Two-color laser PEEM imaging of horizontal and vertical components of femtosecond surface plasmon polaritons

Explicit visualization of different components of surface plasmon polaritons(SPPs) propagating at dielectric/metal interfaces is crucial in offering chances for the detailed design and control of the functionalities of plasmonic nanodevices in the future. Here, we reported independent imaging of the vertical and horizontal components of SPPs launched from a rectangular trench in the gold film by a 400-nm laser-assisted near-infrared(NIR) femtosecond laser time-resolved photoemission electron microscopy(TR-PEEM). The experiments demonstrate that distinct imaging of different components of SPPs field can be easily achieved by introducing the 400-nm laser. It can circumvent the risk of sample damage and information loss of excited SPPs field that is generally confronted in the usual NIR laser TR-PEEM scheme. The underlying mechanism for realizing distinct imaging of different components of the SPPs field with two-color PEEM is revealed via measuring the double logarithmic dependence of photoemission yield with the 800-nm and 400-nm pulse powers of different polarizations. Moreover, it is found that the PEEM image quality of the vertical and horizontal components of the SPPs field is nearly independent of the 400-nm pulse polarization. These results pave a way for SPPs-based applications and offer a possible solution for drawing a space-time field of SPPs in three dimensions.

Real time detection of antibody-antigen interaction using a laser scanning confocal imaging-surface plasmon resonance system

A laser scanning confocal imaging-surface plasmon resonance （LSCI-SPR） instrument integrated with a wavelength-dependent surface plasmon resonance （SPR） sensor and a laser scanning confocal microscopy （LSCM） is built to detect the bonding process of human IgG and fluorescent-labeled affinity purified antibodies in real time. The shifts of resonant wavelength at different reaction time stages are obtained by SPR, corresponding well with the changes of the fluorescence intensity collected by using LSCM. The instrument shows the merits of the combination and complementation of the SPR and LSCM, with such advantages as quantificational analysis, high spatial resolution and real time monitor, which are of great importance for practical applications in biosensor and life science.

LABEL-FREE DETECTION OF PROTEIN MICROARRAY WITH HIGH THROUGHPUT SURFACE PLASMON RESONANCE IMAGING(SPRI)

A surface plasmon resonance imaging(SPRI)system was developed for the discrimination of proteins on a gold surface.As a label-free and high-throughput technique,SPRI enables simultaneously monitoring of the biomolecular interactions at low concentrations.We used SPRI as a label-free and parallel method to detect different proteins based on protein microarray.Bovine Serum Albumin(BSA),Casein and Immunoglobulin G(IgG)were immobilized onto the Au surface of a gold-coated glass chip as spots forming a 6×6 matrix.These proteins can be discriminated directly by changing the incident angle of light.Excellent reproducibility for label-free detection of protein molecules was achieved.This SPRI platform represents a simple and robust method for performing high-sensitivity detection of protein microarray.

Imaging Ultrafast Plasmon Dynamics within a Complex Dolmen Nanostructure Using Photoemission Electron Microscopy

We report direct nanoscale imaging of ultrafast plasmon in a gold dolmen nanostructure excited with the 7is laser pulses by combining the interferometric time-resolved technology with the three-photon photoemission electron microscopy （PEEM）. The interferometric time-resolved traces show that the plasmon mode beating pattern appears at the ends of the dimer slabs in the dolmen nanostructure as a result of coherent superposition of multiple localized surface plasmon modes induced by broad bandwidth of the ultrafast laser pulses. The PEEM measurement further discloses that in-phase of the oscillation field of two neighbor defects are surprisingly observed, which is attributed to the plasmon coupling between them. Furthermore, the control of the temporal delay between the pump and probe laser pluses could be utilized for manipulation of the near-field distribution. These findings deepen our understanding of ultrafast plasmon dynamics in a complex nanosystem.

Nano-infrared imaging of localized plasmons in graphene nano-resonators

We conduct in-situ near-field imaging of propagating and localized plasmons（cavity and dipole modes） in graphene nano-resonator. Compared with propagating graphene plasmons, the localized modes show twofold near-field amplitude and high volume confining ability（- 10^6）. The cavity resonance and dipole mode of graphene plasmons can be effectively controlled through optical method. Furthermore, our numerical simulation shows quantitative agreement with experimental measurements. The results provide insights into the nature of localized graphene plasmons and demonstrate a new way to study the localization of polaritons in Van der Waals materials.

