Perylene Research Articles

Ultrasensitive detection of histamine in spoiled meat employing silver nanoparticles decorated Perylene: An experimental-computational conjugation

Meat spoilage has been acquiring increasing attention recently and is directly associated with food safety and human health. Biogenic amines are the spying organic compounds fostered from the microorganism-mediated decarboxylation of amino acids during meat spoilage. Histamine, a biogenic amine acts as a model analyte and is toxic if consumed substantially. It is crucial to monitor histamine levels in meat due to its adverse effects. In this study, a simple and quick fluorescent sensor was fabricated for sensitive and selective detection of histamine. Citrate-capped silver nanoparticles (AgNP) were loaded onto Perylene (PER) to develop a sensing probe that was characterized using UV–visible, FTIR, XRD, and FESEM, and its optical behavior toward histamine was investigated. Moreover, the binding affinity between histamine and PER@AgNP was assessed using a DFT-based computer simulation. Under optimal conditions, the sensor showed linear relationships for histamine concentrations from 25 μM to 3200 μM with LOD 13.52 μM.

Utilizing Activated Carbon Nanopores for Electrochemical Oxidation of Perylene to Redox-Active 3,10-Perylenedione: Application in Electrochemical Capacitor Electrodes.

We demonstrate that nanopores of activated carbon (AC) function as nanoreactors that oxidize perylene (PER) to a redox-active organic compound, 3,10-perylenedione (PERD), without any metal catalysts or organic solvents. PER is first adsorbed on AC in the gas phase, and the PER-adsorbed AC is subjected to electrochemical oxidation in aqueous H2SO4 as the electrolyte. Because gas-phase adsorption is solvent-free, PER is completely adsorbed on AC as long as the amount of PER does not exceed the saturated adsorption capacity of the AC, which enables accurate control of the amount adsorbed. PER is electrochemically oxidized to PERD in the nanopores of AC at above 0.7 V vs Ag/AgCl. The hybridized PERD undergoes a rapid reversible two-electron redox reaction in the nanopores owing to the large contact interface between the conductive carbon pore surfaces and PERD. The resulting AC/PERD hybrids serve as electrodes for electrochemical capacitors, utilizing the rapid redox reaction of PERD. The hybridization method is advantageous for quantitatively optimizing electrochemical capacitor performance by adjusting the amount of adsorbed PER. Moreover, because PERD hybridization in the AC nanopores does not expand the electrode volume, the volumetric capacitance increases with increasing hybridized PERD content. In three-electrode cell measurements, the volumetric capacitance at 0.05 A g-1 reaches 299 F cm-3, and 61% of this capacitance is retained at 10 A g-1 when 5 mmol of PER is used per gram of AC. Meanwhile, pristine AC delivers 117 F cm-3 at 0.05 A g-1 with a capacitance retention of 46% at 10 A g-1. Two-electrode cell measurements reveal that self-discharge is significantly suppressed by the hybridized PERD when AC/PERD hybrids and AC are used as cathodes and anodes, respectively, compared to that of a symmetrical AC cell. Moreover, PERD does not undergo cross-diffusion in the asymmetrical cells during self-discharge tests for 24 h.

Structure and Bonding in π-Stacked Perylenes: The Impact of Charge on Pancake Bonding.

Perylene (PER) is a prototype of polycyclic aromatic hydrocarbons (PAHs), which play a pivotal role in various functional and electronic materials due to favorable molecule-to-molecule overlaps, which enhance electronic transport. This study provides guidelines regarding the impact of molecular charge on pancake bonding, a form of strong π-stacking interaction. Pancake bonding significantly boosts interaction energies within the monopositive dimer ([(C20H12)2]•+ or PER2+), crucial for stabilizing aggregation and crystal formation. We discovered energetically feasible sliding and rotation pathways within the [(C20H12)2]•+ dimer, connecting different configurations found in the Cambridge Structural Database (CSD). The dimer's charge profoundly influences the pancake bond order (PBO) and the strength and structural preferences of pancake bonding. The most stable configuration is found in the monocationic state (PER2+), featuring a pancake bond order of 1/2 with one-electron multicenter bonding (1e/mc) with similar characteristics for charge -1. Increasing the total charge of the dimer to +2 or -2 leads to an unstable local minimum. Diverse distribution of pancake bonding types present in crystal structures is interpreted with modeling based on dimer computations with varying charges.

