Anthracene Derivatives Research Articles

Cyclic (amino)(barrelene)carbenes: an original family of CAACs through a novel synthetic pathway.

A novel family of cyclic (alkyl)(amino)carbenes, which we name cyclic (amino)(barrelene)carbenes (CABCs) is reported. The key synthetic step involves an intramolecular [4+2] cyclization of an anthracene derivative with an alkyne. This synthetic approach allows for the attachment of both aryl and alkyl groups on the nitrogen atom. When used as ligand, two of the barrelene hydrogens are in close contact with the metal, which could stabilize low valent catalytic intermediates.

Highly sensitive detection of Tb3+ and ATP based on a novel asymmetric anthracene derivative.

A novel fluorescent sensor based on an asymmetric anthracene derivative (SSAPA) was designed and synthesized. Using this molecule, a rapid and sensitive assay for detecting Tb3+ and ATP in aqueous solutions was established. The SSAPA molecule had excellent aggregation-induced emission (AIE) performance and good aqueous dispersion ability. This molecule could coordinate with Tb3+ and the fluorescence quenched linearly with the increase in the concentration of Tb3+ from 0.005 to 1.2 μM. Since both Tb3+ and adenosine triphosphate (ATP) have strong binding ability, ATP can compete with Tb3+ from the SSAPA/Tb3+ complex leading to fluorescence recovery. In this way, a brand-new fluorescent "turn-on" assay for ATP in the range from 0.01 to 0.4 μM was developed using the Tb3+-based complex probe. The detection limits for Tb3+ and ATP both reached single-digit nanomole per millilitre (2.8 nM and 4.5 nM, respectively), which demonstrated that this method has high sensitivity. Besides, Tb3+ and ATP also could be well detected in other complex environments such as real water samples or serum samples. This study provides a feasible assay for detecting trace amounts of Tb3+ and ATP in aqueous solutions.

Изучение химического состава надземной части щавеля приморского (Rumex maritimus L.) методом высокоэффективной жидкостной хроматографии

Introduction. Golden dock (Rumex maritimus L.) is a poorly studied annual plant from the buckwheat family (Polygonaceae Juss.), used by the peoples of South-East Asia to treat a number of diseases. The methanol extract of golden dock has several beneficial properties, including antibacterial activity. At the same time, the chemical composition of the plant is studied fragmentarily. Aim. To determine the qualitative composition of the aerial part of golden dock by high-performance liquid chromatography (HPLC). Materials and Methods. The dried aerial part of the plant at the stage of flowering and the beginning of fruiting was crushed and extracted with 95% ethanol. Ethanol was distilled off, and the extraction was treated sequentially with chloroform, ethyl acetate and n-butanol. We analyzed the obtained fractions and the aqueous residue of ethanol extraction after removal by reversed-phase HPLC. Compounds were identified using standard samples and literature data on the spectral characteristics of substances. Results. Phytochemical analysis of the aerial part of golden dock by reversed-phase HPLC showed the presence of such substances as anthraquinones, flavonoids, stilbenes, phenolic acids. In the chloroform fraction, anthracene derivatives of emodin, chrysophanol, fiscion, isochrysophanol, the flavonoid vogeletin were identified; in the ethyl acetate fraction – phenolic acids: gallic, syringic, p-coumaric, ferulic, trans-stilbene derivative resveratrol, as well as the flavonoids rutin and quercetin; in the butanol fraction – caffeic acid and catechin; in the aqueous residue – epigallocatechin-3-gallate and epicatechin-3-gallate.

Arrangements of fluorophores in the salts of imidazole tethered anthracene derivatives with pyridinedicarboxylic acids influencing photoluminescence

Self-assemblies of salts of 9-N-(3-imidazolylpropylamino)methylanthracene with pyridinedicarboxylic acids, ionic-cocrystals with 1,3-dihydroxybenzene and their aggregation induced emissions in the solid state were studied.

Study on the different mechanoluminescence of anthracene derivatives

The mechanoluminescence (ML) properties of anthracene derivatives were studied.

