Perylene Derivatives Research Articles

Synthesis, characterization, anti-cancer evaluation, and DNA-binding study of new bay-substituted perylene derivatives

Two new perylene derivatives 1,7-di(3,5-diamino-pyrimidoxyl) perylene-3,4,9,10- tetracarboxylic acid bisanhydride (4) and 1,7-di(2-[3-[(4-amino-2-methylpyrimidin-5-yl)methyl]-4-methyl-1,3-thiazol-3-ium-5-yl]) ethoxyperylene-3,4,9,10-tetracarboxylic bisanhydride (6) have been synthesized. We aimed to study their interactions with G-quadruplex (G4) structures as potent G4 ligands and telomerase inhibitors. We used a PCR-amplified guanine-rich region from the human beta-globin gene, oligonucleotide from human telomeres (a-coreTT), an oncogene (c-kit), and SK-HEP-1 adenocarcinoma cells to characterize those compounds’ binding and stabilizing abilities to G4 structures and anti-cancer potential. All results obtained through UV-visible and fluorescence spectroscopies, agarose gel electrophoresis, and MTT assay on SK-HEP-1 adenocarcinoma cells were in good agreement. Compounds 4 and 6 are promising DNA-binding and cytotoxic compounds with a relatively antiproliferative effect on the selected tumour. In all studies, the formal positive charge carrier, compound 6, showed higher activity in terms of anti-cancer effects. These results may help elucidate the feasibility of the perylene derivatives as future chemo-therapeutic agents.

Antiviral activity of singlet oxygen-photogenerating perylene compounds against SARS-CoV-2: Interaction with the viral envelope and photodynamic virion inactivation

The coronavirus disease 2019 (COVID-19) pandemic, caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has prompted great interest in novel broad-spectrum antivirals, including perylene-related compounds. In the present study, we performed a structure–activity relationship analysis of a series of perylene derivatives, which comprised a large planar perylene residue, and structurally divergent polar groups connected to the perylene core by a rigid ethynyl or thiophene linker. Most of the tested compounds did not exhibit significant cytotoxicity towards multiple cell types susceptible to SARS-CoV-2 infection, and did not change the expressions of cellular stress-related genes under normal light conditions. These compounds showed nanomolar or sub-micromolar dose-dependent anti-SARS-CoV-2 activity, and also suppressed the in vitro replication of feline coronavirus (FCoV), also termed feline infectious peritonitis virus (FIPV). Perylene compounds exhibited high affinity for liposomal and cellular membranes, and efficiently intercalated into the envelopes of SARS-CoV-2 virions, thereby blocking the viral–cell fusion machinery. Furthermore, the studied compounds were demonstrated to be potent photosensitizers, generating reactive oxygen species (ROS), and their anti-SARS-CoV-2 activities were considerably enhanced after irradiation with blue light. Our results indicated that photosensitization is the major mechanism underlying the anti-SARS-CoV-2 activity of perylene derivatives, with these compounds completely losing their antiviral potency under red light. Overall, perylene-based compounds are broad-spectrum antivirals against multiple enveloped viruses, with antiviral action based on light-induced photochemical damage (ROS-mediated, likely singlet oxygen-mediated), causing impairment of viral membrane rheology.

Effects of the Solvent Vapor Exposure on the Optical Properties and Photocatalytic Behavior of Cellulose Acetate/Perylene Free-Standing Films.

The search to deliver added value to industrialized biobased materials, such as cellulose derivatives, is a relevant aspect in the scientific, technological and innovation fields at present. To address these aspects, films of cellulose acetate (CA) and a perylene derivative (Pr) were fabricated using a solution-casting method with two different compositions. Consequently, these samples were exposed to dimethylformamide (DMF) solvent vapors so that its influence on the optical, wettability, and topographical properties of the films could be examined. The results demonstrated that solvent vapor could induce the apparent total or partial preferential orientation/migration of Pr toward the polymer-air interface. In addition, photocatalytic activities of the non-exposed and DMF vapor-exposed films against the degradation of methylene blue (MB) in an aqueous medium using light-emitting diode visible light irradiation were comparatively investigated. Apparently, the observed improvement in the performance of these materials in the MB photodegradation process is closely linked to the treatment with solvent vapor. Results from this study have allowed us to propose the fabrication and use of the improved photoactivity "all-organic" materials for potential applications in dye photodegradation in aqueous media.