Analytical quality by design using a D-optimal design and parallel factor analysis in an automatic solid phase extraction system coupled to liquid chromatography. Determination of nine PAHs in coffee samples

Optimizing a multi-residue analysis when using an automatic SPE (solid phase extraction) system and complex matrices becomes a difficult problem because of the large number of experimental factors that can influence the recovery of the analytes. Furthermore, in most cases, the conditions of the factors that enhance the response of one analyte are in conflict with those suitable for some others.In this work, AQbD (Analytical Quality by Design) is applied to the development of an analytical procedure based on automatic SPE coupled to HPLC-FLD in the determination of nine polycyclic aromatic hydrocarbons (PAHs) in coffee samples.Focussing on the SPE, the elution volume, the dry time, and volume in the wash stage, and the organic solvent (at two, three, three, and four levels, respectively) were considered.The first problem is to handle these four factors (control method parameters, CMPs) at different levels to optimize responses (critical quality attributes, CQAs). This task has been carried out using a D-optimal design that, starting from a full factorial design of four factors with 72 experiments, reduced this number to 19, maintaining the precision of the estimates, saving time and costs in the laboratory.The second problem is related to the choice of CQAs to apply the AQbD methodology. A complex matrix such as coffee contains impurities that interferes with the target analytes and may even coelute in the chromatographic determination. A PARAFAC decomposition allows avoiding this problem and uses the “second order advantage” to unequivocally identify each analyte. Then, the obtained sample loadings were used as responses. Specifically, each CQA is the difference between spiked and blank coffee samples. All these CQAs must be maximized.Once the experimental data were obtained, two alternatives were posed: on the one hand, the classical optimization based on the estimation of the effects of CMPs on the CQAs, and on the other hand, applying the AQbD methodology to construct the design space that allows to increase the knowledge of the automatic SPE system.Because the experimental domain of CMPs is discrete and the SPE system performs differently for each analyte, it is not possible to obtain the maximum of all CQAs at the same factor levels. Therefore, the design space of the CMPs is obtaining through the Pareto front of the non-dominated values of CQAs.The nine PAHs selected were phenanthrene (PHE), anthracene (ANT), fluoranthene (FLN), pyrene (PYR), chrysene (CHR), benzo[a]anthracene (BaA), perylene (PER), benzo[b]fluoranthene (BbF) and benzo[a]pyrene (BaP). European regulations amending foodstuff set maximum levels for BaP and the sum of the content of four compounds (PAH4): BaP, BaA, BbF and CHR.

Liquid Crystal Nanoparticle Conjugates for Scavenging Reactive Oxygen Species in Live Cells.

The elevated intracellular production of or extracellular exposure to reactive oxygen species (ROS) causes oxidative stress to cells, resulting in deleterious irreversible biomolecular reactions (e.g., lipid peroxidation) and disease progression. The use of low-molecular weight antioxidants, such as 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), as ROS scavengers fails to achieve the desired efficacy because of their poor or uncontrolled cellular uptake and off-target effects, such as dysfunction of essential redox homeostasis. In this study, we fabricated a liquid crystal nanoparticle (LCNP) conjugate system with the fluorescent dye perylene (PY) loaded in the interior and poly (ethylene glycol) (PEG) decorated on the surface along with multiple molecules of TEMPO (PY-LCNP-PEG/TEMPO). PY-LCNP-PEG/TEMPO exhibit enhanced cellular uptake, and efficient ROS-scavenging activity in live cells. On average, the 120 nm diameter PY-LCNPs were conjugated with >1800 molecules of TEMPO moieties on their surface. PY-LCNP-PEG/TEMPO showed significantly greater reduction in ROS activity and lipid peroxidation compared to free TEMPO when the cells were challenged with ROS generating agents, such as hydrogen peroxide (H2O2). We suggest that this is due to the increased local concentration of TEMPO molecules on the surface of the PY-LCNP-PEG/TEMPO NPs, which efficiently bind to the plasma membrane and enter cells. Overall, these results demonstrate the enhanced capability of TEMPO-conjugated LCNPs to protect live cells from oxidative stress by effectively scavenging ROS and reducing lipid peroxidation.

Scalable and Precise Synthesis of Armchair-Edge Graphene Nanoribbon in Metal-Organic Framework.

