Nonlinear Optical Techniques Research Articles

Antenna-coupled infrared nanospectroscopy of intramolecular vibrational interaction

Many photonic and electronic molecular properties, as well as chemical and biochemical reactivities are controlled by fast intramolecular vibrational energy redistribution (IVR). This fundamental ultrafast process limits coherence time in applications from photochemistry to single quantum level control. While time-resolved multidimensional IR-spectroscopy can resolve the underlying vibrational interaction dynamics, as a nonlinear optical technique it has been challenging to extend its sensitivity to probe small molecular ensembles, achieve nanoscale spatial resolution, and control intramolecular dynamics. Here, we demonstrate a concept how mode-selective coupling of vibrational resonances to IR nanoantennas can reveal intramolecular vibrational energy transfer. In time-resolved infrared vibrational nanospectroscopy, we measure the Purcell-enhanced decrease of vibrational lifetimes of molecular vibrations while tuning the IR nanoantenna across coupled vibrations. At the example of a Re-carbonyl complex monolayer, we derive an IVR rate of (25±8) cm-1 corresponding to (450±150) fs, as is typical for the fast initial equilibration between symmetric and antisymmetric carbonyl vibrations. We model the enhancement of the cross-vibrational relaxation based on intrinsic intramolecular coupling and extrinsic antenna-enhanced vibrational energy relaxation. The model further suggests an anti-Purcell effect based on antenna and laser-field-driven vibrational mode interference which can counteract IVR-induced relaxation. Nanooptical spectroscopy of antenna-coupled vibrational dynamics thus provides for an approach to probe intramolecular vibrational dynamics with a perspective for vibrational coherent control of small molecular ensembles.

Value of multiphoton microscopy in uro-oncology: a narrative review.

Multi-photon microscopy (MPM) is a 3-dimension fluorescence imaging technique that combines the excitation of two low-energy photons, enabling less photo-bleaching and deeper penetration of the imaged tissue. Two signals are detected, autofluorescence (AF), from natural intracellular fluorophores [such as nicotinamide adenine dinucleotide phosphate (NADP) and flavine adenine dinucleotide (FAD) transformation], and second harmonic generation (SHG), a physical property of the laser enhancing non-centrosymmetric structures such as collagen fibers. MPM can give both visual and quantitative information of a fresh tissue (without the need of processing, cutting or staining the tissue), aiding in the progress towards optimizing a real-time imaging device. The objective of this review is to show the value and benefits of the use of MPM in uro-oncology. A structured literature review was performed using PubMed and Web of Sciences, including all articles with the following keywords: "multiphoton microscopy", "two-photon microscopy", "non-linear microscopy", "second harmonic generation", "urology", "prostate", "bladder", "kidney", "upper tract", "oncology", "surgical margins", "frozen section". Articles were reviewed to summarize the use of this tool in performing biopsies, assessing surgical margins, staging and grading complementary tool, and real-time imaging. A total of 476 articles were identified with these keywords, and later screened for inclusion. We finally included 47 publications that were relevant to our topic. The advantages of this technique have led to its application in the management of several cancers, allowing cellular description as well as quantitative measurements of AF or SHG and their correlation with clinical outcomes. MPM has shown great improvement in providing a real time assessment of fresh tissue, giving oncologic diagnosis, performing in vivo imaging and quantitative analysis of the tissue as well as increasing precision of the diagnosis. This nonlinear optical technique has the potential of guiding both biopsy and surgery, as well as helping the surgeon with interesting additional tissue information intra-operatively.

Crystallographic parameters of spherulitic structures in ferroelectric film

The symmetry and structure of ferroelectric films determine most of their properties. Nonlinear optical technique of second harmonic generation (SHG) is widely accepted for remote and fast qualitative characterization of ferroelectric films. In this article, we develop a method for quantitative characterization of the local symmetry and structure of PZT thin films. Depending on the annealing time of pyrochlore phase two types of structure have been obtained: continuous perovskite polycrystalline film consisting of truncated spherulites and isolated spherulites embedded into pyrochlore matrix. The method is based on the SHG azimuthal dependences measurements followed by fitting procedure and gives the ratio of monoclinic to tetragonal phases as well as the fraction of differently oriented crystallographic faces of both of these phases.

