Discovery and Manipulation of van der Waals Polarons in Sb2O3 Ultrathin Molecular Crystal.

Manipulating single electrons at the atomic scale is vital for mastering complex surface processes governed by the transfer of individual electrons. Polarons, composed of electrons stabilized by electron-phonon coupling, offer a pivotal medium for such manipulation. Here, using scanning tunneling microscopy and spectroscopy (STM/STS) and density functional theory (DFT) calculations, we report the identification and manipulation of a new type of polaron, dubbed van der Waals (vdW) polaron, within mono- to trilayer ultrathin films composed of Sb2O3 molecules that are bonded via vdW attractions. The Sb2O3 films were grown on a graphene-covered SiC(0001) substrate via molecular beam epitaxy. Unlike prior molecular polarons, STM imaging observed polarons at the interstitial sites of the molecular film, presenting unique electronic states and localized band bending. DFT calculations revealed the lowest conduction band as an intermolecular bonding state, capable of ensnaring an extra electron through locally diminished intermolecular distances, thereby forming an intermolecular vdW polaron. We also demonstrated the ability to generate, move, and erase such vdW polarons using an STM tip. Our work uncovers a new type of polaron stabilized by coupling with intermolecular vibrations where vdW interactions dominate, paving the way for designing atomic-scale electron transfer processes and enabling precise tailoring of electron-related properties and functionalities.

Quasi-Emulsion Confined Synthesis of Edge-Rich Ultrathin MoS2 Nanosheets/Graphene Hybrid for Enhanced Hydrogen Evolution.

High-purity hydrogen produced by water splitting is considered as one of the most promising fuels to replace traditional fossil fuels. Developing highly efficient electrocatalysts toward hydrogen evolution is vital for the realization of large-scale H2 generation. Glycerol is used herein in a facile solvothermal process to synthesize edge-rich ultrathin MoS2 /reduced graphene oxide (RGO) composites. The introduction of glycerol plays an important role in the formation of such interesting structures. The MoS2 /RGO electrocatalyst exhibits excellent hydrogen evolution reaction (HER) activity and remarkable stability, owing to the rich active edges and improved electrical conductivity of the catalyst composites. This work provides new insights to engineer the structures of MoSx -based composites and thus achieves more active and efficient electrocatalysts.

Molybdenum Carbide-Based Electrocatalysts for Hydrogen Evolution Reaction.

Electrocatalytic water splitting is a promising approach for clean and sustainable hydrogen production. Its large-scale application relies on the availability of low cost and efficient electrocatalysts. Earth-abundant transition-metal carbides, especially molybdenum carbides (Mox C), are regarded as potential candidates to replace state-of-art but expensive platinum-group electrocatalysts. In this Review, we summarize recent progress in Mox C electrocatalysts for hydrogen evolution reaction (HER). Nanostructure engineering on the design and preparation of highly efficient electrocatalysts based on Mox C is presented, followed by the comparison and discussion of HER performance on Mox C-based electrocatalysts. Finally, we offer a perspective on the future development of Mox C-based electrocatalysts towards HER.

Quasimolecules in Compressed Lithium.

Under high pressure, some materials form electrides, with valence electrons separated from all atoms and occupying interstitial regions. This is often accompanied by semiconducting or insulating behavior. The interstitial quasiatoms (ISQ) that characterize some high pressure electrides have been postulated to show some of the chemical features of atoms, including the potential of forming covalent bonds. It is argued that in the observed high-pressure semiconducting Li phase (oC40, Aba2), an example of such quasimolecules is realized. The theoretical evaluation of electron density, electron localization function, Wannier orbitals, and bond indices forms the evidence for covalently bonded ISQ pairs in this material. The quasimolecule concept thus provides a simple chemical perspective on the unusual insulating behavior of such materials, complementing the physical picture previously presented where the global crystal symmetry of the system plays the major role.

Highly Robust Nanopore-Based Dual-Signal-Output Ion Detection System for Achieving Three Successive Calibration Curves.

