Our latest publication employed PalmGRET, a bioluminescence-resonance-energy-transfer (BRET)-based EV reporter, to discover an abundant release of big EVs (bEVs; >200 nm) by aggressive breast cancers when compared to epithelial and less malignant cells. bEVs have been largely overshadowed by small EVs (sEVs; <200 nm) in EV research in the past decades. This is the first study to accurately detect and systematically compare biophysical property and in vivo profiles of breast cancer bEVs and sEVs. This is followed by the identification of EV surface oncoproteins, and their role in modulating organotropism and tumorigenic potential of the bEVs and sEVs. Our landmark findings impart a broad and deep reference for upcoming EV studies, with an emphasis on EV engineering for diagnosis and therapeutic applications.
Phase Modulation of Self-Gating in Ionic Liquid-Functionalized InSe Field-Effect Transistors
Chih-Yi Cheng, Wei-Liang Pai, Yi-Hsun Chen, Naomi Tabudlong Paylaga, Pin-Yun Wu, Chun-Wei Chen, Chi-Te Liang, Fang-Cheng Chou, Raman Sankar, Michael S. Fuhrer, Shao-Yu Chen*, and Wei-Hua Wang*
Understanding the Coulomb interactions between two-dimensional (2D) materials and adjacent ions/impurities is essential to realizing 2D material-based hybrid devices. Electrostatic gating via ionic liquids (ILs) has been employed to study the properties of 2D materials. However, the intrinsic interactions between 2D materials and ILs are rarely addressed. This work studies the intersystem Coulomb interactions in IL-functionalized InSe field-effect transistors by displacement current measurements. We uncover a strong self-gating effect that yields a 50-fold enhancement in interfacial capacitance, reaching 550 nF/cm2 in the maximum. Moreover, we reveal the IL-phase-dependent transport characteristics, including the channel current, carrier mobility, and density, substantiating the self-gating at the InSe/IL interface. The dominance of self-gating in the rubber phase is attributed to the correlation between the intra- and intersystem Coulomb interactions, further confirmed by Raman spectroscopy. This study provides insights into the capacitive coupling at the InSe/IL interface, paving the way to developing liquid/2D material hybrid devices.
Employing direct Z-scheme semiconductor heterostructures in photocatalysis offers efficient charge carrier separation and isolation of both redox reactions, thus beneficial to reduce CO2 into solar fuels. Here, a ZnS/ZnIn2S4 heterostructure, comprising cubic ZnS nanocrystals on hexagonal ZnIn2S4 (ZIS) nanosheets, is successfully fabricated in a single-pot hydrothermal approach. The composite ZnS/ZnIn2S4 exhibits microstrain at its interface with an electric field favorable for Z-scheme. At an optimum ratio of Zn:In (~ 1:0.5), an excellent photochemical quantum efficiency of around 0.8% is reached, nearly 200-fold boost compared with pristine ZnS. Electronic levels and band alignments are deduced from ultraviolet photoemission spectroscopy and UV-Vis. Evidence of the direct Z-scheme and carrier dynamics is verified by photo-reduction experiment, along with photoluminescence (PL) and time-resolved PL. Finally, diffuse-reflectance infrared Fourier transformed spectroscopy explores the CO2 and related intermediate species adsorbed on the catalyst during the photocatalytic reaction. This microstrain-induced direct Z-scheme approach opens a new pathway for developing next-generation photocatalysts for CO2 reduction.
