Short-lived Component Research Articles

Synthesis and Characterization of Folic Acid-Conjugated Terbium Complexes as Luminescent Probes for Targeting Folate Receptor-Expressing Cells.

Several conjugates between folic acid and a series of kinetically stable lanthanide complexes have been synthesized, using amide coupling and azide-alkyne cycloaddition methodologies to link the metal-binding domain to folate through a variety of spacer groups. While all these complexes exhibit affinity for the folate receptor, it is clear that the point of attachment to folate is essential, with linkage through the γ-carboxylic acid giving rise to significantly enhanced receptor affinity. All the conjugates studied show affinities consistent with displacing biological circulating folate derivatives, 5-methyltetrahydrofolate, from folate receptors. All the complexes exhibit luminescence with a short-lived component arising from ligand fluorescence overlaid on a much longer lived terbium-centered component. These can be separated using time-gating methods. From the results obtained, the most promising approach to achieve sensitized luminescence in these systems requires incorporating a sensitizing chromophore close to the lanthanide.

Solid Solution Behavior of High Performance BiOBrxI1-X Photoanodes Probed Using Solid-State NMR, XRD and Optical Spectroscopy

Bismuth oxyhalides (BIOX) are a family of solution-synthesizable 2D layered semiconductors constituted of earth-abundant elements namely bismuth, oxygen and the halogens. BIOX based thin films and heterojunctions are the subject of immense scientific interest due to their impressive performance in photocatalytic and photoelectrochemical devices. Solid solutions of Br/I bismuth oxyhalides exhibit continuously tunable absorption and emission spectra similar to that observed in mixed halide MAPbClxBryI3-x-y perovskites and mixed anion III-V GaAsxP1-x semiconductors. The excited state decay showed two components for all the mixed halide BiOX semiconductors with a dominant short-lived component in the nanosecond range and a weaker longer-lived component of ~100 ns. The average photoluminescence (PL) lifetime varied from 5.4 ns in bare BiOI to 1.49 ns in bare BiOBr with intermediate compositions exhibiting monotonically increasing average PL lifetimes with increasing iodine content. Using a combination of characterization techniques such as solid-state nuclear magnetic resonance (ssNMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and optical spectroscopy, we demonstrate the formation of atomic level solid solutions in Br/I bismuth oxyhalides. Through refinement of the lattice parameters using powder XRD and complementary atomic-level 209Bi SSNMR spectroscopy, we found that Vegard's law was obeyed by the BIOBrxI1-x solid solutions. By varying the Br:I ratio, it is also possible to tune the electronic band gap as well as the energy levels corresponding to the conduction band minimum (ECB, min) and the valence band maximum (EVB, max), thus allowing control over the thermodynamic driving force available to drive chemical reactions using photogenerated or electrically injected charge carriers. Suppression of the longitudinal optical phonon in solid solutions of Br/I bismuth oxyhalides is suggestive of lower phonon scattering of charge carriers and improved electronic transport. A synergistic enhancement of more than 1 order of magnitude in the photoelectrochemical water-splitting performance was obtained for the optimized solid solution (BiOBr0.67I0.33) under AM 1.5G 1 sun illumination. Our results pave the way for a one pot synthesis protocol to form BiOX thin films, powders and colloidal suspensions with deterministic control over the stoichiometry.

Efficient photoredox catalysis in C–C cross-coupling reactions by two-coordinated Au(I) complex

