Charge carrier dynamics and photovoltaic properties of near-infrared absorbing squaraine incorporated solution-processed additive-free PTB7:PCBM based ternary solar cells

The introduction of a third component vehemently modifies the morphology and charge carrier dynamics in the blend of a donor-acceptor pair, thereby affecting the photovoltaic properties of organic solar cells (OSCs). Combining steady-state, impedance, and transient spectroscopic measurements, photovoltaic properties of 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (DIB SQ) incorporated additive-free PTB7:PC70BM OSCs are assessed. As observed from steady-state measurements, concomitant enhancement in open-circuit voltage and short-circuit current has caused 33% enhancement in power conversion efficiency with good reliablity and reproducibility. On introducing 25 wt.% SQ to the OSCs, VOC has increased from 0.74 to 0.80 V while JSC has improved from 11.3 to 13.9 mAcm-2 with an increment in exciton dissociation probability rate from 81.5% to 94.9%. However, the fill factor values show inconsistent marginal variations with SQ addition. Equivalent circuit modeling of bias-voltage dependent impedance spectra along with transient photovoltage measurements reveal an improvement in effective charge carrier lifetime for the SQ incorporated OSCs, in comparison to the binary device. The addition of SQ also ensures better charge transport and extraction, as evidenced from photo-CELIV and transient photocurrent analysis. Atomic force microscopic (AFM) images confirm effective tuning of the morphology of the active layer when SQ is introduced into the binary blend, favoring efficient charge dissociation and transport. The possible operation mechanism of SQ incorporated ternary OSCs is proposed based on photoluminescence and AFM measurements. Moreover, the un-encapsulated OSC with 25 wt.% SQ has retained 91% of the initial PCE, while for the binary device, the PCE has declined to ~ 75% of the initial value after 200 hours of continous 1 sun illumination from a white LED in ambient atmosphere.

MD Simulations on a Well-Built Docking Model Reveal Fine Mechanical Stability and Force-Dependent Dissociation of Mac-1/GPIbα Complex

Interaction of leukocyte integrin macrophage-1 antigen (Mac-1) to platelet glycoprotein Ibα (GPIbα) is critical for platelet–leukocyte crosstalk in hemostasis and inflammatory responses to vessel injuries under hemodynamic environments. The mechano-regulation and its molecular basis for binding of Mac-1 to GPIbα remain unclear, mainly coming from the lack of crystal structure of the Mac-1/GPIbα complex. We herein built a Mac-1/GPIbα complex model through a novel computer strategy, which included a flexible molecular docking and system equilibrium followed by a “force-ramp + snapback” molecular dynamics (MD) simulation. With this model, a series of “ramp-clamp” steered molecular dynamics (SMD) simulations were performed to examine the GPIbα–Mac-1 interaction under various loads. The results demonstrated that the complex was mechano-stable for both the high rupture force (>250 pN) at a pulling velocity of 3 Å/ns and the conformational conservation under various constant tensile forces (≤75 pN); a catch-slip bond transition was predicted through the dissociation probability, examined with single molecular AFM measurements, reflected by the interaction energy and the interface H-bond number, and related to the force-induced allostery of the complex; besides the mutation-identified residues D222 and R218, the residues were also dominant in the binding of Mac-1 to GPIbα. This study recommended a valid computer strategy for building a likely wild-type docking model of a complex, provided a novel insight into the mechanical regulation mechanism and its molecular basis for the interaction of Mac-1 with GPIbα, and would be helpful for understanding the platelet–leukocyte interaction in hemostasis and inflammatory responses under mechano-microenvironments.

In-Depth Analysis of Organic Solar Cells Using Transport Equation and Optical Transfer Matrix Method with Detailed Analytical Derivations

Thin-film organic solar cell (OSC) performances have been investigated in detail by improved analytical computation in this work. The generation of excitons inside OSC has been estimated by using the optical transfer matrix method (OTMM) to include the optical phenomena of the incident light. The dissociation of these excitons into free charge carriers has been investigated to find the most appropriate one. OSC performances have been evaluated by an improved analytical solution of electrical transport equations including (i) exciton generation obtained from OTMM, (ii) dissociation probability incorporating Gaussian distribution to account for the natural fact of the difference in photon-energy producing excitons, (iii) recombination of charge carriers, all together. OSC properties such as JSC, VOC, FF, PCE, Pmax, absorbance, and quantum efficiency have been investigated with the variation of different parameters; this might be useful to improve OSC. Again, the presented detailed derivations of analytical expressions would be helpful for clear understanding.

Biphasic Force-Regulated Phosphorylation Site Exposure and Unligation of ERM Bound with PSGL-1: A Novel Insight into PSGL-1 Signaling via Steered Molecular Dynamics Simulations