Macroscopic quantum electrodynamics approach to multichromophoric excitation energy transfer. I. Formalism [Special Issue: 2022 JCP Emerging Investigators Special Collection]
Siwei Wang, Yi-Ting Chuang and Liang-Yan Hsu*
In this study, we develop a theory of multichromophoric excitation energy transfer (MC-EET) in the framework of macroscopic quantum electrodynamics. The theory we present is general for studying the interplay between energy transfer and fluorescence in the presence of arbitrary inhomogeneous, dispersive, and absorbing media. The dynamical equations of MC-EET, including energy-transfer kernels and fluorescence kernels, allow us to describe the combined effects of molecular vibrations and photonic environments on excitation energy transfer. To demonstrate the universality of the MC-EET theory, we show that under specific conditions, the MC-EET theory can be converted to three representative theories. First, under the Markov approximation, we derive an explicit Förster-type expression for plasmon-coupled resonance energy transfer [Hsu et al., J. Phys. Chem. Lett. 8, 2357 (2017)] from the MC-EET theory. In addition, the MC-EET theory also provides a parameter-free formula to estimate transition dipole–dipole interactions mediated by photonic environments. Second, we generalize the theory of multichromophoric Förster resonance energy transfer [Jang et al., Phys. Rev. Lett. 92, 218301 (2004)] to include the effects of retardation and dielectric environments. Third, for molecules weakly coupled with photonic modes, the MC-EET theory recovers the previous main result in Chance–Prock–Silbey classical fluorescence theory [Chance et al., J. Chem. Phys. 60, 2744 (1974)]. This study opens a promising direction for exploring light–matter interactions in multichromophoric systems with possible applications in the exciton migration in metal–organic framework materials and organic photovoltaic devices.
Cavity-Free Quantum-Electrodynamic Electron Transfer Reactions
Yu-Chen Wei and Liang-Yan Hsu*
Richard Feynman stated that “The theory behind chemistry is quantum electrodynamics”. However, harnessing quantum-electrodynamic (QED) effects to modify chemical reactions is a grand challenge and currently has only been reported in experiments using cavities due to the limitation of strong light–matter coupling. In this article, we demonstrate that QED effects can significantly enhance the rate of electron transfer (ET) by several orders of magnitude in the absence of cavities, which is implicitly supported by experimental reports. To understand how cavity-free QED effects are involved in ET reactions, we incorporate the effect of infinite one-photon states into Marcus theory, derive an explicit expression for the rate of radiative ET, and develop the concept of “electron transfer overlap”. Moreover, QED effects may lead to a barrier-free ET reaction whose rate is dependent on the energy-gap power law. This study thus provides new insights into fundamental chemical principles, with promising prospects for QED-based chemical reactions.
Explorations of symmetry and topology have led to important breakthroughs in quantum optics, but much richer behaviors arise from the non-Hermitian nature of light-matter interactions. A high-reflectivity, non-Hermitian optical mirror can be realized by a two-dimensional subwavelength array of neutral atoms near the cooperative resonance associated with the collective dipole modes. Here we show that exceptional points develop from a nondefective degeneracy by lowering the crystal symmetry of a square atomic lattice, and dispersive bulk Fermi arcs that originate from exceptional points are truncated by the light cone. From its nontrivial energy spectra topology, we demonstrate that the geometry-dependent non-Hermitian skin effect emerges in a ribbon geometry. Furthermore, skin modes localized at a boundary show a scale-free behavior that stems from the long-range interaction and whose mechanism goes beyond the framework of non-Bloch band theory. Our work opens the door to the study of the interplay among non-Hermiticity, topology, and long-range interaction.
Synchronized two-color time-resolved dual-comb spectroscopy for quantitative detection of HOx radicals formed from Criegee intermediates
Pei-Ling Luo* and I-Yun Chen
A novel spectrometer has been developed based on synchronized two-color time-resolved dual-comb spectroscopy (TRDCS), enabling high-resolution hyperspectral measurements. The proposed approach with TRDCS exhibits great potential in quantitative diagnostics of multispecies and opens opportunities to decipher key reaction mechanisms in atmospheric chemistry. In this work, we perform simultaneous measurements in two distinct molecular fingerprint regions near 2.9 and 7.8 μm by employing the new approach with synchronized two-color TRDCS. Upon flash photolysis of CH2I2/O2/N2 gas mixtures, multiple reaction species, involving the simplest Criegee intermediates (CH2OO), formaldehyde (CH2O), hydroxyl (OH) and hydroperoxy (HO2) radicals are simultaneously detected with microsecond time resolution. The concentration of each molecule can be determined based on high-resolution rovibrational absorption spectroscopy. With quantitative detection and simulation of temporal concentration profiles of the targeted molecules at various conditions, the underlying reaction mechanisms and pathways related to the formation of the HOx radicals, which can be generated from decomposition of initially energized and vibrationally excited Criegee intermediates, are explored.