In recent years, artificial stimuli-responsive bioinspired nanopores have attracted a lot of attention due to their unique property of confined spaces and flexibility in terms of shapes and sizes. Most of the nanopore systems demonstrated their transmembrane properties and applications in target detections. However, almost all of the nanopores can be used only once due to either the irreversible reactions between targets and probes or the plugged nanopores not easily being unplugged again. In this work, we propose a dual-signal-output nanopore system that could detect the cations (Hg(2+)) inducing the plugged nanopores. The detection system is highly recoverable by the anions (S(2-)) inducing the unplugged nanopores. More importantly, as far as we know, it is seldom reported for the same nanopores to achieve successive calibration curves for three times by subsequent reversible plug-unplug processes, which strongly demonstrates the high robustness of this novel nanopore-detection system. In addition, unlike monitoring the plug-unplug phenomena by only one type of signal, we combined the ionic current signal with the fluorescence output and could directly observe that the change of ionic current does in fact correspond to the plug-unplug of the nanopores by the target stimuli.

Facile Probe Design: Fluorescent Amphiphilic Nucleic Acid Probes without Quencher Providing Telomerase Activity Imaging Inside Living Cells.

Nowadays, the probe with fluorophore but no quencher is promising for its simple preparation, environmental friendliness, and wide application scope. This study designs a new amphiphilic nucleic acid probe (ANAP) based on aggregation-caused quenching (ACQ) effect without any quencher. Upon binding with targets, the dispersion of hydrophobic part (conjugated fluorene, CF) in ANAP is enhanced as a signal-on model for proteins, nucleic acids, and small molecules detection or the aggregation of CF is enhanced as a signal-off model for ion detection. Meanwhile, because of the high specificity of ANAP, a one-step method is developed powerfully for monitoring the telomerase activity not only from the cell extracts but also from 50 clinic urine samples (positive results from 45 patients with bladder cancer and negative results from 5 healthy people). ANAPs can also readily enter into cells and exhibit a good performance for distinguishing natural tumor cells from the tumor cells pretreated by telomerase-related drugs or normal cells. In contrast to our previous results ( Anal. Chem. 2015 , 87 , 3890 - 3894 ), the present CF is a monomer which is just the structure unit of the previous fluorescent polymer. Since the accurate molecular structure and high DNA/CF ratio of the present CF, these advanced experiments obtain an easier preparation of probes, an improved sensitivity and specificity, and broader detectable targets.

High-pressure electrides: the chemical nature of interstitial quasiatoms.

Building on our previous chemical and physical model of high-pressure electrides (HPEs), we explore the effects of interaction of electrons confined in crystals but off the atoms, under conditions of extreme pressure. Electrons in the quantized energy levels of voids or vacancies, interstitial quasiatoms (ISQs), effectively interact with each or with other atoms, in ways that are quite chemical. With the well-characterized Na HPE as an example, we explore the ionic limit, ISQs behaving as anions. A detailed comparison with known ionic compounds points to high ISQ charge density. ISQs may also form what appear to be covalent bonds with neighboring ISQs or real atoms, similarly confined. Our study looks specifically at quasimolecular model systems (two ISQs, a Li atom and a one-electron ISQ, a Mg atom and two ISQs), in a compression chamber made of He atoms. The electronic density due to the formation of bonding and antibonding molecular orbitals of the compressed entities is recognizable, and a bonding stabilization, which increases with pressure, is estimated. Finally, we use the computed Mg electride to understand metallic bonding in one class of electrides. In general, the space confined between atoms in a high pressure environment offers up quantized states to electrons. These ISQs, even as they lack centering nuclei, in their interactions with each other and neighboring atoms may show anionic, covalent, or metallic bonding, all the chemical features of an atom.

Anionic chemistry of noble gases: formation of Mg-NG (NG = Xe, Kr, Ar) compounds under pressure.

While often considered to be chemically inert, the reactivity of noble gas elements at elevated pressures is an important aspect of fundamental chemistry. The discovery of Xe oxidation transformed the doctrinal boundary of chemistry by showing that a complete electron shell is not inert to reaction. However, the reductive propensity, i.e., gaining electrons and forming anions, has not been proposed or examined for noble gas elements. In this work, we demonstrate, using first-principles electronic structure calculations coupled to an efficient structure prediction method, that Xe, Kr, and Ar can form thermodynamically stable compounds with Mg at high pressure (≥125, ≥250, and ≥250 GPa, respectively). The resulting compounds are metallic and the noble gas atoms are negatively charged, suggesting that chemical species with a completely filled shell can gain electrons, filling their outermost shell(s). Moreover, this work indicates that Mg2NG (NG = Xe, Kr, Ar) are high-pressure electrides with some of the electrons localized at interstitial sites enclosed by the surrounding atoms. Previous predictions showed that such electrides only form in Mg and its compounds at very high pressures (>500 GPa). These calculations also demonstrate strong chemical interactions between the Xe 5d orbitals and the quantized interstitial quasiatom (ISQ) orbitals, including the strong chemical bonding and electron transfer, revealing the chemical nature of the ISQ.

