Pt-group metals.

Giant piezoresponse in nanoporous (Ba,Ca)(Ti,Zr)O3 thin film.

Lattice strain effects on the piezoelectric properties of crystalline ferroelectrics have been extensively studied for decades; however, the strain dependence of the piezoelectric properties at nano-level has yet to be investigated. Herein, a new overview of the super-strain of nanoporous polycrystalline ferroelectrics is reported for the first time using a nanoengineered barium calcium zirconium titanate composition (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 (BCZT). Atomic-level investigations show that the controlled pore wall thickness contributes to highly strained lattice structures that also retain the crystal size at the optimal value (<30 nm), which is the primary contributor to high piezoelectricity. The strain field derived from geometric phase analysis at the atomic level and aberration-corrected high-resolution scanning transmission electron microscopy (STEM) yields of over 30% clearly show theoretical agreement with high piezoelectric properties. The uniqueness of this work is the simplicity of the synthesis; moreover the piezoresponse d 33 becomes giant, at around 7500 pm V-1. This response is an order of magnitude greater than that of lead zirconate titanate (PZT), which is known to be the most successful ferroelectric over the past 50 years. This concept utilizing nanoporous BCZT will be highly useful for a promising high-density electrolyte-free dielectric capacitor and generator for energy harvesting in the future.

Bridged Pt-OH-Mn Mediator in N-coordinated Mn Single Atoms and Pt Nanoparticles for Electrochemical Biomolecule Oxidation and Discrimination.

The rational design of efficient catalysts for uric acid (UA) electrooxidation, as well as the establishment of structure-activity relationships, remains a critical bottleneck in the field of electrochemical sensing. To address these challenges, herein, a hybrid catalyst that integrates carbon-supported Pt nanoparticles and nitrogen-coordinated Mn single atoms (PtNPs/MnNC) is developed. The metal-metal interaction during annealing affords the construction of metallic-bonded Pt-Mn pairs between PtNPs and Mn single atoms, facilitating the electron transfer from PtNPs to the support and thereby optimizing the electronic structure of catalysts. More importantly, experiments and theoretical calculations provide visual proof for the 'incipient hydrous oxide adatom mediator' mechanism for UA oxidation. The Pt-Mn pairs first adsorb OH* to construct the bridged Pt-OH-Mn mediators to serve as a highly active intermediate for N-H bond dissociation and proton transfer. Benefiting from the unique electronic and geometric structure of the catalytic center and reactive intermediates, PtNPs/MnNC exhibits superior electrooxidation performance. The electrochemical sensor based on PtNPs/MnNC enables sensitive detection and discrimination of UA and dopamine in serum samples. This work offers new insights into the construction of novel electrocatalysts for sensitive sensing platforms.

Photo-triggered Phase Transition of Crystals and Photoactuation.

Photo-triggered phase transition is a new type of phase transition in which a photochromic crystal with a thermal phase transition transforms into an identical high-temperature phase in a temperature region lower than the thermal phase transition temperature upon light irradiation. Here, we report a second crystal that exhibits a photo-triggered phase transition, thereby demonstrating that the photo-triggered phase transition is a general phenomenon that occurs in crystals. When the chiral salicylidenephenylethylamine crystal was irradiated with ultraviolet (UV) light, the photo-triggered phase transition occurred in the temperature range -30 to -10 °C. The photo-triggered phase transition is induced by local stress due to trans-keto molecules produced by photoisomerization near the irradiated surface. Crystal cantilevers exhibited stepwise bending by the combination of the photo-triggered phase transition and photoisomerization. Alternate irradiation with UV and visible light achieved locomotion of single crystals driven by repeated stepwise bending. Finally, a detailed comparison of photo-triggered and non-photo-triggered phase transition crystals revealed that a sufficient molecular conformation change in affordable crystal voids, smooth photoisomerization, and most likely a chiral molecular arrangement are required for inducing the photo-triggered phase transition.

DeepLabCut-based daily behavioural and posture analysis in a cricket.

