Synthesis of 5-(Aryl)amino-1,2,3-triazole-containing 2,1,3-Benzothiadiazoles via Azide-Nitrile Cycloaddition Followed by Buchwald-Hartwig Reaction.

An efficient access to the novel 5-(aryl)amino-1,2,3-triazole-containing 2,1,3-benzothiadiazole derivatives has been developed. The method is based on 1,3-dipolar azide-nitrile cycloaddition followed by Buchwald-Hartwig cross-coupling to afford the corresponding N-aryl and N,N-diaryl substituted 5-amino-1,2,3-triazolyl 2,1,3-benzothiadiazoles under NHC-Pd catalysis. The one-pot diarylative Pd-catalyzed heterocyclization opens the straightforward route to triazole-linked carbazole-benzothiadiazole D-A systems. The optical and electrochemical properties of the compound obtained were investigated to estimate their potential application as emissive layers in OLED devises. The quantum yield of photoluminescence (PLQY) of the synthesized D-A derivatives depends to a large extent on electron-donating strengths of donor (D) component, reaching in some cases the values closed to 100%. Based on the most photoactive derivative and wide bandgap host material mCP, a light-emitting layer of OLED was made. The device showed a maximum brightness of 8000 cd/m2 at an applied voltage of 18 V. The maximum current efficiency of the device reaches a value of 3.29 cd/A.

Charge Carrier Mobility in Poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine Composites with Electron Acceptor Molecules.

Polymer composites based on poly(N,N'-bis-4-butylphenyl-N,N'-bisphenyl)benzidine (poly-TPD) with PCBM and copper(II) pyropheophorbide derivative (Cu-PP) were developed. In thin films of the poly-TPD and Cu-PP composites, the charge carrier mobility was investigated for the first time. In the ternary poly-TPD:PCBM:Cu-PP composite, the electron and hole mobilities are the most balanced compared to binary composites and the photoconductivity is enhanced due to the sensitization by Cu-PP in blue and red spectral ranges. The new composites are promising for use in the development of photodetectors.

Synthesis, Photo- and Electroluminescence of New Polyfluorene Copolymers Containing Dicyanostilbene and 9,10-Dicyanophenanthrene in the Main Chain.

Using palladium-catalyzed Suzuki polycondensation, we synthesized new light-emitting fluorene copolymers containing the dicyano derivatives of stilbene and phenanthrene and characterized them by gel permeation chromatography, UV-vis absorption spectroscopy, spectrofluorimetry, and cyclic voltammetry. The photoluminescence spectra of the synthesized polymers show significant energy transfer from the fluorene segments to the dicyanostilbene and 9,10-dicyanophenanthrene units, which is in agreement with the data of theoretical calculations. OLEDs based on these polymers were fabricated with an ITO/PEDOT-PSS (35 nm)/p-TPD (30 nm)/PVK (5 nm)/light emitting layer (70-75 nm)/PF-PO (20 nm)/LiF (1 nm)/Al (80 nm) configuration. Examination of their electroluminescence revealed that copolymers of fluorene with dicyanostilbene show yellow-green luminescence, while polymers with 9,10-dicyanophenanthrene have a greenish-blue emission. The 9,10-dicyanophenanthrene units have a more rigid structure compared to dicyanostilbene and, in OLEDs based on them, an increase in maximum brightness is observed with an increase in the content of the additive to the polymer chain. In particular, the device using fluorene copolymer with 9,10-dicyanophenanthrene (2.5 mol%) exhibited a maximum brightness of 9230 cd/m2 and a maximum current efficiency of 3.33 cd/A.

Propylene Oxide Addition Effect on the Chemical Speciation of a Fuel-Rich Premixed n-Heptane/Toluene Flame.

1,2-Propylene oxide (PO, C3H6O) is considered as a promising agent for improving fuel. In this work, the effect of PO additives on the species pool in a premixed burner-stabilized fuel-rich (ϕ = 1.6) flame fueled by n-heptane/toluene mixture (7/3 by volume of liquids) at atmospheric pressure is studied by the flame-sampling molecular beam mass spectrometry and numerical modeling in order to get insight into the chemical aspects of the influence of oxygenates with an epoxy group on the formation of abundant intermediates (including PAH precursors) during combustion of fossil fuels. The flames with various loadings of PO in the fuel blend (from 0 to 16.3% in mole basis) are examined, and detailed kinetic mechanisms available in the literature are validated against the measurements of mole fraction profiles of reactants, major products, and many intermediate species. A higher reactivity of the fresh mixture and a reduction in the peak mole fractions of intermediates playing an important role in PAH formation (benzene, styrene, ethylbenzene, phenol, acetylene, diacetylene, etc.) are observed when PO is added. This was found to be due to simultaneously two factors: the partial replacement of "sooting" fuel (toluene, which is the main precursor of these species) with oxygenated additive, and the changes in the flame radical pool caused by PO addition. Propylene oxide additive was found to change the ratio between H, OH, O, and CH3 toward an increase in the proportion of O and CH3. The detailed kinetic mechanisms considered in the work are found to overpredict the peak mole fraction of acetylene, a key species playing a crucial role in PAH growth. Its chemistry is revisited in order to provide a better prediction of C2H2 and, as a result, PAHs.

