Limiting factors for charge generation in low-offset fullerene-based organic solar cells.

Free charge generation after photoexcitation of donor or acceptor molecules in organic solar cells generally proceeds via (1) formation of charge transfer states and (2) their dissociation into charge separated states. Research often either focuses on the first component or the combined effect of both processes. Here, we provide evidence that charge transfer state dissociation rather than formation presents a major bottleneck for free charge generation in fullerene-based blends with low energetic offsets between singlet and charge transfer states.

On the Mechanism of the Inverse Vulcanization of Elemental Sulfur: Structural Characterization of Poly(sulfur--(1,3-diisopropenylbenzene)).

Organosulfur polymers, such as those derived from elemental sulfur, are an important new class of macromolecules that have recently emerged via the inverse vulcanization process. Since the launching of this new field in 2013, the development of new monomers and organopolysulfide materials based on the inverse vulcanization process is now an active area in polymer chemistry. While numerous advances have been made over the last decade concerning this polymerization process, insights into the mechanism of inverse vulcanization and structural characterization of the high-sulfur-content copolymers that are produced remain challenging due to the increasing insolubility of the materials with a higher sulfur content.

Towards Efficient and Stable Donor-Acceptor Luminescent Radicals.

In contrast to closed-shell luminescent molecules, the electronic ground state and lowest excited state in organic luminescent radicals are both spin doublet, which results in spin-allowed radiative transitions. Most reported luminescent radicals with high photoluminescent quantum efficiency (PLQE) have a donor-acceptor (D-A•) chemical structure where an electron-donating group is covalently attached to an electron-withdrawing radical core (A•). Understanding the main factors that define the efficiency and stability of D-A• type luminescent radicals remains challenging.

Ion-modulated radical doping of spiro-OMeTAD for more efficient and stable perovskite solar cells.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis(,-di--methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4--butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping).

Impact of secondary donor units on the excited-state properties and thermally activated delayed fluorescence (TADF) efficiency of pentacarbazole-benzonitrile emitters.

The performance of organic light-emitting diodes based on thermally activated delayed fluorescence emitters depends on the efficiency of reverse intersystem crossing (RISC) processes, which are promoted by a small energy gap between the lowest singlet (S) and triplet (T) excited states and large spin-orbit couplings. Recently, it was proposed that the introduction of secondary donor units into 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN) can significantly increase the mixing between triplet states with charge-transfer (CT) and local-excitation characteristics and consequently increase the spin-orbit couplings. Here, the results of long-range corrected density functional theory calculations show that the main impact on the RISC rates of substituting 5CzBN with secondary donors is due to a decrease in adiabatic singlet-triplet energy gaps and intramolecular reorganization energies rather than to a change in spin-orbit couplings.

Organic Neutral Radical Emitters: Impact of Chemical Substitution and Electronic-State Hybridization on the Luminescence Properties.

Neutral donor-acceptor (D-A) organic radicals have recently attracted a great deal of attention as promising luminescent materials due to their strong doublet emission. Here, we consider a series of emitters based on substituted triarylamine (TAA) donors and a radical-carrying perchlorotriphenylmethyl (PTM) acceptor. We evaluate, by means of quantum-chemical calculations and theoretical modeling, how chemical substitution affects the electronic structures and radiative and nonradiative decay rates.

Electronic Structure of Multicomponent Organic Molecular Materials: Evaluation of Range-Separated Hybrid Functionals.

Range-separated hybrid (RSH) functionals have become a tool of choice to study the and -molecular electronic states in organic materials. These functionals provide the most accurate descriptions of the electronic structure when the range-separation parameter is optimally tuned (OT). However, since the range-separation parameter is molecule dependent, this approach faces consistency issues when applied to the multicomponent systems typically found in the active layers of organic solar cells or organic light-emitting diodes (OLEDs).

Spherical Macroporous Carbon Nanotube Particles with Ultrahigh Sulfur Loading for Lithium-Sulfur Battery Cathodes.

A carbon host capable of effective and uniform sulfur loading is the key for lithium-sulfur batteries (LSBs). Despite the application of porous carbon materials of various morphologies, the carbon hosts capable of uniformly impregnating highly active sulfur is still challenging. To address this issue, we demonstrate a hierarchical pore-structured CNT particle host containing spherical macropores of several hundred nanometers.

In Situ Spectroscopic and Computational Studies on a MnO-CuO Catalyst for Use in Volatile Organic Compound Decomposition.

In situ near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory calculations were conducted to demonstrate the decomposition mechanism of propylene glycol methyl ether acetate (PGMEA) on a MnO-CuO catalyst. The catalytic activity of MnO-CuO was higher than that of MnO at low temperatures, although the pore properties of MnO were similar to those of MnO-CuO. In addition, whereas the chemical state of MnO remained constant following PGMEA dosing at 150 °C, MnO-CuO was reduced under identical conditions, as confirmed by in situ NEXAFS spectroscopy.

2q37 Deletion syndrome confirmed by high-resolution cytogenetic analysis.

Chromosome 2q37 deletion syndrome is a rare chromosomal disorder characterized by mild to moderate developmental delay, brachydactyly of the third to fifth digits or toes, short stature, obesity, hypotonia, a characteristic facial appearance, and autism spectrum disorder. Here, we report on a patient with 2q37 deletion presenting with dilated cardiomyopathy (DCMP). Congenital heart malformations have been noted in up to 20% of patients with 2q37 deletions.

