Tuning Pore Size in Graphene in the Angstrom Regime for Highly Selective Ion-Ion Separation.

Zero-dimensional pores spanning only a few angstroms in size in two-dimensional materials such as graphene are some of the most promising systems for designing ion-ion selective membranes. However, the key challenge in the field is that so far a crack-free macroscopic graphene membrane for ion-ion separation has not been realized. Further, methods to tune the pores in the Å-regime to achieve a large ion-ion selectivity from the graphene pore have not been realized. Herein, we report an Å-scale pore size tuning tool for single layer graphene, which incorporates a high density of ion-ion selective pores between 3.5 and 8.5 Å while minimizing the nonselective pores above 10 Å. These pores impose a strong confinement for ions, which results in extremely high selectivity from centimeter-scale porous graphene between monovalent and bivalent ions and near complete blockage of ions with the hydration diameter, DH, greater than 9.0 Å. The ion diffusion study reveals the presence of an energy barrier corresponding to partial dehydration of ions with the barrier increasing with DH. We observe a reversal of K+/Li+ selectivity at elevated temperature and attribute this to the relative size of the dehydrated ions. These results underscore the promise of porous two-dimensional materials for solute-solute separation when Å-scale pores can be incorporated in a precise manner.

Mechanistic Insights on Functionalization of Graphene with Ozone.

The exposure of graphene to O3 results in functionalization of its lattice with epoxy, even at room temperature. This reaction is of fundamental interest for precise lattice patterning, however, is not well understood. Herein, using van der Waals density functional theory (vdW-DFT) incorporating spin-polarized calculations, we find that O3 strongly physisorbs on graphene with a binding energy of -0.46 eV. It configures in a tilted position with the two terminal O atoms centered above the neighboring graphene honeycombs. A dissociative chemisorption follows by surpassing an energy barrier of 0.75 eV and grafting an epoxy group on graphene reducing the energy of the system by 0.14 eV from the physisorbed state. Subsequent O3 chemisorption is preferred on the same honeycomb, yielding two epoxy groups separated by a single C-C bridge. We show that capturing the onset of spin in oxygen during chemisorption is crucial. We verify this finding with experiments where an exponential increase in the density of epoxy groups as a function of reaction temperature yields an energy barrier of 0.66 eV, in agreement with the DFT prediction. These insights will help efforts to obtain precise patterning of the graphene lattice.

Unraveling the Oxidation of a Graphitic Lattice: Structure Determination of Oxygen Clusters.

Unraveling the oxidation of graphitic lattice is of great interest for atomic-scale lattice manipulation. Herein, we build epoxy cluster, atom by atom, using Van der Waals' density-functional theory aided by Clar's aromatic π-sextet rule. We predict the formation of cyclic epoxy trimers and its linear chains propagating along the armchair direction of the lattice to minimize the system's energy. Using low-temperature scanning tunneling microscopy on oxidized graphitic lattice, we identify linear chains as bright features that have a threefold symmetry, and which exclusively run along the armchair direction of the lattice confirming the theoretical predictions.

Selective Photonic Gasification of Strained Oxygen Clusters on Graphene for Tuning Pore Size in the Å Regime.

Controlling the size of single-digit pores, such as those in graphene, with an Å resolution has been challenging due to the limited understanding of pore evolution at the atomic scale. The controlled oxidation of graphene has led to Å-scale pores; however, obtaining a fine control over pore evolution from the pore precursor (i.e., the oxygen cluster) is very attractive. Herein, we introduce a novel "control knob" for gasifying clusters to form pores. We show that the cluster evolves into a core/shell structure composed of an epoxy group surrounding an ether core in a bid to reduce the lattice strain at the cluster core. We then selectively gasified the strained core by exposing it to 3.2 eV of light at room temperature. This allowed for pore formation with improved control compared to thermal gasification. This is because, for the latter, cluster-cluster coalescence via thermally promoted epoxy diffusion cannot be ruled out. Using the oxidation temperature as a control knob, we were able to systematically increase the pore density while maintaining a narrow size distribution. This allowed us to increase H2 permeance as well as H2 selectivity. We further show that these pores could differentiate CH4 from N2, which is considered to be a challenging separation. Dedicated molecular dynamics simulations and potential of mean force calculations revealed that the free energy barrier for CH4 translocation through the pores was lower than that for N2. Overall, this study will inspire research on the controlled manipulation of clusters for improved precision in incorporating Å-scale pores in graphene.