Phytochemical Study and Evaluation of the Antiradical Activity of Extracts of Oleaginous Seeds of <i>Panda oleosa</i> and <i>Isolona hexaloba</i> from Gabon

Our study focused on phytochemical tests and evaluation of the anti-free radical activity of seed extracts of two oleaginous plants from Gabon used in traditional medicine or as condiments: Panda oleosa and Isolona hexaloba. The extraction was carried out by maceration with solvents of increasing polarity: cyclohexane, trichloroethylene, acetone, ethanol and finally distilled water. The total yields of the extracts are about 69.50% for Panda oleosa and 34.28% for Isolona hexaloba. The phytochemical tests carried out on the extracts of the seeds of Panda and Isolona highlight in both seeds the presence of alkaloids, polyphenols, triterpenes, carotenoids, reducing compounds, flavonoids, total sugars, coumarins, anthraquinones, free quinones, free anthracene derivatives, and terpenoids. Isolona seeds also contain leucoanthocyanins, sterols, cardiac glycosides and saponins. Phytochemical tests revealed the absence of tannins and mucilage in both seeds. The free radical scavenging activity was measured by scavenging the free radical cation of 2,2’-azino-bis[3-ethylbenzothiazoline-6-sulfonic acid] (ABTS-+) with gallic acid as the reference antioxidant. The results of the free radical scavenging activity of the aqueous and ethanolic extracts of both seeds showed that the aqueous extracts were more active than the ethanolic extracts. The IC50s of the aqueous and ethanolic extracts of Panda seeds are 40 and 60 μg·mL-1 respectively, and those of the aqueous and ethanolic extracts of Isolona are 37.5 and 95 μg·mL-1 respectively. Gallic acid, the reference antioxidant (IC50 = 0.37 μg·mL-1) is about 10 times more active than the aqueous extracts of both seeds, 16 times more active than the ethanolic extract of Panda and 25 times more active than the ethanolic extract of Isolena.

Anthracene and carbazole based asymmetric fluorescent materials for high-efficiency deep-blue non-doped organic light emitting devices with CIEy=0.06

Deep-Blue emitting materials have important applications in field of optoelectronics. However, their development with high color purity faces great challenges due to inherent wide energy gap. Herein, three anthracene-based fluorescent materials (pCzAnN, mCzAnN and 3CzAnN) were designed and synthesized by adjusting the linking position of anthracene to carbazole. These three twisted anthracene derivatives exhibited deep blue emission in toluene solution and thin film. Their electroluminescent performances was investigated by fabricating non-doped organic light-emitting diodes (OLEDs), exhibiting deep-blue emission with peaks at 444, 440 and 448 nm. The device performance based on pCzAnN as the emitter achieved a low turn-on voltage of 3.3 V, external quantum efficiency of 6.0%, deep-blue emission at 444 nm with good color purity CIE coordinates (0.15, 0.07) and a narrow full width at half maximum of 50 nm.

Study on the relationship between structure and fluorescence properties of anthracene derivatives

We have designed and synthesized five anthracene derivatives using quinoa perch ether and 2-acetaldehyde pyridine or 4-acetaldehyde pyridine as raw material. Five compounds are 2-(9,10- dihydro-2,3,6,7-tetramethoxy-10-(pyridin-2-yl) anthracen-9- yl)pyridine (1), 2-(2,3,6, 7-tetramethoxy-10-(pyridin-2-yl)anthracen-9-yl) pyridine (2), 4-(9,10-dihydro-2,3,6,7 -tetramethoxy-10-(pyridin-4-yl) anthracen-9-yl) pyridine (3), 4-(2,3,6,7-tetramethoxy- 10-(pyridin-4-yl)anthracen-9-yl) pyridine (4), and 4-(2,3,6,7- tetramethoxy-10-(pyridine-4-yl)anthracen-9-yl) pyridine nitrate (5), respectively. Their single crystals were obtained and determined by X-ray diffraction analysis, and their Hirshfeld surface analysis has also been done. Different compounds with different structures can be obtained from the same raw material by changing the reaction conditions and the concentration of acid. Their fluorescence properties also changed greatly. Structural analysis showed that compounds (1) and (3) were chiral compounds. Both C9, C18 in compound (1) and C6, C15 in compound (3) are chiral carbon atoms. However, when compounds (1) and (3) lose their two protons and become compounds (2) and (4), respectively, which can form an π-conjugated system, there are no chiral carbon atoms and have fluorescence. It lays a foundation for the potential applications of these compounds in the future.

