Visualizing and Regulating Dynamic Evolution of Interfacial Electrolyte Configuration during De-solvation Process on Lithium-Metal Anode.

Acting as a passive protective layer, solid-electrolyte interphase (SEI) plays a crucial role in maintaining the stability of the Li-metal anode. Derived from the reductive decomposition of electrolytes (e.g., anion and solvent), the SEI construction presents as an interfacial process accompanied by the dynamic de-solvation process during Li-metal plating. However, typical electrolyte engineering and related SEI modification strategies always ignore the dynamic evolution of electrolyte configuration at the Li/electrolyte interface, which essentially determines the SEI architecture. Herein, by employing advanced electrochemical in situ FT-IR and MRI technologies, we directly visualize the dynamic variations of solvation environments involving Li+-solvent/anion. Remarkably, a weakened Li+-solvent interaction and anion-lean interfacial electrolyte configuration have been synchronously revealed, which is difficult for the fabrication of anion-derived SEI layer. Moreover, as a simple electrochemical regulation strategy, pulse protocol was introduced to effectively restore the interfacial anion concentration, resulting in an enhanced LiF-rich SEI layer and improved Li-metal plating/stripping reversibility.

A novel derivative synchronous fluorescence method for the rapid, non-destructive and intuitive differentiation of denitrifying bacteria.

It is challenging to differentiate bacteria residing in the same habitat by direct observation. This difficulty impedes the harvest, application and manipulation of functional bacteria in environmental engineering. In this study, we developed a novel method for rapid differentiation of living denitrifying bacteria based on derivative synchronous fluorescence spectroscopy, as exemplified by three heterotrophic nitrification-aerobic denitrification bacteria having the maximum nitrogen removal efficiencies greater than 90%. The intact bacteria and their living surroundings can be analyzed as an integrated target, which eliminates the need for the complex pre-processing of samples. Under the optimal synchronous scanning parameter (Δλ = 40 nm), each bacterium possesses a unique fluorescence spectral structure and the derivative synchronous fluorescence technique can significantly improve the spectral resolution compared to other conventional fluorescence methods, which enables the rapid differentiation of different bacteria through derivative synchronous fluorescence spectra as fast as 2 min per spectrum. Additionally, the derivative synchronous fluorescence technique can extract the spectral signals contributed by bacterial extracellular substances produced in the biological nitrogen removal process. Moreover, the results obtained from our method can reflect the real-time denitrification properties of bacteria in the biological nitrogen removal process of wastewater. All these merits highlight derivative synchronous fluorescence spectroscopy as a promising analytic method in the environmental field.

High-Quality Reconstruction for Laplace NMR Based on Deep Learning.

Laplace nuclear magnetic resonance (NMR) exploits relaxation and diffusion phenomena to reveal information regarding molecular motions and dynamic interactions, offering chemical resolution not accessible by conventional Fourier NMR. Generally, the applicability of Laplace NMR is subject to the performance of signal processing and reconstruction algorithms involving an ill-posed inverse problem. Here, we propose a proof-of-concept of a deep-learning-based method for rapid and high-quality spectra reconstruction from Laplace NMR experimental data. This reconstruction method is performed based on training on synthetic exponentially decaying data, which avoids a vast amount of practically acquired data and makes it readily suitable for one-dimensional relaxation and diffusion measurements by commercial NMR instruments.

High-resolution NMR spectroscopy for measuring complex samples based on chemical-shift-difference selection.

NMR spectroscopy serves as an immensely powerful tool for component assignments and molecular structure elucidations. However, proton NMR spectra are generally trapped with spectral congestion caused by limited frequency differences and complex multiplets. 2D NMR can effectively relieve spectral congestion, but its resolution and acquisition efficiency are restricted by the broad spectral bandwidth. Herein, we introduce an NMR method based on chemical-shift-difference selection by chirp excitation to record high-resolution 2D NMR spectra for extracting coupling correlation networks and multiplet structures, suitable for measurements on complex samples. The performance of the proposed method is illustrated in determining diastereotopic methylene protons, small frequency-difference coupled proton pairs of furanose, pyranose and benzene rings. This study is expected to benefit molecular structure elucidation and composition analysis of complex samples in chemistry, biochemistry and metabonomics.