Study on the self-assembly performance of a perylene derivative

Perylene diimide (PBI) had high thermal stability and solubility, so it could be used as a practical new type material of energy saving and environmental protection. The solubilization and photoelectrical properties of the bays can be effectively improved by introducing substituents in the bays. On the other hand, the imide group has a strong ability to absorb electrons, and the alkoxy group after the bay site substitution makes it easy to form micro-nano fiber in good and bad solvents. In other words, most of the properties of PBI derivatives are related to their ability to form micro-nano fiber. A systematic study of N, N' -isoctyl-1, 7-bis (octanoxy) perylene diimide (DFPBI) was carried out by UV-VIS spectrophotometry, thermogravimetry and fluorescence spectrophotometry. A number of test results show that DFPBI has better solubility and thermal stability than PBI, and can grow micro-nano fiber in both good and bad solvent systems. Therefore, DFPBI has broad application prospects in sensors.

Quaternary Phosphonium Salt-functionalized Graphene Filter for Effective Water Disinfection

To access safe water, a facile and low-cost quaternary phosphonium salt-functionalized graphene filter (PYQP-G filter) was developed via pi-pi stacking interaction between perylene and graphene surface. We first synthesized a new perylene derivative with two QPS groups at its amide sides denoted as PYQP. Next, shellac was used as a carbon source to coat the graphene material onto the surface of a porous SiO2 substrate in a chemical vapor deposition (CVD) process. Thus, a graphene filter (G-filter) was obtained. Third, the PYQP was attached to the graphene surface through π-π stacking to generate the PYQP-G filter. Due to the high bacterial accumulation and killing ability of the assembled PYQP, the PYQP-G filter showed high efficiency in water disinfection. When the bacterial concentration is blown at 105 CFU/mL, one PYQP-G filter can purify up to 500 ml of water.

Perylene nanostructured films optimization for organic electronics: Molecular, structural, and electrochemical characterization

The deposition technique, structure, and thermal treatment can influence the optical and electrical properties of perylene derivatives films. In this work, the nanostructured Langmuir-Schaefer films of bis(n-propylimide) perylene (PTCD-Pr) with thermal treatment were optimized for an electrochemical application. The PTCD-Pr film before and after thermal treatment was characterized by ultraviolet-visible absorption, infrared absorption spectroscopy, micro-Raman scattering, and voltammetry. Brewster angle microscopy images confirmed the higher aggregation degree of molecules on Langmuir film. The PTCD-Pr deposition showed a linear growth, forming H, J, and null aggregates. The infrared absorption spectroscopy indicates a preferential head-on orientation with a slight chromophore deviation. After thermal treatment (200 °C for 2 h), the PTCD-Pr film showed a decrease in the contribution of null aggregates while maintaining the same molecular orientation. The Raman and surface-enhanced Raman spectroscopy measurements also confirmed the presence of PTCD-Pr molecules distributed throughout the substrate surface, and the thermal treatment conditions did not degrade the PTCD-Pr molecule. Moreover, thermal treatment contributes to the increase of stability of the film at the electrode surface for electrochemical measurements. In the presence of active species (paraquat in this case), the thermally treated film showed promising electrocatalytic properties compared to the unmodified electrode.

Photophysical and Photochemical Properties of Perylene–(Cyanine Dye) Dyad in the VIS–NIR Spectrum Region

The photophysical properties of an original covalently-bonded dyad based on a perylene derivative and IR-780 cyanine dye were studied. The dyad has pronounced absorption in the NIR region of the spectrum and a strong fluorescence signal, which is weakly quenched by the influence of the perylene derivative. Upon excitation of the dyad in the absorption region of perylene, a fluorescence signal from IR-780 is detected due to the Förster energy transfer mechanism. It is shown that the dyad does not generate singlet oxygen upon photoexcitation in the NIR region of the spectrum. However, it can generate superoxide anion radicals, indicating the presence of the photoinduced electrons transfer from the dye to the perylene.