Miniaturization of Anthracene-Containing Nonapeptides for Selective Precipitation/Recovery of Metallic Gold from Aqueous Solutions Containing Gold and Platinum Ions

The separation and recovery of noble metals is increasingly of interest, in particular the recovery of gold nanocrystals, which have applications in medicine and industry. Typically, metal recovery is performed using liquid–liquid extraction or electrowinning. However, it is necessary to develop noble metal recovery systems providing high selectivity in conjunction with a one-pot setup, ready product recovery, and the use of dilute aqueous solutions. In prior work, our group developed a selective gold recovery process using peptides. This previous research showed that RU065, a nonapeptide containing an anthracene moiety (at a concentration of 2.0 × 10−4 M), is capable of selective reduction of HAuCl4 to recover gold from a solution of HAuCl4 and H2PtCl6, each at 5.0 × 10−5 M. However, peptide molecules are generally costly to synthesize, and therefore it is important to determine the minimum required structural features to design non-peptide anthracene derivatives that could reduce operational costs. In this study, we used RU065 together with 23 of its fragment peptides and investigated the selective precipitation/recovery of metallic gold. RU0654–8, a fragment peptide comprising five amino acid residues (having two lysine, one L-isoleusine, and one L-alanine residue (representing six amide groups) along with an L-2-anthrylalanine residue) provided an Au/Pt atomic ratio of approximately 8, which was comparable to that for the full-length original RU065. The structural features identified in this study are expected to contribute to the design of non-peptide anthracene derivatives for low-cost, one-pot selective gold recovery.

Synthesis and photophysical properties of tricyclic boron compounds. Experimental and theoretical study

The one pot reaction of 5-formyl-2-furanboronic acid, arylamines (aniline, 2-aminoanthracene or 1-aminopyrene) and aminophenol derivatives (2-aminophenol, 2-amino-5-chlorophenol or 2-amino-5-nitrophenol) yielded tricyclic boronate species, involving an open furan ring process. The boron compounds obtained have a π delocalized structural skeleton having photophysical properties. All seven compounds showed colorimetric properties in solvents with different dielectric constant, and the solvatochromic effect was denoted from the UV–vis spectra. Compounds also showed luminescence when irradiated with UV to 365 nm, nevertheless low fluorescence quantum yield in DMSO was observed (8–33%). Compounds present stability in DMSO solution up to for 96 h but degradation is recorded in THF solution in only 2.5 h. Computational studies were carried out using DFT/PBE1PBE for S0 state and TD-DFT/PBE1PBE for S1 state. The effect of solvent on transition wavelengths was simulated using the polarizable continuum model (PCM). It was observed that the substitution of the hydrogen atom by the chlorine atom stabilize the HOMO and LUMO levels, therefore, the transition energy values decrease for those orbitals in chlorophenol derivative compounds (3, 5 and 7), in comparison with the aminophenol analogues (2, 4 and 6). Furthermore, energy difference between the HOMO – LUMO orbitals decrease for structures having a major π conjugation extension, thus, the band gap energy for pyrene and anthracene derivatives is smaller than in phenyl derivatives.

Breaking the Efficiency Limit of Deep-Blue Fluorescent OLEDs Based on Anthracene Derivatives.