Signal Enhancements in Plasmon Assisted Fluorescence Ratiometric Imaging Optodes

The objective of this study was to benchmark the different signal enhancements found in a recently exploited fluorescence ratiometric optode design used for nano-molar imaging of ammonium and ammonia. The sensing scheme of these optodes are based on a mediated transfer of the analyte together with a fluorescent dye in a two-phase system consisting of a gold nanoparticle (GNP) doped ether (organic phase), emulsified in a hydrogel (hydrous phase). The coextraction of the ion dye pair causes changes in fluorescence in relation to the analyte concentration. Performances of optodes with and without GNPs using the gradually improved instrumentation and signal processing were evaluated and normalized to be comparable. Signal to noise was enhanced due to signal processing based on ensemble averaging (1.7× - 3.2×), CCD sensitivity (2×), and plasmon assisted fluorescence (10× - 100×), which altogether with the ratiometric treatment of the fluorescence contributed to the great sensitivity for ammonium and ammonia. The study shows that GNP doped sensors are relatively more sensitive to matrix effects but if they are isolated by a protective layer they will dramatically increase in sensitivity. Proper isolation of the active chemical components from the matrix will make the sensor design one of the most powerful and versatile concepts for chemical imaging and single point detection in complex environments as the optodes likely can be constructed for most ions that have selective ionophores.

Imaging Array SPR Biosensor Immunoassays for Sulfamethoxazole and Sulfamethazine

A homemade array surface plasmon resonance （SPR）-based imaging biosensor was used to develop sensitive and fast immunoassays to determine sulfamethoxazole （SMOZ） and sulfamethazine （SMT） in buffer. Two conjugations of sulfonamide-bovine serum albumin （BSA） were separately immobilized on two different rows of the array chip with one row as reference. The immobilization was carried out in the instrument to monitor the quantity of the conjugations immobilized. The antibody mixed with the sulfonamide in the buffer was injected over the surface of the chip to get a relative response which was inversely proportional to the concentration of the sulfonamide in the PBS buffer. Two calibration curves were constructed and the limit of detection for sufamethoxazole in buffer was 3.5 ng/mL and for sulfamethazine 0.6 ng/mL. The stability and specificity of the antibody were also studied. The monoclonal antibody did not bind with BSA.

Tunable plasmofluidic lens for subwavelength imaging

A tunable plasmofluidic lens consisting of nanoslit arrays on a metal film is proposed for subwavelength imaging in far field at different wavelengths.The nanoslit arrays with constant depths but varying widths could generate desired optical phase retardations based on the propagation property of the surface plasmon polaritons(SPPs)through the metal-dielectric-metal(MDM)nanoslit waveguide.We demonstrate the tunability of the plasmofluidic lens for subwavelength imaging by changing the surrounding dielectric fluid.This work provides a novel approach for developing integrative tunable plasmofluidic lens for a variety of lab-on-chip applications.

Geometrical condition for observing Talbot effect in plasmonics infinite metallic groove arrays

The plasmonics Talbot effect in metallic layer with infinite periodic grooves is presented in this study. Numerical approach based on the finite element method is employed to verify the derived Talbot carpet on the non-illumination side. The groove depth is less than the metallic layer thickness; however, for specific conditions, surface plasmons polaritons(SPPs)can penetrate through grooves, propagate under the metallic layer, and form Talbot revivals. The geometrical parameters are specified via groove width, gap size, period, and wavelength, and their proper values are determined by introducing two opening ratio parameters. To quantitatively compare different Talbot carpets, we introduce new parameters such as R-square that characterizes the periodicity of Talbot images. The higher the R-square of a carpet, the more coincident with non-paraxial approximation the Talbot distance becomes. We believe that our results can help to understand the nature of SPPs and also contribute to exploring this phenomenon in Talbot-image-based applications, including imaging, optical systems, and measurements.

Real-Time analysis of exosome secretion of single cells with single molecule imaging

The exosome-mediated response can promote or restrain the diseases by regulating the intracellular pathways,making the exosome become an effective marker for diagnosis and therapeutic control at the single-cell level.However,real-time analysis is hard to be achieved with traditional approaches because the exosomes usually need to be enriched by ultracentrifugation for a measurable signal-to-noise ratio.Recently developed label-free single-molecule imaging approaches may become an real-time quantitative tool for the analysis of single exosomes and related secretion behaviors of single living cells owing to their extreme sensitivity.

Improvement of femtosecond SPPs imaging by two-color laser photoemission electron microscopy

Clear imaging of surface plasmon polaritons(SPPs)is a prerequisite for SPPs-based applications.In this work,we demonstrate an improvement of near-field imaging of SPPs via directly comparing the visibility of the photoemission electron microscopy(PEEM)image of SPPs under one-and two-color laser excitation(also known as one-or two-color laser PEEM).By measuring the photoelectron yield and the contrast of the interference fringes of SPPs,we demonstrate that in addition to enhancing the photoemission yield,two-color laser PEEM can significantly improve the contrast between bright and dark fringes(nearly 4 times higher than that of one-color laser case).By recording the nonlinear order of the photoelectrons ejected from the bright and dark fringes,respectively,the underlying mechanism for the improved visibility is revealed.In addition,the influences of the polarization direction of 400-nm laser on the PEEM images of the SPPs with different wave vector directions are shown.These results can provide technical support for the development of SPPs-based communication devices and catalysis.