A potential-resolved ratiometric electrochemiluminescence aptasensor for Pb2+: Gold nanoclusters and amino-terminated perylene derivative as both emitters and resonance energy transfer donor-acceptor pair

Searching for a pair of electrochemiluminescence (ECL) emitters that can be simultaneously applied as energy donor-acceptor pair is very vital for ECL resonance energy transfer strategy (ECL-RET)-based ratiometric ECL aptasensors, as it can avoid the complex design caused by the addition of exogenous donor or acceptor. Herein, gold nanoclusters (AuNCs) with aggregation-induced emission property and amino-terminated perylene derivative (PTC-NH2) with a broad absorption range were firstly combined to generate the anodic and cathodic ECL signals, respectively. Importantly, they were also operated as a novel ECL-RET donor-acceptor pair due to their favorable spectral overlap. On this basis, a potential-resolved ratiometric ECL aptasensor was established to detect lead ions (Pb2+). Specifically, the energy of AuNCs was absorbed by PTC-NH2 in the absence of Pb2+, leading to a decrease of the anodic ECL signal and the appearance of the cathodic ECL signal. Upon the addition of Pb2+, the ECL-RET process was impeded, and the ECL signals were reversed. By measuring the ratio of AuNCs and PTC-NH2 ECL intensities, the developed ratiometric ECL aptasensor displayed a low detection limit of 0.05 pM with excellent selectivity and satisfactory stability. Finally, the proposed aptasensor presented favorable feasibility for Pb2+ assays in soil samples.

Perylene derivative and persulfate as highly efficient electrochemical system for constructing sensitive amperometric aptasensor

To design highly efficient electrochemistry system was important for construct simple and sensitive biosensors, which was crucial in clinical diagnosis and therapy. In this work, a novel electrochemistry probe N,N′-di (1-hydroxyethyl dimethylaminoethyl) perylene diimide (HDPDI) with positive charges was reported to show two-electron redox behavior in neutral phosphate buffer solution between 0 and -1.0 V. And K2S2O8 in solution could significantly increase the reduction current of HDPDI at −0.29 V, which was interpreted with cyclic catalysis mechanism of K2S2O8. Moreover, HDPDI as electrochemical probe and K2S2O8 as signal enhancer was used to design aptasensors for protein detection. Thrombin was used as target model protein. Thiolate ssDNA with thrombin-binding sequence was immobilized on gold electrode to selectively capture thrombin and adsorb HDPDI. The thiolate ssDNA without binding with thrombin was with random coil structure and could adsorb HDPDI through electrostatic attraction interaction. However, the thiolate ssDNA binding with thrombin became G-quadruplex structure and hardly adsorbed HDPDI. Thus, with increasing the concentration of thrombin, the current signal stepwisely decreased and was taken as detection signal. Compared with other aptasensors based on electrochemistry molecules without signal enhancer, the proposed aptasensors exhibited wider linear response for thrombin between 1 pg mL−1 and 100 ng mL−1 with lower detection limit 0.13 pg mL−1. In addition, the proposed aptasensor showed good feasibility in human serum samples.

Red light-driven electron sacrificial agents-free photoreduction of inert aryl halides via triplet-triplet annihilation

Selective photoactivation of inert aryl halides is a fundamental challenge in organic synthesis. Specially, the long-wavelength red light is more desirable than the widely-applied blue light as the excitation source for photoredox catalysis, due to its superior penetration depth. However, the long-wavelength red light-driven photoactivation of inert aryl halides remains a challenge, mainly because of the low energy of the single long-wavelength red photon. Herein, we report the photoreduction of aryl bromides/chlorides with 656 nm LED via triplet-triplet annihilation (TTA) strategy. This method is based on our discovery that the commonly used chromophore of perylene can serve as an efficient and metal-free photocatalyst to enable the photoreduction of inert aryl halides without the conventional need for electronic sacrificial agents. By introducing a red light-absorbing photosensitizer to this perylene system, we accomplish the long-wavelength red light-driven photoreduction of aryl halides via sensitized TTA mechanism. Moreover, the performance of such a TTA-mediated photoreduction can be significantly enhanced when restricting the rotation freedom of phenyl moiety for perylene derivatives to suppress their triplet nonradiative transition, in both small and large-scale reaction settings.