Rational designed bipolar, conjugated polymer-DNA composite beacon for the sensitive detection of proteins and ions.

Nature owns remarkable capabilities in sensing target molecules, while the artificial biosensor lags far behind nature. Inspired by nature, we devise a new sensing platform that can specifically bind the molecules and synchronously initiate a specific signal response. We rationally designed a type of bipolar probe that is comprised of a hydrophilic DNA part and a hydrophobic conjugated polymer (CP) unit. In aqueous solution, they can form micelles with a hydrophobic CP core and a hydrophilic DNA shell. The aggregation-caused quenching suppresses the fluorescence of CP. Adding telomerase, the hydropathical profile of the bipolar probes is drastically regulated that results in the collapse of micelles and liberates fluorescence simultaneously. The probe has been used in both mimic systems and real urine samples (38 samples). We achieve sensitive and specific detection of telomerase and obtain clearly classification for normal people and cancer patients. It can also be used in a signal off sensor that is used to detect mercury ions.

High pressure electrides: a predictive chemical and physical theory.

Electrides, in which electrons occupy interstitial regions in the crystal and behave as anions, appear as new phases for many elements (and compounds) under high pressure. We propose a unified theory of high pressure electrides (HPEs) by treating electrons in the interstitial sites as filling the quantized orbitals of the interstitial space enclosed by the surrounding atom cores, generating what we call an interstitial quasi-atom, ISQ. With increasing pressure, the energies of the valence orbitals of atoms increase more significantly than the ISQ levels, due to repulsion, exclusion by the atom cores, effectively giving the valence electrons less room in which to move. At a high enough pressure, which depends on the element and its orbitals, the frontier atomic electron may become higher in energy than the ISQ, resulting in electron transfer to the interstitial space and the formation of an HPE. By using a He lattice model to compress (with minimal orbital interaction at moderate pressures between the surrounding He and the contained atoms or molecules) atoms and an interstitial space, we are able to semiquantitatively explain and predict the propensity of various elements to form HPEs. The slopes in energy of various orbitals with pressure (s > p > d) are essential for identifying trends across the entire Periodic Table. We predict that the elements forming HPEs under 500 GPa will be Li, Na (both already known to do so), Al, and, near the high end of this pressure range, Mg, Si, Tl, In, and Pb. Ferromagnetic electrides for the heavier alkali metals, suggested by Pickard and Needs, potentially compete with transformation to d-group metals.

Molecular CsF5 and CsF2+.

D5h star-like CsF5 , formally isoelectronic with known XeF5 (-) ion, is computed to be a local minimum on the potential energy surface of CsF5 , surrounded by reasonably large activation energies for its exothermic decomposition to CsF+2 F2 , or to CsF3 (three isomeric forms)+F2 , or for rearrangement to a significantly more stable isomer, a classical Cs(+) complex of F5 (-) . Similarly the CsF2 (+) ion is computed to be metastable in two isomeric forms. In the more symmetrical structures of these molecules there is definite involvement in bonding of the formally core 5p levels of Cs.

Mercury under Pressure acts as a Transition Metal: Calculated from First Principles.

The inclusion of Hg among the transition metals is readily debated. Recently, molecular HgF4 was synthesized in a low-temperature noble gas but the potential of Hg to form compounds beyond a +2 oxidation state in a stable solid remains unresolved. We propose high-pressure techniques to prepare unusual oxidation states of Hg-based compounds. Using an advanced structure search algorithm and first-principles electronic structure calculations, we find that under high pressure Hg in Hg-F compounds transfers charge from the d orbitals to the F, thus behaving as a transition metal. Oxidizing Hg to +4 and +3 yielded the thermodynamically stable compounds HgF4 and HgF3. The former consists of HgF4 planar molecules, a typical geometry for d(8) metal centers. HgF3 is metallic and ferromagnetic owing to the d(9) configuration of Hg, with a large gap between its partially occupied and unoccupied bands under high pressure.

