Ultrafast measurement of photoacoustic parameters with mid-infrared frequency comb transients.

The photoacoustic (PA) effect has been widely used in various applications, including highly sensitive spectroscopy and label-free, non-invasive imaging. In this work, we demonstrate a fast and precise measurement of PA parameters for light-absorbing liquids using mid-infrared asynchronous sampling pump-probe measurements. To simulate the observed PA oscillation signals and extract various PA parameters as a function of pump power, we derived analytical solutions of the PA wave equation driven by a train of ultrashort Gaussian pump pulses. By fitting the analytical solution to the measured PA signals using a nonlinear curve fitting method, we could measure the PA parameters, including damping rate, viscosity, and natural frequency. Furthermore, the dynamic response of thermophysical properties of the chloroform solution is also investigated by measuring the variation of the Grüneisen parameter with pump power. We anticipate that this work will open new possibilities for precise in situ measurements of the thermal properties of light-absorbing liquids.

Time-resolved spectroscopy of thioflavin T solutions: Asynchronous optical sampling method with two frequency-upconverted mode-locked lasers.

We carried out transient absorption spectroscopy of thioflavin T (ThT) molecules in various solvents employing an asynchronous optical sampling (ASOPS) scheme with dual synchronized and frequency up-converted mode-lock lasers in the near UV (NUV) spectral region. We developed a pair of synchronized femtosecond lasers with tunable center wavelengths ranging from 380 to 430 nm and spectral bandwidths of 30 nm. As a proof-of-principle experiment, we measured interferometrically detected time and frequency-resolved pump-probe signals of ThT in various solvents to study the twisted intramolecular charge transfer process of photo-excited ThT molecules. Both single-color NUV-NUV and two-color NUV-near IR (NIR) pump-probe measurements reveal that the vibronic coupling strengths of two vibrational modes with frequencies of 214 and 526 cm-1 in the excited state of ThT are reduced when ThT is dissolved in a chlorine-containing solvent, e.g., chloroform. We confirm theoretically that these vibrational modes have relatively high electric dipole moments in the excited state. As a result, the intramolecular charge transfer process of ThT in chloroform, which is driven by the solvation process of surrounding polar solvent molecules, could occur less efficiently, which results in an increase in the fluorescence quantum yield. Here, we demonstrate that the NUV-NUV and NUV-NIR ASOPS-transient absorption could be useful techniques for studying ultrafast photochemical reactions in condensed phases.

Vibrational Modes Promoting Exciton Relaxation in the B850 Band of LH2.

Exciton relaxation dynamics in multichromophore systems are often modeled using Redfield theory, where bath fluctuations mediate the relaxation among the exciton eigenstates. Identifying the vibrational or phonon modes that are implicated in exciton relaxation allows more detailed understanding of exciton dynamics. Here we focus on a well-studied light-harvesting II complex (LH2) isolated from the photosynthetic purple bacterium Rhodoblastus acidophilus strain 10050. Using two synchronized mode-locked lasers, we carried out a polarization-dependent two-dimensional electronic spectroscopy (2DES) study of an ultrafast exciton relaxation in the B850 band of LH2. 2DES data with different polarization configurations enable us to investigate the exciton relaxation between the k = ±1 exciton states. Then, we identify vibrational modes coupled to the exciton relaxation by analyzing the coherent wavepackets in the 2DES signals. Focusing on the coherent vibrational wavepackets, the data suggest that certain symmetry-breaking modes of monomeric units play a key role in exciton relaxation.

Quantitative complementarity of wave-particle duality.

To test the principle of complementarity and wave-particle duality quantitatively, we need a quantum composite system that can be controlled by experimental parameters. Here, we demonstrate that a double-path interferometer consisting of two parametric downconversion crystals seeded by coherent idler fields, where the generated coherent signal photons are used for quantum interference and the conjugate idler fields are used for which-path detectors with controllable fidelity, is useful for elucidating the quantitative complementarity. We show that the quanton source purity µ s is tightly bounded by the entanglement E between the quantons and the remaining degrees of freedom by the relation [Formula: see text], which is experimentally confirmed. We further prove that the experimental scheme using two stimulated parametric downconversion processes is an ideal tool for investigating and understanding wave-particle duality and Bohr's complementarity quantitatively.