Improving the Predictive Accuracy for Ketene in Diacetyl Laminar Premixed Flames: Experiment and Model Analysis.

Ketene is an important species in core mechanisms for the combustion of hydrocarbon and oxygenated fuels, but direct experiments with ketene are challenging to conduct due to its high reactivity. Diacetyl can be used as a precursor of ketene, and abundant ketene is present in premixed flames of diacetyl. However, predictions of ketene in diacetyl flames with previous models have significant uncertainties. The study of Sun et al. [Sun, W.; Wang, J.; Huang, C.; Hansen, N.; Yang, B. Combust. Flame, 2019, 205, 11-21, DOI: 10.1016/j.combustflame.2019.03.037] shows that the flame structure measurements should be performed under certain conditions to improve the predictive accuracy of ketene in diacetyl flames. In this work, the structures of three laminar premixed flames of diacetyl under atmospheric pressure in a range of equivalence ratios are examined with flame-sampling molecular-beam mass spectrometry (MBMS). With the new experimental data and the data available in literature, Bayesian analysis is performed to optimize the kinetic model. The obtained optimized model is compared with the original one, and the results show that the optimized model agrees better with the experimental data than the original one. The uncertainties of the rate coefficients of some key reactions are constrained with these experimental data, which eventually leads to smaller modeling uncertainties for ketene concentrations under studied conditions.

The Influence of Structural Variants of the CES1 Gene on the Pharmacokinetics of Enalapril, Presumably Due to Linkage Disequilibrium with the Intronic rs2244613.

Variants in the CES1 gene encoding carboxylesterase 1 may affect the metabolism of enalapril to the active metabolite enalaprilat. It was shown that the A allele of rs71647871 and the C allele of rs2244613 led to a decrease in plasma enalaprilat concentrations. This study aimed to estimate the effect of structural haplotypes of CES1 containing the pseudogene CES1P1, or a hybrid of the gene and the pseudogene CES1A2, on the pharmacokinetics of enalapril. We included 286 Caucasian patients with arterial hypertension treated with enalapril. Genotyping was performed using real-time PCR and long-range PCR. Peak and trough plasma enalaprilat concentrations were lower in carriers of CES1A2. The studied haplotypes were in linkage disequilibrium with rs2244613: generally, the A allele was in the haplotype containing the CES1P1, and the C allele was in the haplotype with the CES1A2. Thus, carriers of CES1A2 have reduced CES1 activity against enalapril. Linkage disequilibrium of the haplotype containing the CES1P1 or CES1A2 with rs2244613 should be taken into account when genotyping the CES1 gene.

The Influence of the CES1 Genotype on the Pharmacokinetics of Enalapril in Patients with Arterial Hypertension.

The angiotensin-converting enzyme inhibitor enalapril is hydrolysed to an active metabolite, enalaprilat, in the liver via carboxylesterase 1 (CES1). Previous studies show that variant rs71647871 in the CES1 gene affects the pharmacokinetics of enalapril on liver samples as well as healthy volunteers. This study included 286 Caucasian patients with arterial hypertension who received enalapril. The concentrations of enalapril and enalaprilat were determined before subsequent intake of the drug and 4 h after it with high-performance liquid chromatography (HPLC) and mass spectrometric detection. The study included genetic markers as follows: rs2244613, rs71647871 (c.428G>A, p.G143E) and three SNPs indicating the presence of a subtype CES1A1c (rs12149368, rs111604615 and rs201577108). Mean peak and trough enalaprilat concentrations, adjusted by clinical variables, were significantly lower in CES1 rs2244613 heterozygotes (by 16.6% and 19.6%) and in CC homozygotes (by 32.7% and 41.4%) vs. the AA genotype. In CES1A1c homozygotes, adjusted mean enalaprilat concentrations were 75% lower vs. heterozygotes and wild-type (WT) homozygotes. Pharmacogenetic markers of the CES1 gene may be a promising predictor for individualisation when prescribing enalapril.

New Unsymmetrically Substituted Benzothiadiazole-Based Luminophores: Synthesis, Optical, Electrochemical Studies, Charge Transport, and Electroluminescent Characteristics.