Striking effect of intra- versus intermolecular hydrogen bonding on zwitterions: physical and electronic properties.

We report the synthesis, characterization, and application of novel zwitterions. The zwitterionic structures consist of a positively charged cyanine and negatively charged dienolate moieties, confirmed by experimental observations and theoretical calculations. Single crystal X-ray studies revealed that BIT-(NPh)2 is a coplanar molecule that forms 1-D chains via π-π interactions. In contrast, BIT-(NHexyl)2 is a twisted molecule with a dihedral angle of 78° between the charged planes. In charge transport studies, thin films of the flat zwitterion show semiconducting properties, with a hole mobility of 2.1 × 10(-4) cm(2) V(-1) s(-1) while the twisted zwitterion is a high resistivity insulator.

[Feasibility of the aging males' symptoms scale for the male population of Shanghai].

OBJECTIVE: To assess the reliability and validity of the Aging Males' Symptoms (AMS) scale in the male population of Shanghai. METHODS: We enrolled 973 males aged 40 years and over in a community of Shanghai, China. Using the AMS scale, we calculated the split-half reliability coefficient and Cronbach's alpha coefficient, assessed the validity through confirmatory factor analysis and correlation analysis, and obtained the domain scores of different people by analysis of variance and independent sample test. RESULTS: The split-half reliability was > 0.78 (P < 0.01) and Cronbach's alpha coefficients of all the dimensions > 0.82 (P < 0.01). Confirmatory factor analysis showed 3 domains in the AMS scale, Pearson correlation coefficients of all the items to their domains were > 0.49 (P < 0.01), and the total testosterone level was not correlated with AMS scores, with Pearson correlation coefficient of -0.04 (P > 0.05). Statistically significant differences were found in AMS scores among different age groups as well as among those with different chronic disease histories, but not in the psychological domain among different age groups. CONCLUSION: The reliability and validity of the AMS scale are acceptable in assessing aging males'symptoms among the male population of Shanghai, but further studies are needed to determine whether it could be used as a tool for screening late-onset hypogonadism (LOH) in males.

Manipulating single excess electrons in monolayer transition metal dihalide.

Polarons are entities of excess electrons dressed with local response of lattices, whose atomic-scale characterization is essential for understanding the many body physics arising from the electron-lattice entanglement, yet difficult to achieve. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we show the visualization and manipulation of single polarons in monolayer CoCl2, that are grown on HOPG substrate via molecular beam epitaxy. Two types of polarons are identified, both inducing upward local band bending, but exhibiting distinct appearances, lattice occupations and polaronic states. First principles calculations unveil origin of polarons that are stabilized by cooperative electron-electron and electron-phonon interactions. Both types of polarons can be created, moved, erased, and moreover interconverted individually by the STM tip, as driven by tip electric field and inelastic electron tunneling effect. This finding identifies the rich category of polarons in CoCl2 and their feasibility of precise control unprecedently, which can be generalized to other transition metal halides.

Trends in the electronic structure of extended gold compounds: implications for use of gold in heterogeneous catalysis.

First-principles electronic structure calculations are presented on a variety of Au compounds and species--encompassing a wide range of formal oxidation states, coordination geometries, and chemical environments--in order to understand the potentially systematic behavior in the nature and energetics of d states that are implicated in catalytic activity. In particular, we monitor the position of the d-band center, which has been suggested to signal catalytic activity for reactions such as CO oxidation. We find a surprising absence of any kind of correlation between the formal oxidation state of Au and the position of the d-band center. Instead, we find that the center of the d band displays a nearly linear dependence on the degree of its filling, and this is a general relationship for Au irrespective of the chemistry or geometry of the particular Au compound. Across the compounds examined we find that even small calculated changes in the d-band filling result in a relatively large effect on the position of the d-band center. The results presented here have some important implications for the question of the catalytic activity of Au and indicate that the formal oxidation state is not a determining factor.

A novel all-nitrogen molecular crystal N16 as a promising high-energy-density material.

