DNAzyme-activated CRISPR/Cas assay for sensitive and one-pot detection of lead contamination.

Hazardous lead ions (Pb2+) even at a minute level can pose side effects on human health, highlighting the need for tools for trace Pb2+ detection. Herein, we present a DNAzyme-activated CRISPR assay (termed DzCas12T) for sensitive and one-pot detection of lead contamination. Using an extension-bridged strategy eliminates the need for separation to couple the DNAzyme recognition and CRISPR reporting processes. The tandem design endowed the DzCas12T assay with high specificity and sensitivity down to the pM-level. This assay has been used to detect lead contamination in food and water samples, indicating the potential for monitoring lead-associated environmental and food safety.

Lithium Ion Intercalation-Induced Metal-Insulator Transition in Inclined-Standing Grown 2D Non-Layered Cr2S3 Nanosheets.

Gate-controlled ionic intercalation in the van der Waals gap of 2D layered materials can induce novel phases and unlock new properties. However, this strategy is often unsuitable for densely packed 2D non-layered materials. The non-layered rhombohedral Cr2S3 is an intrinsic heterodimensional superlattice with alternating layers of 2D CrS2 and 0D Cr1/3. Here an innovative chemical vapor deposition method is reported, utilizing strategically modified metal precursors to initiate entirely new seed layers, yields ultrathin inclined-standing grown 2D Cr2S3 nanosheets with edge instead of face contact with substrate surfaces, enabling rapid all-dry transfer to other substrates while ensuring high crystal quality. The unconventional ordered vacancy channels within the 0D Cr1/3 layers, as revealed by cross-sectional scanning transmission electron microscope, permitting the insertion of Li+ ions. An unprecedented metal-insulator transition, with a resistance modulation of up to six orders of magnitude at 300 K, is observed in Cr2S3-based ionic field-effect transistors. Theoretical calculations corroborate the metallization induced by Li-ion intercalation. This work sheds light on the understanding of growth mechanism, structure-property correlation and highlights the diverse potential applications of 2D non-layered Cr2S3 superlattice.

Ferrielectricity controlled widely-tunable magnetoelectric coupling in van der Waals multiferroics.

The discovery of various primary ferroic phases in atomically-thin van der Waals crystals have created a new two-dimensional wonderland for exploring and manipulating exotic quantum phases. It may also bring technical breakthroughs in device applications, as evident by prototypical functionalities of giant tunneling magnetoresistance, gate-tunable ferromagnetism and non-volatile ferroelectric memory etc. However, two-dimensional multiferroics with effective magnetoelectric coupling, which ultimately decides the future of multiferroic-based information technology, has not been realized yet. Here, we show that an unconventional magnetoelectric coupling mechanism interlocked with heterogeneous ferrielectric transitions emerges at the two-dimensional limit in van der Waals multiferroic CuCrP2S6 with inherent antiferromagnetism and antiferroelectricity. Distinct from the homogeneous antiferroelectric bulk, thin-layer CuCrP2S6 under external electric field makes layer-dependent heterogeneous ferrielectric transitions, minimizing the depolarization effect introduced by the rearrangements of Cu+ ions within the ferromagnetic van der Waals cages of CrS6 and P2S6 octahedrons. The resulting ferrielectric phases are characterized by substantially reduced interlayer magnetic coupling energy of nearly 50% with a moderate electric field of 0.3 V nm-1, producing widely-tunable magnetoelectric coupling which can be further engineered by asymmetrical electrode work functions.

Unveiling the aromatic differences of low-salt Chinese horse bean-chili-paste using metabolomics and sensomics approaches.