Graphene nanoribbons (GNRs), narrow and straight-edged stripes of graphene, attract a great deal of attention because of their excellent electronic and magnetic properties. As of yet, there is no fabrication method for GNRs to satisfy both precision at the atomic scale and scalability, which is critical for fundamental research and future technological development. Here, we report a methodology for bulk-scale synthesis of GNRs with atomic precision utilizing a metal-organic framework (MOF). The GNR was synthesized by the polymerization of perylene (PER) or its derivative within the nanochannels of the MOF. Molecular dynamics simulations showed that PER was uniaxially aligned along the nanochannels of the MOF through host-guest interactions, which allowed for regulated growth of the nanoribbons. A series of characterizations of the GNR, including NMR, UV/vis/NIR, and Raman spectroscopy measurements, confirmed the formation of the GNR with well-controlled edge structure and width.

Determination of Structural Properties of Some Important Polymers Used as Interfacial Layer in Fabrication of Schottky Barrier Diodes (SBDs)

In this study, structural, electronic and thermal properties of important polymers such as Perylene (PER), Polypyrrole (PPy) and Polyvinyl alcohol (PVA) commonly used in the production of metal-polymer-semiconductor (MPS) type Schottky Barrier Diodes (SBDs) were determined. Since the opto-electronic properties of the materials depend on the electronic band gap, the High Occupied Molecular Orbital (HOMO) and Low Unoccupied Molecular Orbital (LUMO) energies for the polymeric structures and the gap between of energy levels were calculated. In addition, entropy, heat capacity and total thermal energy values were calculated over a wide temperature range and it was determined how thermochemical properties of polymers were affected with temperature. The obtained results showed that while PER has a planar structure, PPy and PVA has a non-planar structure. PER also has the highest chemical reactivity among the polymers examined with large band gap calculated as 3.03 eV. In addition, thermochemical parameters of all polymers increase with increasing temperature almost as linearly.

ROLE OF YEAST CONSORTIUM FOR THE REMEDIATION OF PERYLENE FROM AQUEOUS ENVIRONMENT: PROCESS OPTIMIZATION

Perylene (PRL), a five- ring nuclear polycyclic aromatic hydrocarbon (PAH) has attracted attention because of its toxic properties. This study aimed to evaluate the efficiency of yeast consortium YC02 to remediate PRL in presence of ZnO nanoparticles and produced biosurfactant in the growth medium. Response surface methodology (RSM), 3- level five variables Box-Behnken design (BBD) was employed to optimize the factors viz. pH 7.0, temperature 30ºC, shaking speed 130 rpm, inoculum dosage 3% and zinc oxide nanoparticles (ZnO) concentration 2 g L-1 after a period of 6 days of incubation for the enhanced degradation of PRL (74 ± 0.01%) using yeast consortium. It was well in close agreement with the predicated value obtained by RSM model yield (74 ± 0.8%). Analysis of variance (ANOVA) showed F-value of 58.13, R2 of 0.9790, probability of

Highly Efficient Orange-Red/Red Excimer Fluorescence from Dimeric π–π Stacking of Perylene and Its Nanoparticle Applications

To achieve high-efficiency red excimer fluorescence, two novel perylene (PE) derivatives (mTPA-3PE and 2SF-3PE) are designed and synthesized with different monosubstituent triphenylamine (TPA) and spirofluorene (SF), respectively. The photophysical investigations reveal that mTPA-3PE and 2SF-3PE exhibit red/orange-red excimer fluorescence (637 and 610 nm) with long lifetimes (37.86 and 72.41 ns) in crystals but significantly different photoluminescence efficiencies (24 and 77%). Both crystal structure and excited-state property emphasize that the discreteness of the PE dimer with π–π stacking is essentially responsible for the high-efficiency excimer emission in the crystal. Using PE as a π–π emissive core in this work, highly efficient red excimer fluorescence is harvested in the crystal for the first time. Moreover, their nanoparticles with the same excimer fluorescence exhibit the advantage of easy processing and the promising application in cell imaging. Once again, our results validate the mechanism ...