Triplet harvesting is important for the realization of high-efficiency fluorescent organic light-emitting diodes (OLEDs). Triplet-triplet annihilation (TTA) is one triplet-harvesting strategy. However, for blue-emitting anthracene derivatives, the theoretical maximum radiative singlet-exciton ratio generated from the TTA process is known to be 15% in addition to the initially generated singlets of 25%, which is insufficient for high-efficiency fluorescent devices. In this study, nearly 25% of the radiative singlet-exciton ratio is realized by TTA using an anthracene derivative, breaking the theoretical limit. As a result, efficient deep-blue TTA fluorescent devices are developed, exhibiting external quantum efficiencies of 10.2% and 8.6% with Commission Internationale de l'Eclairage color coordinates of (0.134, 0.131) and (0.137, 0.076), respectively. The theoretical model provided herein explains the experimental results considering both the TTA and reverse intersystem crossing to a singlet state from higher triplet states formed by the TTA, clearly demonstrating that the radiative singlet ratio generated from TTA can reach 37.5% (total radiative singlet-exciton ratio: 62.5%), well above 15% (total 40%), despite the molecule having S1 , T2 <2T1 < Q1 energy levels, which will lead to the development of high-efficiency fluorescent OLEDs with external quantum efficiencies exceeding 28% if the outcoupling efficiency is 45%.

Recycling of Triplets into Singlets for High‐Performance Organic Lasers

AbstractAchieving continuous‐wave (CW) lasing in organic semiconductors is known to be a difficult task because long‐lived triplets quench radiative singlets via singlet–triplet annihilation (STA). To avoid STA and operate organic lasers in CW or long‐pulse photoexcitation, the triplets need to be removed from an organic laser gain medium. However, this triplet removal leads to a loss of excitons. In addition to removing the detrimental triplets, here it is reported a triplet recycling process, which includes triplet scavenging and successive triplet upconversion via triplet–triplet annihilation (TTA) to regenerate emissive singlet excitons in a laser medium. An anthracene derivative of 9‐(1‐naphthalenyl)‐10‐(4‐(2‐naphthalenyl)phenyl)anthracene (NaNaP‐A) and a laser dye of 4,4′‐bis[4‐(diphenylamino)styryl]biphenyl (BDAVBi) are used as the triplet recycling sensitizer and the emitting laser dye, respectively. In this laser system, NaNaP‐A can efficiently scavenge the triplets formed on BDAVBi because the triplet level is deeper for NaNaP‐A than for BDAVBi, and then NaNaP‐A successively recycles the triplets into the BDAVBi's singlet state via TTA. The TTA compensates and overcomes the STA in this laser system. Hence, these laser devices can be operated with long pulse widths of up to 10 ms. This unique triplet recycling behavior is confirmed by transient photoluminescence (PL) and electroluminescence (EL) studies.

Ring Construction by 1,1‐Carboboration; Making Anthracene Derivatives from a Tetra(alkynyl)benzene

Abstract1,2,4,5‐Tetrakis(trimethylsilylethynyl)benzene reacted with two molar equivalents of the boranes R−B(C6F5)2 (R=C6F5, Me, Ph) in a series of sequential 1,1‐carboboration reactions to give ca. 1 : 1 mixtures of the two‐fold benzannulated products, namely the respective C2h and C2v symmetric tetra‐silyl, bis‐boryl substituted anthracenes. Their active B(C6F5)2 substituents were used for consecutive Suzuki‐Miyaura C−C coupling reactions to give boron‐free phenyl or 2‐pyridyl substituted anthracene products.

Constructing Highly Efficient Blue OLEDs with External Quantum Efficiencies up to 7.5 % Based on Anthracene Derivatives

Acquiring desirable device performance with deep-blue color purity that fulfills practical application requirements is still a challenge. Bipolar fluorescent emitters with hybrid local and charge transfer (HLCT) state may serve to address this issue. Herein, by inserting anthracene core in the deep-blue building blocks, the authors successfully developed two highly twisted D-π-A fluorescent emitters, ICz-An-PPI and IP-An-PPI, featuring different acceptor groups. Both exhibited superb thermal stabilities, high photo luminescent quantum yields and excellent bipolar transport capabilities. The non-doped OLEDs using ICz-An-PPI and IP-An-PPI as the emitting layers showed efficient blue emission with an external quantum efficiency (EQEmax ) of 4.32 % and 5.41 %, and the CIE coordinates of (0.147, 0.180) and (0.149, 0.150), respectively. In addition, the deep blue doped device based on ICz-An-PPI was achieved with an excellent CEmax of 5.83 cd A-1 , EQEmax of 4.6 % and the CIE coordinate of (0.148, 0.078), which is extremely close to the National Television Standards Committee (NTSC) standard. Particularly, IP-An-PPI-based doped device had better performance, with an EQEmax of 7.51 % and the CIE coordinate of (0.150, 0.118), which was very impressive among the recently reported deep-blue OLEDs with the CIEy <0.12. Such high performance may be attributed to the hot exciton HLCT mechanism via T7 to S2 . Our work may provide a new approach for designing high-efficiency deep-blue materials.