Broadband Infrared Spectroscopy of Molecules in Solutions with Two Intrapulse Difference-Frequency-Generated Mid-Infrared Frequency Combs.

Mid-infrared (mid-IR) spectroscopy is an incisive tool for studying structures and dynamics of complicated molecules in condensed phases. Developing a compact and broadband mid-IR spectrometer has thus been a long-standing challenge. Here, we show that a highly coherent and broadband mid-IR frequency comb can be generated by using an intrapulse difference-frequency-generation with a train of pulses from a few-cycle pulse Ti:sapphire oscillator. By tightly focusing the oscillator output beam into a single-pass, fan-out-type periodically poled lithium niobate crystal and tilting the orientation of the crystal, we show that a mid-IR frequency comb with more than an octave spectral bandwidth from 1550 cm-1 (46 THz) to 3650 cm-1 (110 THz) and vanishing carrier-envelope-offset phase can be generated. Using two coherent mid-IR frequency combs with different repetition frequencies, we demonstrate that a broadband mid-IR dual-frequency comb spectroscopy of aromatic compounds or amino acids in solutions is feasible. We thus anticipate that researchers will find our mid-IR frequency combs useful for developing ultrafast and broadband linear and nonlinear IR spectroscopy of chemically reactive or biologically important molecules in condensed phases.

Two-dimensional electronic spectroscopy of bacteriochlorophyll a with synchronized dual mode-locked lasers.

How atoms and electrons in a molecule move during a chemical reaction and how rapidly energy is transferred to or from the surroundings can be studied with flashes of laser light. However, despite prolonged efforts to develop various coherent spectroscopic techniques, the lack of an all-encompassing method capable of both femtosecond time resolution and nanosecond relaxation measurement has hampered various applications of studying correlated electron dynamics and vibrational coherences in functional materials and biological systems. Here, we demonstrate that two broadband (>300 nm) synchronized mode-locked lasers enable two-dimensional electronic spectroscopy (2DES) study of chromophores such as bacteriochlorophyll a in condensed phases to measure both high-resolution coherent vibrational spectrum and nanosecond electronic relaxation. We thus anticipate that the dual mode-locked laser-based 2DES developed and demonstrated here would be of use for unveiling the correlation between the quantum coherence and exciton dynamics in light-harvesting protein complexes and semiconducting materials.

Time-Resolved Impulsive Stimulated Raman Spectroscopy with Synchronized Triple Mode-Locked Lasers.

A complete understanding of a photochemical reaction dynamics begins with real-time measurements of both electronic and vibrational structures of photoexcited molecules. Time-resolved impulsive stimulated Raman spectroscopy (TR-ISRS) with femtosecond actinic pump, Raman pump, and Raman probe pulses is one of the incisive techniques enabling one to investigate the structural changes of photoexcited molecules. Herein, we demonstrate that such femtosecond TR-ISRS is feasible with synchronized triple mode-locked lasers without using any time-delay devices. Taking advantage of precise control of the three repetition rates independently, we could achieve automatic scanning of two delay times between the three pulses, which makes both rapid data acquisition and wide dynamic range measurement of the fifth-order TR-ISRS signal achievable. We thus anticipate that the present triple mode-locked laser-based TR-ISRS technique will be of critical use for long-term monitoring of photochemical reaction dynamics in condensed phases and biological systems.

Interferometric quantum spectroscopy with undetected photons via distinguishability modulation.

