GM-CSF Production Allows the Identification of Immunoprevalent Antigens Recognized by Human CD4+ T Cells Following Smallpox Vaccination

The threat of bioterrorism with smallpox and the broad use of vaccinia vectors for other vaccines have led to the resurgence in the study of vaccinia immunological memory. The importance of the role of CD4+ T cells in the control of vaccinia infection is well known. However, more CD8+ than CD4+ T cell epitopes recognized by human subjects immunized with vaccinia virus have been reported. This could be, in part, due to the fact that most of the studies that have identified human CD4+ specific protein-derived fragments or peptides have used IFN-γ production to evaluate vaccinia specific T cell responses. Based on these findings, we reasoned that analyzing a large panel of cytokines would permit us to generate a more complete analysis of the CD4 T cell responses. The results presented provide clear evidence that TNF-α is an excellent readout of vaccinia specificity and that other cytokines such as GM-CSF can be used to evaluate the reactivity of CD4+ T cells in response to vaccinia antigens. Furthermore, using these cytokines as readout of vaccinia specificity, we present the identification of novel peptides from immunoprevalent vaccinia proteins recognized by CD4+ T cells derived from smallpox vaccinated human subjects. In conclusion, we describe a “T cell–driven” methodology that can be implemented to determine the specificity of the T cell response upon vaccination or infection. Together, the single pathogen in vitro stimulation, the selection of CD4+ T cells specific to the pathogen by limiting dilution, the evaluation of pathogen specificity by detecting multiple cytokines, and the screening of the clones with synthetic combinatorial libraries, constitutes a novel and valuable approach for the elucidation of human CD4+ T cell specificity in response to large pathogens

The role of fullerenes in the environmental stability of polymer:fullerene solar cells

Environmental stability is a common challenge for the commercialisation of low cost, encapsulation-free organic opto-electronic devices. Understanding the role of materials degradation is the key to address this challenge, but most such studies have been limited to conjugated polymers. Here we quantitatively study the role of the common fullerene derivative PCBM in limiting the stability of benchmark organic solar cells, showing that a minor fraction (<1%) of photo-oxidised PCBM, induced by short exposure to either solar or ambient laboratory lighting conditions in air, consistent with typical processing and operating conditions, is sufficient to compromise device performance severely. We identify the effects of photo-oxidation of PCBM on its chemical structure, and connect this to specific changes in its electronic structure, which significantly alter the electron transport and recombination kinetics. The effect of photo-oxidation on device current–voltage characteristics, electron mobility and density of states could all be explained with the same model of photoinduced defects acting as trap states. Our results demonstrate that the photochemical instability of PCBM and chemically similar fullerenes remains a barrier for the commercialisation of organic opto-electronic devices

Author Correction: Drivers of seedling establishment success in dryland restoration efforts

1 Pág. Correción errata.In the version of this Article originally published, the surname of author Tina Parkhurst was incorrectly written as Schroeder. This has now been corrected.Peer reviewe

Effect of multiple adduct fullerenes on charge generation and transport in photovoltaic blends with poly(3-hexylthiophene-2,5-diyl)

The effect of replacing [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) by its multiadduct analogs (bis-PCBM and tris-PCBM) in bulk heterojunction organic solar cells with poly(3-hexylthiophene-2,5-diyl) (P3HT) is studied in terms of blend film microstructure, photophysics, electron transport properties, and device performance. Although the power conversion efficiency of the blend with bis-PCBM is similar to the blend with PCBM, the performance of the devices with tris-PCBM is considerably lower as a result of small photocurrent. Despite the lower electron affinity of the fullerene multiadducts, μs-ms transient absorption measurements show that the charge generation efficiency is similar for all three fullerenes. The annealed blend films with multiadducts show a lower degree of fullerene aggregation and lower P3HT crystallinity than the annealed blend films with PCBM. We conclude that the reduction in performance is due largely to poorer electron transport in the blend films from higher adducts, due to the poorer fullerene network formation as well as the slower electron transport within the fullerene phase, confirmed here by field effect transistor measurements. © 2010 Wiley Periodicals, Inc

