An extremely stable hydrogen-bonded organic framework, HOF-8, was fabricated. HOF-8 is not only thermally stable but also stable in water and common organic solvents. More interestingly, desolvated ...HOF-8 exhibits high CO2 adsorption as well as highly selective CO2 and C6H6 adsorption at ambient temperature.
MicroRNAs (miRs) are involved in lymphoma progression by regulating tumor cell interaction with microenvironment. MiR155 is overexpressed in diffuse large B-cell lymphoma (DLBCL) and its biological ...effect on tumor microenvironment needs to be futher investigated.
MiR155 was detected by quantitative real-time PCR in patients with newly diagnosed DLBCL. The mechanism of action of miR155 on lymphoma progression and tumor microenvironment was examined in vitro in B-lymphoma cell lines and in vivo in a murine xenograft model.
Serum miR155 was significantly elevated, correlated with tumor miR155 expression, and indicated poor disease outcome in DLBCL. MiR155 overexpression was associated with decreased peripheral blood CD8+T cells and inhibition of T-cell receptor signaling. Of note, EBV-positive patients showed higher serum miR155 than EBV-negative patients. In co-culture systems of B-lymphoma cells with immune cells, miR155 induced Fas-mediated apoptosis of CD8+T cells, which could be targeted by anti-PD-1 and anti-PD-L1 antibodies. Moreover, miR155 enhanced lymphoma cell PD-L1 expression, recruited CD8+T cells by PD-1/PD-L1 interaction and inhibited CD8+T cell function via dephosphorylating AKT and ERK. MiR155-induced AKT/ERK inactivation was more obvious in CD8+T cells co-cultured with EBV-infected B-lymphoma cells. In vivo in a murine xenograft model established with subcutaneous injection of A20 cells, PD-L1 blockade particularly retarded miR155-overexpressing tumor growth, consistent with maintenance of CD8+T cells and their function.
As a oncogenic biomarker of B-cell lymphoma, serum miR155 was related to lymphoma progression through modulating PD-1/PD-L1-mediated interaction with CD8+T cells of tumor microenvironment, indicating the sensitivity of B-cell lymphoma to PD-L1 blockade. Also CD8+T cells could be a therapeutic mediator of immune checkpoint inhibitors in treating EBV-associated lymphoid malignancies.
Charge transfer is vital in determining the optoelectronic properties of atomically thin materials, yet remains elusive in type I heterostructures. Here, distinct two‐step charge transfer processes ...in a type I MoS2/PtSe2 heterostructure are reported. By exclusively exciting the smaller bandgap PtSe2, strong exciton photobleaching peaks of the larger bandgap MoS2 are observed, indicating primary hot carrier transfer from PtSe2 to MoS2 within 70 fs. More importantly, the amplitude of the exciton peaks shows a secondary increase after the initial rapid decay. These dynamics are distinctly different from the monotonic decrease in monolayer MoS2 and indicate a secondary charge transfer process that is attributed to hot carriers re‐generated in PtSe2 by intralayer Auger recombination. Concurrently, the exciton energy blue shifts within 100 ps, probing the dynamic buildup of a charge‐transfer induced electric field across the heterostructure interface, which displaces electron and hole wavefunctions of MoS2 excitons and reduces the exciton binding energy. The results are corroborated by carrier dynamics and transient absorption spectra simulations by considering the two‐step charge transfer processes. The work reveals Auger‐assisted hot carrier transfer processes in type I heterostructures and suggests the possibility for optoelectronic and photocatalytic applications by optical sub‐bandgap excitation.
This work reports distinct primary and Auger‐assisted secondary hot carrier transfer processes from PtSe2 to MoS2 in a type I MoS2/PtSe2 heterostructure. Concurrently, the exciton energy blue shifts within 100 ps, probing the dynamic buildup of a charge‐transfer induced electric field across the heterostructure interface. The results are valuable for optoelectronic applications of type I heterostructure under sub‐bandgap excitation conditions.