Quantum spectroscopy with undetected photons (QSUP) utilizing the quantum entanglement of parametrically down-converted photons has emerged as a new spectroscopic platform. Here, we demonstrate a high-resolution and remote-measurement QSUP, where light-matter interactions and photon detections are performed in spectrally and spatially different regions. A dual-stimulated parametric down-conversion scheme with an optical frequency-comb pump and ultra-narrow coherent seed beam in an idler mode is used to generate path-entangled pairs of the undetected idler and measured frequency-comb signal photons. To demonstrate the frequency resolution of this scheme, a Fabry-Pérot cavity with a narrow bandwidth is used as a sample that modulates the distinguishability of one-photon-added coherent idler beams, which directly affects the interference fringe visibility of the entangled signal photons. We thus anticipate that the remote QSUP whose frequency resolution is determined by the linewidth of the coherent seed laser will enable the development of quantum spectroscopy featuring high resolution.

Enhancing entanglement detection of quantum optical frequency combs via stimulated emission.

We investigate the performance of a certain nonclassicality identifier, expressed via integrated second-order intensity moments of optical fields, in revealing bipartite entanglement of quantum-optical frequency combs (QOFCs), which are generated in both spontaneous and stimulated parametric down-conversion processes. We show that, by utilizing that nonclassicality identifier, one can well identify the entanglement of the QOFC directly from the experimentally measured intensity moments without invoking any state reconstruction techniques or homodyne detection. Moreover, we demonstrate that the stimulated generation of the QOFC improves the entanglement detection of these fields with the nonclassicality identifier. Additionally, we show that the nonclassicality identifier can be expressed in a factorized form of detectors quantum efficiencies and the number of modes, if the QOFC consists of many copies of the same two-mode twin beam. As an example, we apply the nonclassicality identifier to two specific types of QOFC, where: (i) the QOFC consists of many independent two-mode twin beams with non-overlapped spatial frequency modes, and (ii) the QOFC contains entangled spatial frequency modes which are completely overlapped, i.e., each mode is entangled with all the remaining modes in the system. We show that, in both cases, the nonclassicality identifier can reveal bipartite entanglement of the QOFC including noise, and that it becomes even more sensitive for the stimulated processes.

Interferometric Measurement of Transient Absorption and Refraction Spectra with Dual Frequency Comb.

We demonstrate that a dual frequency comb-transient absorption (DFC-TA) technique can be combined with a time-domain interferometric detection to measure both the transient absorption and refraction spectra of molecules in solution. To do this, the pump-probe signal field of DFC-TA is allowed to interfere with a time-delayed local oscillator field in a time domain. We show that this DFC interferometric pump-probe spectroscopy (DFC-IPS) technique has a unique ability to extract the phase and amplitude information on the pump-probe signal using just a single-scan data, while conventional techniques require an independent signal measured without the pump field for the normalization of the pump-probe spectrum. As a proof-of-principle experiment, we here show that the DFC-IPS enables us to simultaneously measure the frequency-resolved (from 650 to 950 nm) transient absorption and refraction signals with an exceptionally broad dynamic range from femtosecond to nanosecond without using a mechanical translational stage for pump-probe time-scanning. We anticipate that our DFC-IPS technique with femtosecond time-resolution capability will be useful to investigate photoinduced chemical and biological reactions covering broad dynamic ranges.

Influence of glass-based dental ceramic type and thickness with identical shade on the light transmittance and the degree of conversion of resin cement.

The purpose of this study was to assess the influence of the types and thicknesses of glass ceramic plates on light transmittance and compare the degrees of conversion (DC) of resin cement under the ceramic materials. Three ceramic plates with thicknesses of 0.5, 1.0, 2.0, and 4.0 mm were fabricated from each of five commercial ceramic blocks in shade A2: high-translucency and low-translucency IPS Empress CAD (Emp_HT and Emp_LT); high-translucency and low-translucency IPS e.max CAD (Emx_HT and Emx_LT); and Vita Mark II (Vita). The translucency parameter was obtained using a colorimeter. The light transmittance rate was measured using a photodetector attached to an optical power meter. The DC of a resin cement (Variolink N) underneath the ceramic plates was examined by Fourier transform infrared spectroscopy. The translucency parameter, light transmittance rate, and DC showed significant differences by ceramic type and thickness (P < 0.05). The Emp_HT specimens showed the highest light transmission and DCs, and the Emx_LT showed the least light transmission and the lowest DCs. The high-translucency Empress showed significantly higher DCs than the low-translucency types (P < 0.05), but there was no significant difference in e.max (P > 0.05). Both type and thickness of the glass ceramics significantly influenced the light transmittance and DC of the light-cured resin cement beneath the ceramic of the same shade.