Quantifying Losses in Open-Circuit Voltage in Solution-Processable Solar Cells

The maximum open-circuit voltage of a solar cell can be evaluated in terms of its ability to emit light. We herein verify the reciprocity relation between the electroluminescence spectrum and subband-gap quantum efficiency spectrum for several photovoltaic technologies at different stages of commercial development, including inorganic, organic, and a type of methyl-ammonium lead- halide CH3NH3PbI3−xClx perovskite solar cells. Based on the detailed balance theory and reciprocity relations between light emission and light absorption, voltage losses at open circuit are quantified and assigned to specific mechanisms, namely, absorption edge broadening and nonradiative recombination. The voltage loss due to nonradiative recombination is low for inorganic solar cells (0.04–0.21 V), while for organic solar cell devices it is larger but surprisingly uniform, with values of 0.34–0.44 V for a range of material combinations. We show that, in CH3NH3PbI3−xClx perovskite solar cells that exhibit hysteresis, the loss to nonradiative recombination varies substantially with voltage scan conditions. We then show that for different solar cell technologies there is a roughly linear relation between the power conversion efficiency and the voltage loss due to nonradiative recombination

Effect of multiple adduct fullerenes on microstructure and phase behavior of P3HT:Fullerene blend films for organic solar cells

The bis and tris adducts of [6,6]phenyl-C61-butyric acid methyl ester (PCBM) offer lower reduction potentials than PCBM and are therefore expected to offer larger open-circuit voltages and more efficient energy conversion when blended with conjugated polymers in photovoltaic devices in place of PCBM. However, poor photovoltaic device performances are commonly observed when PCBM is replaced with higher-adduct fullerenes. In this work, we use transmission electron microscopy (TEM), steady-state and ultrafast time-resolved photoluminescence spectroscopy (PL), and differential scanning calorimetry (DSC) to probe the microstructural properties of blend films of poly(3-hexylthiophene-2,5-diyl) (P3HT) with the bis and tris adducts of PCBM. TEM and PL indicate that, in as-spun blend films, fullerenes become less soluble in P3HT as the number of adducts increases. PL indicates that upon annealing crystallization leads to phase separation in P3HT:PCBM samples only. DSC studies indicate that the interactions between P3HT and the fullerene become weaker with higher-adduct fullerenes and that all systems exhibit eutectic phase behavior with a eutectic composition being shifted to higher molar fullerene content for higher-adduct fullerenes. We propose two different mechanisms of microstructure development for PCBM and higher-adduct fullerenes. P3HT:PCBM blends, phase segregation is the result of crystallization of either one or both components and is facilitated by thermal treatments. In contrast, for blends containing higher adducts, the phase separation is due to a partial demixing of the amorphous phases. We rationalize the lower photocurrent generation by the higher-adduct fullerene blends in terms of film microstructure

Competition between the Charge Transfer State and the Singlet States of Donor or Acceptor Limiting the Efficiency in Polymer:Fullerene Solar Cells

We study the appearance and energy of the charge transfer (CT) state using measurements of electroluminescence (EL) and photoluminescence (PL) in blend films of high-performance polymers with fullerene acceptors. EL spectroscopy provides a direct probe of the energy of the interfacial states without the need to rely on the LUMO and HOMO energies as estimated in pristine materials. For each polymer, we use different fullerenes with varying LUMO levels as electron acceptors, in order to vary the energy of the CT state relative to the blend with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). As the energy of the CT state emission approaches the absorption onset of the blend component with the smaller optical bandgap, <i>E</i>_opt,min ≡ min­{<i>E</i>_opt,donor; <i>E</i>_opt,acceptor}, we observe a transition in the EL spectrum from CT emission to singlet emission from the component with the smaller bandgap. The appearance of component singlet emission coincides with reduced photocurrent and fill factor. We conclude that the open circuit voltage <i>V</i>_OC is limited by the smaller bandgap of the two blend components. From the losses of the studied materials, we derive an empirical limit for the open circuit voltage: <i>V</i>_OC ≲ <i>E</i>_opt,min/<i>e</i> – (0.66 ± 0.08)­eV