Bias-drift insensitive full-field frequency response characterization of a thin-film lithium niobate-based intensity modulator.

We propose a rapid and precise scheme for characterizing the full-field frequency response of a thin-film lithium niobate-based intensity modulator (TFLN-IM) via a specially designed multi-tone microwave signal. Our proposed scheme remains insensitive to the bias-drift of IM. Experimental verification is implemented with a self-packaged TFLN-IM with a 3 dB bandwidth of 30 GHz. In comparison with the vector network analyzer (VNA) characterization results, the deviation values of the amplitude-frequency response (AFR) and phase-frequency response (PFR) within the 50 GHz bandwidth are below 0.3 dB and 0.15 rad, respectively. When the bias is drifted within 90% of the Vπ range, the deviation fluctuation values of AFR and PFR are less than 0.3 dB and 0.05 rad, respectively. With the help of the full-field response results, we can pre-compensate the TFLN-IM for the 64 Gbaud PAM-4 signals under the back-to-back (B2B) transmission, achieving a received optical power (ROP) gain of 2.3 dB. The versatility of our proposed full-field response characterization scheme can extend to various optical transceivers, offering the advantage of low cost, robust operation, and flexible implementation.

Insight into the solvent effects on ethanol oxidation on Ir(100).

Solvent effects have always been a non-negligible factor for aqueous catalytic reactions, though few studies have been devoted towards the molecular understanding and impact of solvent effects on catalysis. In this work, we investigated ethanol dehydrogenation and C-C bond cleavage over Ir(100) in an aqueous solution using density functional theory calculations with both the implicit and explicit solvent models and transition state theory-based kinetics simulations. The results show that solvent polarization assists the α- and ß-dehydrogenation of ethanol on Ir(100) in the aqueous solution and hydrogen bonding also assists the ethanol ß-dehydrogenation and C-C bond cleavage in CH2CO. The hydrogen bond between the ethanol and water molecule hinders ethanol hydroxyl dehydrogenation while the CHCO⋯H2O hydrogen bond radically alters the adsorption configuration of CHCO, which leads to an increase in the C-C cleavage barrier by 2.5 fold. Furthermore, the solvent changes the reaction pathways significantly. In an aqueous solution, ethanol ß-dehydrogenation on Ir(100) is the dominant ethanol dehydrogenation pathway and C-C bond cleavage occurs predominantly via CH2CO species.

Simultaneous Spatiotemporal Measurement of Structural Evolution in Dynamic Complex Media.

When the properties of soft materials evolve in time, the simultaneous measurement of different characteristics is critical. Here, we demonstrate an experimental system that permits monitoring both the spatial and temporal evolution of the optical and mechanical properties. An integrated fiber-optic-based system allows determining the mechanical vibrations of structural elements over 5 orders of magnitude and over a broad frequency range. At the same time, the optical properties can be obtained within seconds from high-resolution measurements of the path-length distribution of reflected light. With proper cyclical scanning, the temporal evolution of the mesoscopic light scattering properties can be obtained in a depth-resolved manner. The performance of this integrated measurement is validated in the particular case of drying paint films. For these typical nonstationary media, we show how our approach provides unique access to the spatiotemporal material properties and how this information permits identifying the specific stages of structural evolution.

Insights and Activation Energy Surface of the Dehydrogenation of C2 Hx O Species in Ethanol Oxidation Reaction on Ir(100).

Dehydrogenation of an organic compound is the first and the most fundamental elementary reaction in many organic reactions. In ethanol oxidation reaction (EOR) to form CO2 , there are a total of 46 pathways in C2 Hx O (x=1-6) species leading to the removal of all six hydrogen atoms in five C-H bonds and one O-H bond. To investigate the degree of dehydrogenation in EOR under operando conditions, we performed density function theory (DFT) calculations to study 28 dehydrogenation steps of C2 Hx O on Ir(100). An activation energy surface was then constructed and compared with that of the C-C bond cleavages to understand the importance of the degree of dehydrogenation in EOR. The results show that there are likely 28 dehydrogenations in EOR under fuel cell temperatures and the last two hydrogens in C2 H2 O are less likely cleaved. On the other hand, deep dehydrogenation including 45 dehydrogenations can occur under ethanol steam reforming conditions.

Passive high-frequency microrheology of blood.