Nonlinear optical microscopy for skinin vivo: Basics, development and applications

Multi-photon microscopy (MPM) and coherent anti-Stokes Raman scattering (CARS) are two advanced nonlinear optical imaging techniques, which provide complementary information and have great potential in combination for noninvasive in vivo biomedical applications. This paper provides a detailed discussion of the basics, development and applications of these technologies for in vivo skin research, covering the following topics: The principle and advantage of MPM and CARS, instrumentation development for in vivo applications, MPM and CARS of normal skin, application of MPM and CARS in skin cancer and disease diagnosis; application of MPM in skin disease intervention, i.e., imaging guided two-photon photothermolysis.

Liquid Crystal-Based Geometric Phase-Enhanced Platform for Polarization and Wavefront Analysis Techniques with the Short-TeraHertz FEL Oscillator TerRa@BriXSinO

In this work, we propose to design a liquid crystal–based modular and extendable platform of cutting-edge optical technologies for studying materials based on the analysis of polarization and wavefront of light in the wavelength range of 10–50 μm, which is considered to work even in the longer wavelengths range. This platform will be driven by the future THz-FEL source TerRa@BriXSinO that produces high power radiation in THz-range from 6 THz up to 30 THz (Mid-/Far-IR). The lack of optical infrastructures in this range has been tackled by fabricating liquid crystal–based geometric phase components that have been specifically designed for this purpose. This is in order to optimally exploit all the source’s potential for maximum accuracy and efficiency in determining polarization- and wavefront-sensitive properties of materials. We present an overview of a few experiments for characterizing bulk inhomogeneities, dielectric anisotropy, surface roughness, cracks, impact damages, and stress and strain effects with special emphasis on non-destructive tests on composite structures. The tools for wavefront shaping developed within our platform will be exploited to add a further degree of freedom, i.e., orbital angular momentum, to nonlinear optics techniques, such as Terahertz Hyper-Raman spectroscopy, for investigating chiral agents’ properties.

Monitoring membranes: The exploration of biological bilayers with second harmonic generation.

Nature's seemingly controlled chaos in heterogeneous two-dimensional cell membranes stands in stark contrast to the precise, often homogeneous, environment in an experimentalist's flask or carefully designed material system. Yet cell membranes can play a direct role, or serve as inspiration, in all fields of biology, chemistry, physics, and engineering. Our understanding of these ubiquitous structures continues to evolve despite over a century of study largely driven by the application of new technologies. Here, we review the insight afforded by second harmonic generation (SHG), a nonlinear optical technique. From potential measurements to adsorption and diffusion on both model and living systems, SHG complements existing techniques while presenting a large exploratory space for new discoveries.

Application of Ultrashort Lasers in Developmental Biology: A Review

The evolution of laser technologies and the invention of ultrashort laser pulses have resulted in a sharp jump in laser applications in life sciences. Developmental biology is no exception. The unique ability of ultrashort laser pulses to deposit energy into a microscopic volume in the bulk of transparent material without disrupting the surrounding tissues makes ultrashort lasers a versatile tool for precise microsurgery of cells and subcellular components within structurally complex and fragile specimens like embryos as well as for high-resolution imaging of embryonic processes and developmental mechanisms. Here, we present an overview of recent applications of ultrashort lasers in developmental biology, including techniques of noncontact laser-assisted microsurgery of preimplantation mammalian embryos for oocyte/blastomere enucleation and embryonic cell fusion, as well as techniques of optical transfection and injection for targeted delivery of biomolecules into living embryos and laser-mediated microsurgery of externally developing embryos. Possible applications of ultrashort laser pulses for use in Assisted Reproductive Technologies are also highlighted. Moreover, we discuss various nonlinear optical microscopy techniques (two-photon excited fluorescence, second and third harmonic generation, and coherent Raman scattering) and their application for label-free non-invasive imaging of embryos in their unperturbed state or post-laser-induced modifications.