Synthesis and Characterization of Swallow-Tail Perylene Bisimide as Organic Phosphor for Hybrid LED

Synthesis and Characterization of Swallow-Tail Perylene Bisimide as Organic Phosphor for Hybrid LED

Ethylene Vinyl Alcohol Copolymer (EVOH) as a Functional Barrier against Surrogate Components Migrating from Paperboard

Ethylene vinyl alcohol copolymer (EVOH) is a key material of interest as a functional barrier against substances migrating from recycled paperboard, due to its outstanding barrier properties. Three multilayer films containing two different grades of EVOH, L171B (3 µm) and F171B (3 and 5 µm), were benchmarked against a multilayer film containing polyamide 6/6.6 copolymer (PA 6/6.6, 3 µm) and monolayer polyethylene terephthalate (PET, 12 µm). The 5 films were evaluated as barrier materials against 5 surrogate substances simulating different migrants potentially present in recycled paperboard: n-heptadecane (C17) as a mineral oil-saturated hydrocarbon (MOSH), 4-methylbenzophenone (MBP) as a photoinitiator, di-n-propyl phthalate (DPP) as a plasticiser, and anthracene (ANT) and perylene (PER) as mineral oil aromatic hydrocarbons (MOAHs). The test was accelerated at 60°C for 25 days, which is equivalent to a shelf life of 2 years at 25°C. All films containing 3 or 5 µm EVOH were found to be good barriers, showing no breakthrough values over 1% of the initial concentration found in the paperboard, and they could easily compete with 12 µm PET. The multilayer with 3 µm PA 6/6.6 showed higher breakthrough values for both MBP and DPP than the other materials although still below the 1% threshold value. However, ANT showed substantial breakthrough values of nearly 2%, indicating that PA 6/6.6 might not offer enough protection against low-weight MOAH components.

Hybrid Liquid Crystal Nanocarriers for Enhanced Zinc Phthalocyanine-Mediated Photodynamic Therapy.

Current challenges in photodynamic therapy (PDT) include both the targeted delivery of the photosensitizer (PS) to the desired cellular location and the maintenance of PS efficacy. Zinc phthalocyanine (ZnPc), a macrocyclic porphyrin and a potent PS for PDT, undergoes photoexcitation to generate reactive singlet oxygen that kills cells efficiently, particularly when delivered to the plasma membrane. Like other commonly employed PS, ZnPc is highly hydrophobic and prone to self-aggregation in aqueous biological media. Further, it lacks innate subcellular targeting specificity. Cumulatively, these attributes pose significant challenges for delivery via traditional systemic drug delivery modalities. Here, we report the development and characterization of a liquid crystal nanoparticle (LCNP)-based formulation for the encapsulation and targeted tethering of ZnPc to the plasma membrane bilayer. ZnPc was coloaded with the organic fluorophore, perylene (PY), in the hydrophobic polymeric matrix of the LCNP core. PY facilitated the fluorescence-based tracking of the LCNP carrier while also serving as a Förster resonance energy transfer (FRET) donor to the ZnPc acceptor. This configuration availed efficient singlet oxygen generation via enhanced excitation of ZnPc from multiple surrounding PY energy donors. When excited in a FRET configuration, cuvette-based assays revealed that singlet oxygen generation from the ZnPc was ∼1.8-fold greater and kinetically 12 times faster compared to when the ZnPc was excited directly. The specific tethering of the LCNPs to the plasma membrane of HEK 293 T/17 and HeLa cells was achieved by surface functionalization of the NPs with PEGylated cholesterol. In HeLa cells, LCNPs coloaded with PY and ZnPc, when photoexcited in a FRET configuration, mediated 70% greater cell killing compared to LCNPs containing ZnPc alone (direct excitation of ZnPc). This was attributed to a significant increase of the oxidative stress in the cells during the PDT. Overall, this work details the ability of the LCNP platform to facilitate (1) the specific tethering of the PY-ZnPc FRET pair to the plasma membrane and (2) the FRET-mediated, augmented singlet oxygen generation for enhanced PDT relative to the direct excitation of ZnPc alone.

Room-Temperature Columnar Nematic and Soft Crystalline Columnar Assemblies of a New Series of Perylene-Centred Disc Tetramers.