Circadian rhythms are indispensable intrinsic programs that regulate the daily rhythmicity of physiological processes, such as feeding and sleep. The cricket has been employed as a model organism for understanding the neural mechanisms underlying circadian rhythms in insects. However, previous studies measuring rhythm-controlled behaviours only analysed locomotive activity using seesaw-type and infrared sensor-based actometers. Meanwhile, advances in deep learning techniques have made it possible to analyse animal behaviour and posture using software that is devoid of human bias and does not require physical tagging of individual animals. Here, we present a system that can simultaneously quantify multiple behaviours in individual crickets - such as locomotor activity, feeding, and sleep-like states - in the long-term, using DeepLabCut, a supervised machine learning-based software for body keypoints labelling. Our system successfully labelled the six body parts of a single cricket with a high level of confidence and produced reliable data showing the diurnal rhythms of multiple behaviours. Our system also enabled the estimation of sleep-like states by focusing on posture, instead of immobility time, which is a conventional parameter. We anticipate that this system will provide an opportunity for simultaneous and automatic prediction of cricket behaviour and posture, facilitating the study of circadian rhythms.

Pt Nanoparticle-Mn Single-Atom Pairs for Enhanced Oxygen Reduction.

The intrinsic roadblocks for designing promising Pt-based oxygen reduction reaction (ORR) catalysts emanate from the strong scaling relationship and activity-stability-cost trade-offs. Here, a carbon-supported Pt nanoparticle and a Mn single atom (PtNP-MnSA/C) as in situ constructed PtNP-MnSA pairs are demonstrated to be an efficient catalyst to circumvent the above seesaws with only ∼4 wt % Pt loadings. Experimental and theoretical investigations suggest that MnSA functions not only as the "assist" for Pt sites to cooperatively facilitate the dissociation of O2 due to the strong electronic polarization, affording the dissociative pathway with reduced H2O2 production, but also as an electronic structure "modulator" to downshift the d-band center of Pt sites, alleviating the overbinding of oxygen-containing intermediates. More importantly, MnSA also serves as a "stabilizer" to endow PtNP-MnSA/C with excellent structural stability and low Fenton-like reactivity, resisting the fast demetalation of metal sites. As a result, PtNPs-MnSA/C shows promising ORR performance with a half-wave potential of 0.93 V vs reversible hydrogen electrode and a high mass activity of 1.77 A/mgPt at 0.9 V in acid media, which is 19 times higher than that of commercial Pt/C and only declines by 5% after 80,000 potential cycles. Specifically, PtNPs-MnSA/C reaches a power density of 1214 mW/cm2 at 2.87 A/cm2 in an H2-O2 fuel cell.

Synthesis of millimeter-scale ZIF-8 single crystals and their reversible crystal structure changes.

Among various metal-organic frameworks (MOFs), the zeolitic imidazole framework (ZIF), constructed by the regular arrangement of 2-methylimidazole and metal ions, has garnered significant attention due to its distinctive crystals and pore structures. Variations in the sizes and shapes of ZIF crystals have been reported by changing the synthesis parameters, such as the molar ratios of organic ligands to metal ions, choice of solvents, and temperatures. Nonetheless, the giant ZIF-8 single crystals beyond the typical range have rarely been reported. Herein, we present the synthesis of millimeter-scale single crystal ZIF-8 using the solvothermal method in N,N-diethylformamide. The resulting 1-mm single crystal is carefully characterized through N2 adsorption-desorption isotherms, scanning electron microscopy, and other analytical techniques. Additionally, single-crystal X-ray diffraction is employed to comprehensively investigate the framework's mobility at various temperatures.

Millimeter-sized ZIF-8 single crystals were synthesized using the solvothermal method. These crystals exhibit a notable BET surface area of 1681 m²âˆ™g⁻¹ and demonstrate a reversible change in their crystal structure.

Negative to positive axial thermal expansion switching of an organic crystal: contribution to multistep photoactuation.