Indicative of various pathologies, blood properties are under intense scrutiny. The hemorheological characteristics are traditionally gauged by bulk, low-frequency indicators that average out critical information about the complex, multi-scale, and multi-component structure. In particular, one cannot discriminate between the erythrocytes contribution to global rheology and the impact of plasma. Nevertheless, in their fast stochastic movement, before they encounter each other, the erythrocytes probe the subtle viscoelasticity of their protein-rich environment. Thus, if these short time scales can be resolved experimentally, the plasma properties could be determined without having to separate the blood components; the blood is practically testing itself. This microrheological description of blood plasma provides a direct link between the composition of whole blood and its coagulability status. We present a parametric model for the viscoelasticity of plasma, which is probed by the erythrocytes over frequency ranges of kilohertz in a picoliter-sized volume. The model is validated both in vitro, using artificial hemo-systems where the composition is controlled, as well as on whole blood where continuous measurements provide real-time information. We also discuss the possibility of using this passive microrheology as an in vivo assay for clinically relevant situations where the blood clotting condition must be observed and managed continuously for diagnosis or during therapeutic procedures at different stages of hemostatic and thrombotic processes.

Continuous Optical Measurement of Internal Dynamics in Drying Colloidal Droplets.

Accessing the colloidal dynamics non-invasively and continuously during the phase transition of a colloidal system is challenging but critical. Here, we demonstrate the use of spatiotemporal coherence-gated light scattering for studying the internal dynamics of drying colloidal droplets. The continuously acquired signal originates from a picoliter-sized volume located at the droplet-substrate interface. The measurement is non-contact, non-invasive, and label free and permits real-time observations of both optical and mechanical changes in the measurement volume. Additionally, some macroscopic descriptors of the drying process can be constructed from the microscopic measurement, providing ample information of the process. Implemented with an endoscopic-like probe, this system can be easily incorporated into the existing drop profiling instruments, which is potential for the full characterization of dynamic colloidal droplets.

Colloidal density control with Bessel-Gauss beams.

Optical manipulation of colloidal systems is of high interest for both fundamental studies and practical applications. It has been shown that optically induced thermophoresis and nonlinear interactions can significantly affect the properties of dense colloidal media. However, macroscopic scale phenomena can also be generated at thermal equilibrium. Here, we demonstrate that steady-state variations of particle density can be created over large, three-dimensional regions by appropriately structured external optical fields. We prove analytically and experimentally that an optical vortex beam can dynamically control the spatial density of microscopic particles along the direction of its propagation. We show that these artificial steady-states can be generated at will and can be maintained indefinitely, which can be beneficial for applications such as path clearing and mass transportation.

Composites of Vanadium (III) Oxide (V2O3) Incorporating with Amorphous C as Pt-Free Counter Electrodes for Low-Cost and High-Performance Dye-Sensitized Solar Cells.

To replace precious Pt-based counter electrodes (CEs) with a low-cost Pt-free catalyst of CEs is still a motivating hotspot to decrease the fabrication cost of dye-sensitized solar cells (DSSCs). Herein, four different V2O3@C composite catalysts were synthesized by pyrolysis of a precursor under N2 flow at 1100 °C and further served as catalytic materials of CEs for the encapsulation of DSSCs. The precursors of V2O3@C composites have been prepared via a sol-gel method using different proportions of V2O5 with soluble starch in a H2O2 solution. Power conversion efficiencies (PCEs) of 3.59, 4.79, 5.15, and 5.06% were obtained from different V2O3@C composites, with soluble starch-to-V2O5 mass ratios (S/V) of 1:2, 1:1, 2:1, and 4:1, respectively, as CEs to reduce iodide/triiodide in DSSCs. The improvement of electrode performance is due to the combined effects on the increased specific surface area and the enhanced conductivity of V2O3@C composite catalysts.

Impact of the degree of dehydrogenation in ethanol C-C bond cleavage on Ir(100).