Limited methods are available for investigating the reorientational dynamics of A-site cations in two-dimensional organic–inorganic hybrid perovskites (2D OIHPs), which play a pivotal role in determining their physical properties. Here, we describe an approach to study the dynamics of A-site cations using solid-state NMR and stable isotope labelling. 2H NMR of 2D OIHPs incorporating methyl-d3-ammonium cations (d3-MA) reveals the existence of multiple modes of reorientational motions of MA. Rotational-echo double resonance (REDOR) NMR of 2D OIHPs incorporating 15N- and 13C-labeled methylammonium cations (13C,15N-MA) reﬂects the averaged dipolar coupling between the C and N nuclei undergoing different modes of motions. Our study reveals the interplay between the A-site cation dynamics and the structural rigidity of the organic spacers, so providing a molecular-level insight into the design of 2D OIHPs.
Chromatin is a DNA–protein complex that is densely packed in the cell nucleus. The nanoscale chromatin compaction plays critical roles in the modulation of cell nuclear processes. However, little is known about the spatiotemporal dynamics of chromatin compaction states because it remains difficult to quantitatively measure the chromatin compaction level in live cells. Here, we demonstrate a strategy, referenced as DYNAMICS imaging, for mapping chromatin organization in live cell nuclei by analyzing the dynamic scattering signal of molecular fluctuations. Highly sensitive optical interference microscopy, coherent brightfield (COBRI) microscopy, is implemented to detect the linear scattering of unlabeled chromatin at a high speed. A theoretical model is established to determine the local chromatin density from the statistical fluctuation of the measured scattering signal. DYNAMICS imaging allows us to reconstruct a speckle-free nucleus map that is highly correlated to the fluorescence chromatin image. Moreover, together with calibration based on nanoparticle colloids, we show that the DYNAMICS signal is sensitive to the chromatin compaction level at the nanoscale. We confirm the effectiveness of DYNAMICS imaging in detecting the condensation and decondensation of chromatin induced by chemical drug treatments. Importantly, the stable scattering signal supports a continuous observation of the chromatin condensation and decondensation processes for more than 1 h. Using this technique, we detect transient and nanoscopic chromatin condensation events occurring on a time scale of a few seconds. Label-free DYNAMICS imaging offers the opportunity to investigate chromatin conformational dynamics and to explore their significance in various gene activities.Link to the paper: https://pubs.acs.org/doi/10.1021/acsnano.1c09748Recommended in Faculty Opinion: https://facultyopinions.com/prime/741388510Reported by Science Promotion & Engagement Center: https://spec.ntu.edu.tw/20220322-research-chem/
We here report on the direct observation of ferroelectric properties of water ice in its 2D phase. Upon nanoelectromechanical confinement between two graphene layers, water forms a 2D ice phase at room temperature that exhibits a strong and permanent dipole which depends on the previously applied field, representing clear evidence for ferroelectric ordering. Characterization of this permanent polarization with respect to varying water partial pressure and temperature reveals the importance of forming a monolayer of 2D ice for ferroelectric ordering which agrees with ab-initio and molecular dynamics simulations conducted. The observed robust ferroelectric properties of 2D ice enable novel nanoelectromechanical devices that exhibit memristive properties. A unique bipolar mechanical switching behavior is observed where previous charging history controls the transition voltage between low-resistance and high-resistance state. This advance enables the realization of rugged, non-volatile, mechanical memory exhibiting switching ratios of 106, 4 bit storage capabilities and no degradation after 10,000 switching cycles.