Revealing natural fluorescence in transparent insect wings by linear and nonlinear optical techniques

For most natural organisms, the physical, chemical and biological aspects of fluorescence emission are poorly understood. For example, to the best of our knowledge, fluorescence from the transparent wings of any of the 3000 known species of cicadas has never been reported in the literature. These wings are known to exhibit anti-reflective properties arising from quasi-periodic arrays of nipples. Our study, using linear and nonlinear optical techniques, including spectrofluorimetry, two-photon fluorescence spectroscopy and Second Harmonic Generation (SHG), reveals the fluorescence properties in the wings the grey and the common cicadas (Cicada orni and Lyristes (Tibicen) plebejus, respectively), as well as the broad-bordered bee hawk-moth (Hemaris fuciformis). The study suggests that fluorescence would be more widespread in transparent insect wings than what was previously believed. Comparing this result to the fluorescence emission from the wings of the Bornean damselfly (Vestalis amabilis), we inferred that this emission probably arises from resilin, a protein reported to enhance wing flexibility. Moreover, the nonlinear optical investigation of the insects’ wings provided further insight into wing structure, indicating that multiphoton techniques add valuable information for the analysis of insect integuments. The strong SHG signal detected from the wing veins implies that these veins are materially organised in a non-centrosymmetric and hence non-random fashion.

Pulse-Picking Multimodal Nonlinear Optical Microscopy.

Nonlinear optical microscopy techniques can map chemical compositions in biological samples in a label-free manner. Commonly used nonlinear optical processes for imaging include multiphoton excitation fluorescence (MPEF), second harmonic generation (SHG), and coherent Raman scattering (CRS). Femtosecond lasers are typically used for MPEF and SHG due to the requirement of high peak power for excitation, while picosecond lasers are preferred for CRS due to the need for high spectral resolution. Therefore, it is challenging to integrate CRS with MPEF and SHG for chemical imaging. We develop a pulse-picking strategy based on an acousto-optic modulator that can program the duty cycle of the laser pulse train, significantly increasing the pulse peak power at low input average power. This approach offers strong enhancement of nonlinear optical signals and makes hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy compatible with MPEF and SHG for multimodal imaging at low laser average power. The pulse-picking method also enables the evaluation and comparison of phototoxicity of laser pulses at different average and peak power levels. The photo-perturbations to biological samples are evaluated using cellular dynamics and sample morphological changes, allowing the selection of optimal laser power for the best sensitivity and minimal phototoxicity.

Characteristic of fixed abrasive polishing for KDP in an anhydrous environment.

High grade optical components are rapidly being employed in a wide range of applications due to their great performance. Among these, KDP (potassium dihydrogen phosphate) is the preferred choice for frequency doubling components because to its large non-linear optical technique and high laser damage threshold. In this research, KDP is treated employing fixed polishing in an anhydrous environment. Copper oxide is utilized as abrasive, and toner and phenolic resin are combined to form pellets for KDP polishing. Calculation of the temperature field on the surface of the workpiece based on the relationship of the movement. The ideal polishing parameters are also determined from the findings of the temperature field and the optimum process parameters are 5kPa pressure, 150rpm and 8mm eccentricity. A new material removal model is presented and based on this, a unique processing technique to increase the material removal depth is provided. Interestingly, with this form of polishing, the surface roughness of the workpiece remains about Ra 20nm after a quick shift and does not alter with re-pressing.

Multiplex Chemical Imaging Based on Broadband Stimulated Raman Scattering Microscopy

Stimulated Raman scattering (SRS) microscopy is a nonlinear optical technique for label-free chemical imaging. This analytical tool delivers chemical maps at high speed, and high spatial resolution of thin samples by directly interrogating their molecular vibrations. In its standard implementation, SRS microscopy is narrowband and forms images with only a single vibrational frequency at a time. However, this approach not only hinders the chemical specificity of SRS but also neglects the wealth of information encoded within vibrational spectra. These limitations can be overcome by broadband SRS, an implementation capable of extracting a vibrational spectrum per pixel of the image in parallel. This delivers hyperspectral data that, when coupled with chemometric analysis, maximizes the amount of information retrieved from the specimen. Thus, broadband SRS improves the chemical specificity of the system, allowing the quantitative determination of the concentration of the different constituents of a sample. Here, we report a protocol for chemical imaging with broadband SRS microscopy, based on a home-built SRS microscope operating with a custom differential multichannel-lock-in amplifier detection. It discusses the sample preparation, alignment of the SRS apparatus, and chemometric analysis. By acquiring vibrational Raman spectra, the protocol illustrates how to identify different chemical species within a mixture, determining their relative concentrations.

Multiplex Chemical Imaging Based on Broadband Stimulated Raman Scattering Microscopy.