Subcycle surface electron emission driven by strong-field terahertz waveforms.

The advent of intense terahertz (THz) sources opened a new era when the demonstration of the acceleration and manipulation of free electrons by THz pulses became within reach. THz-field-driven electron emission was predicted to be confined to a single burst due to the single-cycle waveform. Here we demonstrate the confinement of single-cycle THz-waveform-driven electron emission to one of the two half cycles from a solid surface emitter. Either the leading or the trailing half cycle was active, controlled by reversing the field polarity. THz-driven single-burst surface electron emission sources, which do not rely on field-enhancement structures, will impact the development of THz-powered electron acceleration and manipulation devices, all-THz compact electron sources, THz waveguides and telecommunication, THz-field-based measurement techniques and solid-state devices.

Unit-cell-thick zeolitic imidazolate framework films for membrane application.

Zeolitic imidazolate frameworks (ZIFs) are a subset of metal-organic frameworks with more than 200 characterized crystalline and amorphous networks made of divalent transition metal centres (for example, Zn2+ and Co2+) linked by imidazolate linkers. ZIF thin films have been intensively pursued, motivated by the desire to prepare membranes for selective gas and liquid separations. To achieve membranes with high throughput, as in ångström-scale biological channels with nanometre-scale path lengths, ZIF films with the minimum possible thickness-down to just one unit cell-are highly desired. However, the state-of-the-art methods yield membranes where ZIF films have thickness exceeding 50 nm. Here we report a crystallization method from ultradilute precursor mixtures, which exploits registry with the underlying crystalline substrate, yielding (within minutes) crystalline ZIF films with thickness down to that of a single structural building unit (2 nm). The film crystallized on graphene has a rigid aperture made of a six-membered zinc imidazolate coordination ring, enabling high-permselective H2 separation performance. The method reported here will probably accelerate the development of two-dimensional metal-organic framework films for efficient membrane separation.

Unsymmetrical Phosphodiesters as GPR84 Antagonists with High Blood Exposure for the Treatment of Lung Inflammation.

GPR84 is a proinflammatory G protein-coupled receptor that mediates myeloid immune cell functions. Blocking GPR84 with antagonists is a promising approach for treating inflammatory and fibrotic diseases. Previously, a GPR84 antagonist 604c, with a symmetrical phosphodiester structure, has displayed promising efficacy in a mouse model of ulcerative colitis. However, the low blood exposure resulting from physicochemical properties prevented its uses in other inflammatory diseases. In this study, a series of unsymmetrical phosphodiesters with lower lipophilicity were designed and tested. The representative compound 37 exhibited a 100-fold increase in mouse blood exposure compared to 604c while maintaining in vitro activity. In a mouse model of acute lung injury, 37 (30 mg/kg, po) significantly reduced the infiltration of proinflammatory cells and the release of inflammatory cytokines and ameliorated pathological changes equally or more effectively than N-acetylcysteine (100 mg/kg, po). These findings suggest that 37 is a promising candidate for treating lung inflammation.

In Situ Nucleation-Decoupled and Site-Specific Incorporation of Å-Scale Pores in Graphene Via Epoxidation.

Generating pores in graphene by decoupled nucleation and expansion is desired to achieve a fine control over the porosity, and is desired to advance several applications. Herein, epoxidation is introduced, which is the formation of nanosized epoxy clusters on the graphitic lattice as nucleation sites without forming pores. In situ gasification of clusters inside a transmission electron microscope shows that pores are generated precisely at the site of the clusters by surpassing an energy barrier of 1.3 eV. Binding energy predictions using ab initio calculations combined with the cluster nucleation theory reveal the structure of the epoxy clusters and indicate that the critical cluster is an epoxy dimer. Finally, it is shown that the cluster gasification can be manipulated to form Å-scale pores which then effectively sieve gas molecules based on their size. This decoupled cluster nucleation and pore formation will likely pave the way for an independent control of pore size and density.

Water dynamics in the hydration shell of hyper-branched poly-ethylenimine.