A Pure Shift-Based Nuclear Magnetic Resonance Method for In-Phase Three-Dimensional Diffusion-Ordered Spectroscopy.

Diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY) plays a vital role in mixture studies. However, its applications to complex mixture samples are generally limited by spectral congestion along the chemical shift domain caused by extensive J coupling networks and abundant compounds. Herein, we develop the in-phase multidimensional DOSY strategy for complex mixture analyses by simultaneously revealing molecular self-diffusion behaviors and multiplet structures with optimal spectral resolution. As a proof of concept, two pure shift-based three-dimensional (3D) DOSY protocols are proposed to record high-resolution 3D spectroscopic view with separated mixture components and their resolved multiplet coupling structures, thus suitable for analyzing complex mixtures that contain abundant compounds and complicated molecular structures, even under adverse magnetic field conditions. Therefore, this study shows a promising tool for component analyses and multiplet structure studies on practical mixture samples.

Smart Nano-switch with Flexible Modulation of Ion Transport Using Multiple Environmental Stimuli.

In this work, we demonstrate a unique nano-switch with triple environmental stimuli based on the action of functional copolymer brushes in a single conical nanochannel. This nanodevice flexibly and efficiently modulates ion transport properties under the influence of three environmental stimuli: light, pH and temperature. The triple factors can not only play a regulatory role independently, but their synergistic cooperation could fully activate the ionic gate and reversibly control the gating direction. In addition, the nano-switch can switch transport properties on demand in the face of complex combinations of different factors. This work promotes the development of intelligent bionic ion channels, which holds promise for biosensing, energy conversion and biomedical research.

Au-Ag Alloy Nanoshuttle Mediated Surface Plasmon Coupling for Enhanced Fluorescence Imaging.

Surface plasmon-coupled emission (SPCE), a novel signal enhancement technology generated by the interactions between surface plasmons and excited fluorophores in close vicinity to metallic film, has shown excellent performance in bioimaging. Variable-angle nanoplasmonic fluorescence microscopy (VANFM), based on an SPCE imaging system, can selectively modulate the imaging depth by controlling the excitation angles. In order to further improve the imaging performance, Au-Ag alloy nanoshuttles were introduced into an Au substrate to mediate the plasmonic properties. Benefiting from the strong localized plasmon effect of the modified SPCE chip, better imaging brightness, signal-to-background ratio and axial resolution for imaging of the cell membrane region were obtained, which fully displays the imaging advantages of SPCE system. Meanwhile, the imaging signal obtained from the critical angle excitation mode was also amplified, which helps to acquire a more visible image of the cell both from near- and far-field in order to comprehensively investigate the cellular interactions.

Label-Free Fluorescent Nanofilm Sensor Based on Surface Plasmon Coupled Emission: In Situ Monitoring the Growth of Metal-Organic Frameworks.

We have proposed a universal label-free fluorescent nanofilm sensor based on surface plasmon coupled emission (SPCE). A metal-dye-dielectric (MDD) structure was fabricated to mediate the label-free monitoring based on SPCE. The nonfluorescent dielectric film smartly borrowed the fluorescence signal from the bottom dye layer and led to a new SPCE response through the adjacent metal film. The fluorescence emission angle and polarization strongly depended on the thickness of the nonfluorescent dielectric film on the MDD structure. As a demonstration, the growth of a two-dimensional zeolitic imidazolate framework film (ZIF-L) was in situ monitored in the liquid phase by MDD-SPCE for the first time. The label-free fluorescent sensors are facilely prepared by a spin coating technique, with the potential to be widely spread for in situ studies, especially toward nanomaterial growth processes.

Plasmon Coupling Enhanced Micro-Spectroscopy and Imaging for Sensitive Discrimination of Membrane Domains of a Single Cell.