Handheld high-throughput plasmonic biosensor using computational on-chip imaging

We demonstrate a handheld on-chip biosensing technology that employs plasmonic microarrays coupled with a lens-free computational imaging system towards multiplexed and high-throughput screening of biomolecular interactions for point-of-care applications and resource-limited settings.This lightweight and field-portable biosensing device,weighing 60 g and 7.5 cm tall,utilizes a compact optoelectronic sensor array to record the diffraction patterns of plasmonic nanostructures under uniform illumination by a single-light emitting diode tuned to the plasmonic mode of the nanoapertures.Employing a sensitive plasmonic array design that is combined with lens-free computational imaging,we demonstrate label-free and quantitative detection of biomolecules with a protein layer thickness down to 3 nm.Integrating large-scale plasmonic microarrays,our on-chip imaging platform enables simultaneous detection of protein mono-and bilayers on the same platform over a wide range of biomolecule concentrations.In this handheld device,we also employ an iterative phase retrieval-based image reconstruction method,which offers the ability to digitally image a highly multiplexed array of sensors on the same plasmonic chip,making this approach especially suitable for high-throughput diagnostic applications in field settings.

Gold Nanostars-AIE Theranostic Nanodots with Enhanced Fluorescence and Photosensitization Towards Effective Image-Guided Photodynamic Therapy

Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT).However,designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging.In this work,we report a new nanohybrid consisting of gold nanostar(AuNS)and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications.The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots(665 nm)is carefully selected using five different AuNSs with distinct localized surface plasmon(LSPR)peaks.Results show that all the AuNS s can enhance the 1 O2 production of AIE-PS dots,among which the AuNS with LSPR peak at 585 nm exhibited the highest 1 O2 enhancement factor of15-fold with increased fluorescence brightness.To the best of our knowledge,this is the highest enhancement factor reported for the metalenhanced singlet oxygen generation systems.The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro.This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems,opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.

Dual activated NIR-Ⅱ fluorescence and photoacoustic imaging-guided cancer chemo-radiotherapy using hybrid plasmonic-fluorescent assemblies

Multimodal imaging in the second near-infrared window(NIR-II)guided cancer therapy is a highly precise and efficient cancer theranostic strategy.However,it is still a challenge to develop activated NIR-II optical imaging and therapy agents.In this study,we develop a pH-responsive hybrid plasmonic-fluorescent vesicle by self-assembly of amphiphilic plasmonic nanogapped gold nanorod(AuNNR)and fluorescent down-conversion nanoparticles(DCNP)(AuNNR-DCNP Ve),showing remarkable and activated NIR-II fluorescence(FL)/NIR-II photoacoustic(PA)imaging performances.The hybrid vesicle also exhibited superior loading capacity of doxorubicin as a superior drug carrier and efficient radiosensitizer for X-ray-induced radiotherapy.Interestingly,the accumulated hybrid AuNNR-DCNP Ve in the tumor resulted in a recovery of NIR-II FL imaging signal and a variation in NIR-II PA imaging signal.Dual activated NIR-II PA and FL imaging of the hybrid vesicle could trace drug release and precisely guided cancer radiotherapy to ultimately reduce the side effects to healthy tissue.

Revealing the plasmon coupling in gold nanochains directly from the near field

We studied the near-field properties of localized surface plasmon resonances in finite linear gold nanochains using photoemission electron microscopy(PEEM).The localization of the electromagnetic field in the near-field region was mapped at high spatial resolution.By tuning the excitation laser wavelength,we can obtain the near-field spectra,from which the energy splitting between longitudinal(L)and transverse(T)plasmon modes can be revealed.In particular,the L-mode red shifts and the T-mode blue shifts with increasing chain length.The red shift of the L-mode is highly dependent on the gap distance.In contrast,the T-mode almost remains constant within the range of gap distance we investigated.This energy splitting between the L-mode and the T-mode of metallic chains is in agreement with previous far-field measurements,where it was explained by dipole-dipole near-field coupling.Here,we provide direct proof of this near-field plasmon coupling in nanochains via the above-described near-field measurements using PEEM.In addition,we explore the energy transport along the gold nanochains under excitation at oblique illumination via PEEM measurements together with numerical simulations.