We performed THz and GHz dielectric relaxation spectroscopy to investigate the reorientational dynamics of water molecules in the hydration shell of amphiphilic hyper-branched poly-ethylenimine (HPEI). Four Debye equations were employed to describe four types of water in the hydration shell, including bulk-like water, under-coordinated water, slow water (water molecules hydrating the hydrophobic groups and water molecules accepting hydrogen bonds from the NH2 groups) and super slow water (water molecules donating hydrogen bonds to and accepting hydrogen bonds from NH groups). The time scales of undercoordinated and bulk-like water show a slight decline from 0.4 to 0.1 ps and from 8 to 2 ps, respectively. Because of hydrophilic amino groups, HPEI molecules exhibit a strong retardation effect, where the time scales of slow and super slow water increase with concentration from 17 to 39.9 ps and from 88 to 225 ps, respectively.

Structure Evolution of Graphitic Surface upon Oxidation: Insights by Scanning Tunneling Microscopy.

Oxidation of graphitic materials has been studied for more than a century to synthesize materials such as graphene oxide, nanoporous graphene, and to cut or unzip carbon nanotubes. However, the understanding of the early stages of oxidation is limited to theoretical studies, and experimental validation has been elusive. This is due to (i) challenging sample preparation for characterization because of the presence of highly mobile and reactive epoxy groups formed during oxidation, and (ii) gasification of the functional groups during imaging with atomic resolution, e.g., by transmission electron microscopy. Herein, we utilize a low-temperature scanning tunneling microscope (LT-STM) operating at 4 K to solve the structure of epoxy clusters form upon oxidation. Three distinct nanostructures corresponding to three stages of evolution of vacancy defects are found by quantitatively verifying the experimental data by the van der Waals density functional theory. The smallest cluster is a cyclic epoxy trimer. Their observation validates the theoretical prediction that epoxy trimers minimize the energy in the cyclic structure. The trimers grow into honeycomb superstructures to form larger clusters (1-3 nm). Vacancy defects evolve only in the larger clusters (2-3 nm) in the middle of the cluster, highlighting the role of lattice strain in the generation of vacancies. Semiquinone groups are also present and are assigned at the carbon edge in the vacancy defects. Upon heating to 800 °C, we observe cluster-free vacancy defects resulting from the loss of the entire epoxy population, indicating a reversible functionalization of epoxy groups.

Divergent Connectivity Changes in Gray Matter Structural Covariance Networks in Subjective Cognitive Decline, Amnestic Mild Cognitive Impairment, and Alzheimer's Disease.

Alzheimer's disease (AD) has a long preclinical stage that can last for decades prior to progressing toward amnestic mild cognitive impairment (aMCI) and/or dementia. Subjective cognitive decline (SCD) is characterized by self-experienced memory decline without any evidence of objective cognitive decline and is regarded as the later stage of preclinical AD. It has been reported that the changes in structural covariance patterns are affected by AD pathology in the patients with AD and aMCI within the specific large-scale brain networks. However, the changes in structural covariance patterns including normal control (NC), SCD, aMCI, and AD are still poorly understood. In this study, we recruited 42 NCs, 35 individuals with SCD, 43 patients with aMCI, and 41 patients with AD. Gray matter (GM) volumes were extracted from 10 readily identifiable regions of interest involved in high-order cognitive function and AD-related dysfunctional structures. The volume values were used to predict the regional densities in the whole brain by using voxel-based statistical and multiple linear regression models. Decreased structural covariance and weakened connectivity strength were observed in individuals with SCD compared with NCs. Structural covariance networks (SCNs) seeding from the default mode network (DMN), salience network, subfields of the hippocampus, and cholinergic basal forebrain showed increased structural covariance at the early stage of AD (referring to aMCI) and decreased structural covariance at the dementia stage (referring to AD). Moreover, the SCN seeding from the executive control network (ECN) showed a linearly increased extent of the structural covariance during the early and dementia stages. The results suggest that changes in structural covariance patterns as the order of NC-SCD-aMCI-AD are divergent and dynamic, and support the structural disconnection hypothesis in individuals with SCD.

Bottom-up synthesis of graphene films hosting atom-thick molecular-sieving apertures.

