Change In Absorption Cross Section Research Articles

Unusually Strong Biexciton Repulsion Detected in Quantum Confined CsPbBr3 Nanocrystals with Two and Three Pulse Femtosecond Spectroscopy.

Transient absorption measurements were conducted on pristine and monoexciton saturated CsPbBr3 nanocrystals varying in size within the regime of a strong quantum confinement. Once the difference spectra were translated to absolute transient changes in absorption cross section, a single exciton is shown to completely bleach the band edge absorption peak and induce a new absorption roughly two times weaker ∼100 meV to the blue. Difference spectra obtained during Auger recombination of biexciton demonstrate that the addition of a second exciton, rather than double the effect of a first, bleaches the blue-induced absorption band without producing a net stimulated emission at the band edge. Accompanied by high time resolution transient absorption spectra pumping at the lowest exciton band, these results identify the blue-induced absorption as the second transition to 1Se1Sh which is shifted in energy due to unusually strong and promptly rising biexciton repulsion. Possible mechanisms giving rise to this repulsion and prospects for applying it to enhance optical gain applications of these particles are discussed.

Laboratory studies of fresh and aged biomass burning aerosol emitted from east African biomass fuels – Part 1: Optical properties

Abstract. An accurate measurement of the optical properties of aerosol is critical for quantifying the effect of aerosol on climate. Uncertainties persist and results of measurements vary significantly. Biomass burning (BB) aerosol has been extensively studied through both field and laboratory environments for North American fuels to understand the changes in optical and chemical properties as a function of aging. There is a need for a wider sampling of fuels from different regions of the world for laboratory studies. This work represents the first such study of the optical and chemical properties of wood fuel samples commonly used for domestic purposes in east Africa. In general, combustion temperature or modified combustion efficiency (MCE) plays a major role in the optical properties of the emitted aerosol. For fuels combusted with MCE of 0.974±0.015, which is referred to as flaming-dominated combustion, the single-scattering albedo (SSA) values were in the range of 0.287 to 0.439, while for fuels combusted with MCE of 0.878±0.008, which is referred to as smoldering-dominated combustion, the SSA values were in the range of 0.66 to 0.769. There is a clear but very small dependence of SSA on fuel type. A significant increase in the scattering and extinction cross section (with no significant change in absorption cross section) was observed, indicating the occurrence of chemistry, even during dark aging for smoldering-dominated combustion. This fact cannot be explained by heterogeneous oxidation in the particle phase, and we hypothesize that secondary organic aerosol formation is potentially happening during dark aging. After 12 h of photochemical aging, BB aerosol becomes highly scattering with SSA values above 0.9, which can be attributed to oxidation in the chamber. Aging studies of aerosol from flaming-dominated combustion were inconclusive due to the very low aerosol number concentration. We also attempted to simulate polluted urban environments by injecting volatile organic compounds (VOCs) and BB aerosol into the chamber, but no distinct difference was observed when compared to photochemical aging in the absence of VOCs.

Thylakoid membrane dynamics and state transitions in Chlamydomonas reinhardtii under elevated temperature.

Moderately elevated temperatures can induce state transitions in higher plants by phosphorylation of light-harvesting complex II (LHCII). In this study, we exposed unicellular algae Chlamydomonas reinhardtii to moderately elevated temperatures (38°C) for short period of time in the dark to understand the thylakoid membrane dynamics and state transition mechanism. Here we report that under elevated temperatures (1) LHCII gets phosphorylated similar to higher plants and (2) there is decreased absorption cross section of photosystem II (PSII), whereas (3) there is no change in absorption cross section of photosystem I (PSI) indicating that LHCII trimers are largely disconnected with both photosystems under moderately elevated temperatures and (4) on return to room temperature after elevated temperature treatment there is a formation of state transition complex comprising of PSII-LHCII-PSI. The temperature-induced state transition mechanism also depends on stt7 kinase-like in light-induced state transition. The protein content was stable at the moderately elevated temperature treatment of 40°C; however, at 45°C severe downregulation in photosynthetic performance and protein content was observed. In addition to the known changes to photosynthetic apparatus, elevated temperatures can destabilize the PSII-LHCII complex that can result in decreased photosynthetic efficiency in C. reinhardtii. We concluded that the membrane dynamics of light-induced state transitions differs considerably from temperature-induced state transition mechanisms in C. reinhardtii.