A lack of comprehensive studies of the C-C bond cleavage in organic molecules hampers the rational design of catalysts for many applications, such as in fuel cells and steam reforming technologies. Employing ethanol on Ir(100) as an example, we studied 14 C-C bond cleavages of various species involved in the ethanol oxidation reaction using density functional theory calculations and used the degree of dehydrogenation (DoDH) of the reactant species as a variable to correlate the C-C bond cleavage barrier and reaction energy. This correlation method was also applied to the dehydrogenation reactions of ethanol on various catalysts, and great insight was obtained. The results show that the C-C cleavage barrier generally decreases with DoDH, with a local minimum around 33.3% DoDH. For reactants having more than 50% DoDH, the C-C cleavage is more ready to take place than the dehydrogenation and can occur at room temperature. Furthermore, the O atom in the reactive species plays a critical role in lowering the C-C bond cleavage barrier. The results provide necessary inputs for kinetic studies of ethanol reactions under operando conditions, where a reaction network beyond the minimum energy pathway is needed. The results will also serve as a benchmark for future studies of the ethanol C-C cleavage on other facets of Ir catalysts or on different catalysts. Furthermore, this work demonstrates that the proposed method opens up a new and effective way of correlating catalytic activities for the C-C bond cleavage involving long-chain alkanes and alcohols.

Nonstationary Intensity Statistics in Diffusive Waves.

It is a long-standing belief that, in the diffusion regime, the intensity statistics is always stationary and its probability distribution follows a negative exponential decay. Here, we demonstrate that, in fact, in reflection from strong disordered media, the intensity statistics changes through different stages of the diffusion. We present a statistical model that describes this nonstationary property and takes into account the evolving balance between recurrent scattering and near field coupling. The predictions are further verified by systematic experiments in the optical regime. This statistical nonstationary is akin to the nonequilibrium but steady-state diffusion of particulate systems.

Bio-derived yellow porous TiO2: the lithiation induced activation of an oxygen-vacancy dominated TiO2 lattice evoking a large boost in lithium storage performance.

Oxygen deficient TiO2 has attracted extensive attention owning to its narrow bandgap and high electrical conductivity. In this work, novel yellow TiO2 with hierarchically porous architecture is fabricated by a facile pyrolysis method in air via a biomass template. The obtained yellow TiO2 exhibits interesting lithiation induced activation during cycling, which gives rise to a phase change from poorly crystallized TiO2 to an amorphous phase, accompanied by a colour change from yellow to black. In contrast to the intercalation mechanism reported in most of the literature on the TiO2 anode of LIBs, notably, the reversible redox reaction between Ti3+ and metal Ti can be verified in this case, demonstrating the novel conversion reaction mechanism of the TiO2 electrode. Based on this, the yellow porous TiO2 delivers enhanced electrochemical performance as an anode for LIBs with a superior capacity of 480 mA h g-1 at 5 A g-1 and a high capacity of 206 mA h g-1 at 10 A g-1 after 8000 cycles.

Tubulin Polarizability in Aqueous Suspensions.

We report accurate optical measurements of tubulin polarizability in aqueous suspensions. We determined the dependence of polarizability on tubulin concentration and on the suspension's pH, providing benchmark numbers for quantifying the optical response of this protein in various artificial and cellular environments. We compare our measurement data with a few estimates found in the previous literature and also with our simplified model estimations.

Marine-Biomass-Derived Porous Carbon Sheets with a Tunable N-Doping Content for Superior Sodium-Ion Storage.

Synthesis of the electrode materials of sodium-ion storage devices from sustainable precursors via green methods is highly desirable. In this work, we fabricated a unique N, O dual-doped biocarbon nanosheet with hierarchical porosity by direct pyrolysis of low-cost cuttlebones and simple air oxidation activation (AOA) technique. With prolonging AOA time, thickness of the carbon sheets could be reduced controllably (from 35 to 5 nm), which may lead to tunable preparation of carbon nanosheets with a certain thickness. Besides, an unexpected increase in N-doping amount from 7.5 to 13.9 atom % was observed after AOA, demonstrating the unique role of AOA in tuning the doped heteroatoms of carbon matrix. This was also the first example of increasing N-doping content in carbons by treatment in air. More importantly, by optimizing the thickness of carbon sheets and heteroatom doping via AOA, superior sodium capacity-cycling retention-rate capability combinations were achieved. Specifically, a current state-of-the-art Na+ storage capacity of 640 mAh g-1 was obtained, which was comparable with the lithium-ion storage in carbon materials. Even after charging/discharging at large current densities (2 and 10 A g-1) for 10 000 cycles, the as-obtained samples still retained the capacities of 270 and 138 mAh g-1, respectively, with more than 90% retention. The assembled sodium-ion capacitors also delivered a high integrated energy-power density (36 kW h kg-1 at an ultrahigh power density of 53 000 W kg-1) and good cycling stability (90.5% of capacitance retention after 8000 cycles at 5 A g-1).