Red Light Absorption of [ReI(CO)3(α-diimine)Cl] Complexes through Extension of the 4,4'-Bipyrimidine Ligand's π-System.

Rhenium(I) complexes of type [Re(CO)3(NN)Cl] (NN = α-diimine) with MLCT absorption in the orange-red region of the visible spectrum have been synthesized and fully characterized, including single crystal X-ray diffraction on two complexes. The strong bathochromic shift of MLCT absorption was achieved through extension of the π-system of the electron-poor bidiazine ligand 4,4'-bipyrimidine by the addition of fused phenyl rings, resulting in 4,4'-biquinazoline. Furthermore, upon anionic cyclization of the twisted bidiazine, a new 4N-doped perylene ligand, namely, 1,3,10,12-tetraazaperylene, was obtained. Electrochemical characterization revealed a significant stabilization of the LUMO in this series, with the first reduction of the azaperylene found at E1/2(0/-) = -1.131 V vs. Fc+/Fc, which is the most anodic half-wave potential observed for N-doped perylene derivatives so far. The low LUMO energies were directly correlated to the photophysical properties of the respective complexes, resulting in a strongly red-shifted MLCT absorption band in chloroform with a λmax = 586 nm and high extinction coefficients (ε586nm > 5000 M-1 cm-1) ranging above 700 nm in the case of the tetraazaperylene complex. Such low-energy MLCT absorption is highly unusual for Re(I) α-diimine complexes, for which these bands are typically found in the near UV. The reported 1,3,10,12-tetraazaperylene complex displayed the [Re(CO)3(α-diimine)Cl] complex with the strongest MLCT red shift ever reported. UV-Vis NIR spectroelectrochemical investigations gave further insights into the nature and stability of the reduced states. The electron-poor ligands explored herein open up a new path for designing metal complexes with strongly red-shifted absorption, thus enabling photocatalysis and photomedical applications with low-energy, tissue-penetrating red light in future.

Perylene Derivative and K2s2o8 as Highly Efficient Electrochemical System for Constructing Sensitive Amperometric Aptasensor

Perylene Derivative and K2s2o8 as Highly Efficient Electrochemical System for Constructing Sensitive Amperometric Aptasensor

5-(Perylen-3-ylethynyl)uracil as an antiviral scaffold: Potent suppression of enveloped virus reproduction by 3-methyl derivatives in vitro

Amphipathic nucleoside and non-nucleoside derivatives of pentacyclic aromatic hydrocarbon perylene are known as potent non-cytotoxic broad-spectrum antivirals. Here we report 3-methyl-5-(perylen-3-ylethynyl)-uracil-1-acetic acid and its amides, a new series of compounds based on a 5-(perylen-3-ylethynyl)-uracil scaffold. The compounds demonstrate pronounced in vitro activity against arthropod-borne viruses, namely tick-borne encephalitis virus (TBEV) and yellow fever virus (YFV), in plaque reduction assays with EC50 values below 1.9 and 1.3 nM, respectively, and Chikungunya virus (CHIKV) in cytopathic effect inhibition test with EC50 values below 3.2 μM. The compounds are active against respiratory viruses as well: severe acute respiratory syndrome-related coronavirus 2 (SARS-CoV-2) in cytopathic effect inhibition test and influenza A virus (IAV) in virus titer reduction experiments are inhibited – EC50 values below 51 nM and 2.2 μM, respectively. The activity stems from the presence of a hydrophobic perylene core, and all of the synthesized compounds exhibit comparable 1O2 generation rates. Nonetheless, activity can vary by orders of magnitude depending on the hydrophilic part of the molecule, suggesting a complex mode of action. A time-of-addition experiment and fluorescent imaging indicate that the compounds inhibit viral fusion in a dose-dependent manner. The localization of the compound in the lipid bilayers and visible damage to the viral envelope suggest the membrane as the primary target. Dramatic reduction of antiviral activity with limited irradiation or under treatment with antioxidants further cements the idea of photoinduced ROS-mediated viral envelope damage being the mode of antiviral action.