Absorption Measurements in Liquid Core Waveguides Using Cavity Ring-Down Spectroscopy

Short liquid core waveguides (LCWs) were included into a fiber-loop cavity ring-down absorption spectrometer to reduce the detection limit over, both, single pass absorption in a LCW and cavity-enhanced absorption using a conventional fiber-loop cavity. LCWs of 5 and 10 cm length were interfaced with a pressure-flow system and a multimode fiber-loop cavity using concave fiber lenses with matching numerical apertures and diameters. Two red dyes, Allura Red AC and Congo Red, were detected with a 532 nm pulsed laser at a 5 nM limit of detection in a detection volume of less than 1 μL, corresponding to a minimal detectable absorbance of less than 4 × 10(-4) cm(-1) and a minimal detectable change in absorption cross section, σ(min) = V(det) × ε × C(LOD), of about 14 μm(2) (Allura Red AC) and 37 μm(2) (Congo Red).

Ion-induced stacking of photosensitizer molecules can remarkably affect the luminescence detection of singlet oxygen inCandida albicanscells

Singlet oxygen (¹O₂) is an important reactive intermediate in photodynamic reactions, particularly in antimicrobial PDT (aPDT). The detection of ¹O₂ luminescence is frequently used to elucidate the role of ¹O₂ in various environments, particularly in microorganisms and human cells. When incubating the fungus, Candida albicans, with porphyrins XF73 (5,15-bis-[4-(3-Trimethylammonio-propyloxy)-phenyl]-porphyrin) or TMPyP (5,10,15,20-Tetrakis(1-methyl-4-pyridinio)-porphyrin tetra(p-toluenesulfonate)), the ¹O₂ luminescence signals were excellent for TMPyP. In case of XF73, the signals showed strange rise and decay times. Thus, ¹O₂ generation of XF73 was investigated and compared with TMPyP. Absorption spectroscopy of XF73 showed a change in absorption cross section when there was a change in the concentration from 1×10⁻⁶M to 1×10⁻³ M indicating an aggregation process. The addition of phosphate buffered saline (PBS) substantially changed ¹O₂ luminescence in XF73 solution. Detailed experiments provided evidence that the PBS constituents NaCl and KCl caused the change of ¹O₂ luminescence. The results also indicate that Cl- ions may cause aggregation of XF73 molecules, which in turn enhances self-quenching of ¹O₂ via photosensitizer molecules. These results show that some ions, e.g., those present in cells in vitro or added by PBS, can considerably affect the detection and the interpretation of time-resolved luminescence signals of ¹O₂, particularly in in vitro and in vivo. These effects should be considered for any other photosensitizer used in photodynamic processes.

Silica-Coated Gold Nanorods as Photoacoustic Signal Nanoamplifiers

Photoacoustic signal generation by metal nanoparticles relies on the efficient conversion of light to heat, its transfer to the environment, and the production of pressure transients. In this study we demonstrate that a dielectric shell has a strong influence on the amplitude of the generated photoacoustic signal and that silica-coated gold nanorods of the same optical density are capable of producing about 3-fold higher photoacoustic signals than nanorods without silica coating. Spectrophotometry measurements and finite difference time domain (FDTD) analysis of gold nanorods before and after silica coating showed only an insignificant change of the extinction and absorption cross sections, hence indicating that the enhancement is not attributable to changes in absorption cross section resulting from the silica coating. Several factors including the silica thickness, the gold/silica interface, and the surrounding solvent were varied to investigate their effect on the photoacoustic signal produced from silica-coated gold nanorods. The results suggest that the enhancement is caused by the reduction of the gold interfacial thermal resistance with the solvent due to the silica coating. The strong contrast enhancement in photoacoustic imaging, demonstrated using phantoms with silica-coated nanorods, shows that these hybrid particles acting as "photoacoustic nanoamplifiers" are high efficiency contrast agents for photoacoustic imaging or photoacoustic image-guided therapy.