We here demonstrate the multifunctional properties of atomically thin heterojunctions that are enabled by strong interfacial interactions and their integration into ultra-high performance, self-powered sensors. Epitaxial alignment between tin diselenide and graphene through direct growth produces thermoelectric and mechanoelectric properties beyond the ability of either component. An unprecedented ZT of 2.43 originated from the synergistic combination of graphene’s high carrier conductivity and SnSe2 mediated thermal conductivity lowering. Moreover, strong interaction at the SnSe2/graphene interface produces stress localization that results in a novel 2D-crack-assisted strain sensing mechanism whose sensitivity (GF=450) is superior to all other 2D materials. Finally, the graphene-assisted growth process, permits the formation of high-quality heterojunctions directly on polymeric substrates for flexible and transparent self-powered sensors that achieve fast and reliable strain sensing from a small temperature gradient. Our work enhances the fundamental understanding of multifunctionality at the atomic scale and provide a route towards structural health monitoring through ubiquitous and smart devices.
Multiplexed bioluminescence-mediated tracking of DNA double strand break repairs in vitro and in vivo
Jasper Che-Yung Chien, Christian E. Badr* and Charles Pin-Kuang Lai*
The dynamics of DNA double-strand break (DSB) repairs including homology-directed repair and nonhomologous end joining play an important role in diseases and therapies. However, investigating DSB repair is typically a low-throughput and cross-sectional process, requiring disruption of cells and organisms for subsequent nuclease-, sequencing- or reporter-based assays. In this protocol, we provide instructions for establishing a bioluminescent repair reporter system using engineered Gaussia and Vargula luciferases for noninvasive tracking of homology-directed repair and nonhomologous end joining, respectively, induced by SceI meganuclease, SpCas9 or SpCas9 D10A nickase-mediated editing. We also describe complementation with orthogonal DSB repair assays and omics analyses to validate the reporter readouts. The bioluminescent repair reporter system provides longitudinal and rapid readout (~seconds per sample) to accurately and efficiently measure the efficacy of genome-editing tools and small-molecule modulators on DSB repair. This protocol takes ~2–4 weeks to establish, and as little as 2 h to complete the assay. The entire bioluminescent repair reporter procedure can be performed by one person with standard molecular biology expertise and equipment. However, orthogonal DNA repair assays would require a specialized facility that performs Sanger sequencing or next-generation sequencing.
Giant exciton-enhanced shift currents and direct current conduction with subbandgap photo excitations produced by many-electron interactions
Y. H. Chan, Diana Y. Qiu, Felipe H. da Jornada, and Steven G. Louie
Shift current is a direct current generated from nonlinear light–matter interaction in a noncentrosymmetric crystal and is considered a promising candidate for next-generation photovoltaic devices. The mechanism for shift currents in real materials is, however, still not well understood, especially if electron–hole interactions are included. Here, we employ a first-principles interacting Green’s-function approach on the Keldysh contour with real-time propagation to study photocurrents generated by nonlinear optical processes under continuous wave illumination in real materials. We demonstrate a strong direct current shift current at subbandgap excitation frequencies in monolayer GeS due to strongly bound excitons, as well as a giant excitonic enhancement in the shift current coefficients at above bandgap photon frequencies. Our results suggest that atomically thin two-dimensional materials may be promising building blocks for next-generation shift current devices.
Complex vibrational features of solvated hydronium ion, H3O+, in 3 μm enable us to look into the vibrational coupling among O-H stretching modes and other degrees of freedom. Two anharmonic coupling schemes have often been engaged to explain observed spectra: coupling with OH bending overtone, known as Fermi resonance (FR), has been proposed to account for the splitting of the OH stretch band at ~3300 cm-1 in H3O+…Ar3, but an additional peak in H3O+…(N2)3 at the similar frequency region has been assigned to a combination band (CB) with the low-frequency intermolecular stretches. While even stronger vibrational coupling is expected in H3O+…(H2O)3, such pronounced peaks are absent. In the present study, vibrational spectra of H3O+…Kr3 and H3O+…(CO)3 are measured to complement the existing spectra. Using ab initio anharmonic algorithms, we are able to assign the observed complex spectral features, to resolve seemingly contradictory notions in the interpretations, and to reveal simple pictures of the interplay between FR and CB.