Photocatalysis provides a versatile approach to redox activation of various organic substrates for synthetic applications. To broaden the scope of photoredox catalysis, developing catalysts with strong oxidizing or reducing power in the excited state is imperative. Catalysts that feature highly cathodic oxidation potentials and long lifetimes in their excited states are particularly in demand. In this research, we demonstrate the catalytic utility of two-coordinate Au(I) complex photocatalysts that exhibit an exclusive ligand-to-ligand charge-transfer (LLCT) transition in C–C cross-coupling reactions between N-heterocycles and (hetero)aryl halides, including redox-resistant (hetero)aryl chlorides. Our photocatalysis system can steer reactions under visible-light irradiation at a catalyst loading as low as 0.1 mol% and exhibits a broad substrate scope with high chemo- and regioselectivity. Our mechanistic investigations provide direct spectroscopic evidence for each step in the catalysis cycle and demonstrate that the LLCT-active Au(I) complex catalysts offer several benefits, including strong visible-light absorption, a 210 ns-long excited-state lifetime without short-lived components, and a 91% yield in the production of free-radical intermediates. Given the wide structural versatility of the proposed catalysts, we envision that our research will provide useful insights into the future utilization of the LLCT-active Au(I) complex for organic transformations.

Fluorescence lifetime imaging and phasor analysis of intracellular porphyrinic photosensitizers applied with different polymeric formulations

The fluorescence lifetime of a porphyrinic photosensitizer (PS) is an important parameter to assess the aggregation state of the PS even in complex biological environments. Aggregation-induced quenching of the PS can significantly reduce the yield of singlet oxygen generation and thus its efficiency as a medical drug in photodynamic therapy (PDT) of diseased tissues. Hydrophobicity and the tendency to form aggregates pose challenges on the development of efficient PSs and often require carrier systems. A systematic study was performed to probe the impact of PS structure and encapsulation into polymeric carriers on the fluorescence lifetime in solution and in the intracellular environment. Five different porphyrinic PSs including chlorin e6 (Ce6) derivatives and tetrakis(m-hydroxyphenyl)-porphyrin and -chlorin were studied in free form and combined with polyvinylpyrrolidone (PVP) or micelles composed of triblock-copolymers or Cremophor. Following incubation of HeLa cells with these systems, fluorescence lifetime imaging combined with phasor analysis and image segmentation was applied to study the lifetime distribution in the intracellular surrounding. The data suggest that for free PSs, the structure-dependent cell uptake pathways determine their state and emission lifetimes. PS localization in the plasma membrane yielded mostly monomers with long fluorescence lifetimes whereas the endocytic pathway with subsequent lysosomal deposition adds a short-lived component for hydrophilic anionic PSs. Prolonged incubation times led to increasing contributions from short-lived components that derive from aggregates mainly localized in the cytoplasm. Encapsulation of PSs into polymeric carriers led to monomerization and mostly fluorescence emission decays with long fluorescence lifetimes in solution. However, the efficiency depended on the binding strength that was most pronounced for PVP. In the cellular environment, PVP was able to maintain monomeric long-lived species over prolonged incubation times. This was most pronounced for Ce6 derivatives with a logP value around 4.5. Micellar encapsulation led to faster release of the PSs resulting in multiple components with long and short fluorescence lifetimes. The hydrophilic hardly aggregating PS exhibited a mostly stable invariant lifetime distribution over time with both carriers. The presented data are expected to contribute to optimized PDT treatment protocols and improved PS-carrier design for preventing intracellular fluorescence quenching. In conclusion, amphiphilic and concurrent hydrophobic PSs with high membrane affinity as well as strong binding to the carrier have best prospects to maintain their photophysical properties in vivo and serve thus as efficient photodynamic diagnosis and PDT drugs.

Fire-Extinguishing Dibromomethane Mixtures with Fluorinated Alkanes for Fire and Explosion Protection of Oil and Gas Industry Facilities