Dual-Frequency Comb Transient Absorption: Broad Dynamic Range Measurement of Femtosecond to Nanosecond Relaxation Processes.

We experimentally demonstrate a dual-frequency comb-based transient absorption (DFC-TA) technique, which has a 12 fs time resolution and an ultrafast scan rate. Here, the fast scan rate is achieved by employing asynchronous optical sampling (ASOPS), which utilizes two independent mode-locked lasers with a slightly detuned repetition rates. The ASOPS approach is advantageous because photodegradation damage of optical sample during TA measurements can be minimized by a gated sampling. We show that the vibrational and electronic population relaxations of near-IR dye molecules in solution that occur in the time range from femtoseconds to nanoseconds can be resolved even with a single time scan measurement. The phase coherent nature of our dual-frequency comb lasers is shown to be the key for successful coherent averaging with femtosecond time resolution preserved over many data acquisitions. We anticipate that the present DFC-TA method without using any pump-probe time delay devices could be of use in developing ultrafast TA-based microscopy and time-resolved coherent multidimensional spectroscopy.

Quantum optical measurements with undetected photons through vacuum field indistinguishability.

Quantum spectroscopy and imaging with undetected idler photons have been demonstrated by measuring one-photon interference between the corresponding entangled signal fields from two spontaneous parametric down conversion (SPDC) crystals. In this Report, we present a new quantum optical measurement scheme utilizing three SPDC crystals in a cascading arrangement; here, neither the detection of the idler photons which interact with materials of interest nor their conjugate signal photons which do not interact with the sample is required. The coherence of signal beams in a single photon W-type path-entangled state is induced and modulated by indistinguishabilities of the idler beams and crucially the quantum vacuum fields. As a result, the optical properties of materials or objects interacting with the idler beam from the first SPDC crystal can be measured by detecting second-order interference between the signal beams generated by the other two SPDC crystals further down the set-up. This gedankenexperiment illustrates the fundamental importance of vacuum fields in generating an optical tripartite entangled state and thus its crucial role in quantum optical measurements.

In vivo photothermal treatment by the peritumoral injection of macrophages loaded with gold nanoshells.

Photothermal treatment methods have been widely studied for their target specificity and potential for supplementing the limitations of conventional surgical treatments. In this study, we conducted in vivo photothermal treatments using macrophages containing nanoshells as live vectors. We injected macrophages at the peritumoral sites and observed that they had penetrated into the tumor approximately 48 hours after injection. Afterwards, we irradiated with a near-infrared laser for 2 minutes at 1 W/cm(2), causing cancer cell death. Our study identified the optimal conditions of the photothermal treatment and confirmed the feasibility of its use in in vivo treatments.

Cascaded two-photon spectroscopy of Yb atoms with a transportable effusive atomic beam apparatus.

We present a transportable effusive atomic beam apparatus for cascaded two-photon spectroscopy of the dipole-forbidden transition (6s(2)(1)S0↔ 6s7s (1)S0) of Yb atoms. An ohmic-heating effusive oven is designed to have a reservoir volume of 1.6 cm(3) and a high degree of atomic beam collimation angle of 30 mrad. The new atomic beam apparatus allows us to detect the spontaneously cascaded two-photons from the 6s7s(1)S0 state via the intercombination 6s6p(3)P1 state with a high signal-to-noise ratio even at the temperature of 340 °C. This is made possible in our apparatus because of the enhanced atomic beam flux and superior detection solid angle.

Real-time phase-contrast imaging of photothermal treatment of head and neck squamous cell carcinoma: an in vitro study of macrophages as a vector for the delivery of gold nanoshells.

