Perylene Derivatives Research Articles

Novel perylene liquid crystals: Investigation of the influence of bay-substituents on mesomorphism and photophysical property

A series of perylene liquid crystals with H, Br, phenyl and tert-butylphenyl on bay-positions were synthesized in yields of 50–70%. Their mesomorphic properties and photophysical properties were investigated. The perylene derivatives 6, 7 and 8 with Br, phenyl and tert-butylphenyl at bay-positions have the hexagonal columnar liquid crystalline phase and wider scopes of phase transfer temperatures in comparison with similar perylene liquid crystal 5 with no substituent on bay-position. Compounds 6, 7 and 8 showed stronger fluorescence intensities, larger Stokes shifts and higher quantum yields than that of compound 5. These results indicated that the suitable substituents on bay-positions of perylene liquid crystals were favorable for producing excellent mesomorphic properties and good fluorescence properties.

A sensitive electrochemiluminescent aptasensor based on perylene derivatives as a novel co-reaction accelerator for signal amplification

Herein, a novel signal amplification strategy was designed using the perylene derivative as the co-reaction accelerator toward graphene-CdTe quantum dots (G-CdTe)/S2O82− system to construct a highly sensitive electrochemiluminescent (ECL) aptasensor for thrombin (TB) detection. Firstly, the G-CdTe nanocomposites were prepared by one-step method of in situ generating CdTe quantum dots onto the surface of the graphene oxide by using 3-mercaptopropionic acid as the CdTe QDs stabilizer. Then, a kind of perylene derivative (PTC-Lys), was synthesized by covalently binding L-lysine to 3,4,9,10-perylenetetracarboxylic acid, which was further immobilized onto the G-CdTe by the π-π* stacking and cross-linked the detection thrombin aptamer (TBA II) to obtain the TBA II/PTC-Lys/G-CdTe signal probes. It is worth pointing out that PTC-Lys acting as an efficient co-reaction accelerator interacted with the co-reactant of S2O82− rather than G-CdTe to promote the more oxidant mediators of SO4•−, which could further react with G-CdTe to produce excited state species G-CdTe* for emitting light. Compared with the G-CdTe/S2O82− ECL system, our proposed strategy with the introduction of co-reaction accelerator of PTC-Lys exhibited ultra-high sensitivity to quantify the concentration of TB from 1.0×10−7nM to 10nM with a detection limit of 34aM.

Perylene and coronene derivatives binding to G-rich promoter oncogene sequences efficiently reduce their expression in cancer cells.

A novel approach to cancer therapeutics is emerging in the field of G-quadruplex (G4) ligands, small molecules designed to stabilize four-stranded structures that can form at telomeres as well as in other genomic sequences, including oncogene promoter sequences, 5'-UTR regions and introns. In this study, we investigated the binding activity of perylene and coronene derivatives PPL3C, CORON and EMICORON to G4 structures formed within the promoter regions of two important cancer-related genes, c-MYC and BCL-2, and their biochemical effects on gene and protein expression. In order to fully characterize the ability of the selected ligands to bind and stabilize the G4 structures originated by the c-MYC and BCL-2 promoter sequences, we performed electrospray ionization mass spectrometry (ESI-MS), Fluorescence Resonance Energy Transfer (FRET) measurements, Circular Dichroism (CD) spectra and polymerase stop assay. Altogether our results showed that the ligands had a high capacity in binding and stabilizing the G4 structures within the c-MYC and BCL-2 promoter sequences invitro. Notably, when we evaluated by quantitative real-time PCR and western blotting analysis, the effects of treatment with the different G4 ligands on c-MYC and BCL2 expression in a human melanoma cell line, EMICORON appeared the most effective compound in reducing the mRNA and protein levels of both genes. These results encourage to consider EMICORON as a promising example of multimodal class of an antineoplastic drug, affecting different tumor crucial pathways simultaneously: telomere maintenance (as previously described), cell proliferation and apoptosis via down-regulation of both c-MYC and BCL-2 (this paper).

Bay-Extended, Distorted Perylene Esters Showing Visible Luminescence after Ultraviolet Excitation: Photophysical and Electrochemical Analysis

Perylene derivatives with a unilaterally and bilaterally extended core show luminescence in the visible wavelength range (500–600 nm) that can be excited by absorption in the ultraviolet range (360–370 nm). This unusual behavior is investigated by means of excitation spectroscopy, cyclic voltammetry, and calculations based on (time-dependent) density functional theory. The results indicate that the extended compounds show promising features for optoelectronic applications and even might be used as fluorescent dyes in lasing. This is supported by nonadiabatic ab initio molecular dynamics. With respect to applications in organic optoelectronic nanostructures, nanofilms were prepared via spin-coating and thermal vapor deposition and demonstrated the formation of excimers. The relationship between the excimer-induced bathochromic shift and the interplanar distance of the molecules opens up the possibility to vary the perceived color of a nanofilm via tempering.