Incorporation of a high density of molecular-sieving nanopores in the graphene lattice by the bottom-up synthesis is highly attractive for high-performance membranes. Herein, we achieve this by a controlled synthesis of nanocrystalline graphene where incomplete growth of a few nanometer-sized, misoriented grains generates molecular-sized pores in the lattice. The density of pores is comparable to that obtained by the state-of-the-art postsynthetic etching (1012 cm-2) and is up to two orders of magnitude higher than that of molecular-sieving intrinsic vacancy defects in single-layer graphene (SLG) prepared by chemical vapor deposition. The porous nanocrystalline graphene (PNG) films are synthesized by precipitation of C dissolved in the Ni matrix where the C concentration is regulated by controlled pyrolysis of precursors (polymers and/or sugar). The PNG film is made of few-layered graphene except near the grain edge where the grains taper down to a single layer and eventually terminate into vacancy defects at a node where three or more grains meet. This unique nanostructure is highly attractive for the membranes because the layered domains improve the mechanical robustness of the film while the atom-thick molecular-sized apertures allow the realization of large gas transport. The combination of gas permeance and gas pair selectivity is comparable to that from the nanoporous SLG membranes prepared by state-of-the-art postsynthetic lattice etching. Overall, the method reported here improves the scale-up potential of graphene membranes by cutting down the processing steps.

Probing lattice vibration of alkali halide crystals by broadband terahertz spectroscopy.

Terahertz spectral features of alkali halide crystals were studied with the combination of broadband terahertz time-domain spectroscopy and the solid-state-based density functional theory calculations. To understand the particular modes of the observed terahertz features of the alkali halide crystals, the resonant modes of KCl and CsCl were analyzed using face-centered cubic and body-centered cubic lattice models, respectively. The results show that the characteristic terahertz absorption peaks could be assigned to the lattice vibration of the ionic crystals. Furthermore, the terahertz responses of a series of alkali halides were recorded, and obvious absorption peaks were observed in each salt in the frequency region below 8.5 THz. What is more interestingly is that the frequencies of these observed peaks are red-shifted with the increases of the mass and radius of the ions. This correlation between the resonant frequency of the lattice vibration, the reduced atomic mass, and the equilibrium distance between the ions agrees well with the harmonic oscillator model.

Millisecond lattice gasification for high-density CO2- and O2-sieving nanopores in single-layer graphene.

Etching single-layer graphene to incorporate a high pore density with sub-angstrom precision in molecular differentiation is critical to realize the promising high-flux separation of similar-sized gas molecules, e.g., CO2 from N2 However, rapid etching kinetics needed to achieve the high pore density is challenging to control for such precision. Here, we report a millisecond carbon gasification chemistry incorporating high density (>1012 cm-2) of functional oxygen clusters that then evolve in CO2-sieving vacancy defects under controlled and predictable gasification conditions. A statistical distribution of nanopore lattice isomers is observed, in good agreement with the theoretical solution to the isomer cataloging problem. The gasification technique is scalable, and a centimeter-scale membrane is demonstrated. Last, molecular cutoff could be adjusted by 0.1 Å by in situ expansion of the vacancy defects in an O2 atmosphere. Large CO2 and O2 permeances (>10,000 and 1000 GPU, respectively) are demonstrated accompanying attractive CO2/N2 and O2/N2 selectivities.

Coupling Plasmonic System for Efficient Wavefront Control.

Efficient and flexible manipulation of electromagnetic waves using metasurfaces has attracted continuous attention in recent years. However, previous studies mainly apply sole resonance effect to accomplish the task. Here, we show that introducing a meta-coupling effect would reveal further physical insights in the electromagnetic wave control. To demonstrate this, a reflection-type coupling system composed by two identical linear resonances in a metal-insulator-metal configuration is theoretically proposed using the coupled-mode theory, whose phase diagram can be well controlled upon the coupling changes. Such intriguing optical property is verified by a double C-shaped resonator in the terahertz regime, where the coupling effect can be tuned by changing their either relative distance or rotation. More importantly, the reflection phase shift around the working frequency can be efficiently engineered without having to change the dimensions of the resonators. Two efficient anomalous metasurface deflectors are designed and experimentally characterized, whose maximum measured efficiency is more than 70%. The proposed controlling strategy further enriches the designing freedoms of metasurfaces and may find broad applications in realizing efficient and tunable functional devices.