Investigating the Bulk Level Optoelectronic Characteristics of 10-(1,3-Dithiol-2-Ylidene)Anthracene Based Light Harvesters

Various optoelectronic properties of 10-(1,3-Dithiol-2-ylidene)anthracene based organic light harvesters were probe at solid state bulk surface. Effect of diverse conjugated π-donor-acceptor bridge, 3,4-ethylenedioxythiophene in Comp3 and phenyl for Comps1 and 2, along with two set of electron acceptor entity, an ester moiety for Comp1, a dicyanovinylene moiety for Comp2 and Comp3 was explored on various properties. The 3,4-ethylenedioxythiophene as conjugated π-bridge boost the dielectric constants, conductivity, refractive index and extinction coefficient values significantly. The dicyanovinylene is favorable than the ester group as prior moiety contributes to the p-orbitals from −2.0 to −4.0 eV. The solid states density, relative permittivity’s, extinction coefficient, indices of refraction, reflectance, and electrical conductivity displayed that anthracene derivatives may act as proficient objects in multi-purpose organic semiconductors.

Сенны листья: компонентный состав, фармакологические свойства, стандартизация

Objective: generalization and analysis of scientific data on the component composition, pharmacological properties and standardization of senna leaves. Materials and methods. The article provides an overview of scientific publications in the journals of the search platforms Scopus and PubMed, as well as the databases of the Russian Science Citation Index. The analysis of the range of herbal medicinal products was carried out according to the data of the State Registers of Medicines of the Republic of Belarus, the Russian Federation and the Republic of Kazakhstan using content analysis, comparison and generalization of data. Results. In addition to the laxative effect, determined by the presence of anthracene derivatives in senna leaves, the complex of their biologically active substances has antimicrobial, hypoglycemic, antioxidant, antifungal and antitumor effects. Also, the chemical composition of the plant is represented by fatty acids, triglycerides, flavonoids, macro- and microelements. The analysis of medicinal herbal preparations based on senna leaves registered in the Russian Federation, the Republic of Belarus and the Republic of Kazakhstan has been carried out. The differences in the methods of their standardization, given in the normative documentation on quality, have been revealed. The scientific experience of using the method of high performance liquid chromatography for the determination of anthracene derivatives in senna leaves is generalized. Conclusion. The complex of biologically active substances of senna leaves exhibits various pharmacological effects, which, possibly, will expand the range of combined preparations based on them. The use of a modern and selective method of high-performance liquid chromatography in the analysis of senna leaves is a very promising direction in the field of standardization of this type of medicinal plant material.

THE DEVELOPMENT OF METHODS FOR DETERMINATION THE TOTAL OF ANTHRACENE DERIVATIVES IN RAW MATERIALS AND PREPARATIONS OF ALOE ARBORESCENS MILL.