Monolayer Phases of a Dipolar Perylene Derivative on Au(111) and Surface Potential Build-Up in Multilayers.

9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation.

(Invited) Colour Bricks: Molecule-By-Molecule Supramolecular Arrays of Peryleneimides and Phthalocyanines on Solid Substrates

Highly ordered thin molecular films, from monolayer to multilayer assemblies, promise considerable development for micro- and nanotechnology. In particular, the application of supramolecular chemistry to the direct assembling of functional layers at surfaces added a new and highly diverse class of materials to modern material science. Multicomponent arrays are attractive materials for applications such as nonlinear optical materials, enzyme sensors, solar energy storage devices, and molecular rectifiers in several fields as optics, biotechnology, photo- and electrochemistry. The talk will describe a recently developed set of perylene and phthalocyanine derivatives from which one can build highly organized multilayered structures on metal oxide surfaces. The essential finding is the use of terpyridyl-crowned perylenemonoimides monoanhydrides as the anchoring substances. Another key point is a proper choice of bis(terpyridyl)perylenediimide or terpyridyl-phthalocyanine linkers. Combination of these two factors allows to assemble highly colored and stable multilayered molecular films by a simple and reproducible procedure. As a proof of concept it has been demonstrated that molecular arrays can be successfully used in solid state DSSC even at ambient conditions. One can expect many other potential uses of the proposed multilayers. The tpy-perylene spacers of a fixed length make possible a localization of specific ions or chromophores at a controlled depth inside the layer. This would allow to create a gradient of redox potentials across the film and to achieve, e.g. upon photoexcitation, a charge shift into a certain distance and direction. High absorbance of the multilayered films might eliminate the need of using porous structures, while the possibility to cover easily large surfaces is a great advantage in practical applications. Figure 1

In Vivo Lighted Fluorescence via Fenton Reaction: Approach for Imaging of Hydrogen Peroxide in Living Systems.

By virtue of its high sensitivity and rapidity, Fenton reaction has been demonstrated as a powerful tool for in vitro biochemical analysis; however, in vivo applications of Fenton reaction still remain to be exploited. Herein, we report, for the first time, the design, formation and testing of Fenton reaction for in vivo fluorescence imaging of hydrogen peroxide (H2O2). To realize in vivo fluorescence imaging of H2O2 via Fenton reaction, a functional nanosphere, Fc@MSN-FDNA/PTAD, is fabricated from mesoporous silica nanoparticle (MSN), a Fenton reagent of ferrocene (Fc), ROX-labeled DNA (FDNA), and a cationic perylene derivative (PTAD). The ferrocene molecules are locked in the pore entrances of MSN, and exterior of MSN is covalently immobilized with FDNA. As a key part, PTAD acts as not only the gatekeeper of MSN but also the efficient quencher of ROX. H2O2 can permeate into the nanosphere and react with ferrocene to product hydroxyl radical (·OH) via Fenton reaction, which cleaves FDNA to detach ROX from PTAD, thus in turn, lights the ROX fluorescence. Under physiological condition, H2O2 can be determined from 5.0 nM to 1.0 μM with a detection limit of 2.4 nM. Because of the rapid kinetics of Fenton reaction and high specificity for H2O2, the proposed method meets the requirement for real applications. The feasibility of Fc@MSN-FDNA/PTAD for in vivo applications is demonstrated for fluorescence imaging of exogenous and endogenous H2O2 in cells and mice. We expect that this work will not only contribute to the H2O2-releated studies but also open up a new way to exploit in vivo Fenton reaction for biochemical research.

When the Sequence of Thin Film Deposition Matters: Examination of Organic-on-Organic Heterostructure Formation Using Molecular Beam Techniques and in Situ Real Time X-ray Synchrotron Radiation

We have examined the growth of bilayers and superlattices of pentacene and perylene derivatives (PTCDI-Cn) using in situ real time X-ray synchrotron radiation techniques and ex situ atomic force microscopy. We find that the growth of PTCDI-Cn layers on 1 monolayer (ML) of pentacene is initially 2D layer-by-layer (LbL), eventually transitioning to a mode of growth that is more 3D after several monolayers have been deposited. We find that the extent of 2D LbL growth depends on the length of the alkyl end chains, Cn: the smoothest films are formed with PTCDI-C5, while the roughest are formed with PTCDI-C13. These observations reflect a difference in the Ehrlich–Schwoebel barrier for step-edge crossing with alkyl end-chain length. When the sequence of deposition is reversed, we observe spectacular changes in the evolution of surface roughness for the growth of pentacene thin films on 1 ML of PTCDI-Cn. The growth is immediately 3D, while still remaining crystalline. The morphology of these thin films indicates...