Background-free three-dimensional selective imaging of anisotropic plasmonic nanoparticles

There is an increasing demand for advanced optical imaging techniques that can detect and resolve nanosize objects at a spatial resolution below the optical diffraction limit, especially in three-dimensional （3D） cellular environments. In this study, using a polarization-activated localization scheme based on the orientation-dependent properties of anisotropic plasmonic metal nanoparticles （MNPs）, ＂photoswitchable＂ imaging of single gold nanorods （AuNRs） was accomplished not only in two dimensions but also in three dimensions. Moreover, the Rayleigh scattering background arising from the congested subcellular structures was efficiently suppressed. Thus, we obtained the 3D distributions of both the position and the orientation of the AuNRs inside the cells and investigated their intemalization kinetics. To our knowledge, this is the first demonstration of the confocal-like 3D imaging of non-fluorescence nanoparticles with a high resolution and almost zero background. This technique is easy to implement and should greatly facilitate MNP studies and applications in biomedicine and biology.

Emerging advances in plasmonic nanoassemblies for biosensing and cell imaging

Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties,which are not available for single nanoparticles.Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects.Thus,plasmonic assemblies enable better performance in plasmon-based applications,such as enhanced fluorescence and Raman effects.This makes them hold great potential for trace analyte detection and nanomedicine.Herein,we focus on the recent advances in various plasmonic nanoassembles such as dimers,tetramers,and core-satellite structures,and discuss their applications in biosensing and cell imaging.The fabrication strategies for self-assembled plasmonic nanostructures are described,including top-down strategies,self-assembly methods linked by DNA,ligand,polymer,amino acid,or proteins,and chemical overgrowth methods.Thereafter,their applications in biosensor and cell imaging based on dark-field imaging,surface-enhanced Raman scattering,plasmonic circular dichroism,and fluorescence imaging are discussed.Finally,the remaining challenges and prospects are elucidated.

Surface Plasmon Resonance for C-Reactive Protein Detection in Human Plasma

In this work, we describe an approach of detecting biomarkers by Surface Plasmon Resonance imaging (SPRi) technique in real samples. Two C-Reactive Protein (CRP)-antibody immobilization methods were used: The first method was based on direct physisorption of CRP-antibody onto gold surface;the second one was based on oriented CRP-antibody with protein G intermediate layer. The two developed immunosensors were tested against CRP antigen in phosphate buffer saline solution with the SPRi technique. The response of the developed immunosensors was reproducible and stable. The detection limit of 10 pg&#183mL&#451 and 50 pg&#183mL&#451 CRP-antigen was observed with and without protein G respectively with this technique. Moreover, the developed SPRi immunosensor was used for CRP-antigen detection in human plasma. A detection limit of 5 ng&#183mL&#451 and 10 ng&#183mL&#451 was obtained with and without protein G respectively. These obtained results were compared to those obtained with QCM (Quartz Crystal Microbalance) and Enzyme-Linked Immunosorbent Assay (ELISA) techniques.

基于SPR的重金属离子检测技术研究进展

重金属离子浓度的检测对于人体健康和环境科学等领域具有重要意义。与其它离子检测方法相比,表面等离子体共振(surface plasmon resonance,SPR)技术具有无标记,灵敏度高和检测限低等优点,为重金属离子监测领域带来了新的可能性。本文综述了SPR传感技术在重金属离子检测中的应用及其技术进展。首先介绍了SPR传感的技术原理;然后在传感材料的选择以及表面修饰等方面,针对铅、汞等有害重金属离子,重点阐述了对灵敏度、线性动态范围和特异性等指标的改进;最后介绍了SPR成像传感技术在检测速度、灵敏度等方面取得的重大进展,展望了SPR技术的发展前景。

Direct imaging of the near field and dynamics of surface plasmon resonance on gold nanostructures using photoemission electron microscopy

Localized surface plasmon resonance(LSPR)can be supported by metallic nanoparticles and engineered nanostructures.An understanding of the spatially resolved near-field properties and dynamics of LSPR is important,but remains experimentally challenging.We report experimental studies toward this aim using photoemission electron microscopy(PEEM)with high spatial resolution of sub-10 nm.Various engineered gold nanostructure arrays(such as rods,nanodisk-like particles and dimers)are investigated via PEEM using near-infrared(NIR)femtosecond laser pulses as the excitation source.When the LSPR wavelengths overlap the spectrum of the femtosecond pulses,the LSPR is efficiently excited and promotes multiphoton photoemission,which is correlated with the local intensity of the metallic nanoparticles in the near field.Thus,the local field distribution of the LSPR on different Au nanostructures can be directly explored and discussed using the PEEM images.In addition,the dynamics of the LSPR is studied by combining interferometric time-resolved pump-probe technique and PEEM.Detailed information on the oscillation and dephasing of the LSPR field can be obtained.The results identify PEEM as a powerful tool for accessing the near-field mapping and dynamic properties of plasmonic nanostructures.