Different cell membrane domains play different roles in many cell processes, and the discrimination of these domains is of considerable importance for the elucidation of cellular functions. However, the strategies available for distinguishing these cell membrane domains are limited. A novel technique called plasmon coupling enhanced micro-spectroscopy and imaging to discriminate basal and lateral membrane domains of a single cell combines the application of an additional plasmonic silver film for surface plasmon (SP) excitation to selectively excite and enhance the basal membranes in the near-field with directional enhanced microscopic imaging and spectroscopy. The SP and critical evanescent fields are induced upon excitation through a silver-coated semitransparent coverslip at the surface plasmon resonance and critical angles, respectively. The basal and lateral membrane domains located within the SP and critical evanescent fields can be selectively excited and distinguished by adjusting the incident angle of laser irradiation. Moreover, the brighter images and more intense spectra of membrane-targeting fluorescence-Raman probes under directional excitation than in conventional EPI mode allow clear identification of the membrane domains.

Determining the enantioselectivity of asymmetric hydrogenation through parahydrogen-induced hyperpolarization.

Asymmetric hydrogenation plays an essential role for both academic research and industry to produce enantiomeric pure chiral molecules. Although nuclear magnetic resonance (NMR) is powerful in determining the yields of hydrogenation, it is still challenging to use NMR for chirality-related analysis. Herein, we applied parahydrogen-induced hyperpolarization (PHIP) NMR to determine the enantioselectivity of asymmetric hydrogenation and the absolute chirality of products. We hyperpolarized two types of unsaturated amino acid precursors, i.e., methyl-α-acetoamido cinnamate and (E)-ethyl 3-acetamidobut-2-enoate. Hydrogenation of prochiral substrates with parahydrogen gave temporary hyperpolarized diastereoisomers, which exhibit different PHIP patterns distinguishable in 1H NMR. After assigning the NMR peaks by density functional theory calculations, we simulated the PHIP patterns of all the possible temporary hyperpolarized diastereoisomers and unambiguously assigned the chirality of the products and the enantioselectivity of asymmetric hydrogenation. Our work demonstrates the application and potential of PHIP in revealing the mechanism of asymmetric hydrogenation.

Diffusion Analysis on Complex Mixtures under Adverse Magnetic Field Conditions by Spatially-Selective Pure Shift-Based DOSY.

Diffusion-ordered NMR spectroscopy (DOSY) serves as a noninvasive spectroscopic method for studying intact mixtures and identifying individual components present in mixtures according to their diffusion behaviors. However, DOSY techniques generally fail to discriminate complex compositions which exhibit crowded or overlapped NMR signals, particularly under adverse magnetic field conditions. Herein, we exploit the spatially selective pure shift-based DOSY strategy to address this challenge by eliminating inhomogeneous line broadenings and extracting pure shift singlets, thereby expediting diffusion analyses on complex mixtures. More importantly, this strategy is further applied to observing and analyzing electro-oxidation processes of blended alcohols, suggesting its potential to monitoring in situ electrochemical reactions. This study demonstrates a meaningful NMR trial for diffusion analysis on complex mixtures under adverse experimental circumstances, and particularly, it provides a proof-of-concept technique for electrochemical studies and shows promising prospects for applications in chemistry, biology, energy, etc.

In Situ Real-Time Quantitative Determination in Electrochemical Nuclear Magnetic Resonance Spectroscopy.

For the purpose of acquiring highly sensitive and differential spectra in in situ electrochemical nuclear magnetic resonance (EC-NMR) spectroscopy, uniform distributions of amplitudes and phases of radio frequency (RF) fields in the sample are needed for consistent flip angles of all nuclei under scrutiny. However, intrinsic electromagnetic incompatibility exists between such requirements with electric properties of the conductive material in an electrolytic cell, including metallic electrodes and ionic electrolytes. This proposed work presents the adverse repercussions of gradually varying electrolyte conductivity, which is strongly associated with the change of ion concentrations in a real-time electrochemical reaction, on spatial distributions of RF field amplitude and phase in the detective zone of an NMR probe coil. To compensate for such a non-linear trend of the spatial dependent distribution, we eliminate different excitation effects of the RF field on the build-in external standard and the electrolyte both situated in nearly the same detection area, as well as promote the greater accuracy of quantitative determination of reactant concentrations. The reliability and effectiveness of the improved in situ EC-qNMR (quantitative NMR) method are confirmed by the real-time monitoring of the electrochemical advanced oxidation process for phenol, in which instant concentrations of reactants and products are detected simultaneously to verify the degradation reaction scheme of phenol.