The high fire hazard level is specific to the oil and gas industry due to the circulation of large volumes of flammable gases and liquids. To ensure fire protection at the oil and gas industry facilities, automated gaseous fire extinguishing is widely used. The main fire-extinguishing agents in automated gaseous fire-extinguishing systems are refrigerants HFC 23, 125, 227еа, FC 318c, and fluorinated ketone FK 5-1-12. Upon the adoption of the international agreements on combating global warming, most fluorinated gaseous fire-extinguishing agents currently used for fire extinguishing fell under restrictions. The article indicates the importance of refrigerants HFC 23, 125, 227еа, and FC 318c, whose production volume must be reduced by 85 % by 2036 to ensure the required level of fire and explosion protection of oil and gas industry facilities. A method to reduce the volumes of used fluorinated alkanes by producing highly efficient fire-extinguishing mixtures, one of the components of which is an agent of high global warming potential (GWP) and the other is a chemical compound with a short atmospheric lifetime, has been proposed. Dibromomethane, which fully meets the latest environmental requirements, is to be considered a short-lived component. Based on the well-known kinetic data, the rates of elementary chemical reactions generated in the flame of the methane-oxygen mixture when contacting with refrigerants HFC 23, 227еа, and dibromomethane, have been calculated and compared. The efficiency of using dibromomethane to increase the fire-extinguishing efficiency of refrigerants HFC 23 and 227еа has been substantiated. An experimental determination of the minimum fire-extinguishing efficiency of the generated mixed compositions is conducted to confirm the correctness of theoretical calculations. The obtained mixed gaseous fire-extinguishing agents enable the reduction of the volume of high global warming potential refrigerants by 1.5–2 times. It has been also demonstrated that the obtained mixed compositions have no toxic impact on a human.

An optically thin view of the flaring chromosphere: non-thermal widths in a chromospheric condensation during an X-class solar flare

ABSTRACT The bulk of solar flare energy is deposited in the chromosphere. Flare ribbons and footpoints in the chromosphere therefore offer great diagnostic potential of flare energy release and transport processes. High-quality observations from the Interface Region Imaging Spectrograph (IRIS) spacecraft have transformed our view of the Sun’s atmospheric response to flares. Since most of the chromospheric lines observed by IRIS are optically thick, forward modelling is required to fully appreciate and extract the information they carry. Reproducing certain aspects of the Mg ii lines remain frustratingly out of reach in state-of-the-art flare models, which are unable to satisfactorily reproduce the very broad-line profiles. A commonly proposed resolution to this is to assert that very large values of ‘microturbulence’ is present. We assess the validity of that approach by analysing optically thin lines in the flare chromosphere from the X-class flare SOL2014-10-25T17:08:00, using the derived value of non-thermal width as a constraint to our numerical models. A non-thermal width of the order 10 km s−1 was found within the short-lived red wing components of three spectral lines, with relatively narrow stationary components. Simulations of this flare were produced, and in the post-processing spectral synthesis we include within the downflows a microturbulence of 10 km s−1. While we can reproduce the O i 1355.598 Å line rather well, and we can capture the general shape and properties of the Mg ii line, the synthetic lines are still too narrow.

A multifunctional sensing of two carbon dots based on diaminonaphthalenes for detection of ofloxacin drug

Fluorescent carbon quantum dots (CQDs) have gained increased attention due to their diverse properties in the development of sensors and visualizing dynamic processes. This contribution demonstrates the synthesis of two carbon quantum dots, 2,3-CQDs and 1,8-CQDs from 2,3-Diaminonaphthalene and 1,8-Diaminonaphthalene, respectively by hydrothermal process. The results showed that the two CQDs had distinct optical properties with different sizes and therefore we observed different sensing performance and different dynamics interactions, which is dependent on the geometrical structure of precursors. Both CQDs exhibit bi-exponential decay curves with long and short-lived decay components, corresponding to recombination from the defect and intrinsic states, respectively. The sensing performance of 2,3-CQDs which possess high fluorescence quantum yield (0.2) demonstrates an ability to detect Ofloxacin based on fluorescence-enhanced turn off- on with a low detection limit of 0.46 μM and good linear range of 0–120 μM. Meanwhile the sensing of 1,8-CQDs with a quantum yield of 0.17 was performed for detection of Ofloxacin based on fluorescent turn-on–off due to energy transfer mechanism with wide linear response range of 0–120 μM and a satisfactory detection limit of 24 nM. These results indicate that we can adapt our systems to the intended applications by specifically and selectively altering carbon dots.

