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The ultrafast photochemical reaction mechanism, transient spectra, and transition kinetics of the human blue cone visual pigment have been recorded at room temperature. Ultrafast time-resolved absorption spectroscopy revealed the progressive formation and decay of several metastable photo-intermediates, corresponding to the Batho to Meta-II photo-intermediates previously observed with bovine rhodopsin and human green cone opsin, on the picosecond to millisecond timescales following pulsed excitation. The experimental data reveal several interesting similarities and differences between the photobleaching sequences of bovine rhodopsin, human green cone opsin, and human blue cone opsin. While Meta-II formation kinetics are comparable between bovine rhodopsin and blue cone opsin, the transition kinetics of earlier photo-intermediates and qualitative characteristics of the Meta-I to Meta-II transition are more similar for blue cone opsin and green cone opsin. Additionally, the blue cone photo-intermediate spectra exhibit a high degree of overlap with uniquely small spectral shifts. The observed variation in Meta-II formation kinetics between rod and cone visual pigments is explained based on key structural differences.

Terahertz time-domain spectroscopy (THz-TDS) is a powerful technique that enables the characterization of a large range of bulk materials, devices, and products. Although this technique has been increasingly used in research and industry, the standard THz-TDS configuration relying on the use of a near-infrared (NIR) laser source remains experimentally complex and relatively costly, impeding its availability to those without the expertise to build a high-performance setup based on nonlinear optics or without the financial means to acquire a commercial unit. Broadband THz-TDS systems require an even larger financial investment, primarily because the generation and detection of spectral components exceeding 3 THz typically need an ultrafast NIR source delivering sub-100-fs pulses. Such an ultrafast source can be bulky and cost upwards of $100,000. Here, we present a broadband, compact, and portable THz-TDS system comprising three modules that allow for the implementation of a single low-cost ultrafast laser, hence significantly decreasing the overall cost of the system. In the first module, the output laser pulses are spectrally broadened through nonlinear propagation in a polarization-maintaining optical fiber and then temporally compressed to achieve a higher peak power. The other two modules utilize thick nonlinear crystals with periodically patterned surfaces that diffract NIR pulses and optimize the efficiency of THz generation and detection processes by enabling a noncollinear beam geometry. Phase-matching conditions in the nonlinear crystals are controlled by the period of the gratings to gain access to a large spectral THz bandwidth. The whole system, combining these three modules, provides access to a THz spectrum peaking at 3.5 THz and extending beyond 6 THz with a maximum dynamic range of 50 dB for time-resolved spectroscopy applications. We demonstrate the functionality of this configuration by performing THz spectroscopy measurements of water vapor contained within a closed cell. Our compact system design paves the way towards a high-performance, yet cost-effective, THz-TDS system that can be readily used in academia and industry.

Al-doped ZnO (AZO) thin films were deposited on p-Si (100) by pulsed laser deposition from a composite ceramic target (ZnO:Al₂O₃) by using 355 nm laser at different O₂ background pressure and substrate temperature. Upon ablation at laser fluence of 2 Jcm⁻², plasma plume consists of Zn neutrals and ions, Al neutrals and O neutral are formed. As the O₂ background pressure increases from 3 Pa to 26 Pa, the energy of the plasma species are moderated. The results show that the ions density and velocity reduced significantly above 13 Pa. The velocity of the ions reduced from 14 kms⁻¹ to 11 kms⁻¹ at 13 Pa, while the ions energy reduced from 63 eV to 42 eV respectively. Below 13 Pa, crystalline and homogeneous AZO nanostructured films were formed. Above 13 Pa, the process results in low crystallinity films with higher porosity. The resistivity of the films also increases from 0.1 ohmcm to 24 ohmcm as the pressure increased. At fixed O₂ background pressure of 3 Pa, the adatom mobility of atoms on the substrates is altered by substrate heating. The resistivity of the films decreased to 10^–3 ohmcm when the substrates are heated to 100 °C–300 °C during deposition. The films with highest carrier density of 10²⁰ cm⁻³ and carrier mobility of 13 cmV⁻¹ s⁻¹ are achieved at 200 °C.

Photolabile chelating cages or protecting groups need complex chemical syntheses and require UV, visible, or two-photon NIR light to trigger release. Different cages have different solubilities, reaction rates, and energies required for triggering. Here we show that liposomes containing calcium, adenosine triphosphate, or carboxyfluorescein are tethered to plasmon-resonant hollow gold nanoshells (HGN) tuned to absorb light from 650–950 nm. Picosecond pulses of near infrared (NIR) light provided by a two-photon microscope, or by a stand-alone laser during flow through microfluidic channels, trigger contents release with spatial and temporal control. NIR light adsorption heats the HGN, inducing vapor nanobubbles that rupture the liposome, releasing cargo within milliseconds. Any water-soluble molecule can be released at essentially the same rate from the liposome-HGN. By using liposomes of different composition, or HGN of different sizes or shapes with different nanobubble threshold fluences, or irradiating on or off resonance, two different cargoes can be released simultaneously, one before the other, or in a desired ratio. Calcium release from liposome-HGN can be spatially patterned to crosslink alginate gels and trap living cells. Liposome-HGN provide stable, biocompatible isolation of the bioactive compound from its surroundings with minimal interactions with the local environment.