In situ and sensitive monitoring of configuration-switching involved dynamic adsorption by surface plasmon-coupled directional enhanced Raman scattering.

Surface adsorption studies play a crucial role in numerous fields from surface catalysis to molecular separation. However, investigation on adsorption mechanisms has been restricted to limited analytes and approaches, which calls for an in situ and sensitive surface analysis technique capable of revealing the mechanisms as well as discriminating different adsorbates and their geometry at different adsorption stages. In this study, we employed surface plasmon-coupled directional enhanced Raman scattering (SPCR), a novel technique developed by coupling surface plasmon-coupled emission with SERS, to study conformation-switching involved dynamic adsorption with background suppression and improved sensitivity (nearly 30-fold). We obtained the isotherms for a conformation-changing Raman model analyte, malachite green. An S-type Langmuir model was fitted from the time-resolved SPCR signals sensitively and without any interference from the bulk solution. The reorientation of the analyte from a predominantly parallel configuration to a perpendicular one was captured by the dramatic increase in the intensity ratios of the adsorption-related peaks to the adsorption-unrelated peak. We believe that this new sensitive and selective SPCR technique will be a promising tool for surface adsorption kinetics analysis.

Surface plasmon-coupled emission imaging for biological applications.

Fluorescence imaging technology has been extensively applied in chemical and biological research profiting from its high sensitivity and specificity. Much attention has been devoted to breaking the light diffraction-limited spatial resolution. However, it remains a great challenge to improve the axial resolution in a way that is accessible in general laboratories. Surface plasmon-coupled emission (SPCE), generated by the interactions between surface plasmons and excited fluorophores in close vicinity of the thin metal film, offers an opportunity for optical imaging with potential application in analysis of molecular and biological systems. Benefiting from the highly directional and distance-dependent properties, SPCE imaging (SPCEi) has displayed excellent performance in bioimaging with improved sensitivity and axial confinement. Herein, we give a brief overview of the development of SPCEi. We describe the unique optical characteristics and constructions of SPCEi systems and highlight recent advances in the use of SPCEi for biological applications. We hope this review provides readers with both the insights and future prospects of SPCEi as a new promising imaging platform for potentially widespread applications in biological research and medical diagnostics. Graphical abstract.

Metallic Nanofilm Enhanced Fluorescence Cell Imaging: A Study of Distance-Dependent Intensity and Lifetime by Optical Sectioning Microscopy.

Simple, stable, easily-fabricated smooth metallic nanofilm can improve the imaging intensity and imaging contrast. However, its application in micrometer-scale cells has not been popularized due to the lack of full understanding of their related fluorescence properties. In this study, fluorescence enhancement of cell imaging on smooth Au nanofilm was investigated over a micrometer-scale range via employment of the optical sectioning method available with a laser scanning confocal fluorescence microscope. The fluorescence enhancement reduced with the distance away from the surface of metallic nanofilm, and this distance dependence was determined by the factors of numerical aperture, dye-substrate distance, and emission wavelength. In addition, distance-dependent fluorescence lifetime images of cells were also measured to study the interaction between fluorophores and metallic film. The enhancement effect of Au nanofilm on fluorescence cell imaging can be induced not only by the standing wave formed by the reflected light and exciting light but also by the interaction between fluorophore and surface plasmons on the metallic nanofilm. Our study on smooth metallic nanofilm should pave the way for utilizing its uniform fluorescence enhancement characteristic for biological imaging.

Excitation-Emission Synchronization-Mediated Directional Fluorescence: Insight into Plasmon-Coupled Emission at Vibrational Resolution.