All-nitrogen solids, if successfully synthesized, are ideal high-energy-density materials because they store a great amount of energy and produce only harmless N2 gas upon decomposition. Currently, the only method to obtain all-nitrogen solids is to apply high pressure to N2 crystals. However, products such as cg-N tend to decompose upon releasing the pressure. Compared to covalent solids, molecular crystals are more likely to remain stable during decompression because they can relax the strain by increasing the intermolecular distances. The challenge of such a route is to find a molecular crystal that can attain a favorable phase under elevated pressure. In this work, we show, by designing a novel N16 molecule (tripentazolylamine) and examining its crystal structures under a series of pressures, that the aromatic units and high molecular symmetry are the key factors to achieving an all-nitrogen molecular crystal. Density functional calculations and structural studies reveal that this new all-nitrogen molecular crystal exhibits a particularly slow enthalpy increase with pressure due to the highly efficient crystal packing of its highly symmetric molecules. Vibration mode calculations and molecular dynamics (MD) simulations show that N16 crystals are metastable at ambient pressure and could remain inactive up to 400 K. The initial reaction steps of the decomposition are calculated by following the pathway of the concerted excision of N2 from the N5 group as revealed by the MD simulations.

Planar Heterojunction of Ultrathin CrTe3 and CrTe2 van der Waals Magnet.

The fabrication of planar heterojunctions with magnetic van der Waals ultrathin crystals is essential for constructing miniaturized spintronic devices but is yet to be realized. Here, we report the growth of CrTe3 and CrTe2 ultrathin films with molecular beam epitaxy and characterize their morphological and electronic structure through low-temperature scanning tunneling microscopy/spectroscopy. The former is identified as a Mott insulator, and the latter has shown a robust magnetic order previously. Through vacuum annealing, CrTe3 can be transformed into CrTe2, whose relative ratio is controlled via the annealing time. This renders the feasibility of constructing CrTe3-CrTe2 planar heterojunctions, which express atomically sharp interfaces and smooth band bending. We also identified a superstructure conceivably formed via hybrid units of CrTe3 and CrTe2, whose electronic structure exhibits stunning tunability with the length of the superstructure. Our study sets a foundation for the development of magnetic tunneling junctions for building spintronic circuits and engineering electronic states in artificial superlattice structures.

Spin mapping of intralayer antiferromagnetism and field-induced spin reorientation in monolayer CrTe2.

Intrinsic antiferromagnetism in van der Waals (vdW) monolayer (ML) crystals enriches our understanding of two-dimensional (2D) magnetic orders and presents several advantages over ferromagnetism in spintronic applications. However, studies of 2D intrinsic antiferromagnetism are sparse, owing to the lack of net magnetisation. Here, by combining spin-polarised scanning tunnelling microscopy and first-principles calculations, we investigate the magnetism of vdW ML CrTe2, which has been successfully grown through molecular-beam epitaxy. We observe a stable antiferromagnetic (AFM) order at the atomic scale in the ML crystal, whose bulk is ferromagnetic, and correlate its imaged zigzag spin texture with the atomic lattice structure. The AFM order exhibits an intriguing noncollinear spin reorientation under magnetic fields, consistent with its calculated moderate magnetic anisotropy. The findings of this study demonstrate the intricacy of 2D vdW magnetic materials and pave the way for their in-depth analysis.

Mifepristone-induced abortion and duration of third stage labour in a subsequent pregnancy.

To evaluate the impact of mifepristone-induced abortion (MA) on the duration of third stage labour in a subsequent pregnancy, an observational cohort study was conducted from 1998 to 2001 at antenatal clinics in Shanghai, Beijing and Chengdu, China. A total of 4925 pregnant women with no history of induced abortion (NA) and 4931 pregnant women with one previous MA were enrolled and followed until delivery. Of these, 5139 women who delivered singletons vaginally were used in the present analyses, including 2614 with NA and 2525 with a history of MA. Maternal characteristics, labour duration and other obstetric and gynaecological information were obtained. The incidence rates of prolonged third stage of labour were 1.55% and 1.49% in NA and MA, respectively. After adjusting for age at delivery, maternal education, maternal occupation, area of residence, duration of gestational, type of delivery and pregnancy-induced hypertension, MA was not associated with the risk of prolonged third stage of labour (odds ratios = 0.92, 95% confidence interval 0.58, 1.44). Subgroup analysis of women with MA showed similar results regardless of gestational age at abortion, woman's age at abortion, subsequent curettage/complications and the interpregnancy interval. In conclusion, the data did not provide evidence that one MA was associated with the risk of prolonged third stage of labour in a subsequent pregnancy in primiparae.