Review of Gas-Chromatographic Measurement Methodologies for Atmospheric Halogenated Greenhouse Gases.

Gas chromatography (GC) is crucial for measuring atmospheric halogenated greenhouse gases (hGHGs), usually coupled with electron capture detector (ECD, with higher sensitivity) or mass spectrometry (MS, with higher selectivity). This review compares GC-ECD and GC-MS for analyzing atmospheric hGHGs in terms of analytical methodology, performance, and instrumentation. For hGHGs such as SF6, chlorofluorocarbons, and N2O, ECD can be employed in the single column, forecut-backflush (FCBF), and preconcentration methods. The order of appearance of SF6 and N2O is an important consideration for selecting the separation column to avoid chromatographic interference from the long-tailed N2O and O2 on SF6. Single column and FCBF GC-ECD methods suffer from nonlinear responsivity, but the preconcentration method can compensate for nonlinearity. The last method also offers a low drift, which eliminates the need for multipoint calibration and enables perfect linearity at atmospheric SF6 levels. GC-MS demonstrates strong separability and identification capabilities, and over 60 hGHGs can be qualitatively analyzed by leveraging the separation power of MS and established MS databases. However, GC-MS requires a preconcentrator operating at -165 °C utilizing specialized adsorbents. Two notable preconcentrator-GC-MS systems, Medusa-GC-MS and detachable trap preconcentrator (DTP) GC-MS, differ in trap design, temperature scheme, and separation column type. Medusa-GC-MS employs a three-phased temperature operation before MS. DTP-GC-MS separates the preconcentration cycle into highly and less volatile compounds, using a different temperature scheme from that of Medusa-GC-MS. The preconcentrator-GC-MS system is widely employed for measuring perfluorocarbons, hydrofluorocarbons, and other hGHGs. This method necessitates multiple adsorption traps to discriminate the most abundant air components.

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.

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.

Origin of highly efficient photoluminescence in AgIn5S8 nanoparticles.

The photoluminescence of AgIn5S8 nanoparticles was examined to clarify the emissive relaxation processes of defect states and to explain the highly efficient photoluminescence of defect states. The large Stokes shift of the defect emission was explained by strong electron-phonon coupling in the nanoparticles. Steady-state and time-resolved photoluminescence spectroscopy indicated two emissive defect states with characteristic emission energies and lifetimes. Change of the surface-to-volume ratio in the nanoparticles affected the relative contribution of the two states, implying that defect emission in higher energy was attributable to surface-related defects. The defect emission in lower energy was attributable to intrinsic defects, which were also present in bulk. The quantum yield of the surface defects was larger than that of the intrinsic defects, which accounted for the unusually high quantum yield of AgIn5S8 nanoparticles, although the origin of emission was the defect states, not the exciton recombination found in typical semiconductor nanoparticles.

Self-Assembled Tb3+ Complex Probe for Quantitative Analysis of ATP during Its Enzymatic Hydrolysis via Time-Resolved Luminescence in Vitro and in Vivo.

To more accurately assess the pathways of biological systems, a probe is needed that may respond selectively to adenosine triphosphate (ATP) for both in vitro and in vivo detection modes. We have developed a luminescence probe that can provide real-time information on the extent of ATP, ADP, and AMP by virtue of the luminescence and luminescence lifetime observed from a supramolecular polymer based on a C3 symmetrical terpyridine complex with Tb3+ (S1-Tb). The probe shows remarkable selective luminescence enhancement in the presence of ATP compared to other phosphate-displaying nucleotides including adenosine diphosphate (ADP), adenosine monophosphate (AMP), guanosine triphosphate (GTP), thymidine triphosphate (TTP), H2PO4- (Pi), and pyrophosphate (PPi). In addition, the time-resolved luminescence lifetime and luminescence spectrum of S1-Tb could facilitate the quantitative measurement of the exact amount of ATP and similarly ADP and AMP within living cells. The time-resolved luminescence lifetime of S1-Tb could also be used to quantitatively monitor the amount of ATP, ADP, and AMP in vitro following the enzymatic hydrolysis of ATP. The long luminescence lifetime, which was observed into the millisecond range, makes this S1-Tb-based probe particularly attractive for monitoring biological ATP levels in vivo, because any short lifetime background fluorescence arising from the complex molecular environment may be easily eliminated.

An oxygen-vacancy rich 3D novel hierarchical MoS2/BiOI/AgI ternary nanocomposite: enhanced photocatalytic activity through photogenerated electron shuttling in a Z-scheme manner.

An oxygen-vacancy rich, bismuth oxyiodide-based Z-scheme 3D hierarchical MoS2/BiOI/AgI ternary nanocomposite photocatalyst was fabricated using a simple precipitation process in ethylene glycol and water. The presence of oxygen-vacancies in BiOI and the two-dimensional nature of molybdenum disulfides in the composite prolongs the charge carrier lifetime through a Z-scheme system and enhances the performance of the photocatalyst for the degradation of rhodamine B. On the basis of efficient separation of photoexcited electron-hole pairs, a mechanism is proposed whereby MoS2 and oxygen vacancy states increase charge carrier lifetimes and improve the photocatalytic activity. The Z-scheme mechanism of the photocatalysis is consistent with the results of static and time-resolved photoluminescence, scavenging, and terephthalic acid photoluminescence experiments. Among the as-synthesized photocatalysts, the one containing 2 wt% of MoS2 in a composite of MoS2/BiOI/AgI exhibited the highest photocatalytic activity towards rhodamine B degradation, and its activity was 7 and 16 times higher than that of BiOI/AgI and BiOI, respectively. Degradation of phenol, the colorless model pollutant, was studied to confirm the visible-light photocatalytic performance of the MoS2/BiOI/AgI composite. This easily fabricated Z-scheme based MoS2/BiOI/AgI composite exhibits promising photocatalytic activity and will be useful for potential applications in energy and environmental areas.