The PSGL-1-actin cytoskeleton linker proteins ezrin/radixin/moesin (ERM), an adaptor between P-selectin glycoprotein ligand-1 (PSGL-1) and spleen tyrosine kinase (Syk), is a key player in PSGL-1 signal, which mediates the adhesion and recruitment of leukocytes to the activated endothelial cells in flow. Binding of PSGL-1 to ERM initials intracellular signaling through inducing phosphorylation of Syk, but effects of tensile force on unligation and phosphorylation site exposure of ERM bound with PSGL-1 remains unclear. To answer this question, we performed a series of so-called “ramp-clamp” steered molecular dynamics (SMD) simulations on the radixin protein FERM domain of ERM bound with intracellular juxtamembrane PSGL-1 peptide. The results showed that, the rupture force of complex pulled with constant velocity was over 250 pN, which prevented the complex from breaking in front of pull-induced exposure of phosphorylation site on immunoreceptor tyrosine activation motif (ITAM)-like motif of ERM; the stretched complex structure under constant tensile forces <100 pN maintained on a stable quasi-equilibrium state, showing a high mechano-stabilization of the clamped complex; and, in consistent with the force-induced allostery at clamped stage, increasing tensile force (<50 pN) would decrease the complex dissociation probability but facilitate the phosphorylation site exposure, suggesting a force-enhanced biophysical connectivity of PSGL-1 signaling. These force-enhanced characters in both phosphorylation and unligation of ERM bound with PSGL-1 should be mediated by a catch-slip bond transition mechanism, in which four residue interactions on binding site were involved. This study might provide a novel insight into the transmembrane PSGL-1 signal, its biophysical connectivity and molecular structural basis for cellular immune responses in mechano-microenvironment, and showed a rational SMD-based computer strategy for predicting structure-function relation of protein under loads.

Fluorination Effect for Highly Conjugated Alternating Copolymers Involving Thienylenevinylene-Thiophene-Flanked Benzodithiophene and Benzothiadiazole Subunits in Photovoltaic Application

Two two-dimensional (2D) donor–acceptor (D-A) type conjugated polymers (CPs), namely, PBDT-TVT-BT and PBDT-TVT-FBT, in which two ((E)-(4,5-didecylthien-2-yl)vinyl)- 5-thien-2-yl (TVT) side chains were introduced into 4,8-position of benzo[1,2-b:4,5-bʹ]dithiophene (BDT) to synthesize the highly conjugated electron-donating building block BDT-TVT, and benzothiadiazole (BT) and/or 5,6-difluoro-BT as electron-accepting unit, were designed to systematically ascertain the impact of fluorination on thermal stability, optoelectronic property, and photovoltaic performance. Both resultant copolymers exhibited the lower bandgap (1.60 ~ 1.69 eV) and deeper highest occupied molecular orbital energy level (EHOMO, –5.17 ~ –5.37 eV). It was found that the narrowed absorption, deepened EHOMO and weakened aggregation in solid film but had insignificant influence on thermal stability after fluorination in PBDT-TVT-FBT. Accordingly, a PBDT-TVT-FBT-based device yielded 16% increased power conversion efficiency (PCE) from 4.50% to 5.22%, benefited from synergistically elevated VOC, JSC, and FF, which was mainly originated from deepened EHOMO, increased μh, μe, and more balanced μh/μe ratio, higher exciton dissociation probability and improved microstructural morphology of the photoactive layer as a result of incorporating fluorine into the polymer backbone.

Effect of Flank Rotation on the Photovoltaic Properties of Dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene-Based Narrow Band Gap Copolymers

Side chain engineering has been an effective approach to modulate the solution processability, optoelectronic properties and miscibility of conjugated polymers (CPs) for organic/polymeric photovoltaic cells (PVCs). As compared with the most commonly used method of introducing alkyl chains, the employment of alkyl-substituted aryl flanks would provide two-dimensional (2-D) CPs having solution processability alongside additional merits like deepened highest occupied molecular orbital (HOMO) energy levels, increased absorption coefficient and charger transporting, etc. In this paper, the triple C≡C bond was used as conjugated linker to decrease the steric hindrance between the flanks of 4,5-didecylthien-2-yl (T) and dithieno[2,3-d:2’,3’-d’]benzo[1,2-b:4,5-b’]dithiophene (DTBDT) core. In addition, an alternating CP derived from 4,5-didecylthien-2-yl-ethynyl (TE) flanked DTBDT, and 4,9-bis(4-octylthien-2-yl) naphtho[1,2-c:5,6-c’]bis[1,2,5]thiadiazole (DTNT), named as PDTBDT-TE-DTNT, was synthesized and characterized. As compared with the controlled PDTBDT-T-DTNT, which was derived from 4,5-didecylthien-2-yl flanked DTBDT and DTNT, the results for exciton dissociation probability, density functional theory (DFT), time-resolved photoluminescence (PL) measurements, etc., revealed that the lower steric hindrance between TE and DTBDT might lead to the easier rotation of the TE flanks, thus contributing to the decrease of the exciton lifetime and dissociation probability, finally suppressing the short-circuit current density (JSC), etc., of the photovoltaic devices from PDTBDT-TE-DTNT.

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

The activation of molecular O2 as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2 activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2 dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2 dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2 dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.

Towards controlling the dissociation probability by light-induced conical intersections

Light-induced conical intersections (LICIs) can be formed both by standing or by running laser waves. The position of a LICI is determined by the laser frequency while the laser intensity controls the strength of the nonadiabatic coupling. Recently, it was shown within the LICI framework that linearly chirped laser pulses have an impact on the dissociation dynamics of the D2+molecule (J. Chem. Phys.,143, 014305, (2015);J. Chem. Phys.,144, 074309, (2016)). In this work we exploit this finding and perform calculations using chirped laser pulses in which the time dependence of the laser frequency is designed so as to force the LICI to move together with the field-free vibrational wave packet as much as possible. Since nonadiabaticity is strongest in the vicinity of the conical intersection, this is the first step towards controlling the dissociation processviathe LICI. Our showcase example is again the D2+molecular ion. To demonstrate the impact of the LICIs on the dynamical properties of diatomics, the total dissociation probabilities and the population of the different vibrational levels after the dissociation process are studied and discussed.