Luminescence lifetime tuning of non-conjugated organic clusters through external heavy-atom effect for smartphone-based time-resolved imaging

Clusteroluminescence from non-conjugated organic molecules has attracted extensive attention, and it is extraordinarily important to develop effective methods for tuning the clusteroluminescence lifetime with balanced emission intensity in optical multiplexing for time-resolved luminescence imaging. Herein, chitosan, a renewable polymer, was found to exhibit persistent clusteroluminescence after dehydration. In addition, external heavy-atom effect was successfully utilized for enhancing phosphorescence intensity and regulating its phosphorescence lifetime. By adjusting the doping concentration of bromide salts in chitosan, the phosphorescence lifetime could be gradually tailored from 49 to 647 ms. The heavy atoms could promote phosphorescence transition and avoid the reduction of short-lived luminescence component, which facilitated the lifetime-multiplexed information encryption. This strategy for tuning phosphorescence lifetime could be extended to other phosphorescence materials. Moreover, smartphone-based luminescence imaging of shrimp chitin was realized by enhancing its persistent luminescence, which indicated that our method could be used for label-free luminescence imaging of chitin-containing organisms.

Thermally processed Ni-and Co-struvites as functional materials for proton conductivity.

Here, we describe how to synthesise proton-conductive transition metal phosphates (TMPs) by direct thermal processing of precursor M-struvites, NH4MPO4·6H2O, with M = Ni2+, Co2+. In the as-derived TMP phases their thermal history and bulk proton conductivity were linked with the structural information about the metal coordination, phosphate groups, and volatile compounds. These aspects were investigated with vibrational and synchrotron-based spectroscopic methods (FT-IR, FT-RS, XAS). We elucidated the structures of amorphous and crystalline Ni- and Co phosphate phases in association with different coordination changes and distortion degrees of the metal polyhedra as they developed upon heating. Ni-struvite transformed to a stable amorphous phase over a broad range of temperatures (90 °C < T < 600 °C), in which it remained in an octahedral coordination environment, but the degree of distortion changed with T. In contrast, heating of Co-struvite led to several successive crystalline phases with only unstable transitional and short-lived amorphous components. Among the as-occurring phases, a highly functional layered M-dittmarite NH4MPO4·H2O obtained at low temperatures (T < 200 °C) demonstrated high proton conductivity values of 4.2 × 10-5 S cm-1 for Ni-dittmarite and Co-dittmarite > 10-4 S cm-1 at room temperature. Even at low humidity, these values are comparable with those found for Nafion, MOFs, some perovskites or composite materials. Coprecipitation of phosphates and transition metal cations in the form of struvite is potentially a viable method to extract these elements from wastewater. Thus, we propose that recycled M-struvites could be potentially further directly upcycled into crystalline and amorphous TMPs useful for electrochemical applications.

Exploring site-selective photoluminescence of Eu3+ and Tb3+ ions in Sr10(PO4)6F2 and the development of different phosphor materials

We have developed a wide range of phosphor materials with varying color characteristics in the green, yellow, orange, and red regions based on Sr10(PO4)6F2 matrix and different compositions of Eu3+ & Tb3+ ions. The site-selective Tb3+→Eu3+ energy-transfer dynamics found to play a great role for such tunable color characteristics. DFT based calculations were performed to understand the preference of lattice-site occupancy of the two dopant ions, which suggested that while Eu3+ ion prefers both Sr1 & Sr2 sites; Tb3+ only prefers Sr1 site. The site selective distribution has immediate impact on the photoluminescence lifetime values, wherein two different components were observed for both the dopant ions. In case of Eu3+ ion, the short-lived lifetime component of Eu3+ ion is originated when it is placed at Sr1 site and the long-lived component at Sr2 site, which has F-atom in its coordination and provides extra stability to the excited state at Sr2 site. However, for Tb3+ ion, the two lifetime components are explained based on the energy-transfer probability. The site-selective luminescence of Eu3+ & Tb3+ ions was found to play the key role while developing colour tuneable phosphor materials.