Temperature dependence of the partially localized state in a 2D molecular nanoporous network

Two-dimensional organic and metal-organic nanoporous networks can scatter surface electrons, leading to their partial localization. Such quantum states are related to intrinsic surface states of the substrate material. We further corroborate this relation by studying the thermally induced energy shifts of the electronic band stemming from coupled quantum states hosted in a metal-organic array formed by a perylene derivative on Cu(111). We observe by angle-resolved photoemission spectroscopy (ARPES), that both, the Shockley and the partially localized states, shift by the same amount to higher binding energies upon decreasing the sample temperature, providing evidence of their common origin. Our experimental approach and results further support the use of surface states for modelling these systems, which are expected to provide new insight into the physics concerning partially confined electronic states: scattering processes, potential barrier strengths, excited state lifetimes or the influence of guest molecules.

Bay-Annulated Perylene Tetraesters: A New Class of Discotic Liquid Crystals.

Selenium-annulated perylene tetraesters that stabilize the hexagonal columnar phase have been synthesized and characterized, and their thermal and photophysical behavior has been determined. The mesophase range decreased with an increase in chain length. A comparative account of the structure-property relationships of this series of compounds with respect to parent perylene tetraesters, N- and S-annulated perylene tetraesters, in terms of their thermal, photophysical and electrochemical behavior is provided. The bay-annulation of perylene tetraesters is a good option to modify the thermal and photophysical properties of perylene derivatives and it can provide a new avenue for the synthesis of several technologically important self-assembling perylene derivatives.

Proton induced aggregation of water soluble isophthalic acid appended arylene diimides: justification with perylene derivative

We report the self-assembly behaviour of five water soluble arylene diimides based on benzene, naphthalene and perylene moieties, by utilizing the essentiality of two major reversible supramolecular interactions, π-stacking and hydrogen bonding.

The role of film composition and nanostructuration on the polyphenol sensor performance

The recent advances in the supramolecular control in nanostructured films have improved the performance of organic-based devices. However, the effect of different supramolecular arrangement on the sensor or biosensor performance is poorly studied yet. In this paper, we show the role of the composition and nanostructuration of the films on the impedance and voltammetric-based sensor performance to catechol detection. The films here studied were composed by a perylene derivative (PTCD-NH2) and a metallic phthalocyanine (FePc), using Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. The deposition technique and intrinsic properties of compounds showed influence on electrical and electrocatalytic responses. The PVD PTCD-NH2 shows the best sensor performance to the detection of catechol. Quantification of catechol contents in mate tea samples was also evaluated, and the results showed good agreement compared with Folin-Ciocalteu standard method for polyphenol detection.

Novel derivatives of 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid: synthesis, electrochemical and optical properties

Facile synthesis and opto-electrochemical properties of various unsymmetrically “peri”-substituted perylene derivatives, with four chloro-atoms at the bay-positions, have been reported.

Supramolecular aggregates as sensory ensembles.

As a new emerging area in chemical sensing, sensing using supramolecular aggregates exhibits unique advantages over that using conventional small-molecule chemical sensors, in terms of high sensitivity and selectivity, and the simplicity of the sensory building blocks. This Feature Article outlines the recent research progress made in sensing based on induced supramolecular aggregation-disaggregation. The reviewed sensory building blocks, in general, in the form of a small molecular sensor, yet with a much simpler structure, which form aggregates, are those of perylene derivatives, pyrene derivatives, tetraphenylethylene derivatives, metallophilic species and metal-organic frameworks.

Cationic-perylene-G-quadruplex complex based fluorescent biosensor for label-free detection of Pb2+

In this work we use a water-soluble cationic perylene derivative (compound 1) as the G-quadruplex (G4) structure fluorescence indicator to construct a fluorescent biosensor for simple, rapid and label-free detection of Pb2+. In the absence of Pb2+, strong electrostatic interactions between compound 1 and the G-rich DNA probe (PW17) induced the aggregation of compound 1 and resulted in the fluorescence quenching. In the presence of Pb2+, the PW17 formed Pb2+-stabilized G4 structure, which reduced the aggregation of compound 1 and gave rise to high fluorescence. This allowed us to use convenient “mix-and-detect” protocol for quantitative analysis of Pb2+. Since Pb2+ can specially induce PW17 to form compact DNA fold, our proposed biosensor displayed high selectivity for Pb2+. It also exhibited a high sensitivity to Pb2+, with a limit of detection of 5.0nM observed. Furthermore, the biosensor was applied for the detection of Pb2+ in urine and paint samples, and both showed satisfactory results.