Picosecond time-resolved fluorescence studies on excitation energy transfer in a histidine 117 mutant of the D2 protein of photosystem II in Synechocystis 6803.

The role of the peripheral reaction center chlorophyll a molecule associated with His117 of the D2 polypeptide in photosystem II was investigated in Synechocystis sp. PCC 6803 using a combination of steady state, pump-probe, and picosecond time-resolved fluorescence spectroscopy. Data were obtained from intact cells and isolated thylakoid membranes of a control mutant and a D2-H117T mutant, both of which lacked photosystem I. Excitation energy transfer and trapping were investigated by analyzing the data with a kinetic model that used an exact numerical solution of the Pauli master equation, taking into account available photosystem II spectral and structural information. The results of our kinetic analysis revealed the observed difference in excited-state dynamics between the H117T mutant and the control to be consistent with a retardation of the rate of excitation energy transfer from the peripheral chlorophyll of D2 (Chl at His117) to the electron-transfer pigments and an increase of the rate constant for charge recombination in the H117T mutant. The kinetic model was able to account for the experimentally observed changes in absorption cross section and fluorescence decay kinetics between the control and mutant by invoking changes in only these two rate constants. The results rule out quenching of excitation by a chlorophyll cation radical as a mechanism responsible for the lower efficiency of excitation energy utilization in the H117T mutant. Our work also demonstrates the importance of the chlorophyll associated with His117 of the D2 protein for excitation energy transfer to the PSII electron-transfer pigments and for the effective stabilization of the primary radical pair.

Solvation and intramolecular reorganization in 9,9′-bianthryl: Analysis of resonance Raman excitation profiles and ab initio molecular orbital calculations

The observations of a clear solvent-dependence of resonance Raman intensities, but an absence of concommitant changes in absorption cross-sections, are reported for the molecule 9,9′-bianthryl (BA). Displacements obtained by analysis of the nonpolar solvent data are found to reproduce the absorption spectra recorded in all solvents studied, but not the resonance Raman intensities in polar solvents. Moreover, transform theory is found to be unsuccessful in reproducing the resonance Raman intensities in any solvent. These observations suggest that ultrafast relaxation dynamics (on the timescale probed by the resonance Raman experiment) are changing the displacements of the intramolecular vibrational modes. The changes in the displacements determined by analysis of the data are consistent with a correlation between the total reorganization energy accompanying the charge transfer and the solvent dielectric properties (i.e., the mode-specific reorganization is found to increase with solvent dielectric properties). In effect, the immediate free energy surface “seen” by the molecule changes dramatically with time and causes significant intramolecular reorganization, at least for the initial stages of evolution of the emissive state. These findings are supported by ab initio molecular orbital (MO) geometry optimization, analytical frequencies, and excited state calculations (CIS/3-21G*, HF/6-31G*). It is shown that most of the normal modes of the S0 state of BA are splittings of corresponding anthracene modes, however, for the relaxed S1 geometry of BA (i.e., gas phase equilibrium geometry), the modes are calculated to be red-shifted and have significantly greater splittings. Furthermore, the dipole moment of this relaxed S1 state is calculated to be 0.099 debye in the gas phase, compared to 0.00 debye for the equilibrium ground state and the vertical, unrelaxed, S1 state. The optimized S1 geometry of BA is found to be a “90°” geometry (i.e., torsion angle between the anthracene ring planes), similar to that of the ground state except for subtle asymmetries in each anthracene ring which lower the symmetry from D2. We suggest that these results provide direct evidence for the importance of solvent-dependent intramolecular reorganization in this molecule.