Phosphorescence lifetime measurements with sensor materials: Comparison of the four different detection platforms

Using several types of Pt-porphyrin based oxygen sensing materials and conditions, we evaluated comparatively four different detection platforms that perform phosphorescence lifetime (PLT) measurements in the microsecond time domain. The time-resolved fluorescence reader Victor 2, which utilises Rapid Lifetime Determination method and Xe-flash lamp excitation, produced stable but inaccurate readings at PLT values < 15 µs, affected by the flash-lamp afterglow and sensor heterogeneity in oxygenated conditions. The luminescence spectrometer Cary Eclipse, which utilises multi-point phosphorescence decay method, was able to partly correct these interfering factors and produce more accurate PLT values from mono- and bi-exponential fits, however short PLT values were still affected by Xe-flash lamp afterglow. The wide-field Tpx3Cam cam-era-based macroscope and the confocal laser-scanning FLIM/PLIM microscope, which use short-pulse excitation (ns LED or ps diode laser pulses, respectively) and TCSPC method, revealed the presence of short-lived components (1.5–6.0 µs) in sample decays, which have to be considered in PLT calculations. The imaging platforms produced more accurate and in-formative PLT data, but they operate with large volumes of raw and processed data. Overall, for each PLT platform a number of potential sources of error and measurement artefacts have been revealed, which can be minimised by careful optimisation of settings and validation with alternative platforms and sensor materials.

Optical characterization and emission enhancement property of Ag nanomesh structure fabricated by nanosphere lithography

A metal nanomesh structure with regularly arranged nanosized holes has a light transmission property at a certain wavelength region and good conductivity; therefore, it can be applied to the wavelength-selective electrode of optical devices such as organic light-emitting diodes (OLEDs) and solar cells. In this study, Ag nanomesh structures with hole arrays of different sizes and periods were fabricated, and their electrical and optical properties were evaluated. Alq3, a green light-emitting material for OLEDs, was deposited on the fabricated Ag nanomesh, and its transmission, scattering, and photoluminescence (PL) spectra were investigated. The PL intensity of Alq3 was approximately four times higher than that without the Ag nanomesh. Time-resolved PL measurements showed the presence of a short-lived component in all samples with Ag nanomesh, indicating plasmonic emission enhancement. These results indicate that Ag nanomeshes can be applied as plasmonic electrodes in optical devices.

Exciton Dynamics in J- and H-Aggregates of a Tricarbocyanine Near-Infrared Dye

Intermolecular interactions in J- and H-aggregates of π-conjugated molecules provide fascinating incentives for excitonic pathways. Investigation regarding exciton dynamics in aggregates of tricarbocyanine near-infrared dyes by transient absorption spectroscopy revealed unusual intermolecular communications not only within different aggregates but also between different aggregates. To this end, aggregation was accompanied by a short-lived excitonic component, that is, on the picosecond time scale, due to additional relaxation channels and a long-lived component, that is, on the nanosecond to microsecond time scales. All of the aforementioned are in sharp contrast to what was found for the monomer. For the monomer, monoexponential exciton dynamics of about 0.5 ns was registered. Overall, the long-lived component in aggregates accounts for 1–5% of all excitons. In J-aggregates, it involves the formation of charge transfer/polaron states. In mixtures of J- and H-aggregates, contributions from the long-lived component further increased. We conclude that interactions between J- and H-aggregates open additional channels for exciton relaxation. One of them is a photoinduced charge transfer from, for example, the bright state in J-aggregates to the dark exciton states in H-aggregates, from where electrons are transferred into the continuum of states.

