Evanescent wave cavity-based spectroscopic techniques as probes of interfacial processes

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) is a surface sensitive technique, which allows optical absorption measurements at interfaces with good time resolution. In EW-CRDS, a pulsed or modulated laser beam is coupled into an optical cavity which consists of at least one optical element, such as a silica prism, at the surface of which the beam undergoes total internal reflection (TIR). At the position of TIR, an evanescent field is established whose amplitude decays exponentially with distance from the boundary. This evanescent field can be exploited to investigate interfacial properties and processes such as adsorption and surface reactions, with most applications hitherto focusing on solid/liquid and solid/air interfaces. As highlighted herein, EW-CRDS is particularly powerful for investigations of interfacial processes when combined with other techniques such as basic electrochemical measurements and microfluidic or hydrodynamic techniques. In this tutorial review, the basic elements of EW-CRDS will be introduced and the relative merits of different configurations for EW-CRDS discussed, along with various aspects of instrumentation and design. The type of information which may be obtained using EW-CRDS is illustrated with a focus on recent examples such as molecular adsorption/desorption, deposition/dissolution of nanostructures and interfacial redox reactions. The comparatively new, but complementary, cavity technique of EW-broadband cavity enhanced absorption spectroscopy (EW-BB-CEAS) is also introduced and its advantages compared with EW-CRDS are discussed. Finally, future developments and trends in EW-cavity based spectroscopy are predicted. Notably, the potential for extending the technique to probe other interfaces is exemplified with a discussion of initial interfacial absorbance measurements at a water-air interface.     

A versatile total internal reflection photometric detection cell for flow analysis

A total internal reflection (TIR) flow-through cell that is highly tolerant of schlieren effects, has limited hydrodynamic dispersion and does not trap gas bubbles, and which is suitable for sensitive photometric measurements in flow analysis, is described. Light from an optical fibre is introduced into a short length of quartz capillary through the sidewall at an incident angle of ca. 53°. Under this condition, incident light undergoes total internal reflection from the external air-quartz interface and is propagated by successive reflections from the external walls through the aqueous liquid core of the cell. Detection of the transmitted beam is enabled by intentionally introducing an optical coupling medium at a predetermined distance along the capillary wall, which allows the internally reflected light to be captured by a second optical fibre connected to a charge-couple device detector.This configuration embodies a number of the desirable features of a liquid core waveguide cell (i.e. total internal reflection), a multi-reflection (MR) flow cell (i.e. minimum susceptibility to schlieren effects, low hydrodynamic dispersion and little tendency to trap bubbles), and a conventional Z-cell (wide dynamic range). When employed with a flow injection system, a limit of detection of 2.0 μg PL⁻¹ was achieved for the determination of reactive phosphate using the TIR cell, compared with LOD values of 3.8 μg PL⁻¹ and 4.9 μg PL⁻¹ obtained using the MR and Z-cells with same manifold.The combined advantages of schlieren-tolerance and lack of bubble entrapment of the MR cell with the higher S/N ratio and wider dynamic range of a conventional Z-cell, make the TIR cell eminently useful for photometric measurements of samples with widely differing refractive indices.     

Photothermally and optomechanically induced transparency in a hybrid optomechanical system

We theoretically investigated the photothermally and optomechanically induced transparency (PTIT and OMIT) in an optomechanical system filled with quantum dots (QDs). In our proposed system, the right mechanical resonator couples with the optical cavity via radiation pressure, and the left mechanical resonator couples with the optical cavity through the photothermal effects. The system is driven by a strong pump field and a weak probe field. It is shown that double transparency windows can be observed due to PTIT and OMIT. When considering the Jaynes-Cummings coupling between the QDs and the optical cavity, three transparency windows are observed. We also show that the PTIT can be adjusted by the OMIT and the QDs in the optical cavity. What is more, the coupling strength and the frequency detuning can be used effectively to change the system absorption and dispersion in the PITT transparency window. This indicates that the group delay of the probe light can also be manipulated by the system parameters. The obtained results may be applied in the optical communication such as optical buffer, and so forth.     