Investigation of spatially resolved light absorption in a spark-ignition engine fueled with propane/air

UV absorption in the combustion phase of spark-ignition engines strongly influences laser-induced-fluorescence measurements and flame-emission techniques because of the attenuation of a laser and/or signal light. This absorption was assessed with spatial, spectral, and temporal resolutions in an optically accessible research engine. Absorption was measured along a line for different crank-angle positions throughout the combustion phase of the engine by use of spectrally resolved transmittance measurements of both broadband illumination from a deuterium lamp and emission of laser-excited hot oxygen. Evaluating the spatial patterns of absorptivity revealed that no increased absorption can be attributed to the flame-front region and that homogeneous absorption cross sections for the whole burned-gas region can be assumed. The temporal change of absorption was shown to depend on the pressure effect with only negligible changes in absorption cross sections. Results obtained from the absorption measurements are applied for spatially resolved corrections of two-dimensional laser-induced-fluorescence measurements of NO concentration fields obtained under different operating conditions.

Complementary changes in absorption cross-sections of Photosystems I and II due to phosphorylation and Mg 2+-depletion in spinach thylakoids

An open question regarding the changes of energy distribution between Photosystems (PS) I and II following protein phosphorylation and thylakoid destacking is whether or not excitation energy redirected from PS II antenna is effectively trapped by PS I reaction centers. In this report, we measured the effects in spinach thylakoids of Mg 2+-depletion and of phosphorylation at 5 and 1 mM MgCl 2 on: (1) the effective absorption cross-sections (σ) of both PS II and PS I determined simultaneously from single-turnover flash saturation curves of Ch1 a fluorescence and of the absorbance change at 820 nm, respectively; (2) the absolute changes in 77 K fluorescence yields emitted by PS II and PS I; and (3) the quenching of room temperature Ch1 a fluorescence. In all experiments, we observed complementary changes between σ PS I and σ PS II, σ PS I consistently increasing at the expense of σ PS II. ATP-induced decreases of σ PS II were 6.9% and 11.2% at 5 and 1 mM MgCl 2, respectively, whereas σ PS I increased by 12% and 18.6% under these conditions. In absence of Mg 2+, σ PS II and σ PS I changed respectively by −26.2% and +38.9% relative to thylakoids resuspended in presence of 5 mM MgCl 2. These relative increases of σ PS I are larger than the relative decreases of σ PS II by a factor of 1.5 – 1.7, probably due to the stoichiometry between PS II and PS I complexes typically found in sun-adapted spinach leaves. Also, we observed that the increases of σ PS I correspond closely to the increases of 77 K fluorescence yields emitted at 735 nm by PS I. However, no clear relationship could be detected between the changes of σ PS II and the quenching of both room temperature and 77 K PS II fluorescence. The reasons for such discrepancy are discussed.

Photoacoustic Study of Changes in the Energy Storage of Photosystems I and II during State 1-State 2 Transitions

Using photoacoustic spectroscopy, state 1-state 2 transitions were demonstrated in vivo in intact sugar maple leaves (Acer saccharum Marsh.) by following the changes in energy storage of photosystems (PS) I and II. Energy storage measured with 650 nm modulated light (light 2) in the presence of background white light indicated the total energy stored by both photosystems (ES(t)), and in the presence of background far-red light showed the energy stored by PSI (ES(psi)). The difference between ES(t) and ES(psi) gave the energy stored by PSII (ES(psii)). While ES(t) remained nearly constant during state transitions, both ES(psi) and ES(psii) changed considerably. The ratio of ES(psii) to ES(psi), an indicator of the energy distribution between the two photosystems, decreased or increased during transition to state 2 or state 1, respectively. State transitions were completed in about 20 min and were fully reversible. During transition from state 1 to state 2, the fraction of excitation energy gained by PSI was nearly equal to that lost by PSII. This fraction of excitation energy transferred from PSII to PSI accounted for about 5% of the absorbed light (fluorescence is not considered), 19% of ES(t), 34% of ES(psii), and 43% of ES(psi) in state 2. NaF treatment inhibited the transition to state 1. Data in the present study confirm the concept of changes in absorption cross-section of photosystems during state transitions.