A Review on X-ray Excited Emission Decay Dynamics in Inorganic Scintillator Materials

Scintillator materials convert high-energy radiation into photons in the ultraviolet to visible light region for radiation detection. In this review, advances in X-ray emission dynamics of inorganic scintillators are presented, including inorganic halides (alkali-metal halides, alkaline-earth halides, rare-earth halides, oxy-halides, rare-earth oxyorthosilicates, halide perovskites), oxides (binary oxides, complex oxides, post-transition metal oxides), sulfides, rare-earth doped scintillators, and organic-inorganic hybrid scintillators. The origin of scintillation is strongly correlated to the host material and dopants. Current models are presented describing the scintillation decay lifetime of inorganic materials, with the emphasis on the short-lived scintillation decay component. The whole charge generation and the de-excitation process are analyzed in general, and an essential role of the decay kinetics is the de-excitation process. We highlighted three decay mechanisms in cross luminescence emission, exitonic emission, and dopant-activated emission, respectively. Factors regulating the origin of different luminescence centers controlling the decay process are discussed.

Strategic molecular design of closo-ortho-carboranyl luminophores to manifest thermally activated delayed fluorescence.

In this paper, we propose a strategic molecular design of closo-o-carborane-based donor–acceptor dyad system that exhibits thermally activated delayed fluorescence (TADF) in the solution state at ambient temperature. Planar 9,9-dimethyl-9H-fluorene-based compounds with closo- and nido-o-carborane cages appended at the C2-, C3-, and C4-positions of each fluorene moiety (closo-type: 2FC, 3FC, 4FC, and 4FCH, and nido-type: nido-4FC = [nido-form of 4FC]·[NBu4]) were prepared and characterized. The solid-state molecular structure of 4FC exhibited a significantly distorted fluorene plane, which suggests the existence of severe intramolecular steric hindrance. In photoluminescence measurements, 4FC exhibits a noticeable intramolecular charge transition (ICT)-based emission in all states (solution at 298 K and 77 K, and solid states); however, emissions by other closo-compounds were observed in only the rigid state (solution at 77 K and film). Furthermore, nido-4FC did not exhibit emissive traces in any state. These observations verify that all radiative decay processes correspond to ICT transitions triggered by closo-o-carborane, which acts as an electron acceptor. Relative energy barriers calculated by TD-DFT as dihedral angles around o-carborane cages change in closo-compounds, which indicates that the structural formation of 4FC is nearly fixed around its S0-optimized structure. This differs from that for other closo-compounds, wherein the free rotation of their o-carborane cages occurs easily at ambient temperature. Such rigidity in the structural geometry of 4FC results in ICT-based emission in solution at 298 K and enhancement of quantum efficiency and radiative decay constants compared to those for other closo-compounds. Furthermore, 4FC displays short-lived (∼0.5 ns) and long-lived (∼30 ns) PL decay components in solution at 298 K and in the film state, respectively, which can be attributed to prompt fluorescence and TADF, respectively. The calculated energy difference (ΔEST) between the first excited singlet and triplet states of the closo-compounds demonstrate that the TADF characteristic of 4FC originates from a significantly small ΔEST maintained by the rigid structural fixation around its S0-optimized structure. Furthermore, the strategic molecular design of the o-carborane-appended π-conjugated (D–A) system, which forms a rigid geometry due to severe intramolecular steric hindrance, can enhance the radiative efficiency for ICT-based emission and trigger the TADF nature.

Activated PD-1+ CD4+ T cells represent a short-lived part of the viral reservoir and predict poor immunologic recovery upon initiation of ART.