Double Functionalization of Carbon Nanotubes with Purine and Pyrimidine Derivatives

Herein, we have developed a synthetic strategy for the covalent double functionalization of single‐walled carbon nanotubes (SWCNTs) with a combination of purine–pyrimidine and purine–purine nucleobase systems. The nucleobases were introduced on the sidewall of oxidized SWCNTs through 1,3‐dipolar cycloaddition and by amidation of the carboxylic acids located at the tips and defect sites of the nanotubes. The new nanohybrids were characterized by transmission electron microscopy, thermogravimetric analysis, FTIR and Raman spectroscopy, magic‐angle spinning NMR spectroscopy, and Kaiser test. The nucleobase/SWCNT conjugates can be envisaged for the modulation of the interactions with nucleic acids by means of base pairing, thereby opening new possibilities in the development of DNA/CNT nanobioconjugates.     

Research on Dispersive Detection Technology Based on Digital Micromirror Device by Atomic Fluorescence Spectrometry

A ultraviolet (UV) digital micromirror spectrometer using a digital micromirror device (DMD) as a spatial light modulator, a grating as a spectroscope and a photomultiplier tube (PMT) as a detector, was specially designed for dispersive hydride generation atomic fluorescence spectrometry (HG-AFS). To improve the detection ability of the UV digital micromirror spectrometer for weak fluorescence signals at 180–320 nm, a high UV transmittance DMD was used and the signal acquisition system was improved, and the control parameters of DMD and PMT negative high voltage were optimized. The feasibility of the spectrometer was demonstrated with standard sample analyzing of As, Sb, Bi, and Hg, the emission and atomic fluorescence spectra were obtained, and the scattering interference caused by the light source was discussed. The results showed that the UV digital micromirror spectrometer had a preliminary ability for the excitation fluorescence analysis by HG-AFS. In addition, due to no macroscopic moving parts, the UV digital micromirror spectrometer had simple construction and fast analysis speed (0.848 s per spectrum scan).     

A fabrication platform for electrically mediated optically active biofunctionalized sites in BioMEMS

We report a new approach for microfluidic optical bioanalysis that is based on the electrically driven assembly of bio-components on a transparent sidewall and the optical detection of the assembled components using planar waveguides. This allows localized electrical signals for bio-assembly and optical signals for bio-detection that can easily be applied in MEMS systems. We demonstrate a BioMEMS design incorporating this scheme and its output signal when using fluorescent detection.     

Identifying the inhibition of TIR proteins involved in TLR signalling as an anti-inflammatory strategy

Toll/IL1 receptor (TIR) adaptor proteins continue to be an integral part of Toll-like receptors’ (TLR) signalling involved in inflammation. Signalling is likely to be initiated by these TIR adaptors when they are recruited to a TIR–TIR interface formed by TLR dimerization. Among these, myeloid differentiation factor-88 (MyD88), MyD88 adapter-like protein (Mal), TIR domain-containing adaptor protein inducing interferon-β (TRIF) and TRIF-related adaptor molecule (TRAM) play pivotal roles at many steps in the signalling events leading to inflammation. The presence of the conserved BB loop residues in the TIR domain of all these important adaptor proteins make them possible targets for inhibition by synthetic compounds. We have designed compounds based on an already known MyD88 TIR dimerization inhibitor, T6167923, which binds well not only to the original target but also to the TIR domains of Mal, TRIF and TRAM. The designed inhibitors are based on modifications of the bromophenyl-sulphonyl-thiophenyl-piperazine-carboxamide series of compounds. We have further suggested modifications in these high-affinity compounds for efficient absorption inside the body. Further, a pharmacophore model highlighting important structural interaction features has been developed. The screened compounds are better in binding to the TIR proteins then the parent compound and hence are good starting points for multi-TIR inhibition.     

基于DFB型半导体激光器的腔增强吸收光谱研究

The Cavity enhanced absorption spectroscopy based on a tunable DFB diode laser (TDL-CEAS) was described. A brief introduction of cavity enhanced absorption spectroscopy development and experimental scheme was given, the effective absorption path of the medium in the optical cavity was interpreted from the way of Fabry Perot cavity. It is pointed out that the main reason why CEAS has high detection sensitivity is that the medium in the cavity can get a long absorption path. A tunable DFB diode laser which center wavelength is 1.573 μm was used as the light source, and an optical cavity which consists of two high reflectivity mirrors (near 1.573 μm, R about 0.994) separated at a distance of 34 cm was used as the absorption cell. Laser radiation was coupled into the optical cavity via accidental coincidences of laser frequency with the cavity mode when scanning the cavity and the laser. An absorption spectrum of carbon dioxide near 1.573 μm was obtained and a detection sensitivity of about 1.66×10-5 cm-1 was achieved. It is experimentally demonstrated that the CEAS is a highly sensitive and high resolution spectrum technology, and it has the advantage of simple experimental setup and easy operation.     