Supramolecular Architecture and Electrical Properties of a Perylene Derivative in Physical Vapor Deposited Films

The supramolecular structure of organic thin films is a key factor in their optical and electrical properties and, consequently, in the technological applications involving organic electronic. Here, thin films of a perylene derivative, the bis butylimido perylene (BuPTCD), were produced by vacuum thermal evaporation (PVD, physical vapor deposition). The main objective is to investigate the supramolecular structure of the BuPTCD in these PVD films, which implies to control their thickness at nanometer scale and to determine their molecular organization, morphology at micro and nanometer scales and crystallinity. The ultraviolet-visible absorption reveals a uniform growth of the PVD films. The optical and atomic force microscopy images show a homogeneous surface of the film at micro and nanometer scales, respectively. The X-ray diffraction indicates that both powder and PVD film are in the crystalline form. Complementary, a preferential head-on orientation of the molecules in the PVD films is determined via infrared absorption spectroscopy. Besides, the annealing process (200oC) did not affect the molecular organization of the PVD films, revealing a thermal stability of the BuPTCD molecules within the PVD films. Through DC electrical measurements, an electrical conductivity of 7.45x10-10 S/m was determined for BuPTCD PVD films onto Au interdigitated electrodes (IDE-structured devices), which can be enhanced, under illumination, by two orders of magnitude (photoconductivity effect). As proof-of-concept, the IDE-structured devices are tested as gas sensor for trifluoroacetic acid.

Morphology-controlled growth of perylene derivative induced by double-hydrophilic block copolymers

Controlled growth of technically relevant perylene derivative 3, 4, 9, 10-perylenetetracarboxylic acid potassium salt (PTCAPS), with tuneable morpologies, has been successfully realized by a recrystallization method using a double-hydrophilic block copolymer poly (ethylene glycol)-block poly (ethyleneimine) (PEG-b-PEI) as the structure directing agent. The {001} faces of PTCAPS are most polar and adsorb the oppositively charged polymer additive PEG-b-PEI well by electrostatic attraction. By simply adjusting the PEG-b-PEI concentration, systematic morphogenesis of PTCAPS from plates to microparticles composed of various plates splaying outwards could be realized. Furthermore, the variation of pH value of the recrystallization solution could induce the change of the interaction strength between PEG-b-PEI additive and PTCAPS and thus modify the morphology of PTCAPS from microparticles composed of various plates to ultralong microbelts.

Water-soluble aminoacid functionalized perylene diimides: The effect of aggregation on the optical properties in organic and aqueous media

We report on the straightforward preparation and photophysical characterization of four symmetrically substituted water soluble perylene diimides, obtained by functionalizing the imide positions with l-threonine, l-aspartic acid, l-cysteine and l-methionine. The presence of carboxylic groups on the two sides of the aromatic structure conveys a pH-dependent water solubility to all the molecules. The combined effect of the hydrophobic perylene core with the specific aminoacidic functionalities leads to different aggregation behaviors in both aqueous and organic media affecting the optical absorption and emission of the aromatic chromophore. By a comparative study of the optical properties we shed light on the main characteristics of these perylene derivatives in organic and aqueous diluted solution. These aminoacid perylene diimide molecules have the potential to be exploited in new sensing applications based on assembly/disassembly-driven fluorescence switching off-on in aqueous media.

Label-free fluorescence turn-on detection of microRNA based on duplex-specific nuclease and a perylene probe

A novel fluorescence turn-on microRNA (miRNA) detection method based on duplex-specific nuclease (DSN) and a perylene probe is presented in this study. A positively charged perylene derivative (compound 1) was used as the fluorescent probe. Compound 1 exhibits strong monomer fluorescence in an aqueous buffer solution. It is well known that single-stranded DNA is a polyanion in nature. Thus, it can induce the aggregation of compound 1 through strong electrostatic, hydrophobic and π−π stacking interactions. As a result, the fluorescence of compound 1 was efficiently quenched. When the target miRNA was added, the formation of DNA-RNA hybridized duplex initiated the cleavage of the DNA strand by DSN cycle reaction, which resulted in disaggregation of compound 1. A fluorescence turn-on signal was detected, and a novel miRNA sensing method was therefore established. The presented method is label-free, simple, cost effective, sensitive and selective.

Perylene Derivatives As Useful SERRS Reporters, Including Multiplexing Analysis.

Five perylene bisimide (PBI) derivatives were designed and synthesized, on the basis of quantum-chemical calculations. The influence of halogen substituents on the shape and energy of the frontier orbitals and the Raman spectra were calculated, in the prospect use in surface-enhanced resonance Raman scattering (SERRS) studies. The corresponding experiments confirmed a very strong SERRS response in the presence of pristine (i.e., uncoated) gold nanoparticles. These spectra can be used for multiplexing measurements, namely measurements in which, by using a single laser excitation, one can recognize the simultaneous presence of several analytes.