Efficient removal of particulate matter (PM) is the major goal for various air cleaning technologies due to its huge impact on human health. Here, a washable high‐efficiency triboelectric air filter ...(TAF) that can be used multiple times is presented. The TAF consists of five layers of the polytetrafluoroethylene (PTFE) and nylon fabrics. Compared with traditional electrostatic precipitator, which requires a high‐voltage power supply, the TAF can be charged by simply rubbing the PTFE and nylon fabrics against each other. The electrical properties of the TAF are evaluated through the periodic contacting–separating of the PTFE and nylon fabrics using a linear motor, and an open‐circuit voltage of 190 V is achieved. After charging, the TAF has a removal efficiency of 84.7% for PM0.5, 96.0% for PM2.5, which are 3.22 and 1.39 times as large as the uncharged one. Most importantly, after washing several times, the removal efficiency of the TAF maintains almost the same, while the commercial face mask drops to 70% of its original efficiency. Furthermore, the removal efficiency of the PM2.5 is very stable under high relative humidity. Therefore, the TAF is promising for fabricating a reusable and high‐efficiency face mask.
A multilayer triboelectric air filter consists of five layers of polytetrafluoroethylene (PTFE) and nylon fabrics. A high removal efficiency is achieved by rubbing the fabrics against each other, and the removal efficiency maintains high under high humidity, in a durability test or after several washing cycles. Moreover, a face mask made of this air filter can be used in daily life.
Surface and interfaces play key roles in heterogeneous catalysis, electrochemistry and photo(electro)chemistry. Tip-enhanced Raman spectroscopy (TERS) combines plasmon-enhanced Raman spectroscopy ...with scanning probe microscopy to simultaneously provide a chemical fingerprint and morphological information for the sample at the nanometer spatial resolution. It is an ideal tool for achieving an in-depth understanding of the surface and interfacial processes, so that the relationship between structure and chemical performance can be established. We begin with the background of surfaces and interfaces and TERS, followed by a detailed discussion on some issues in experimental TERS, including tip preparation and TERS instrument configuration. We then focus on the progress of TERS for studying the surfaces and interfaces under different conditions, from ambient, to UHV, solid-liquid and electrochemical environments, followed by a brief introduction to the current understanding of the unprecedented high spatial resolution and surface selection rules. We conclude by discussing the future challenges for TERS practical applications in surfaces and interfaces.
TERS offers the high spatial resolution to establish structure-function correlation for surfaces and interfaces.
Improving electrochemical activity of graphene is crucial for its various applications, which requires delicate control over its geometric and electronic structures. We demonstrate that precise ...control of the density of vacancy defects, introduced by Ar+ irradiation, can improve and finely tune the heterogeneous electron transfer (HET) rate of graphene. For reliable comparisons, we made patterns with different defect densities on a same single layer graphene sheet, which allows us to correlate defect density (via Raman spectroscopy) with HET rate (via scanning electrochemical microscopy) of graphene quantitatively, under exactly the same experimental conditions. By balancing the defect induced increase of density of states (DOS) and decrease of conductivity, the optimal HET rate is attained at a moderate defect density, which is in a critical state; that is, the whole graphene sheet becomes electronically activated and, meanwhile, maintains structural integrity. The improved electrochemical activity can be understood by a high DOS near the Fermi level of defective graphene, as revealed by ab initio simulation, which enlarges the overlap between the electronic states of graphene and the redox couple. The results are valuable to promote the performance of graphene-based electrochemical devices. Furthermore, our findings may serve as a guide to tailor the structure and properties of graphene and other ultrathin two-dimensional materials through defect density engineering.
Resolving atomic site‐specific electronic properties and correlated substrate–molecule interactions is challenging in real space. Now, mapping of sub‐10 nm sized Pt nanoislands on a Au(111) surface ...was achieved by tip‐enhanced Raman spectroscopy, using the distinct Raman fingerprints of adsorbed 4‐chlorophenyl isocyanide molecules. A spatial resolution better than 2.5 nm allows the electronic properties of the terrace, step edge, kink, and corner sites with varying coordination environments to be resolved in real space in one Pt nanoisland. Calculations suggest that low‐coordinate atomic sites have a higher d‐band electronic profile and thus stronger metal–molecule interactions, leading to the observed blue‐shift of Raman frequency of the N≡C bond of adsorbed molecules. An experimental and theoretical study on Pt(111) and mono‐ and bi‐atomic layer Pt nanoislands on a Au(111) surface reveals the bimetallic effect that weakens with the increasing number of deposited Pt adlayer.