Fabrication and characterization of active polymer optical fibers with a ring-doped structure

This paper employs the solution-doping technique for the fabrication of polymer optical fibers (POFs) doped with two perylene derivatives, Lumogen Yellow 083 and Lumogen Red 305, in different combinations. With the solution-doping technique is very easy to control the amount of dopant penetration into the core of non-doped uncladded fibers, allowing the fabrication of active POFs with a novel ring-doped structure. In addition to manufacturing the fibers, these have also been optically characterized. Specifically, the influence of the combination of dopants, pumping power and wavelength, as well as the light propagation distance, have been measured and analyzed. Furthermore, time-resolved emission characteristics have also been measured to determine the fluorescence lifetimes and to extract information about the energy transfer between the dopants. Finally, the aim of this work has been to investigate the performance of the aforementioned POFs for fluorescent lighting applications, with a special focus on tunable light sources, and also for sensing applications.

Nucleoside Analogs and Perylene Derivatives Modulate Phase Separation of SARS-CoV-2 N Protein and Genomic RNA In Vitro

The life cycle of severe acute respiratory syndrome coronavirus 2 includes several steps that are supposedly mediated by liquid-liquid phase separation (LLPS) of the viral nucleocapsid protein (N) and genomic RNA. To facilitate the rational design of LLPS-targeting therapeutics, we modeled N-RNA biomolecular condensates in vitro and analyzed their sensitivity to several small-molecule antivirals. The model condensates were obtained and visualized under physiological conditions using an optimized RNA sequence enriched with N-binding motifs. The antivirals were selected based on their presumed ability to compete with RNA for specific N sites or interfere with non-specific pi-pi/cation-pi interactions. The set of antivirals included fleximers, 5'-norcarbocyclic nucleoside analogs, and perylene-harboring nucleoside analogs as well as non-nucleoside amphiphilic and hydrophobic perylene derivatives. Most of these antivirals enhanced the formation of N-RNA condensates. Hydrophobic perylene derivatives and 5'-norcarbocyclic derivatives caused up to 50-fold and 15-fold enhancement, respectively. Molecular modeling data argue that hydrophobic compounds do not hamper specific N-RNA interactions and may promote non-specific ones. These findings shed light on the determinants of potent small-molecule modulators of viral LLPS.

Perylene-Mediated Electron Leakage in Respiratory Chain to Trigger Endogenous ROS Burst for Hypoxic Cancer Chemo-Immunotherapy.

Perylene derivatives can be stimulated by the hypoxic tumor microenvironment to generate radical anion that is proposed to arouse electron exchange with oxidizing substance, and in turn, realize reactive oxygen species (ROS) burst. Here, three perylene therapeutic agents, PDI-NI, PDIB-NI, and PDIC-NI, are developed and it is found that the minimum lowest unoccupied molecular orbital (LUMO) energy level makes PDIC-NI most easily accept electrons from the oxidative respiratory chain to form lots of anions, and the resultant maximum ROS generation, establishing an unambiguous mechanism for the formation of perylene radical anions in the cell, presents solid evidence for LUMO energy level determining endogenous ROS burst. Stirringly, PDIC-NI-induced ROS generation arouses enhanced mitochondrial oxidative stress and concurrently activates immunogenic cell death (ICD), which not only efficiently kills lung tumor cells but also reprograms immunosuppressive tumor microenvironment, including the cytokine secretion, dendritic cell maturation, as well as cytotoxic T lymphocytes activation, to inhibit the growth of xenografted and metastasis tumor, presenting a proof-of-concept demonstration of perylene that acts as an integrated therapeutic agent to well realize hypoxia-activated chemotherapy with ICD-induced immunotherapy on lung cancer.