To achieve salt reduction while ensuring flavor quality of Chinese horse bean-chili-paste (CHCP), we comprehensively explored the effect of indigenous strains Tetragenococcus halophilus and Candida versatilis on the aroma profiles of low-salt CHCP by metabolomics and sensomics analysis. A total of 129 volatiles and 34 aroma compounds were identified by GC × GC-MS and GC-O-MS, among which 29 and 20 volatiles were identified as significant difference compounds and aroma-active compounds, respectively. Inoculation with the two indigenous strains could effectively relieve the undesired acidic and irritative flavor brought by acetic acid and some aldehydes in salt-reduction samples. Meanwhile, inoculated fermentation provided more complex and richer volatiles in low-salt batches, especially for the accumulation of 3-methylbutanol, 1-octen-3-ol, benzeneacetaldehyde, phenylethyl alcohol, and 4-ethyl-phenol etc., which were confirmed as essential aroma compounds of CHCP by recombination and omission tests. The research elucidated the feasibility of bioturbation strategy to achieve salt-reducing fermentation of fermented foods.

The structural stability of Mn3Sn Heusler compound under high pressure.

Pressure engineering has attracted growing interest in the understanding of structural changes and structure-property relations of layered materials. In this study, we investigated the effect of pressure on the crystal structure of Mn3Sn.In-situhigh-pressure x-ray diffraction experiments revealed that Mn3Sn maintained hexagonal lattice symmetry within the pressure range of ambient to 50.4 GPa. The ratio of lattice constantsc/ais almost independent of the pressure and remains constant at 0.80, indicating a stable cell shape. Density functional theory calculations revealed the strong correlation between the crystal structure and the localization ofdelectrons. The Mn3Sn has been found in flat energy bands near the Fermi level, exhibiting a large density of states (DOS) primarily contributed by thedelectrons. This large DOS near the Fermi level increases the energy barrier for a phase transition, making the transition from the hexagonal phase to the tetragonal phase challenging. Our results confirm the structural stability of Mn3Sn under high pressure, which is beneficial to the robustness of spintronic devices.

Surface-Phosphorylated Ceria for Chlorine-Tolerance Catalysis.

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) identified a predominantly HPO4 active structure on CeO2(110) and CeO2(111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO4. Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl•) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO2-supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.

Giant and Nonanalytic Negative Piezoelectric Response in Elemental Group-Va Ferroelectric Monolayers.

Materials with negative longitudinal piezoelectric response have been a focus of recent research. So far, reported examples are mostly three-dimensional bulk materials, either compounds with strong ionic bonds or layered materials with van der Waals interlayer gaps. Here, we report the first example in two-dimensional elemental materials-the class of group-Va monolayers. From first-principles calculations, we show that these materials possess giant negative longitudinal piezoelectric coefficient e_{11}. Importantly, its physical mechanism is also distinct from all previous proposals, connected with the special buckling driven polarization in these elemental systems. As a result, the usually positive internal strain contribution to piezoelectricity becomes negative and even dominates over the clamped ion contribution in Bi monolayers. Based on this new mechanism, we also find several 2D crystal structures that may support negative longitudinal piezoelectricity. As another consequence, piezoelectric response in Bi monolayers exhibits a significant nonanalytic behavior, namely, the e_{11} coefficient takes sizably different values (differed by ∼18%) under tensile and compressive strains, a phenomenon not known before and helpful for the development of novel electromechanical devices.

Two-Dimensional Atomically Thin Titanium Nitride via Topochemical Conversion.

Titanium nitride as a typical transition metal nitride (TMN) has attracted increasing interest for its fascinating characteristics and widespread applications. However, the synthesis of two-dimensional (2D) atomically thin titanium nitride is still challenging which hinders its further research in electronic and optoelectronic fields. Here, 2D titanium nitride with a large area was prepared via in situ topochemical conversion of the titanate monolayer. The titanium nitride reveals a thickness-dependent metallic-to-semiconducting transition, where the atomically thin titanium nitride with a thickness of ∼1 nm exhibits an n-type semiconducting behavior and a highly sensitive photoresponse and displays photoswitchable resistance by repeated light irradiation. First-principles calculations confirm that the chemisorbed oxygen on the surface of the titanium nitride nanosheet depletes its electrons, while the light irradiation induced desorption of oxygen leads to increased electron doping and hence the conductance of titanium nitride. These results may allow the scalable synthesis of ultrathin TMNs and facilitate their fundamental physics research and next-generation optoelectronic applications.