We use vibrational sum-frequency generation (VSFG) spectroscopy to study the structure of hen egg-white lysozyme (HEWL) aggregates adsorbed to DOPG/D₂O and air/D₂O interfaces. We find that aggregates with a parallel and antiparallel β-sheet structure together with smaller unordered aggregates and a denaturated protein are adsorbed to both interfaces. We demonstrate that to retrieve this information, fitting of the VSFG spectra is essential. The number of bands contributing to the VSFG spectrum might be misinterpreted, due to interference between peaks with opposite orientation and a nonresonant background. Our study identified hydrophobicity as the main driving force for adsorption to the air/D₂O interface. Adsorption to the DOPG/D₂O interface is also influenced by hydrophobic interaction; however, electrostatic interaction between the charged protein’s groups and the lipid’s headgroups has the most significant effect on the adsorption. We find that the intensity of the VSFG spectrum at the DOPG/D₂O interface is strongly enhanced by varying the pH of the solution. We show that this change is not due to a change of lysozyme’s and its aggregates’ charge but due to dipole reorientation at the DOPG/D₂O interface. This finding suggests that extra care must be taken when interpreting the VSFG spectrum of proteins adsorbed at the lipid/water interface.

The black body remains the most prominent source of light for absolute radiometry. Its main alternative, synchrotron radiation, requires costly and large facilities. Quantum optics offers a new radiometric source: parametric down-conversion (PDC), a nonlinear optical process, in which pairwise photon correlations enable absolute calibration of photodetectors. Since the emission rate crucially depends on the brightness of the electromagnetic field, quantum-mechanical fluctuations of the vacuum can be seen as a seed of spontaneous PDC, and their amplitude is a natural radiometric standard. Thus, they allow for the calibration of the spectral radiance of light sources by measuring the ratio between seeded and unseeded PDC. Here, we directly use the frequency spectrum of the electromagnetic vacuum to trigger spontaneous PDC and employ the generated light to infer the spectral response of a spectrometer over a broad spectral range. Then, we deduce the absolute quantum efficiency from the spectral shape of PDC in the high-gain regime, without relying on a seed or reference detector. Our results compare well with the ones obtained with a reference lamp, demonstrating a promising primary radiation standard.

A thin film of poly(4-methylpentene-1) (P4MP1) was prepared on a quartz substrate, which was a model system of an interface in filler-reinforced semicrystalline polymer composites. Grazing-incidence wide-angle X-ray diffraction measurements revealed that P4MP1 in the thin film after isothermal crystallization formed a Form I crystal polymorph composed of a tetragonal unit cell with a 7₂ helix, in which the chain axis was oriented along the direction parallel to the quartz interface. Combining sum-frequency generation vibrational spectroscopy with molecular dynamics simulation enabled us to gain access to the local conformation of P4MP1 chains at the quartz interface and the changes that occurred with isothermal crystallization. Finally, the way in which the initial chain orientation at the substrate interface impacted the crystalline structure in the thin film was discussed.

Direct generation of gold nanoparticles on ITO glass using a nanosecond laser is presented and the electrochemical properties of the gold modified ITO electrodes for detection of the ascorbic acid are analyzed. Gold nanoparticles were generated by nanosecond laser pulse irradiation of thin, 3–30 nm thick, gold films. It was found that diameters and the number of generated nanoparticles per unit area strongly depends on the thickness of the gold film when it is less than 10 nm. Furthermore, experiments have shown that the influence of laser processing parameters (the laser pulse energy and pulse number) to the size, the distribution and the area density of generated gold nanoparticles on ITO glass is negligible. Characterization of the electrochemical properties of the gold modified ITO electrodes by nanosecond laser showed that the fabricated electrodes could be employed in electrochemical sensing. Therefore, the demonstrated generation of gold nanoparticles on ITO by using the nanosecond laser approach opens new opportunities for the development of highly sensitive and low-cost electrochemical sensors.

Organic solid-state lasers (OSSLs) with distributed feedback (DFB) structures or distributed Bragg reflectors (DBRs) are promising for potential application in bio-sensing and hazardous materials detection. Here, the laser performances of the all-organic DFB waveguide lasers with various grating heights ranging from 0.4 to 4.7 μm were investigated. The grating structures used as the lasing cavity were fabricated using a two-photon absorption (TPA) direct laser writing (DLW) method with an SU-8 negative photoresist. The laser active layer consisted of a rhodamine 6G (R6G) laser dye and a cellulose acetate (CA) matrix. The R6G/CA solution was spin-coated onto the quartz substrate with the cavity (grating) structures to fabricate the DFB waveguide laser devices. The diffraction order of lasing ranged from m = 4 to 7. As the grating height was increased to 1.9 μm, the slope efficiency increased for all diffraction orders and the threshold decreases for each diffraction order. The dependence of the cavity (grating) length on the laser performances was investigated. The slope efficiency increased as the cavity length increased to 300 μm. The effect of the cavity (grating) position on the slope efficiency and the threshold position of the cavity (grating) was also studied. A maximum slope efficiency of 10.2% was achieved for the DFB waveguide laser device with a cavity (grating) length of 300 μm, a cavity position at 6 mm from the emission edge of the waveguide, and an aspect ratio ≈3 between the grating height of 1.74 μm and the grating width of 0.6 μm for the diffraction order m = 6 for lasing.

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.