Excited State and Transient Chemistry of a Perylene Derivative (DBP). An Untold Story.

Transient chemistry of sensitizing dyes is important to obtain insights into the photochemical conversion processes of light harvesting assemblies. We have now employed transient absorption spectroscopy (pulsed laser and pulse radiolysis) to characterize the excited state and radical intermediates of a perylene derivative, (5,10,15,20-Tetraphenylbisbenz[5,6]indeno[1,2,3-cd:1',2',3'-lm]perylene (DBP). The distinguishable transient absorption features for the singlet and triplet excited states and radical anion and radical cation provide spectral fingerprints to identify the reaction intermediates in photochemical energy and electron transfer processes of composite systems involving DBP. For example, identifying these transients in the energy transfer processes of the rubrene-DBP system would aid in establishing their role as annihilator-emitter for triplet-triplet annihilation up-conversion (TTA-UC). The transient characterization thus serves as an important mechanistic fingerprint for elucidating mechanistic details of systems employing DBP in optoelectronic applications.

An Unlimited Color Palette from Perylene Derivative Molecules Dispersed within Hybrids

An Unlimited Color Palette from Perylene Derivative Molecules Dispersed within Hybrids

Modelling the electric field in non-fullerene organic solar cells: The effect of 1-chloronaphthalene additive

In this work, a perylene derivative was used as electron acceptor in organic solar cells and the morphology was optimized by using the 1-chlronaphthalene (CN) as additive. The power dissipation was simulated along the structure of OPV devices taking into count the interference occurring in stacked thin films under normal incidence by using the transfer matrix method (TMM). The TMM model has been used to simulate the electric field in organic solar cells having fullerene derivatives as electron acceptor. In opposite to the fullerenes, the perylene derivative also contributes to the photocurrent and, its optical and electrical features changed upon CN additive. Therefore, the monitoring through ellipsometry and TMM modelling contribute to understand the behaviour of the electromagnetic wave inside the device, providing insights about proper optimizations that can be performed in order to increase the G(x) rate and the Jsc parameter. This model takes into count the experimental values of refractive index n and extinction coefficient k acquired from the D:A film to simulate the spatial distribution of the electric field and provide valuable information about photovoltaic parameters. The results pointed out that chemical or physical modifications are required to improve the PDIC5 acceptor distribution along the bulk, as well as changes on the crystallinity, which can be achieved with the use of CN as additive.

Microscopic, Spectroscopic, and Electrochemical Characterization of Novel Semicrystalline Poly(3-hexylthiophene)-Based Dendritic Star Copolymer.

In this study, electron-donating semicrystalline generation 1 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene) star copolymer, G1PPT-co-P3HT was chemically prepared for the first time. Copolymerization was achieved with high molecular weight via facile green oxidative reaction. 1H NMR analyses of the star copolymer demonstrated the presence of 84% regioregular (rr) head-to-tail (HT) P3HT, which accounts for the molecular ordering in some grain regions in the macromolecule’s morphology, as revealed by the high-resolution scanning electron microscopy (HRSEM) and Selected Area Electron Diffraction (SAED) images, and X-ray diffraction spectroscopy (XRD) measurements. The star copolymer also exhibited good absorption properties in the ultraviolet-visible (UV-Vis) and the near infrared (NIR) spectral regions, which give rise to an optical energy bandgap value as low as 1.43 eV. A HOMO energy level at −5.53 eV, which is below the air-oxidation threshold, was obtained by cyclic voltammetry (CV). Electrochemical impedance spectroscopy (EIS) ascertained the semiconducting properties of the macromolecule, which is characterized by a charge transfer resistance, Rct, value of 3.57 kΩ and a Bode plot-phase angle value of 75°. The combination of the EIS properties of G1PPT-co-P3HT and its highly electron-donating capability in bulk heterojunction (BHJ) active layer containing a perylene derivative, as demonstrated by photoluminescence quenching coupled to the observed Förster Resonance charge transfer, suggests its suitability as an electron-donor material for optoelectronic and photovoltaic devices.