Strong Fermi resonance associated with proton motions revealed by vibrational spectra of asymmetric proton bound dimers
Qian-Rui Huang, Ryunosuke Shishido, Chih-Kai Lin, Chen-Wei Tsai, Jake A. Tan, Asuka Fujii* and Jer-Lai Kuo*
Experimental infrared spectra between 2600 to 3800 cm-1 for a series of asymmetric proton bound dimers with protonated trimethylamine (TMA–H+) as the proton donor were recorded and analyzed. Based on conventional wisdom, the frequency of the N-H+ stretching mode is expected to red shift as the proton affinity of proton acceptors (Ar, N2, CO, C2H2, H2O, CH3OH, and C2H5OH) increases. The observed band, however, shows a peculiar splitting of ≈300 cm-1 with the intensity shifting pattern resembling a two-level system. Theoretical investigation based on ab initio anharmonic algorithms reveals that the observed band splitting and its extraordinarily large gap of ≈300 cm-1 is a result of strong coupling between fundamental of the proton stretching mode and overtone states of the two proton bending modes, that is commonly known as Fermi resonance (FR). We also provide a simple and general theoretical model to link the strong FR coupling to the quasi-two-level system behavior in the observed band intensity. Since the model does not depend on the molecular specification of TMA–H+, the strong coupling we observed here is an intrinsic property associated with proton motions in a wide range of molecular systems.
Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt–nitrogen–carbon (Co–N x /C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. material design strategies for high-performance electrocatalysts for fuel cell applications. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co–O species formation. These experimental findings, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high performance electrocatalysts for fuel cell applications.
Zan Nie, Chih-Hao Pai, Jie Zhang, Xiaonan Ning, Jianfei Hua, Yunxiao He, Yipeng Wu, Qianqian Su, Shuang Liu, Yue Ma, Zhi Cheng, Wei Lu1, Hsu-Hsin Chu, Jyhpyng Wang, Chaojie Zhang, Warren B. Mori, and Chan Joshi
Availability of relativistically intense, single-cycle, tunable infrared sources will open up newareas of relativistic nonlinear optics of plasmas, impulse IR spectroscopy and pump-probeexperiments in the molecular fingerprint region. However, generation of such pulses is still achallenge by current methods. Recently, it has been proposed that time dependent refractiveindex associated with laser-produced nonlinear wakes in a suitably designed plasma densitystructure rapidly frequency down-converts photons. The longest wavelength photons slipbackwards relative to the evolving laser pulse to form a single-cycle pulse within the nearlyevacuated wake cavity. This process is called photon deceleration. Here, we demonstrate thisscheme for generating high-power (~100 GW), near single-cycle, wavelength tunable(3–20 μm), infrared pulses using an 810 nm drive laser by tuning the density profile of theplasma. We also demonstrate that these pulses can be used to in-situ probe the transient andnonlinear wakes themselves.
Nitrogen-Vacancy Centers in Diamond for High-Performance Detection of Vacuum Ultraviolet, Extreme Ultraviolet, and X‑rays
1National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 300, Taiwan 2Institute of Atomic and Molecular Sciences, Academia Sinica, 1 Section 4, Roosevelt Road, Taipei 106, Taiwan
Fluorescent nanodiamond (FND) containing nitrogen-vacancy (NV) centers as built-in fluorophores exhibits a nearly constant emission profile over 550 – 750 nm upon excitation by vacuum-ultraviolet (VUV), extreme ultraviolet (EUV), and X- radiations from a synchrotron source over the energy (wavelength) range of 6.2 – 1450 eV (0.86 – 200 nm). The photoluminescence (PL) quantum yield of FND increases steadily with the increasing excitation energy, attaining a value as great as 1700% at 700 eV (1.77 nm). Notably, the yield curve is continuous, having no gap in the VUV to X-ray region. In addition, no significant PL intensity decreases were observed for hours. Applying the FND sensor to measure the absorption cross sections of gaseous O2 over 110 – 200 nm and comparing the measurements with the sodium-salicylate scintillator, we obtained results in agreement with each other within 5%. The superb photostability and broad applicability of FND offer a promising solution for the long-standing problem of lacking a robust and reliable detector for VUV, EUV, and X- radiations.