Emergence of ferroelectricity in a nonferroelectric monolayer.

Ferroelectricity in ultrathin two-dimensional (2D) materials has attracted broad interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, ferroelectricity is barely explored in materials with native centro or mirror symmetry, especially in the 2D limit. Here, we report the first experimental realization of room-temperature ferroelectricity in van der Waals layered GaSe down to monolayer with mirror symmetric structures, which exhibits strong intercorrelated out-of-plane and in-plane electric polarization. The origin of ferroelectricity in GaSe comes from intralayer sliding of the Se atomic sublayers, which breaks the local structural mirror symmetry and forms dipole moment alignment. Ferroelectric switching is demonstrated in nano devices fabricated with GaSe nanoflakes, which exhibit exotic nonvolatile memory behavior with a high channel current on/off ratio. Our work reveals that intralayer sliding is a new approach to generate ferroelectricity within mirror symmetric monolayer, and offers great opportunity for novel nonvolatile memory devices and optoelectronics applications.

Spin-Lattice Coupled Metamagnetism in Frustrated van der Waals Magnet CrOCl.

The long-range magnetic ordering in frustrated magnetic systems is stabilized by coupling magnetic moments to various degrees of freedom, for example, by enhancing magnetic anisotropy via lattice distortion. Here, the unconventional spin-lattice coupled metamagnetic properties of atomically-thin CrOCl, a van der Waals antiferromagnet with inherent magnetic frustration rooted in the staggered square lattice, are reported. Using temperature- and angle-dependent tunneling magnetoconductance (TMC), in complementary with magnetic torque and first-principles calculations, the antiferromagnetic (AFM)-to-ferrimagnetic (FiM) metamagnetic transitions (MTs) of few-layer CrOCl are revealed to be triggered by collective magnetic moment flipping rather than the established spin-flop mechanism, when external magnetic field (H) enforces a lattice reconstruction interlocked with the five-fold periodicity of the FiM phase. The spin-lattice coupled MTs are manifested by drastic jumps in TMC, which show anomalous upshifts at the transition thresholds and persist much higher above the AFM Néel temperature. While the MTs exhibit distinctive triaxial anisotropy, reflecting divergent magnetocrystalline anisotropy of the c-axis AFM ground state, the resulting FiM phase has an a-c easy plane in which the magnetization axis is freely rotated by H. At the 2D limit, such a field-tunable FiM phase may provide unique opportunities to explore exotic emergent phenomena and novel spintronics devices.

Shear stress and plaque microenvironment induce heterogeneity: A multiscale microenvironment evolution model.

BACKGROUND: Both clinical images and in vivo observations have demonstrated the heterogeneity in atherosclerotic plaque composition. However, the quantitative mechanisms that contribute to the heterogeneity, such as the wall shear stress (WSS) and the interplays among microenvironmental factors are still unclear. METHODS: We develop a multiscale model coupling computational fluid dynamics, interactions of microenvironmental factors and evolutions of cellular behaviors to investigate the formation of plaque heterogeneity in a three-dimensional vessel segment. The model involves WSS, lipid deposition and inflammatory response to reveal the dynamic balance existed between the lipid metabolism and the phagocytosis of macrophages. RESULTS: The dynamic balance in microenvironment is influenced by both the WSS and the interactions with microenvironmental factors, and consequently results in the longitudinal heterogeneity observed in plaque pathology. In addition, plaque heterogeneity can be reduced by decreasing low WSS area at downstream, as well as by altering the phagocytic abilities of macrophage on lipoproteins, which may be used to develop future plaque regression strategies. CONCLUSIONS: This multiscale modeling provides a framework to understand the mechanisms in dynamics of plaque composition and also provides quantitative information to better risk stratification of plaque vulnerability in future clinical practice.

Two-dimensional ferroelectricity in a single-element bismuth monolayer.