Stimulated Raman scattering (SRS) microscopy is a nonlinear optical technique for label-free chemical imaging. This analytical tool delivers chemical maps at high speed, and high spatial resolution of thin samples by directly interrogating their molecular vibrations. In its standard implementation, SRS microscopy is narrowband and forms images with only a single vibrational frequency at a time. However, this approach not only hinders the chemical specificity of SRS but also neglects the wealth of information encoded within vibrational spectra. These limitations can be overcome by broadband SRS, an implementation capable of extracting a vibrational spectrum per pixel of the image in parallel. This delivers hyperspectral data that, when coupled with chemometric analysis, maximizes the amount of information retrieved from the specimen. Thus, broadband SRS improves the chemical specificity of the system, allowing the quantitative determination of the concentration of the different constituents of a sample. Here, we report a protocol for chemical imaging with broadband SRS microscopy, based on a home-built SRS microscope operating with a custom differential multichannel-lock-in amplifier detection. It discusses the sample preparation, alignment of the SRS apparatus, and chemometric analysis. By acquiring vibrational Raman spectra, the protocol illustrates how to identify different chemical species within a mixture, determining their relative concentrations.

Water Organization around Inorganic Nanotubes in Suspension Probed by Polarization-Resolved Second Harmonic Scattering

Imogolite nanotube (INT) is a fascinating one-dimensional (1D) material that can be synthesized in the liquid phase. Its behavior in solution is crucial for many applications and depends on the organization of water at the liquid-wall interface. We study here this water organization by using the nonlinear optical technique of polarization-resolved second harmonic scattering (SHS). A microscopic model is proposed to interpret the origin of the coherent SHS signal recovered in this 1D colloidal system. This work demonstrates that the SHS technique is able to probe the shell of water molecules oriented around the nanotubes. Water organization results from the electric field induced by the nanotube walls, and it is strongly dependent on the ionic strength of the suspension.

Coherent and ultrashort soft x-ray pulses from echo-enabled harmonic cascade free-electron lasers

It is a long-standing challenge for laser technologies to generate intense fully coherent pulses in the x-ray regime. Here, we demonstrate an external seeding mechanism, termed echo-enabled harmonic cascade (EEHC) for generating coherent and ultrashort soft x-ray pulses. The mechanism uses echo-enabled harmonic generation as the first stage, producing intense extreme ultraviolet pulses that seed the second stage x-ray free-electron laser (FEL) with the high-gain harmonic generation setup. Benefiting from the low sensitivity to electron-beam imperfections of EEHC, we generated high-power nearly transform-limited soft x-ray pulses. We have also demonstrated a unique feature of EEHC in generating isolated few-femtosecond-long x-ray pulses. The supreme up-frequency conversion efficiency and flexible pulse length control of this EEHC mechanism allow us to exceed the current limitations of seeded FELs while preserving the coherence of the seed. Our results are a step towards fully coherent and ultrashort x-ray lasers and could enable the extension of nonlinear optical techniques to shorter wavelengths.

Nonlinear optical detection of mesoscopic magnetic toroidal dipoles

A vortex-like magnetic state with zero net magnetization—called a magnetic toroidal dipole (MTD)—exhibits a variety of fascinating magnetoelectric (ME) cross-coupling functionalities. However, designing and controlling MTDs in conventional crystals remains challenging. Here, we fabricated a model system of mesoscopic MTDs using planar patterned nanomagnets. By exploiting a symmetry-resolved nonlinear optical technique, we directly detected mesoscopic MTDs whose magnitude and direction are well-controlled using external magnetic fields. This approach may provide a guide for the design and control of nanoscopic-to-mesoscopic functional ME materials working at room temperature.

Liquid-Solid Interfaces under Dynamic Shear Flow: Recent Insights into the Interfacial Slip.