The use of excitation fluorescence spectroscopy in the study of short-term chloroplast membrane reorganisation

The advantages of the use of excitation fluorescence spectroscopy in the investigation of PS I absorption cross-section dynamics during phosphorylation of membrane proteins or heat treatment have been shown. After phosphorylation in the light, there occurred only 15–20% enhancement in absorption cross-section of F735 — PS I peripheral antenna — at the expense of chlorophyll b and short wavelength chlorophyll a species in the region 674–676 mm, which is attributed to the light-harvesting pigment complex of Photosystem II. Phosphorylation in the dark with dithionite caused increases of 30–35% in PS I absorption cross-section at the expense of Chl b, Chl a absorbing at 674–676 mm and long-wavelength PS II internal antenna chlorophyll at 685–687 nm. The same changes in the region of 685–687 mm were found after heat treatment of chloroplasts. The application of excitation fluorescence spectroscopy made it possible to estimate directly for the first time not only the extent of changes in absorption cross-section of PS I but also to describe which complex of PS II is responsible.

Photoacoustic studies on the dependence of state transitions on grana stacking

Photoacoustic detection of oxygen evolution and Emerson enhancement in state 1 and state 2 were compared in a tobacco wild type and mutant (Su/su) deficient in chlorophyll. The mutant shows smaller changes in the distribution of excitation energy between the two photosystems than the wild type. Analysis of Emerson enhancement saturation curves indicates that in the mutant which is deficient in grana partitions and shows less stacking, state 1-state 2 transitions reflect changes in the yield of energy transfer from PS II to PS I (spillover). On the other hand, the wild type containing large grana shows changes in absorption cross-sections of the two photosystems upon state transitions. NaF, a specific phosphatase inhibitor, blocks the transition to state 1, indicating that LHC II phosphorylation has a role in excitation energy regulation in both the mutant as well as the wild type. It is demonstrated that N-ethylmaleimide, a specific sulfhydryl reagent, blocks the transition to state 2, suggesting that a disulfide-sulfhydryl redox couple activates the LHC II kinase in vivo.

Quantitative analysis of State 1–State 2 transitions in intact leaves using modulated fluorimetry — evidence for changes in the absorption cross-section of the two photosystems during state transitions

Using a combination of modulated and non-modulated light with synchronized detection it has been possible to monitor State 1–State 2 transitions in intact leaves as changes in the yield of modulated chlorophyll fluorescence. In the presence of excess far-red non-modulated light (713 nm) absorbed mainly by Photosystem I (PS I), the modulated fluorescence intensity was taken to represent F o — the emission yield which occurs when the reaction centres of Photosystem II (PS II) are all open. On the other hand, superimposing saturating non-modulated wide-band, blue-green light resulted in a transitory maximum yield of modulated chlorophyll fluorescence, F m, due to the total closure of the PS II reaction centres. In the absence of these additional lights the fluorescence level assumed a steady-state value, F s, between F o and F m. All these parameters changed as the leaf slowly adapted to light of a given spectral composition. It was found that both F o and F m increased reversibly (by about 15–20%) during the transition from State 2 to State 1 such that the ratio of F m to F o remained constant, indicative of changes in absorption cross-section of PS II and PS I rather than alterations in ‘spillover’ which would cause preferential changes in F m. It was also possible to estimate the fractions of light, β and α, channeled to PS II and PS I, respectively, from the values of F o, F m and F s. In one approach, β was estimated in State 1, using the assumption that α + β = 1, and its variation during the subsequent state transition was assumed to follow proportional changes in F o (or F m). It was found that in State 2 there is a small loss (about 4%) of the total utilization of light in both photosystems. However, if such loss is neglected, assuming α + β is always unity, the calculated β was found to vary in the same direction and almost with the same magnitude as F o (or F m), indicating independently that a change in absorption cross-section in PS II (and PS I) had occurred. Consistent with these data were the light-saturation curves for the non-modulated far-red light-quenching effect in bringing the fluorescence from F s to F o in States 1 and 2. The ratio of the initial slopes of these curves indicates quantitatively both redistribution of light between PS I and PS II during the State 1–State 2 transitions and a partial loss of excitation energy in State 2.