Total internal reflection Raman spectroscopy

Total internal reflection (TIR) Raman spectroscopy is an experimentally straightforward, surface-sensitive technique for obtaining chemically specific spectroscopic information from a region within approximately 100-200 nm of a surface. While TIR Raman spectroscopy has long been overshadowed by surface-enhanced Raman scattering, with modern instrumentation TIR Raman spectra can be acquired from sub-nm thick films in only a few seconds. In this review, we describe the physical basis of TIR Raman spectroscopy and illustrate the performance of the technique in the diverse fields of surfactant adsorption, liquid crystals, lubrication, polymer films and biological interfaces, including both macroscopic structures such as the surfaces of leaves, and microscopic structures such as lipid bilayers. Progress, and challenges, in using TIR Raman to obtain depth profiles with sub-diffraction resolution are described.     

Infrared spectra of organic monolayer films in a standing wave measured by photon-trap spectroscopy

Photon-trap spectroscopy, a generalized scheme of cavity ringdown spectroscopy, is applied to measure an infrared spectrum of the C-H stretching vibration of alkylsiloxane monolayer films grafted on a silicon substrate. A continuous-wave laser beam is introduced into a high-finesse Fabry-Pérot cavity containing the substrate placed exactly normal to the light beam to minimize optical losses. The lifetime of the light trapped in the cavity is measured to detect optical absorption sensitively. The results show clear dependence of the absorbance on the location of the monolayers with respect to a standing wave formed in the cavity; the absorbance is practically zero when the monolayers on both the surfaces are adjusted at nodes, whereas it is maximized at antinodes. The present experiment is materialized on the basis of the principles established by our previous study [Terasaki et al., J. Opt. Soc. Am. B 22, 675 (2005)].     

A free-flowing soap film combined with cavity ring-down spectroscopy as a detection system for liquid chromatography

We have shown that a free-flowing soap film has sufficiently high-quality optical properties to allow it to be used in the cavity of a ring-down spectrometer (CRDS). The flow rates required to maintain a stable soap film were similar to those used in liquid chromatography and thus allowed interfacing with an HPLC system for use as an optical detector. We have investigated the properties of the system in a relevant analytical application. The soap film/CRDS combination was used at 355 nm as a detector for the separation of a mixture of nitroarenes. These compounds play a role in the residue analysis of areas contaminated with explosives and their decomposition products. In spite of the short absorption path length (9 μm) obtained by the soap film, the high-sensitivity of CRDS allowed a limit of detection of 4 × 10⁻⁶ in absorption units (AU) or less than 17 fmol in the detection volume to be achieved.     

Photoinduced redox cycle of riboflavin at a water/oil interface.

A photoinduced redox reaction cycle of Riboflavin (RF) at a water/CCl4 interface was studied directly by means of both steady-state and time-resolved total internal reflection (TIR) fluorescence spectroscopies. The TIR fluorescence spectrum of RF observed at the water/CCl4 interface with the maximum wavelength of 517 nm was assigned to the pi-pi* transition from the excited singlet-state of the isoalloxazine chromophore in RF. Upon prolonged laser irradiation (400 nm) in the presence of N,N-dioctadecyl-[1,3,5]triazine-2,4,6-triamine (DTT) as a guest for RF in the CCl4 phase, on the other hand, a new TIR fluorescence band appeared at around 480 nm. Furthermore, the fluorescence intensity at around 480 nm increased in the presence of acetic acid in the water phase. Detailed studies demonstrated that the new fluorescence band should be ascribed to 1,5-dihydoroflavin (RFH2). The present results indicated that RFH2 was produced through the photoreaction of the RF-DTT hydrogen-bonded complex formed at the water/CCl4 interface, whose reaction mechanisms were discussed on the basis of the results observed by fluorescence spectra/dynamics measurements under the TIR conditions as well as by transient absorption spectroscopy.     