Exceptional point in a metal-graphene hybrid metasurface with tunable asymmetric loss.

Observation of exceptional points (EPs) in non-Hermitian parity-time (PT) symmetric systems has led to various nontrivial physics and exotic phenomena. Here, a metal-graphene hybrid non-Hermitian metasurface is proposed in the terahertz regime, whose unit cell is composed of two orthogonally oriented split-ring resonators (SRRs) with identical dimensions but only one SRR containing a graphene patch at the gap. An EP in polarization space is theoretically observed at a certain Fermi level of the graphene patch, where the induced asymmetric loss and the coupling strength between the two SRRs match a certain relation predicted by a coupled mode theory. The numerical fittings using the coupled mode theory agree well with the simulations. Besides, an abrupt phase flip around the EP frequency is observed in the transmission in circular polarization basis, which can be very promising in ultra-sensitive sensing applications.

A novel degradation mechanism of the elastic modulus of wet polymer substrates under nanoindentation.

We demonstrated that the formation and solidification of a continuous confined water film played a very important role in changing the elastic modulus of the wet polymer substrate in a nanoindentation process by a coarse-grained molecular dynamics simulation of this process. It was found that as the water content increased, the elastic modulus of the wet polymer substrate showed a non-monotonic change. Relative to the dry polymer substrate, the elastic modulus of the wet polymer first decreased. This is because the appearance of a confined water film caused the force between the polymer substrate and the indenter to change from repulsion to attraction. Subsequently, as the confined water film gradually solidified and then weakened, the elastic modulus of the wet polymer slowly increased and then rapidly increased due to a large number of interstitial water molecules gradually penetrating the polymer substrate. Therefore, it is unreasonable to explain the wet polymer degradation during nanoindentation only from the plasticization and anti-plasticization effects based on the hydrogen bond breaking and formation during stretching. The above-mentioned results will help to more comprehensively understand the degradation mechanism of the polymers' encounter with water, thus promoting further practical applications for polymers.

Polarization-insensitive tunable terahertz polarization rotator.

A rotation-angle variable polarization rotator is proposed and demonstrated using an all-dielectric metasurface doublet. Such a transmissive device can conveniently rotate the polarization of incident light by any desired angles by mechanically changing the relative angle of the double metasurface layers regardless of the incident state of polarization. Under certain conditions the device acts as a full phase modulator for the circularly polarized incident wave. Hence, it has a promising application in polarization and phase control.

Terahertz electric field modulated mode coupling in graphene-metal hybrid metamaterials.

Taking advantage of the tunable conductivity of graphene under high terahertz (THz) electric field, a graphene-metal hybrid metamaterial consisting of an array of three adjoined orthogonally oriented split-ring resonators (SRRs) is proposed and experimentally demonstrated to show a maximum modulation depth of 23% in transmission when the THz peak field reaches 305 kV/cm. The transmission of the sample is dominated by the antisymmetric and symmetric resonant modes originating from the strong magneto-inductive and conductive coupling among the three SRRs, respectively. Numerical simulations and model calculations based on a coupled oscillator theory were performed to explain the modulation process. It is found that the graphene coating impairs the resonances by increasing the damping of the modes and decreasing the coupling between the SRRs whereas the strong THz field restores the resonances by decreasing the conductivity of graphene.

Polarization-dependent electromagnetic responses in an A-shape metasurface.

We numerically and experimentally demonstrate polarization-dependent terahertz responses in a proposed metasurface of A-shape resonators. With the horizontal polarization incidence, the observed transmission window is formed by two resonance dips, corresponding to the inductive-capacitive resonance at the lower frequency and the high-order antisymmetric resonance at a higher frequency, respectively. When the incident wave is perpendicularly polarized, the transmission window arises from the plasmon-induced transparency spectral response. The origin of the polarization-sensitive resonance properties is revealed by mapping the electric field and terahertz-induced surface current in the proposed metamaterials. Moreover, the influence of the geometry of the A-shape microstructures on the transmission spectra is analyzed. These polarization-dependent metamaterials may provide more degrees of freedom in tuning the electromagnetic responses, thus offering a path toward robust metamaterials design.