Ultraviolet absorption cross sections of infrared laser excited UF6

Ultraviolet absorption cross sections of ν3 vibration-excited UF6 molecules were measured in the wavelength region between 230 and 280 nm. The state-selective excitation was accomplished by 16 μm laser pumping of the ground vibrational state of flow-cooled UF6. Maximum changes in the absorption cross sections were observed toward longer wavelengths in the wings of the two charge transfer bands located at 220 and 260 nm. The results are discussed in terms of a transition from the ν3 vibrationally excited state to an upper dissociative potential surface. The change in the UV absorption cross section was also monitored as a function of the IR laser frequency and the sample gas temperature. The IR excitation spectrum follows qualitatively the low resolution contour of the ν3 Q branch. The magnitude in the absorption change is dependent on the fraction of molecules being accessed by the IR laser. The characteristic relaxation time for the ν3 excitation was estimated to be about 0.25 μs Torr at 100 K.

Distribution of light excitation in an intact leaf between the two photosystems of photosynthesis. Changes in absorption cross-sections following state 1-state 2 transitions

Using the photoacoustic technique, state 1-state 2 transitions were studied in an intact leaf by direct monitoring of modulated oxygen evolution, excited by modulated light. States 1 and 2 were characterized by the extent of immediate enhancement of the modulated oxygen evolution — ‘Emerson enhancement’ — and the concomitant fluorescence quenching, resulting from the addition of continuous far-red light (greater than 700 nm), absorbed primarily in Photosystem I (light 1). The extent of Emerson enhancement as well as the saturation curve of this effect by far-red light are very sensitive and quantitative indicators for the ratio of light excitation distributed between Photosystems I and II. The enhancement ratios at 650 nm light, a typical light 2, were in a range 1.4–1.8 in state 1, while values as low as 1.06 were observed in state 2. During the transition from state 2 to state 1, monitored in presence of modulated light 2 and background continuous light 1, the modulated oxygen yield increased considerably, indicating a major increase in excitation flux into Photosystem II. Conversely, with modulated light 2 alone in state 1, the modulated oxygen evolution yield was smaller than in state 2, indicating a decrease of the excitation flux in Photosystem I. In a typical example, of the transition to state 1, the fraction of light absorbed by Photosystem II, β, increased from 0.46 to 0.64, while that absorbed by Photosystem II, α, decreased from 0.43 to 0.36. State 1-state 2 transitions, thus, reflect reciprocal changes in the cross-sections of the two photosystems for light absorption. There is no evidence for the operation of a ‘spill-over’ mechanism. The enhancement effect displayed maxima at 480 and 650 nm, related to chlorophyll- b absorption, as well as another band at 500–550 nm. In a chlorophyll- b-less barley mutant, state 1-state 2 transitions, as monitored by modulated oxygen evolution, were absent, and the resulting enhancement corresponded to state 2. These observations are consistent with the model that the light-harvesting chlorophyll- a b complex plays a role in regulating the distribution of light to the photosystems. It is probable that this complex migrates reversibly in the thylakoid membrane in such a way that it is mainly associated with Photosystem II in state 1, but is more evenly distributed in the two photosystems in state 2.

State 1-State 2 Transitions in a Unicellular Green Algae

A study has been made on the State 1-State 2 transitions exhibited by the unicellular green algae Chlorella pyrenoidosa. Chlorophyll fluorescence induction curves from algae adapted to State 1 or State 2 have been analyzed and a comparison made with similar curves produced by decreasing the intensity of light going to the photosystem II reaction centers. In both cases, quenching of the maximum fluorescence yield (F(m)) and the initial fluorescence yield (F(o)) were observed so that the F(v)/F(m) ratio and the area above the induction curve (A(max)) remained constant. The State 1-State 2 transition also produced changes in the beta(max) component indicative of some alteration within photosystem II organization. The implications of these experiments on the in vivo mechanism for energy redistribution between the two photosystems are discussed in terms of changes in absorption cross-section rather than being due to spillover from photosystem II to photosystem I. These changes may reflect the phosphorylation of the light-harvesting chlorophyll a/b protein complex and its subsequent migration away from the photosystem II core leading to its closer association with photosystem I.