Materials displaying negative thermal expansion (NTE), in contrast to typical materials with positive thermal expansion (PTE), are attractive for both fundamental research and practical applications, including the development of composites with near-zero thermal expansion. A recent data mining study revealed that approximately 34% of organic crystals may present NTE, indicating that NTE in organic crystals is much more common than generally believed. However, organic crystals that switch from NTE to PTE or vice versa have rarely been reported. Here, we report the crystal of N-3,5-di-tert-butylsalicylide-3-nitroaniline in the enol form (enol-1) as the first organic crystal in which the axial thermal expansion changes from negative to positive at around room temperature. When heated, the crystal shrinks along the a-axis below 30 °C and then it expands above 30 °C. Geometric calculations revealed that below 30 °C, the decrease in the tilt angle of the molecule exceeds the increase in the interplanar distance, causing NTE, whereas above 30 °C, the increase in the interplanar distance outweighs the decrease in the tilt angle, resulting in PTE. By combining photoisomerisation and the NTE-PTE switching induced by the photothermal effect, multistep crystal photoactuation was achieved. Moreover, actuation switching of the same crystal sample by changing atmosphere temperature was realised by utilising the NTE-PTE change. Such NTE-PTE switching without a thermal phase transition provides not only new insight into organic crystals but also a new strategy for designing crystal actuators.

Prediction of Photochromism of Salicylideneaniline Crystals Using a Data Mining Approach.

Salicylideneanilines (SAs) are photochromic compounds that undergo enol-keto photoisomerization in the solid state. Research over the past 60 years has revealed empirically that SAs with steric and planar conformations tend to be photochromic and nonphotochromic, respectively. However, increasing counterexamples in the recent literature raise questions about the nature of the relationship between structure and photochromism in SA crystals and whether the photochromism of SA crystals is predictable. This study is the first to construct a data set on SA crystals and conduct a comprehensive analysis to investigate the relationship between molecular and crystal structures and photochromism. A data mining approach revealed that the dihedral angle is the most dominant structural parameter for photochromism, followed by the Hirshfeld surface volume. SAs with neutral bulky hydrocarbon groups, such as the tert-butyl group, tend to be photochromic because such SAs have steric conformation and a loosely packed structure. In contrast, SAs with fluorine, pyridine, and pyrazine are less likely to be photochromic due to their planar conformation and densely packed structures. The photochromism of the SA crystals in our data set was predicted with high accuracy (>85%) using machine learning. The results of this study provide a useful reference for designing SA crystals with desired photochromic properties.

Proliferation of mammalian cells with Chlorococcum littorale algal compounds without serum support.

In recent years, serum-free medium for mammalian cell cultivation has attracted a lot of attention, considering the high cost of production and environmental load involved in developing the conventional animal sera. The use of alternative growth-promoting products in mammalian cell cultivation such as extracts from microalgae has proven to be quite beneficial and environmental-friendly. This research aims to cultivate mammalian cells with growth-promoting factors derived from Chlorococcum littorale. We have established a simple extraction using the ultrasonication method and applied the extract in place of serum on mammalian C2C12 cell lines, 3T3 cell lines, and CHO cell lines to compare and analyze the effectiveness of the extract. Cell passage was conducted in a suspended culture condition with the addition of the extract. The results indicate that the extract from microalgae shows a high proliferation rate in all cell lines without fetal bovine serum. Moreover, it is eco-friendly and has huge potential to replace the traditional cell culture system. It could be applied in the fields of regenerative medicine, gene/cell therapies, as well as cultured meat production.

Enhancing Electrocatalytic Performance via Thickness-Tuned Hollow N-Doped Mesoporous Carbon with Embedded Co Nanoparticles for Oxygen Reduction Reaction.

Improving catalytic performance relies heavily on the rational design of the spatial structure of electrocatalysts, achieved through exposure of active sites, acceleration of the charge/mass transfer rate, and confinement of the reactants. In this study, we have fabricated Co nanoparticles embedded in overhang eave-like hollow N-doped mesoporous carbon (Co@EMPC) by adjusting the thickness of mesoporous polydopamine (mPDA). Thanks to the abundance of short mesoporous channels within the porous structure and the tuned electronic properties resulting from heterojunction structures between metal and carbon, the prepared Co@EMPC provides increased accessibility to active sites and enhanced mass and charge transfer rates. These features contribute to superior performance in the oxygen reduction reaction (ORR), with a half-wave potential of 0.874 V vs RHE, as well as exceptional durability in alkaline media. This study introduces a useful approach to enhance the ORR using eave-like hollow nanoreactors.

Functional Divergence and Origin of the Vertebrate Praja Family.