Designed Synthesis of a Highly Conjugated Hexaethynylbenzene‐Based Host for Supramolecular Architectures

The construction of efficient synthetic functional receptors with tunable cavities, and the self‐organization of guest molecules within these cavities through noncovalent interactions can be challenging. Here we have prepared a double‐cavity molecular cup based on hexaethynylbenzene that possesses a highly π‐conjugated interior for the binding of electron‐rich guests. X‐ray crystallography, NMR spectroscopy, UV/Vis spectroscopy, fluorescent spectroscopy, cyclic voltammetry, and SEM were used to investigate the structures and the binding behaviors. The results indicated that the binding of a guest in one cavity would affect the binding of the same or another guest in the other cavity. The effect of electron transfer in this system suggests ample opportunities for tuning the optical and electronic properties of the molecular cup and the encapsulated guest. The encapsulation of different guests would also lead to different aggregate nanostructures, which is a new way to tune their supramolecular architectures.     

Large spectral tuning of a water-glycerol microdroplet by a focused laser: characterization and modeling

Large spectral tuning of a water-glycerol microdroplet standing on a superhydrophobic surface by local heating with a focused infrared laser is studied both experimentally by optical spectroscopy and computationally using a lumped system formulation of the mass and heat transfer between the microdroplet and the chamber. The effects of optical scattering force, chamber humidity, size of microdroplet and laser power on the tuning mechanism are examined. The reversibility of the tuning mechanism is also studied. In spite of its negligibly small volatility compared to that of water, irreversibility is found to be mainly caused by evaporation of glycerol. It is also found that reversibility increases dramatically with the relative water and glycerol humidities, and spectral tuning can be made almost fully reversible when the chamber is saturated with glycerol vapor and the relative water humidity approaches unity. Some hysteresis effects are observed, especially in large microdroplets, and this behavior is attributed to the whispering-gallery mode resonances in laser absorption. The time response of the tuning mechanism is also analyzed both experimentally and computationally. The technique presented can find applications in optical communication systems, and can be used in fundamental studies in cavity quantum electrodynamics and in characterizing liquid aerosols on a surface.     

Size dependent index of refraction and absorption of a spherical metal cluster

Size-dependent optical properties of large metal clusters are studied on the example of spherical sodium clusters. The model is based on the fact, that a sphere filled with free-electron gas forms a cavity with size dependent eigenfrequencies of the optically excitable TM plasmons. Therefore the dielectric function of the system gains the resonant character. The dielectric function defines the size-dependent indices of absorption and of refraction.     

Molecular simulation of liquid crystal sensor based on competitive inclusion effect

With the progressive understanding of liquid crystal materials that rely on the interface interactions, optical properties of liquid crystal are attracting attention as a detector for chemicals and biomolecules. In this work, a recently reported liquid crystal sensing system based on the competitive inclusion effect of β-cyclodextrin (β-CD) was studied. Quantum mechanical calculations were applied to study different β-CD inclusion complexes of methyl blue (MB), 4-cyano-4′-pentyl biphenyl (5CB), sodium dodecyl sulfonate (SDS), dopamine (DA) and their inclusion processes. The work shows that DA cannot be an analyte for the liquid crystal sensor as it could not compete for the cavity of β-CD with SDS. However, MB molecule can push SDS out of the β-CD cavity so as to induce the change in optical appearance when MB forms a 1:2 inclusion complex. The simulated absorption spectrum is in agreement with experiment results, implying that MB molecule may exist in both 1:1 and 1:2 inclusion complexes in the system of liquid crystal sensor.     