The development of micro/nanofluidic techniques has recently revived interest in dynamic shear flow at liquid-solid interfaces. When the nature of the liquid-solid boundaries was revisited, the slip of the fluids relative to the solid wall was predicted theoretically and confirmed experimentally. This indicates that the molecular-level structures of the liquid-solid interfaces will be influenced by the liquid flow over certain temporal and spatial criteria. However, the fluid flow at the boundary layer still cannot be precisely predicted and effectively controlled, somehow limiting its practical applications. Here, we summarize the recent advances for the microscopic structures at the liquid-solid interfaces upon shear flow. Special attention was given to a second-order nonlinear optical technique, sum frequency generation vibrational spectroscopy, which is a powerful tool for exploring the molecular-level structures and structural dynamics at the liquid-solid interfaces and offering new insights into the molecular mechanisms of the fluid slip at the interfaces. Moreover, we discuss the possible approaches for controlling the interfacial slip at the molecular level and highlight the current challenges and opportunities. Although the theoretical framework of the slip at the liquid-solid interfaces is still incomplete, we hope that this Perspective will complement and enhance our understanding of various interfacial properties and phenomena with respect to practical non-equilibrium dynamic processes happening at the interfaces.

Indole Facilitates Antimicrobial Uptake in Bacteria.

Indole signaling in bacteria plays an important role in antibiotic resistance, persistence, and tolerance. Here, we used the nonlinear optical technique, second-harmonic light scattering (SHS), to examine the influence of exogenous indole on the bacterial uptake of the antimicrobial quaternary ammonium cation (qac), malachite green. The transport rates of the antimicrobial qac across the individual membranes of Escherichia coli and Pseudomonas aeruginosa, as well as liposomes composed of the polar lipid extract of E. coli, were directly measured using time-resolved SHS. Whereas exogenous indole was shown to induce a 2-fold increase in the transport rate of the qac across the cytoplasmic membranes of the wild-type bacteria, it had no influence on a knockout strain of E. coli lacking the tryptophan-specific transport protein (Δmtr). Likewise, indole did not affect the transport rate of the qac diffusing across the liposome membrane. Our findings suggest that indole increases the bacterial uptake of antimicrobials through an interaction with the Mtr permease.

Image encryption using spatial nonlinear optics

Optical technologies have been widely used in information security owing to its parallel and high-speed processing capability. However, the most critical problem with current optical encryption techniques is that the cyphertext is linearly related with the plaintext, leading to the possibility that one can crack the system by solving a set of linear equations with only two cyphertext from the same encryption machine. Many efforts have been taken in the last decade to resolve the linearity issue, but none of these offers a true nonlinear solution. Inspired by the recent advance in spatial nonlinear optics, here we demonstrate a true nonlinear optical encryption technique. We show that, owing to the self-phase modulation effect of the photorefractive crystal, the proposed nonlinear optical image encryption technique is robust against the known plaintext attack based on phase retrieval. This opens up a new avenue for optical encryption in the spatial nonlinear domain.

Self-Suppression of the Giant Coherent Anti-Stokes Raman Scattering Background for Detection of Buried Interfaces with Submonolayer Sensitivity.

Despite its success in many fields, the implementation of coherent anti-Stokes Raman spectroscopy (CARS) in tackling the problems at interfaces was hindered by the enormous resonant and nonresonant background from the bulk. In this work, we have developed a novel CARS scheme that can probe a buried interface via ≥105-fold suppression of the nonresonant and resonant bulk contribution. The method utilizes self-destructive interference between the forward and backward CARS generated in the bulk near the Brewster angle. As a result, we can resolve the vibrational spectrum of submonolayer interfacial polar/apolar species immersed in the surrounding medium with huge CARS responses. We expect that our approach opens up the opportunity to interrogate the interfaces involving apolar molecules and benefits other nonlinear optical spectroscopic techniques, e.g., sum-frequency spectroscopy and four-wave mixing spectroscopy in general, to promote the signal-to-background noise ratio.

Wide-field broadband CARS microscopy

Coherent anti-Stokes Raman scattering is an extremely powerful non-linear optical (NLO) microscopy technique for label-free vibrational imaging allowing for a detailed study of biological samples in their native state. To overcome the long acquisition times associated with raster sample scanning required in NLO microscopy, which impair real-time investigation of fast biological dynamics, we employ here wide-field signal generation over a large field of view, covering tens of micrometers. To this aim, we exploit an innovative approach based on the use of an amplified femtosecond ytterbium laser source delivering high energy (≈μJ) pulses in the near infrared. This enables the generation of stable broadband Stokes pulses to measure the entire fingerprint region of the molecular vibrational spectrum, the richest in chemical information. Our results pave the way for future translational applications and clinical diagnostics with video-rate imaging capabilities. ©2022 The Authors