The Praja family is an E3 ubiquitin ligase, promoting polyubiquitination and subsequent degradation of substrates. It comprises two paralogs, praja1 and praja2. Prior research suggests these paralogs have undergone functional divergence, with examples, such as their distinct roles in neurite outgrowth. However, the specific evolutionary trajectories of each paralog remain largely unexplored preventing mechanistic understanding of functional differences between paralogs. Here, we investigated the phylogeny and divergence of the vertebrate Praja family through molecular evolutionary analysis. Phylogenetic examination of the vertebrate praja revealed that praja1 and praja2 originated from the common ancestor of placentals via gene duplication, with praja1 evolving at twice the rate of praja2 shortly after the duplication. Moreover, a unique evolutionary trajectory for praja1 relative to other vertebrate Praja was indicated, as evidenced by principal component analysis on GC content, codon usage frequency, and amino acid composition. Subsequent motif/domain comparison revealed conserved N terminus and C terminus in praja1 and praja2, together with praja1-specific motifs, including nuclear localization signal and Ala-Gly-Ser repeats. The nuclear localization signal was demonstrated to be functional in human neuroblastoma SH-SY5Y cells using deletion mutant, while praja2 was exclusively expressed in the nucleus. These discoveries contribute to a more comprehensive understanding of the Praja family's phylogeny and suggest a functional divergence between praja1 and praja2. Specifically, the shift of praja1 into the nucleus implies the degradation of novel substrates located in the nucleus as an evolutionary consequence.

Integrative single-cell RNA-seq analysis of vascularized cerebral organoids.

BACKGROUND: Cerebral organoids are three-dimensional in vitro cultured brains that mimic the function and structure of the human brain. One of the major challenges for cerebral organoids is the lack of functional vasculature. Without perfusable vessels, oxygen and nutrient supplies may be insufficient for long-term culture, hindering the investigation of the neurovascular interactions. Recently, several strategies for the vascularization of human cerebral organoids have been reported. However, the generalizable trends and variability among different strategies are unclear due to the lack of a comprehensive characterization and comparison of these vascularization strategies. In this study, we aimed to explore the effect of different vascularization strategies on the nervous system and vasculature in human cerebral organoids. RESULTS: We integrated single-cell RNA sequencing data of multiple vascularized and vascular organoids and fetal brains from publicly available datasets and assessed the protocol-dependent and culture-day-dependent effects on the cell composition and transcriptomic profiles in neuronal and vascular cells. We revealed the similarities and uniqueness of multiple vascularization strategies and demonstrated the transcriptomic effects of vascular induction on neuronal and mesodermal-like cell populations. Moreover, our data suggested that the interaction between neurons and mesodermal-like cell populations is important for the cerebrovascular-specific profile of endothelial-like cells. CONCLUSIONS: This study highlights the current challenges to vascularization strategies in human cerebral organoids and offers a benchmark for the future fabrication of vascularized organoids.

Graph Comparison of Molecular Crystals in Band Gap Prediction Using Neural Networks.

In material informatics, the representation of the material structure is fundamentally essential to obtaining better prediction results, and graph representation has attracted much attention in recent years. Molecular crystals can be graphically represented in molecular and crystal representations, but a comparison of which representation is more effective has not been examined. In this study, we compared the prediction accuracy between molecular and crystal graphs for band gap prediction. The results showed that the prediction accuracies using crystal graphs were better than those obtained using molecular graphs. While this result is not surprising, error analysis quantitatively evaluated that the error of the crystal graph was 0.4 times that of the molecular graph with moderate correlation. The novelty of this study lies in the comparison of molecular crystal representations and in the quantitative evaluation of the contribution of crystal structures to the band gap.

Muscle cell proliferation using water-soluble extract from nitrogen-fixing cyanobacteria Anabaena sp. PCC 7120 for sustainable cultured meat production.

Muscle cell cultivation, specifically the culture of artificial meat from livestock-derived cells in serum-free media is an emerging technology and has attracted much attention. However, till now, the high cost of production and environmental load have been significant deterrents. This study aims to provide an alternate growth-promoting substance that is free from animal derivatives and lowers nitrogen pollution. We have extracted water-soluble compounds from the filamentous nitrogen-fixing cyanobacteria Anabaena sp. PCC 7120 by the ultrasonication method. The heat-inactivated and molecular weight separation experiments were conducted to identify the bioactive compound present in the extract. Finally, the compounds soluble in water (CW) containing the water-soluble pigment protein, phycocyanin as a bioactive compound, was added as a growth supplement to cultivate muscle cells such as C2C12 muscle cells and quail muscle clone 7 (QM7) cells to analyze the effectiveness of the extract. The results indicated that CW had a positive role in muscle cell proliferation. A three-dimensional (3-D) cell-dense structure was fabricated by culturing QM7 cells using the extract. Furthermore, the nitrogen-fixing cyanobacterial extract has vast potential for cultured meat production without animal sera in the near future.