Three new benzothiadiazole (BTD)-containing luminophores with different configurations of aryl linkers have been prepared via Pd-catalyzed cross-coupling Suzuki and Buchwald-Hartwig reactions. Photophysical and electroluminescent properties of the compounds were investigated to estimate their potential for optoelectronic applications. All synthesized structures have sufficiently high quantum yields in film. The BTD with aryl bridged carbazole unit demonstrated the highest electrons and holes mobility in a series. OLED with light-emitting layer (EML) based on this compound exhibited the highest brightness, as well as current and luminous efficiency. The synthesized compounds are not only luminophores with a high photoluminescence quantum yield, but also active transport centers for charge carriers in EML of OLED devices.

Effect of Cp-Ligand Methylation on Rhodium(III)-Catalyzed Annulations of Aromatic Carboxylic Acids with Alkynes: Synthesis of Isocoumarins and PAHs for Organic Light-Emitting Devices.

An efficient protocol was developed for the synthesis of π-extended isocoumarins and polycyclic aromatic hydrocarbons based on the oxidative coupling of aromatic carboxylic acids with internal alkynes catalyzed by (cyclopentadienyl)rhodium complexes. The coupling chemoselectivity strongly depends on whether Cp or the methylated Cp* ligands are used. The pentamethyl derivative [Cp*RhCl2 ]2 predominantly gives isocoumarins, while the non-methylated complex [CpRhI2 ]n produces naphthalene derivatives. The polyaromatic carboxylic acids (such as 1-naphthoic acid, 1-pyrenecarboxylic acid, fluorene-1-carboxylic acid, and dibenzofuran-4-carboxylic acid) are suitable for this approach. A mixture of Cp*H/RhCl3 can be used as a catalyst instead of [Cp*RhCl2 ]2 . The structures of 3,4-diphenylindeno[1,2-h]isochromen-1(11H)-one and 7,10-dimethyl-8,9-diphenylbenzo[pqr]tetraphene were determined by X-ray diffraction. In addition, the optical properties of the prepared compounds were studied. 7,8-Diphenyl-10H-phenaleno[1,9-gh]isochromen-10-one was employed as an emissive layer for OLED manufacturing. The OLED emits yellow-green light with a maximum intensity 1740 cd ⋅ m-2 at 15 V.

Electrical Excitation of Long-Range Surface Plasmons in PC/OLED Structure with Two Metal Nanolayers.

A current-driven source of long-range surface plasmons (LRSPs) on a duplex metal nanolayer is reported. Electrical excitation of LRSPs was experimentally observed in a planar structure, where an organic light-emitting film was sandwiched between two metal nanolayers that served as electrodes. To achieve the LRSP propagation in these metal nanolayers at the interface with air, the light-emitting structure was bordered by a one-dimensional photonic crystal (PC) on the other side. The dispersion of the light emitted by such a hybrid PC/organic-light-emitting-diode structure (PC/OLED) comprising two thin metal electrodes was obtained, with a clearly identified LRSP resonance peak.

LMCT facilitated room temperature phosphorescence and energy transfer in substituted thiophenolates of Gd and Yb.

To obtain luminescent lanthanide complexes with a low energy LMCT state the 2-(2'-mercaptophenyl)benzothiazolates, Ln(SSN)3, and 2-(2'-mercaptophenyl)benzoxazolates, Ln2(OSN)6 (Ln = Gd, Yb), were synthesized by the reaction of amides Ln[N(SiMe3)2]3 with respective thiophenols. Ytterbium complexes were structurally characterized by X-ray diffraction analysis. Cyclic voltammetry revealed that the deprotonated mercaptophenyl ligands have significantly lower oxidation potentials than their phenoxy analogues and some ß-diketones. The photophysical properties of Gd and Yb compounds were studied both in solution and in the solid state. The fluorescence spectra of the compounds in solution display the bands of the keto and enol forms of the ligands. No energy transfer from the organic part to Yb3+ has been detected in solutions of both Yb complexes, whereas in solids an intense metal-centered emission in the near infrared region was observed. The solid Gd compounds exhibited room temperature phosphorescence caused by unusually efficient intersystem crossing facilitated by the essentially reducing properties of OSN and SSN ligands. To explain the sensitization process occurring in solids Yb2(OSN)6 and Yb(SSN)3 a specific non-resonant energy transfer mechanism via a ligand to metal charge transfer state has been proposed. Based on the Yb derivatives, NIR-emitting OLEDs with 860 µW cm-2 maximal irradiance were obtained. Their Gd counterparts showed bright electrophosphorescence (up to 1350 cd m-2) in the devices containing doped emission layers.