Ferroelectric materials are fascinating for their non-volatile switchable electric polarizations induced by the spontaneous inversion-symmetry breaking. However, in all of the conventional ferroelectric compounds, at least two constituent ions are required to support the polarization switching1,2. Here, we report the observation of a single-element ferroelectric state in a black phosphorus-like bismuth layer3, in which the ordered charge transfer and the regular atom distortion between sublattices happen simultaneously. Instead of a homogenous orbital configuration that ordinarily occurs in elementary substances, we found the Bi atoms in a black phosphorous-like Bi monolayer maintain a weak and anisotropic sp orbital hybridization, giving rise to the inversion-symmetry-broken buckled structure accompanied with charge redistribution in the unit cell. As a result, the in-plane electric polarization emerges in the Bi monolayer. Using the in-plane electric field produced by scanning probe microscopy, ferroelectric switching is further visualized experimentally. Owing to the conjugative locking between the charge transfer and atom displacement, we also observe the anomalous electric potential profile at the 180° tail-to-tail domain wall induced by competition between the electronic structure and electric polarization. This emergent single-element ferroelectricity broadens the mechanism of ferroelectrics and may enrich the applications of ferroelectronics in the future.

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current.

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO3 single-crystal substrates by solution reaction at a low temperature of ~200 oC. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm2, corresponding to the highest photoresponsivity of ~4.306×10-3 A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices.

Comprehensive investigation on volatile and non-volatile metabolites in low-salt doubanjiang with different fermentation methods.

Doubanjiang is a well-known fermented condiment in China, but the high-salt concentration in its traditional manufacture process greatly lengthens the fermentation time, and leads to potential health risks. Here, the effects of salt reduction and co-inoculated starters (Tetragenococcus halophilus and Zygosaccharomyces rouxii) on the volatile metabolites (VMs) and non-volatile metabolites (NVMs) of doubanjiang were investigated using metabolomics technology and chemometrics analysis. Results showed that 75 VMs were identified, and 12 of them had significant aroma contribution (ROVAs ≥ 1). In addition, 106 NVMs were defined as significantly different metabolites (p < 0.05; VIP ≥ 1). Salt reduction could significantly increase the concentrations of VMs, but this strategy also promoted some undesirable odors like 2-phetylfuran and hexanoic acid, which could be totally suppressed by inoculation of starter. Moreover, the two starters improved amino acid, ester, and acid metabolites. This study provides a deeper insight into the development of low-salt fermented foods.

CRISPR-Cas based molecular diagnostics for foodborne pathogens.

Foodborne pathogenic infection has brought multifaceted issues to human life, leading to an urgent demand for advanced detection technologies. CRISPR/Cas-based biosensors have the potential to address various challenges that exist in conventional assays such as insensitivity, long turnaround time and complex pretreatments. In this perspective, we review the relevant strategies of CRISPR/Cas-assisted diagnostics on foodborne pathogens, focusing on biosensing platforms for foodborne pathogens based on fluorescence, colorimetric, (electro)chemiluminescence, electrochemical, and surface-enhanced Raman scattering detection. It summarizes their detection principles by the clarification of foodborne pathogenic bacteria, fungi, and viruses. Finally, we discuss the current challenges or technical barriers of these methods against broad application, and put forward alternative solutions to improve CRISPR/Cas potential for food safety.

Direct Observation of the Topological Surface State in the Topological Superconductor 2M-WS2.

The quantum spin Hall (QSH) effect has attracted extensive research interest because of the potential applications in spintronics and quantum computing, which is attributable to two conducting edge channels with opposite spin polarization and the quantized electronic conductance of 2e2/h. Recently, 2M-WS2, a new stable phase of transition metal dichalcogenides with a 2M structure showing a layer configuration identical to that of the monolayer 1T' TMDs, was suggested to be a QSH insulator as well as a superconductor with a critical transition temperature of around 8 K. Here, high-resolution angle-resolved photoemission spectroscopy (ARPES) and spin-resolved ARPES are applied to investigate the electronic and spin structure of the topological surface states (TSS) in the superconducting 2M-WS2. The TSS exhibit characteristic spin-momentum-locking behavior, suggesting the existence of long-sought nontrivial Z2 topological states therein. We expect that 2M-WS2 with coexisting superconductivity and TSS might host the promising Majorana bound states.