Three new oligomeric perylene (PE) tetraester derivatives, consisting of a PE-based core with four pentaalkynylbenzene units attached through flexible alkyl spacers, are reported. These derivatives were investigated for their mesomorphic properties and thermal, photophysical, and electrochemical behaviour. Small- (SAXS) and wide-angle X-ray scattering (WAXS) studies were performed to deduce the exact nature of the phases. To resolve overlapping reflections and facilitate their indexing, grazing-incidence SAXS/WAXS experiments were carried out on oriented thin films on indium tin oxide (ITO)-coated glass substrate. The corresponding electron density maps were derived from the intensities observed in the diffraction pattern. Whereas compounds with shorter alkyl spacers (n=6 and 8) were found to self-organise into soft crystalline columnar assemblies, those with longer spacers (n=10) exhibited a liquid-crystalline columnar nematic mesophase. This is in contrast to previous reports that describe highly symmetric 2D hexagonal and rectangular columnar structures of PE-based mesogens. The morphology of self-assembly was found to transform from soft crystal columnar to nematic columnar phase through simple variation in the number of alkyl spacers. All compounds exhibited excellent fluorescence emission properties with a very good quantum yield and large band gap. Apart from high solubility and good quantum yield, these compounds can serve as standards to measure quantum yields of unknown samples. These compounds also display green luminescence and may find applications for various optoelectronic devices.

The Synthesis and Biological Applications of Water-Soluble Perylene Diimides

The Synthesis and Biological Applications of Water-Soluble Perylene Diimides

Synthesis and Characterization of Red Organic Fluorescent of Perylene Bisimide Derivatives

Synthesis and Characterization of Red Organic Fluorescent of Perylene Bisimide Derivatives

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be ∼61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two-component PY–PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from ∼330 nm to ∼600 nm in aqueous solution.

Current Researches and Applications of Perylene Compounds

Current Researches and Applications of Perylene Compounds

Star-shaped polyfluorene: Design, synthesis, characterization and application towards solar cells

The present manuscript reports the design, synthesis and characterization of three star-shaped polymers consisting of three different arylimides such as perylene (PR)-, naphthalene (NT)- and benzene (BZ) tetracarboxylicdiimide as core and polyfluorene (PF) as arms. Chemical structure of star-shaped polymers was aimed at broadening as much as possible their absorption profile. Arylimide cored star polymers (PF-BZ, PF-NT and PF-PR) were prepared through palladium catalyzed Suzuki polycondensation to tune the band gap of the polymers. The prepared polymers were characterized by elemental analysis, NMR, GPC, UV–Vis, photoluminescence and cyclic voltammetry studies. Electrochemical and optical responses of three polymers revealed the lowering of band gap from linear PF to star-shaped polymers. TCSPC study confirmed the partial energy transfer from PF arms to arylimide cores. The unexpected keto defect in linear PF was also reduced by preparation of star polymer with large arylimide cores. TGA exhibited the enhancement of thermal stability of star polymer than linear PF. By using star polyfluorenes as the donor and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the acceptor, bulk heterojunction (BHJ) solar cells of the structure ITO/PEDOT:PSS/star polymer: PCBM/Al were fabricated and studied with a solar simulator under AM1.5G (100mW/cm2) irradiation intensity. Those cells showed the open circuit voltage (Voc) ∼0.52–0.55V, the short circuit current density (Jsc) ∼0.84–1.13mAcm−2, the fill factor ∼0.39–0.44 and the power conversion efficiency (PCE) ∼0.18–0.26%.

DISTRIBUTION OF POLYCYCLIC AROMATIC HYDROCARBONS IN SURFACE SEDIMENTS OF KOH SICHANG ANCHORAGE AREA, THAILAND

The levels and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in surface sediments of Koh Sichang anchorage area, Thailand using gas chromatography with flame-ionization detection (GC/FID). The total concentrations of 16 PAHs US EPA priority pollutants varied from 65.2 to 18,970 ng/g dw, with a median concentration of 282±3,660 ng/g dw. The sediment samples were classified as moderately contaminated compared to those observed in other regions. PAH compositional signatures of surface sediments of the study area were dominated by higher molecular weight PAHs (4-6 rings) comprising about 87 per cent of total PAHs concentrations. Dibenzo[a,h]anthracene, benzo[b]fluoranthene, benzo[g,h,i]perylene, benzo[a]pyrene, fluoranthene, indeno[1,2,3-cd]pyrene, and pyrene represented the highest fractions in most surface sediment samples. Source apportionment using diagnostic PAH ratios indicated that composition of PAHs in most sediment samples originated mainly from incomplete combustion of organic matter (pyrolytic origin), with a mixture of pyrolytic and petrogenic PAHs were observed in some of the study sites. The presence of almost all human carcinogenic PAHs in the study area indicated that these sediments can be considered contaminated sites, suggesting that future monitoring programs together with an effective coastal management program must be implemented to ensure health and safety for all.

Synthesis of Z-Shape Functionalized Perylenes

Synthesis of Z-Shape Functionalized Perylenes