Covalent Immobilization of Collagen Type I to a Polydimethylsiloxane Surface for Preventing Cell Detachment by Retaining Collagen Molecules under Uniaxial Cyclic Mechanical Stretching Stress.

Surface modification of polydimethylsiloxane (PDMS) with an extracellular matrix (ECM) is useful for enhancing stable cell attachment. However, few studies have investigated the correlation between the stability of deposited ECM and cell behavior on the PDMS surfaces in external stretched cell culture systems. Herein, covalent collagen type I (Col)-immobilized PDMS surfaces were fabricated using 3-aminopropyl-trimethoxysilane, glutaraldehyde, and Col molecules. The immobilized collagen molecules on the PDMS surface were more stable and uniform than the physisorbed collagen. The cells stably adhered to the Col-immobilized surface and proliferated even under uniaxial cyclic mechanical stretching stress (UnCyMSt), whereas the cells gradually detached from the Col-physisorbed PDMS surface, accompanied by a decrease in the number of deposited collagen molecules. Moreover, the immobilization of collagen molecules enhanced cell alignment under the UnCyMSt. This study reveals that cell adhesion, proliferation, and alignment under the UnCyMSt can be attributed to the retention of collagen molecules on the PDMS surface.

Spatial and Sexual Divergence of Gut Bacterial Communities in Field Cricket Teleogryllus occipitalis (Orthoptera: Gryllidae).

The insect gut is colonized by microbes that confer a myriad of beneficial services to the host, including nutritional support, immune enhancement, and even influence behavior. Insect gut microbes show dynamic changes due to the gut compartments, sex, and seasonal and geographic influences. Crickets are omnivorous hemimetabolous insects that have sex-specific roles, such as males producing chirping sounds for communication and exhibiting fighting behavior. However, limited information is available on their gut bacterial communities, hampering studies on functional compartmentalization of the gut and sex-specific roles of the gut microbiota in omnivorous insects. Here, we report a metagenomic analysis of the gut bacteriome of the field cricket Teleogryllus occipitalis using 16S rRNA V3-V4 amplicon sequencing to identify sex- and compartment-dependent influences on its diversity and function. The structure of the gut microbiota is strongly influenced by their gut compartments rather than sex. The species richness and diversity analyses revealed large difference in the bacterial communities between the gut compartments while minor differences were observed between the sexes. Analysis of relative abundance and predicted functions revealed that nitrogen- and oxygen-dependent metabolism and amino acid turnover were subjected to functional compartmentalization in the gut. Comparisons between the sexes revealed differences in the gut microbiota, reflecting efficiency in energy use, including glycolytic and carbohydrate metabolism, suggesting a possible involvement in egg production in females. This study provides insights into the gut compartment dependent and sex-specific roles of host-gut symbiont interactions in crickets and the industrial production of crickets.

Open-Mouthed Hollow Carbons: Systematic Studies as Cobalt- and Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction Reaction.

Although hollow carbon structures have been extensively studied in recent years, their interior surfaces are not fully utilized due to the lack of fluent porous channels in the closed shell walls. This study presents a tailored design of open-mouthed particles hollow cobalt/nitrogen-doped carbon with mesoporous shells (OMH-Co/NC), which exhibits sufficient accessibility and electroactivity on both the inner and outer surfaces. By leveraging the self-conglobation effect of metal sulfate in methanol, a raspberry-structured Zn/Co-ZIF (R-Zn/Co-ZIF) precursor is obtained, which is further carbonized to fabricate the OMH-Co/NC. In-depth electrochemical investigations demonstrate that the introduction of open pores can enhance mass transfer and improve the utilization of the inner active sites. Benefiting from its unique structure, the resulting OMH-Co/NC exhibits exceptional electrocatalytic oxygen reduction performance, achieving a half-wave potential of 0.865 V and demonstrating excellent durability.