With a spatial resolution better than 2.5 nm, tip‐enhanced Raman spectroscopic imaging reveals unprecedented site‐specific electronic properties of different atomic sites with varying coordination numbers within a single, sub‐10 nm sized Pt nanoisland, using the distinct Raman fingerprints of adsorbed molecules. The work pushes forward the atomic‐ and molecular‐level characterization of heterogeneous catalysts.
The integration of metallic plasmonic nanoantennas with quantum emitters can dramatically enhance coherent harmonic generation, often resulting from the coupling of fundamental plasmonic fields to ...higher-energy, electronic or excitonic transitions of quantum emitters. The ultrafast optical dynamics of such hybrid plasmon-emitter systems have rarely been explored. Here, we study those dynamics by interferometrically probing nonlinear optical emission from individual porous gold nanosponges infiltrated with zinc oxide (ZnO) emitters. Few-femtosecond time-resolved photoelectron emission microscopy reveals multiple long-lived localized plasmonic hot spot modes, at the surface of the randomly disordered nanosponges, that are resonant in a broad spectral range. The locally enhanced plasmonic near-field couples to the ZnO excitons, enhancing sum-frequency generation from individual hot spots and boosting resonant excitonic emission. The quantum pathways of the coupling are uncovered from a two-dimensional spectrum correlating fundamental plasmonic excitations to nonlinearly driven excitonic emissions. Our results offer new opportunities for enhancing and coherently controlling optical nonlinearities by exploiting nonlinear plasmon-quantum emitter coupling.
Orbital interactions between adsorbed molecules and the underlying metal surfaces play critical roles in a wide range of surface and interfacial processes. Establishing a correlation between an ...experimental observable (
e.g.
, vibrational frequency shift of the adsorbed molecule) and the orbital interactions is of vital importance. Herein, theoretical calculations are used to investigate the vibrational frequency shift of phenyl isocyanide molecules as a probe molecule adsorbed on mono- and bi-layer Pt and Pd covered Au(111) surfaces and Pd
2
Au
4
and Pt
2
Au
4
clusters. By analyzing the density of states (DOS) of the adsorption system, we show that the orbital overlap area of d electronic DOS with a molecular σ or π* orbital, particularly their ratio (
R
d-σ/d-π*
), can be a meaningful descriptor to explain the frequency shift of the C&z.tbd;N moiety. This hypothesis has been verified by simulations for phenyl isocyanide with electron donating NH
2
- and withdrawing CF
3
- substituent groups, formonitrile and carbon monoxide. Quasi-linear dependence of the frequency shift on
R
d-σ/d-π*
is observed for both the red and blue shift regions. Our findings build up on previous notions of electronic interactions, which will provide a more quantitative and solid footing to understand and analyze the frequency shift of adsorbed molecules on metal surfaces and the related electronic interactions and catalytic properties.
The ratio of orbital overlap integral area between d-σ and d-π* peaks can correlate with the frequency shift.
An atomic- and molecular-level understanding of heterogeneous catalysis is required to characterize the nature of active sites and improve the rational design of catalysts. Achieving this level of ...characterization requires techniques that can correlate catalytic performances to specific surface structures, so as to avoid averaging effects. Tip-enhanced Raman spectroscopy combines scanning probe microscopy with plasmon-enhanced Raman scattering and provides simultaneous topographical and chemical information at the nano/atomic scale from ambient to ultrahigh-vacuum and electrochemical environments. Therefore, it has been used to monitor catalytic reactions and is proposed to correlate the local structure and function of heterogeneous catalysts. Bimetallic catalysts, such as Pd-Au, show superior performance in various catalytic reactions, but it has remained challenging to correlate structure and reactivity because of their structural complexity. Here, we show that TERS can chemically and spatially probe the site-specific chemical (electronic and catalytic) and physical (plasmonic) properties of an atomically well-defined Pd(sub-monolayer)/Au(111) bimetallic model catalyst at 3nm resolution in real space using phenyl isocyanide as a probe molecule (Fig. 1a). We observe a weakened NC bond and enhanced reactivity of phenyl isocyanide adsorbed at the Pd step edge compared with that at the Pd terrace. Density functional theory corroborates these observations by revealing a higher d-band electronic profile for the low-coordinated Pd step edge atoms. The 3nm spatial resolution we demonstrate here is the result of an enhanced electric field and distinct electronic properties at the step edges.
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