Investigation of Thermally Induced Degradation in CHNHPbI Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis.

In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI perovskite film changes to an intermediate phase and decomposes to CHI, NH, and PbI after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CHNH organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI perovskites.

Clinical and endocrine characteristics and genetic analysis of Korean children with McCune-Albright syndrome: a retrospective cohort study.

Background: McCune-Albright syndrome (MAS) is a rare disease defined by the triad of fibrous dysplasia (FD), café au lait spots, and peripheral precocious puberty (PP). Because of the rarity of this disease, only a few individuals with MAS have been reported in Korea. We describe the various clinical and endocrine manifestations and genetic analysis of 14 patients with MAS in Korea.

A Phase II Study of Poziotinib in Patients with Epidermal Growth Factor Receptor ()-Mutant Lung Adenocarcinoma Who Have Acquired Resistance to EGFR-Tyrosine Kinase Inhibitors.

Purpose: We examined the efficacy of poziotinib, a second-generation epidermal growth factor receptor (EGFR)-tyrosine kinase inhibitor (TKI) in patients with lung adenocarcinoma with activating mutations, who developed acquired resistance (AR) to EGFR-TKIs.

Materials And Methods: This single-arm phase II study included -mutant lung adenocarcinoma with AR to erlotinib or gefitinib based on the Jackman criteria. Patients received poziotinib 16 mg orally once daily in a 28-day cycle.

In Situ Thermal Decomposition of Exfoliated Two-Dimensional Black Phosphorus.

With a semiconducting band gap and high charge carrier mobility, two-dimensional (2D) black phosphorus (BP)—often referred to as phosphorene—holds significant promise for next generation electronics and optoelectronics. However, as a 2D material, it possesses a higher surface area to volume ratio than bulk BP, suggesting that its chemical and thermal stability will be modified. Herein, an atomic-scale microscopic and spectroscopic study is performed to characterize the thermal degradation of mechanically exfoliated 2D BP.

Optimal cut-off value of perfusion parameters for diagnosing prostate cancer and for assessing aggressiveness associated with Gleason score.

To determine cut-off value of dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI) parameters for differentiation of prostate malignant from benign and cancer with high-grade Gleason score (GS) (GS>7) from low-grade GS (GS≤7), 35 patients (24 malignant and 11 benign) who underwent DCE-MRI were included. Difference between malignant and benign was statistically significant for all magnetic resonance parameters except Ve. The cut-off values were K(trans)=0.

Effective passivation of exfoliated black phosphorus transistors against ambient degradation.

Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111) versus hydrophilic SiO2.

Use of X-ray diffraction, molecular simulations, and spectroscopy to determine the molecular packing in a polymer-fullerene bimolecular crystal.

The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels.

Chemical characterization of DNA-immobilized InAs surfaces using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure.

Single-stranded DNA immobilized on an III-V semiconductor is a potential high-sensitivity biosensor. The chemical and electronic changes occurring upon the binding of DNA to the InAs surface are essential to understanding the DNA-immobilization mechanism. In this work, the chemical properties of DNA-immobilized InAs surfaces were determined through high-resolution X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS).

Three-dimensional packing structure and electronic properties of biaxially oriented poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) films.

We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C(14)) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.

Photosensitivity reactions to vandetanib: redevelopment after sequential treatment with docetaxel.

Vandetanib (ZD6474, Zactima™) is a novel, orally available inhibitor of different intracellular signaling pathways involved in tumor growth, progression, and angiogenesis, including vascular endothelial growth factor receptor-2, epidermal growth factor receptor, and rearranged during transfection tyrosine kinase activity. The most frequently reported adverse events attributed to vandetanib include diarrhea, elevated aminotransferase, asymptomatic corrected QC interval prolongation, and hypertension. In a few randomized, double-blinded studies, cutaneous adverse events including these general symptoms have been reported, but there are only a few reports on the photosensitivity reaction to vandetanib domestically as conducted by dermatologists.

Toxicological biomarkers of 2,3,4,7,8-pentachlorodibenzofuran in proteins secreted by HepG2 cells.

Using a proteomic approach, a study was conducted for determination of the effects of 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PCDF) on proteins secreted by HepG2 cells. Briefly, HepG2 cells were exposed to various concentrations of 2,3,4,7,8-PCDF for 24 or 48h. MTT and comet assays were then conducted for determination of cytotoxicity and genotoxicity, respectively.

Comet assay analysis of DNA damage in T- and B-lymphocytes separated by MACS for human biomonitoring studies.

In this study, we developed and tested a method for human biomonitoring using Comet assays with human T- and B-lymphocytes obtained by magnetic cell sorting (MACS). We evaluated DNA damage induced by treatment with hydrogen peroxide (H(2)O(2); 5, 25 and 50μM) and methyl methane sulfonate (MMS; 5, 25 and 50μM) in both human B- and T-lymphocytes obtained by MACS, and compared their DNA damage levels. Significant, dose-dependent levels of DNA damage were found in T-lymphocytes and B-lymphocytes.

Identification of toxicological biomarkers of di(2-ethylhexyl) phthalate in proteins secreted by HepG2 cells using proteomic analysis.

The effects of di(2-ethylhexyl) phthalate (DEHP) on proteins secreted by HepG2 cells were studied using a proteomic approach. HepG2 cells were exposed to various concentrations of DEHP (0, 2.5, 5, 10, 25, 50, 100, and 250 microM) for 24 or 48 h.