Aloe arborescens Mill., family Asphodelaceae, is a pharmacopoeial plant, the raw material of which is used for the production of medicinal products for various therapeutic uses. The standardization of Aloe species in accordance with the requirements of the British, Japanese, European Pharmacopoeias and the United States Pharmacopoeia is carried out according to the barbaloin content by the spectrophotometric method. The methods are multistage, provide for preliminary acid hydrolysis in combination with the oxidation, liquid-liquid extraction of the formed aglycones and subsequent complexation with magnesium acetate. A mixture of isomers of aloin A and aloin B (barbaloin) and aloenin were isolated by chromatographic methods. It was determined that in all electronic spectra of the extracts and preparations from the leaves of Aloe arborescens Mill., a bathochromic shift of the long-wavelength band in the alkaline-ammonia solution is observed, which confirms the presence of anthracene derivatives. Under conditions of differential absorption, a maximum absorption is observed in the range of 412–416 nm, which indicates the advisability of using barbaloin in the analysis method, which has a maximum absorption at a wavelength of 412 nm. As a result of the study, there were developed methods for the quantitative determination of the total of anthracene derivatives in leaves and preparations of Aloe arborescens Mill. by using of the differential spectrophotometry calculated on barbaloin at an analytical wavelength of 412 nm. The content of total anthracene derivatives calculated on barbaloin was 0.60±0.03% in Aloe arborescens fresh leaves, 0.5±0.02% in freshly prepared juice, 0.135±0.006% in "Aloe juice" and 0.020±0.001% in "Aloe liquid extract", solution for subcutaneous administration, produced by ZAO "Vifitech" and OAO "Dalkhimpharm".

7,7-Dimethyl-9-(10-phenylanthracen-9-yl)-7H-Benzo[b] Fluoreno[3,4-d]Thiophene Derivatives for Blue Fluorescent Organic Light-Emitting Diodes.

In this study, we designed and synthesized two blue fluorescence materials using 7,7-dimethyl-9-(10-phenylanthracen-9-yl)-7H-benzo[b]fluoreno[3,4-d]thiophene substituted anthracene derivatives. To characterize their electroluminescent properties, we fabricated the OLED devices using these two emitting materials. Particularly, a device using 7,7-dimethyl-9-(10-phenylanthracen-9-yl)-7Hbenzo[ b]fluoreno[3,4-d]thiophene showed maximum values of luminous efficiency, power efficiency, and external quantum efficiency of 2.42 cd/A, 1.48 lm/W, 3.08% at 20 mA/cm2, respectively with CIE (x, y) coordinates of (0.15, 0.09) at 8.0 V.

Synthesis and Structural Studies of Two New Anthracene Derivatives

Anthracene derivatives are an interesting class of compounds and modifications in the anthracene ring, producing different compounds with different properties. Structural analysis of anthracene derivatives with modifications in position 9,10 of the aromatic ring is necessary in order to obtain information about its properties. The introduction of groups with polar substituents increases the possibility to modify the molecule lipophilicity, corroborating its use as bioimaging probes. Anthracene derivatives are used in many biochemical applications. These compounds can react with molecular singlet oxygen [O2 (1Δg)], a reactive oxygen species, through the Diels–Alder reaction [4 + 2] to form the respective endoperoxide and to be used as a chemical trap in biological systems. Thus, the structural and crystalline characterizations of two anthracene derivatives are presented in this work to obtain information about their physical-chemical properties. The compounds were characterized by Fourier-transform infrared spectroscopy, thermogravimetric analyses and scanning electron microscopy. The molecular structures of the compounds were studied by the Density Functional Theory, M06-2X/6-311++G(d,p) level of theory in the gas phase. From the results obtained for the frontier molecular orbitals, HOMO and LUMO, and from the Molecular Electrostatic Potential map, it was possible to predict the chemical properties of both compounds. The supramolecular arrangements were also theoretically studied, whose molecules were kept fixed in their crystallographic positions, through the natural bonding orbitals analysis to check the stability of interactions and the quantum theory of atoms in molecules to verify the type of intermolecular interaction between their molecules, as well as how they occur.

Recent advances in the syntheses of anthracene derivatives.

Anthracene and anthracene derivatives have been extensively studied over the years because of their interesting photophysical, photochemical, and biological properties. They are currently the subject of research in several areas, which investigate their use in the biological field and their application in OLEDs, OFETs, polymeric materials, solar cells, and many other organic materials. Their synthesis remains challenging, but some important preparative methods have been reported, especially in the last decade. This review presents an update of the recent strategies that have been employed to prepare anthracene derivatives. It encompasses papers published over the last twelve years (2008–2020) and focuses on direct and indirect methods to construct anthracene and anthraquinone frameworks.