Photothermal treatment (PTT) using nanoparticles has gained attention as a promising alternative therapy for malignant tumors. One strategy for increasing the selectivity of PTT is the use of macrophages as a cellular vector for delivering nanoparticles. The aim of the present study is to examine the use of macrophages as a cellular vector for efficient PTT and determine the appropriate irradiation power and time of a near-infrared (NIR) laser using real-time phase-contrast imaging. Thermally induced injury and death of cancer cells were found to begin at 44°C to 45°C, which was achieved using the PTT effect with gold nanoshells (NS) and irradiation with a NIR laser at a power of 2 W for 5 min. The peritoneal macrophage efficiently functioned as a cellular vector for the NS, and the cancer cells surrounding the NS-loaded macrophages selectively lost their cellular viability after being irradiated with the NIR laser.

Period-doubling and total mode-locking, and chaotic pulsations in a GaAs ridge wave-guide external-cavity diode laser.

We report on the experimental observations of a period-doubling route to chaos and a total mode-locking between two lowest-order lateral modes of a GaAs ridge wave-guide diode laser at 795 nm. A self-starting passively mode-locking was achieved in an extended-cavity diode laser (ECDL) operating in a gain saturation regime. In the period-doubling mode-locked state, the RF spectra associated with the coherently coupled lateral TE(0) and TE(1) modes, consisted of harmonics (nf(rep)/2, n is an integer) of the half of pulse repetition rate f(rep)/2 and the period (2T) of the pulse train was two-times longer than the pulse round-trip time T. On the other hand, in the total mode-locked state, the RF spectra and the pulse train corresponding to the TE(0) and TE(1) modes had exactly the same features compared to those of the period-doubling mode-locked state, except the RF spectra and the pulse train of the TE(1) mode were shifted by f(ref)/4 in frequency and by T in time, respectively, indicating the pulses actually traveled alternatively through two lateral modes. The total mode-locking and also chaotic pulsations were observed at slightly different operation parameters, e.g. at different feedback angle of the grating, which was used as an output coupler of the ECDL.

Large dynamic range photon detector with a temperature-stabilized Si-based multi-pixel photon counter.

We present an efficient fluorescence detector in the visible region of the spectrum with a photon detection dynamic range over 10 (6) photons/s made of a temperature-stabilized Si-based multi-pixel photon counter at temperature down to 5 degrees C. We show that effective cooling of the device by means of a compact thermo-electric cooler brings several advantages, such as high gain, low dark noise rate, and thus high signal-to-noise ratio in the efficient fluorescence detection at 398.9 nm from the (1)S(0) ? (1)P(1) transition of the ytterbium atoms in an effusive atomic beam. We present also a comparison of the fluorescence detection efficiencies between the device and a side-on photo-multiplier tube with known gain positioned at the symmetric location from the ytterbium atomic beam.

Three-longitudinal-mode He-Ne laser frequency stabilized at 633 nm by thermal phase locking of the secondary beat frequency.

We present a simple scheme for thermal frequency stabilization of a three-longitudinal-mode He-Ne laser at 633 nm with improved short-term (5 x 10(-11) at 1-s average time) and long-term (124-kHz standard deviation for 10 h) frequency stability. A stabilized output power of 3 mW was readily obtained from the central mode by polarization-mode selection. The optical frequency of the central mode could be precisely tuned by an external frequency reference over 160 MHz with high precision or could be optically phase locked to a reference laser by use of a thermal frequency-stabilization circuit and an external acousto-optic modulator. The laser will be useful in various applications for which a laser source with high power and frequency stability is necessary.

Frequency-stabilized high-power violet laser diode with an ytterbium hollow-cathode lamp.

We have demonstrated in an ytterbium laser cooling and trapping experiment a high-power violet extendedcavity diode laser (ECDL) stabilized to the Yb resonant transition at 398.9 nm in an Yb hollow-cathode lamp. A frequency-dispersion signal, which we obtained by applying a modulation-free dichroic-atomic-vapor laser lock technique, allowed us to stabilize the violet ECDL at a frequency stability below 1 MHz at 1-s average time and a useful output power of 15 mW.