Activated (CD38HLA-DR) PD-1 CD4 T cells are strongly associated with virus replication and disease progression in untreated HIV-1 infection, and viral persistence in individuals on ART. Few studies have examined cell-associated viral load (CAVL) in different activated CD4 T-cell populations to measure relative contributions to viral reservoirs. Longitudinal assessment of HIV-1 chronically infected Ugandans initiating ART, to investigate activated CD4 T-cell populations and their contribution to viral reservoirs. We followed 32 HIV-1 chronically infected individuals from Kampala, Uganda, and determined their CD4 T-cell counts and viral load at baseline, 6, and 12 months after the initiation of ART. T-cell populations were sorted based on activation profiles and gag DNA was measured to determine CAVL within these populations. Soluble factors associated with inflammation were measured in plasma using a multiplexed platform. Concomitant with viral load decline and CD4 T-cell count rebound, the activated PD-1 CD4 T-cell population contracted upon initiation of ART. Baseline levels of activated PD-1 CD4 T cells correlated with plasma levels of IP-10 and TNFRII. Interestingly, a higher baseline level of activated PD-1 CD4 T cells was associated with poorer CD4 T-cell recovery after 12 months of ART. This population contributed significantly to the cell-associated HIV DNA load at baseline, whereas their contribution declined on ART, indicating high turnover. Activated PD-1 CD4 T cells are predictors of poor immunologic recovery on ART and may represent a short-lived component of HIV-1 reservoirs.

Length-Dependent Activation of Contractility and Ca-Transient Kinetics in Auxotonically Contracting Isolated Rat Ventricular Cardiomyocytes.

Length-dependent activation (LDA) of contraction is an important mechanism of proper myocardial function that is often blunted in diseases accompanied by deficient contractility and impaired calcium homeostasis. We evaluated how the extent of LDA is related to the decreased force in healthy rat myocardium under negative inotropic conditions that affect the calcium cycle. The length-dependent effects on auxotonic twitch and Ca-transient were compared in isolated rat ventricular cardiomyocytes at room temperature (“25C”) and near-physiological temperature (“35C”) in normal Tyrode and at 25°C with thapsigargin-depleted sarcoplasmic reticulum (“25C + Thap”). At the slack length, a similar negative inotropy in “35C” and “25C + Thap” was accompanied by totally different changes in Ca-transient amplitude, time-to-peak, and time-to-decline from peak to 50% amplitude. End-systolic/end-diastolic tension-sarcomere length relationships were obtained for each individual cell, and the ratio of their slopes, the dimensionless Frank-Starling Gain index, was 2.32 ± 0.16, 1.78 ± 0.09, and 1.37 ± 0.06 in “25C,” “35C” and “25C + Thap,” respectively (mean ± S.E.M.). Ca-transient diastolic level and amplitude did not differ between “25C” and “35C” at any SL, but in “35C” it developed and declined significantly faster. In contrast, thapsigargin-induced depletion of SERCA2a significantly attenuated and retarded Ca-transient. The relative amount of Ca2+ utilized by troponin C, evaluated by the integral magnitude of a short-lived component of Ca-transient decline (“bump”), increased by ~25% per each 0.05 μm increase in SL in all groups. The kinetics of the Ca-TnC dissociation, evaluated by the bump time-to-peak, was significantly faster in “35C” and slower in “25C + Thap” vs. “25C” (respectively, 63.7 ± 5.3 and 253.6 ± 8.3% of the value in “25C,” mean ± S.E.M.). In conclusion, a similar inotropic effect can be observed in rat ventricular myocardium under totally different kinetics of free cytosolic calcium. The extent of LDA is not determined by actual peak systolic tension but is regulated by the level of peak systolic calcium and the kinetics of Ca-transient decline which, in turn, are governed by Ca-TnC dissociation and Ca2+ reuptake by the sarcoplasmic reticulum. Altogether, these findings constitute new evidence about the role of the length-dependent modulation of Ca2+ homeostasis in the mechanisms of calcium regulation of contraction and mechano-calcium feedback in the myocardium.

Application of a Fluorescent Probe for the Online Measurement of PM-Bound Reactive Oxygen Species in Chamber and Ambient Studies.