Plasma membrane associated location of sulfonated meso-tetraphenylporphyrins of different hydrophilicity probed by total internal reflection fluorescence spectroscopy

Sulfonated meso-tetraphenylporphyrins of different hydrophilicity were microspectrofluorimetrically examined in endothelial cells using total internal reflection (TIR) illumination or epi-illumination. Since the penetration depth of the evanescent field during TIR illumination is limited to a few hundred nanometers, photosensitizers were almost selectively examined in close vicinity to the plasma membrane. Pronounced fluorescence signals during TIR illumination were observed for the hydrophilic compounds meso-tetraphenylporphyrin tetrasulfonate (TPPS4) and meso-tetraphenylporphyrin trisulfonate (TPPS3), whereas the more lipophilic compounds meso-tetraphenylporphyrin disulfonate (TPPS2a) and meso-tetraphenylporphyrin monosulfonate (TPPS1) could only be detected under epi-illumination. Irradiation of TPPS1 and TPPS2a in the Soret band led to an increase in fluorescence intensity and formation of a photoproduct with an emission maximum around 610 nm, which was limited to intracellular compartments. In contrast, fluorescence spectra of TPPS3 and TPPS4 obtained by TIR and epi-illumination remained almost unchanged after irradiation in the Soret band. Extralysosomal location of TPPS3 and TPPS4 in close proximity to the plasma membrane was deduced from experiments with the lysosomal markers acridine orange (AO) or lysotracker yellow (LY), which were not detectable under TIR illumination. In conclusion, these results provide for the first time direct evidence for a plasma membrane-associated fraction of the hydrophilic compounds TPPS3 and TPPS4 in living cells.     

Selective crystallization via vibrational strong coupling

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational modes of solvents to cavity vacuum fields can influence the chemical reaction kinetics of dissolved solutes. This suggests that vibrational strong coupling might also effect other important solution-based processes, such as crystallization from solution. Here we test this hitherto unexplored notion, investigating pseudopolymorphism in the crystallization from water of ZIF metal–organic frameworks inside optical microcavities. We find that ZIF-8 crystals are selectively obtained from solution inside optical microcavities, where the OH stretching vibration of water is strongly coupled to cavity vacuum fields, whereas mixtures of ZIF-8 and ZIF-L are obtained otherwise. Moreover, ZIF crystallization is accelerated by solvent vibrational strong coupling. This work suggests that cavity vacuum fields might become a tool for materials synthesis, biasing molecular self-assembly and driving macroscopic material outcomes.

Strong coupling of optical cavity vacuum fields and solvent vibrations leads to selective crystallization in a pseudo-polymorphic MOF system.     

A Modified Z-Type Flow-through Cell for Optical, Electrochemical, and Optoelectrochemical Flow Injection Analysis Measurements

The design and construction of a modified Z-type flow-through cell that can be used for optical, electrochemical, and optoelectrochemical measurements are reported. In optical analysis, the proposed flow cell is placed in the light path of a spectrophotometer and worked as a commercial Z-type optical flow cell. In electrochemical analysis, the working and auxiliary electrodes are two platinum sheets placed at both ends of the cell cavity; the cell cavity is enclosed by two glass windows. The reference electrode is a saturated calomel electrode placed downstream in an overflow tube. The performance of the proposed electrochemical flow cell was studied by analysis of hexacyanoferrate solution as an electroactive species. In optoelectrochemical analysis, the proposed flow cell is operated optically and electrochemically, simultaneously. The flow cell is placed in the light path of a spectrophotometer, constant potential is applied to the electrodes, and the optical and electrochemical signals are recorded simultaneously by the use of two recorders.     

Manipulating valence and core electronic excitations of a transition-metal complex using UV/Vis and X-ray cavities

We demonstrate how optical cavities can be exploited to control both valence- and core-excitations in a prototypical model transition metal complex, ferricyanide ([Fe(iii)(CN)₆]³⁻), in an aqueous environment. The spectroscopic signatures of hybrid light-matter polariton states are revealed in UV/Vis and X-ray absorption, and stimulated X-ray Raman signals. In an UV/Vis cavity, the absorption spectrum exhibits the single-polariton states arising from the cavity photon mode coupling to both resonant and off-resonant valence-excited states. We further show that nonlinear stimulated X-ray Raman signals can selectively probe the bipolariton states via cavity-modified Fe core-excited states. This unveils the correlation between valence polaritons and dressed core-excitations. In an X-ray cavity, core-polaritons are generated and their correlations with the bare valence-excitations appear in the linear and nonlinear X-ray spectra.

We demonstrate how optical cavities can be exploited to control both valence- and core-excitations in a prototypical model transition metal complex, ferricyanide ([Fe(iii)(CN)₆]³⁻), in an aqueous environment.