Light-Matter Interactions in Cesium Lead Halide Perovskite Nanowire Lasers.

Light-matter interactions in inorganic perovskite nanolasers are investigated using single-crystalline cesium lead halide (CsPbX3, X = Cl, Br, and I) nanowires synthesized by the chemical vapor transport method. The perovskite nanowires exhibit a uniform growth direction, smooth surfaces, straight end facets, and homogeneous composition distributions. Lasing occurs in the perovskite nanowires at low thresholds (3 µJ/cm(2)) with high quality factors (Q = 1200-1400) under ambient atmospheric environments. The wavelengths of the nanowire lasers are tunable by controlling the stoichiometry of the halide, allowing the lasing of the inorganic perovskite nanowires from blue to red. The unusual spacing of the Fabry-Pérot modes suggests strong light-matter interactions in the reduced mode volume of the nanowires, while the polarization of the lasing indicates that the Fabry-Pérot modes belong to the same fundamental transverse mode. The dispersion curve of the exciton-polariton model suggests that the group refractive index of the polariton is significantly enhanced.

Unexpected Size Effect Observed in ZnO-Au Composite Photocatalysts.

Semiconductor-metal nanocomposites prepared with well-defined gold nanoclusters, such as Au25, Au144, and Au807, showed size-dependent photocatalytic activities for the reduction of nile blue and azobenzene. Whereas the photoreduction of nile blue was directly related with the charge separation and transfer rate from the photoexcited ZnO to gold nanoclusters, the photoreaction of azobenzene showed unexpected size effect with a clear threshold. Mechanistic investigations revealed that the photoreduction of azobenzene proceeded via a proton-coupled electron transfer process. The photocatalytic activity of the ZnO-Au nanocomposites was also dependent on the excitation intensity, demonstrating that the multielectron/multiproton process was controlled by the charge separation and transfer in the nanocomposites.

Band gap grading and photovoltaic performance of solution-processed Cu(In,Ga)S2 thin-film solar cells.

The photophysical properties of CuInxGa1-xS2 (CIGS) thin films, prepared by solution-based coating methods, are investigated to understand the correlation between the optical properties of these films and the electrical characteristics of solar cells fabricated using these films. Photophysical properties, such as the depth-dependent band gap and carrier lifetime, turn out to be at play in determining the energy conversion efficiency of solar cells. A double grading of the band gap in CIGS films enhances solar cell efficiency, even when defect states disturb carrier collection by non-radiative decay. The combinational stacking of different density films leads to improved solar cell performance as well as efficient fabrication because a graded band gap and reduced shunt current increase carrier collection efficiency. The photodynamics of minority-carriers suggests that the suppression of defect states is a primary area of improvement in CIGS thin films prepared by solution-based methods.

Blue luminescence of dendrimer-encapsulated gold nanoclusters.

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl-terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady-state and time-resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au8 and Au13). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.

MODE-specific deactivation of adenine at the singlet excited states.

The deactivation process of adenine excited near the band origin of the lowest ππ* state ((1)L(b)) is investigated using picosecond (ps) time-resolved photoionization spectroscopy. The transients obtained with a ps pump pulse at the sharp vibronic bands, 36,105 cm(-1) (D) and 36,248 cm(-1) (E), in the resonant two-photon ionization spectrum exhibit a bi-exponential decay with two distinct time constants of τ1 ~ 2 ps and τ2 > 100 ps, whereas the transients with the pump at other wavenumbers in this energy region show a single exponential decay with τ = 1-2 ps. We suggest that the τ1 represents the lifetimes of the (1)nπ∗ energy levels near the D and E peaks, which are excited together by the ps pump pulse having a broad spectral bandwidth, and the τ2 shows the lifetimes of D and E peaks. The long lifetime of D level is attributed to a small barrier for internal conversion from the minimum of the (1)L(b) state to the (1)nπ* state. On the other hand, the long lifetime of E level is ascribed to the nuclear configuration of adenine at this level, which is unfavorable to reach the seam of the conical intersection leading to nearly barrierless deactivation to the electronic ground state. This study shows that the ps time-resolved spectroscopy provides a powerful tool to study mode- and energy-specific deactivation processes occurring in a multi-dimensional potential energy surface.

Light-matter interaction and polarization of single ZnO nanowire lasers.

The optical properties of single zinc oxide (ZnO) nanolasers are investigated. ZnO nanowires with different diameters and lengths are prepared by chemical vapor transport. The diameter plays an important role in the stimulated emission process in nanowires. The spectral shift and spacing of Fabry-Pérot-type modes imply a strong light-matter interaction in the lasing nanowires, which is explained by the exciton-polariton model. The polarization of the electric field in the lasing nanowires is perpendicular to the long axis of the nanowire and parallel to the substrate plane. The coexistence of the transverse modes is distinguished by decomposing the peak shape and the degree of polarization. In addition to the transverse mode of the lasing with the polarization parallel to the substrate plane, the lasing mode with the polarization perpendicular to the substrate plane is observed.