Light-matter interactions have always been a fundamentally significant topic that has attracted much attention. It is important to reveal a fluorophore-plasmon interaction on the nanoscale. However, as a powerful investigative tool, fluorescence spectroscopy still suffers from a limited spectral resolution and the susceptibility to interfering substances. In this work, excitation-emission synchronization-mediated surface-plasmon-coupled emission (EES-SPCE) is proposed to break the bottleneck. By actively screening the energy transitions for observation, an improved spectral resolution has been achieved, which is advantageous to the investigation of the fluorophore-plasmon interactions under different coupling modes. The spectral information related to the plasmonic interactions through tuning vibrational energy levels is clearly distinguished at directional emission angles. EES-SPCE is demonstrated to selectively and efficiently extract the coupled emission from the vibrational resolution, which would open up the opportunity to improve the capability of spectral feature identification and signal collection for practical applications of plasmonic fluorescence spectroscopy.

Variable-Angle Nanoplasmonic Fluorescence Microscopy: An Axially Resolved Method for Tracking the Endocytic Pathway.

The study of endocytosis, which encompasses diverse mechanisms in biology, requires the utilization of high axial resolution to monitor molecular behavior on both the cell surface and interior of the cell. We have designed a novel axially resolved fluorescence microscopic technique, termed variable-angle nanoplasmonic fluorescence microscopy. The proof-of-principle of this approach is achieved by selectively following the events in the vicinity of a cell membrane or in a cell. We use a 30 nm Au-coated semitransparent coverslip as the nanoplasmonic chip to achieve both surface plasmon resonance excitation and critical angle excitation by tuning the incident angles. This approach leads to improved axial resolution compared to total internal reflection fluorescence microscopy, which is a common imaging technique in cell biology. It offers a unique opportunity to semiquantitatively determine fluorophore axial distributions in the cell. Observing the epidermal growth factor receptor-mediated endocytosis in Caski cells clearly demonstrates the potential application of this new method for cell biology studies.

A label-free and ultrasensitive DNA impedimetric sensor with enzymatic and electrical dual-amplification.

In this work, we report a facile, sensitive, selective, and reproducible DNA impedimetric sensor device. We demonstrate that, combined with exonuclease III, the easily prepared electrochemically reduced graphene oxide (rGO) could be a desirable platform to amplify signals in electrochemical impedance spectroscopy for ultrasensitive DNA detection. Guided by enzyme assisted target recycling, efficient interfacial tuning can be obtained, from the situation with high impedance caused by single-stranded DNA probes directly adsorbed onto rGO to the one with low impedance due to the continuous desorption of target-probe DNA hybrids and the consequent digestion of DNA probes. Just a few DNA targets can specifically trigger the enzymatic digestion of a large number of DNA probes. It is the excellent electrical conductivity of rGO that further enlarges the changes of electron transfer resistance after the removal of DNA probes. As a result of synergistically combining both enzymatic and electrical amplification, the enlarged changes of impedimetric signals can be measured to sensitively report DNA targets. The specificity has been guaranteed by the intrinsic recognition of hybrids through both rGO and exonuclease III. A limit of detection as low as 10 aM target DNA in the matrix of cell culture medium, as well as a wide linear range and good discrimination of mismatched sequences even at the one-base level, suggests its great application prospect in biosensing and biomedical analysis. It also has other advantages including easy operation, low cost, and convenient regeneration, with more competitive performance in developing impedimetric biosensors.

Reversing current rectification to improve DNA-sensing sensitivity in conical nanopores.

Herein, we report the ultrasensitive DNA detection through designing an elegant nanopore biosensor as the first case to realize the reversal of current rectification direction for sensing. Attributed to the unique asymmetric structure, the glass conical nanopore exhibits the sensitive response to the surface charge, which can be facilely monitored by ion current rectification curves. In our design, an enzymatic cleavage reaction was employed to alter the surface charge of the nanopore for DNA sensing. The measured ion current rectification was strongly responsive to DNA concentrations, even reaching to the reversed status from the negative ratio (-6.5) to the positive ratio (+16.1). The detectable concentration for DNA was as low as 0.1 fM. This is an ultrasensitive and label-free DNA sensing approach, based on the rectification direction-reversed amplification in a single glass conical nanopore.