Designed Er(3+)-singly doped NaYF4 with double excitation bands for simultaneous deep macroscopic and microscopic upconverting bioimaging.

Simultaneous deep macroscopic imaging and microscopic imaging is in urgent demand, but is challenging to achieve experimentally due to the lack of proper fluorescent probes. Herein, we have designed and successfully synthesized simplex Er(3+)-doped upconversion nanoparticles (UCNPs) with double excitation bands for simultaneous deep macroscopic and microscopic imaging. The material structure and the excitation wavelength of Er(3+)-singly doped UCNPs were further optimized to enhance the upconversion emission efficiency. After optimization, we found that NaYF4:30%Er(3+)@NaYF4:2%Er(3+) could simultaneously achieve efficient two-photon excitation (2PE) macroscopic tissue imaging and three-photon excitation (3PE) deep microscopic when excited by 808 nm continuous wave (CW) and 1480 nm CW lasers, respectively. In vitro cell imaging and in vivo imaging have also been implemented to demonstrate the feasibility and potential of the proposed simplex Er(3+)-doped UCNPs as bioprobe.

Visible-to-visible four-photon ultrahigh resolution microscopic imaging with 730-nm diode laser excited nanocrystals.

Further development of multiphoton microscopic imaging is confronted with a number of limitations, including high-cost, high complexity and relatively low spatial resolution due to the long excitation wavelength. To overcome these problems, for the first time, we propose visible-to-visible four-photon ultrahigh resolution microscopic imaging by using a common cost-effective 730-nm laser diode to excite the prepared Nd(3+)-sensitized upconversion nanoparticles (Nd(3+)-UCNPs). An ordinary multiphoton scanning microscope system was built using a visible CW diode laser and the lateral imaging resolution as high as 161-nm was achieved via the four-photon upconversion process. The demonstrated large saturation excitation power for Nd(3+)-UCNPs would be more practical and facilitate the four-photon imaging in the application. A sample with fine structure was imaged to demonstrate the advantages of visible-to-visible four-photon ultrahigh resolution microscopic imaging with 730-nm diode laser excited nanocrystals. Combining the uniqueness of UCNPs, the proposed visible-to-visible four-photon imaging would be highly promising and attractive in the field of multiphoton imaging.

Optical depletion mechanism of upconverting luminescence and its potential for multi-photon STED-like microscopy.

Simulated emission depletion (STED) microscopy is very powerful, but still suffers from small tissue penetration depth, photobleaching of fluorescent probes and complicated imaging systems. Here, we propose an optical luminescence depletion mechanism employing upconverting nanoparticles (UCNPs) and explore its potential for multi-photon STED-like microscopy. With the addition of Yb³âº ions in NaYF4:Er³âº UCNPs, the two-photon green emission of Er³âº under 795-nm excitation was successfully depleted by 1140-nm laser through the synergetic effect of the excited state absorption and the interionic energy transfer. This STED-like depletion mechanism was systematically investigated using steady-state rate equations, evidenced by the surprising emerging of 478-nm emission. The green emission depletion efficiency was about 30%, limited by the current laser source. Our work indicates that NaYF4:Yb³âº/Er³âº UCNPs will be potential probes for multi-photon super-resolution microscopy with many advantages, including long-wavelength-induced large penetration, non-photobleaching and non-photoblinking properties, cost-effective and simplified imaging systems.

Deep, high contrast microscopic cell imaging using three-photon luminescence of ß-(NaYF4:Er(3+)/NaYF4) nanoprobe excited by 1480-nm CW laser of only 1.5-mW.

It is challenging to achieve deep microscopic imaging for the strong scattering in biotissue. An efficient three-photon luminescence can effectively increase the penetration depth. Here we report that ß-NaYF4: Er(3+)/NaYF4 UCNPs were excited by a 1480-nm CW-laser and emitted 543/653-nm light through a three-photon process. With the merit of the hexagonal crystal phase, sub-milliwatt laser power was utilized to excite the UCNP-probed cells to minimize the heating effect. The polymer-coated UCNPs were shown to be harmless to cells. The deep, high contrast in vitro microscopic imaging was implemented through an artificial phantom. Imaging depth of 800 µm was achieved using only 1.5 mW excitation and a 0.7 NA objective. The green/red emission intensities ratio after penetrating the phantom was studied, indicating that longer emission wavelength is preferred for deep multiphoton microscopy. The proposed and demonstrated ß-UCNPs would have great potential in three-photon microscopy.