Rapid screening of antimicrobial probiotics using CRISPR cascade.

Animal bacterial infection is increasingly threatening human health. Here we report a nucleic acid amplification-free CRISPR genetic assay that allows to rapidly screen potential food-origin antimicrobial probiotics. The assay (termed CRISPRzyme assay) is based on a CRISPR-DNAzyme cascade, where the target gene sequentially activated Cas12a protein and DNAzyme, yielding a limit of detection of 62 CFU Vibrio parahaemolyticus, 86 CFU Salmonella Typhimurium, and 82 CFU Listeria monocytogenes. The elimination of nucleic acid amplification shortens processing time and operational complexity. The assay was used to rapidly screen antimicrobial probiotics by end-measurement of fluorescence of pathogenic bacteria. Particularly, it can estimate the in vivo antimicrobial effect due to its capacity for pathogen quantification in complex samples. We found that isolates of Bacillus and lactic acid bacteria separated from fermented food exhibited strong antimicrobial activity for fish pathogen, Vibrio parahaemolyticus, and identified surfactin as the key antimicrobial component. The CRISPRzyme assay could ease antimicrobial probiotics screening, and constitutes a new tool for combatting pathogenic bacterial contamination and infection.

DNA-mediated assembly of a gold-nanoparticle film with controllable sonic behavior detected by novel electric-induced ultrasound.

Two-dimensional gold-assembled nanomaterials have garnered considerable interest in biomedical applications such as wearable sensors and flexible devices. The assembly can be accomplished via attractive interactions between gold nanoparticles (GNPs) and a standard polymer. It is highly desirable and a great challenge to develop a new assembly method that can provide formed materials with novel properties. In this work, we explored complementary DNA-functionalized gold nanoparticles (DNA-GNPs) as building blocks to establish multifunctional two-dimensional gold nanomaterials via layer-by-layer (LBL) assembly. We found that the DNA-mediated assembly endows GNP films with a superlattice and their sonic behavior could be regulated in a controllable manner through altering the sequence of SH-DNA and linker DNA, which was detected by the electric-induced ultrasound method. Our observation suggested that this DNA-mediated assembly of GNP films with controllable sonic behaviors could greatly promote the biomedical application of two-dimensional assembled-gold nanomaterials.

M4 B6 X6 as a New Family of High-Efficient Electrocatalysts: The Role of Surface Reconstruction in Water Oxidization.

Searching for highly-efficient electrocatalysts for water splitting has been greatly endowed due to the huge demand for green energy sources. Two-dimensional (2D) materials are widely explored for the purpose because of their unique physical and chemical properties, abundant active sites, and easy fabrication. Here, we present a new family of 2D M4 B6 X6 (2D Boridenes) and investigate their physical and chemical properties for their potential applications into electrocatalysis based on first-principles calculations. We demonstrate that 2D M4 B6 X6 (M=Cr, Mo, and W; X=O and F) are dynamically, thermodynamically, and mechanically stable, and show intriguing electronic and catalytic properties. Importantly, we find that M4 B6 O6 are intrinsically active for oxygen evolution reaction (OER). Our results demonstrate that: (1) the adsorbate-escape mechanism dominates the OER process with a low overpotential of 0.652 V on Cr4 B6 O6 ; (2) the partial surface-oxidization can improve the catalytic performance of M4 B6 F6 dramatically; and (3) the surface reconstruction greatly affects the OER performance of M4 B6 X6 . Our findings illustrate that the surface reconstruction is critical to the OER activity, which may provide a new strategy on the design of 2D materials for electrocatalysis and offer theoretical insight into the catalytic mechanism.