This manuscript details the application of a profluorescent nitroxide (PFN) for the online quantification of radical concentrations on particulate matter (PM) using an improved Particle Into Nitroxide Quencher (PINQ). A miniature flow-through fluorimeter developed specifically for use with the 9,10-bis(phenylethynyl)anthracene-nitroxide (BPEAnit) probe was integrated into the PINQ, along with automated gas phase corrections through periodic high efficiency particle arrestor (HEPA) filtering. The resulting instrument is capable of unattended sampling and was operated with a minimum time resolution of 2.5 min. Details of the fluorimeter design and examples of data processing are provided, and results from a chamber study of side-stream cigarette smoke and ambient monitoring campaign in Guangzhou, China are presented. Primary cigarette smoke was shown to have both short-lived (t1/2 = 27 min) and long-lived (t1/2 = indefinite) PM-bound reactive oxygen species (ROS) components which had previously only been observed in secondary organic aerosol (SOA).

Combining Zinc Phthalocyanines, Oligo(p-Phenylenevinylenes), and Fullerenes to Impact Reorganization Energies and Attenuation Factors.

A study on electron transfer in three electron donor-acceptor complexes is reported. These architectures consist of a zinc phthalocyanine (ZnPc) as the excited-state electron donor and a fullerene (C60 ) as the ground-state electron acceptor. These complexes are brought together by axial coordination at ZnPc. The key variable in our design is the length of the molecular spacer, namely, oligo-p-phenylenevinylenes. The lack of appreciable ground-state interactions is in accordance with strong excited-state interactions, as inferred from the quenching of ZnPc centered fluorescence and the presence of a short-lived fluorescence component. Full-fledged femtosecond and nanosecond transient absorption spectroscopy assays corroborated that the ZnPc ⋅ + -C60 ⋅ - charge-separated state formation comes at the expense of excited-state interactions following ZnPc photoexcitation. At a first glance, the ZnPc ⋅ + -C60 ⋅ - charge-separated state lifetime increased from 0.4 to 86.6 ns as the electron donor-acceptor separation increased from 8.8 to 29.1 Å. A closer look at the kinetics revealed that the changes in charge-separated state lifetime are tied to a decrease in the electronic coupling element from 132 to 1.2 cm-1 , an increase in the reorganization energy of charge transfer from 0.43 to 0.63 eV, and a large attenuation factor of 0.27 Å-1 .

Solvated electron formation from the conduction band of liquid methanol: Transformation from a shallow to deep trap state

We report solvated electron (esolv -) formation dynamics from the conduction band of liquid methanol studied using femtosecond time-resolved photoelectron spectroscopy. Liquid methanol is excited with vacuum UV (9.3 eV) pump pulses, and the subsequent electron dynamics are probed with UV pulses. The photoelectron signal exhibits a short-lived component (τ = 85 fs) without spectral evolution followed by a long-lived component with continuous spectral evolution over tens of picoseconds. We ascribe the former to a superexcited state, most likely the Wannier exciton, and the latter to the ground electronic state of esolv -. In order to extract accurate energetics from the observed photoelectron spectra, we employ a spectral retrieval method to account for spectral broadening and shifting due to inelastic scattering of photoelectrons in the liquid. The electron binding energy (eBE) of the initial trap state of an electron is determined to be about 1.5 eV, and its biexponential increase up to 3.4 eV is observed with time constants of 2 and 31 ps, which are greater than 0.27 and 13 ps observed for esolv - created by the charge-transfer-to-solvent reaction from CH3O- to liquid methanol. The solvation dynamics of esolv - created by the electron trapping exhibit a pseudoisosbestic point at a pump-probe delay time of around 15 ps, and the peak energy of the eBE distribution rapidly changes around that time. These results indicate that there exist two trap states, both of which exhibit increasing eBE with time; however, the eBE of the shallow trap state increases only up to 2.1 eV, and transformation to a deep trap state at 25 ps occurs to reach an eBE of 3.4 eV.