ABSTRACT Flexible photothermal materials made of particulate carbon, metal, polymer, or semiconductors often suffer from interfacial incompatibility, leading to cracking and delamination over prolonged use. These limitations make it difficult for flexible composite materials to simultaneously meet the requirements of long‐term interfacial stability and high photothermal performance. Here we circumvented these persistent challenges by using flexible organic crystals, where the absorber is a structurally homogeneous radical cocrystal and strong light absorption is accomplished by charge transfer (CT) between two molecular components. We cocrystallized electron donor perylene (PE) and acceptor naphthalene diimide (NDI) to prepare mechanically flexible, centimeter‐size cocrystals (PE‐NDI), which demonstrate persistent radical characteristics with a spin coherence time of 2.1 µs. Prominent donor–acceptor interaction (−87.7 kJ mol −1 ) facilitates strong light absorption from 200 to 780 nm, while hydrogen bonds are thought to account for the reversible elastic bending. Excitation at 685 nm yields an extraordinarily high photothermal conversion efficiency of 94%. Integration of PE‐NDI in a thermoelectric generator enabled direct solar energy harvesting via a photo‐thermo‐electric conversion sequence, demonstrating the potential of flexible cocrystals for renewable energy harvesting. This work highlights the untapped potential of mechanically compliant organic crystals as flexible, single‐component, lightweight photothermal materials.

Flexible photothermal materials made of particulate carbon, metal, polymer, or semiconductors often suffer from interfacial incompatibility, leading to cracking and delamination over prolonged use. These limitations make it difficult for flexible composite materials to simultaneously meet the requirements of long-term interfacial stability and high photothermal performance. Here we circumvented these persistent challenges by using flexible organic crystals, where the absorber is a structurally homogeneous radical cocrystal and strong light absorption is accomplished by charge transfer (CT) between two molecular components. We cocrystallized electron donor perylene (PE) and acceptor naphthalene diimide (NDI) to prepare mechanically flexible, centimeter-size cocrystals (PE-NDI), which demonstrate persistent radical characteristics with a spin coherence time of 2.1 µs. Prominent donor-acceptor interaction (-87.7kJ mol-1) facilitates strong light absorption from 200 to 780nm, while hydrogen bonds are thought to account for the reversible elastic bending. Excitation at 685nm yields an extraordinarily high photothermal conversion efficiency of 94%. Integration of PE-NDI in a thermoelectric generator enabled direct solar energy harvesting via a photo-thermo-electric conversion sequence, demonstrating the potential of flexible cocrystals for renewable energy harvesting. This work highlights the untapped potential of mechanically compliant organic crystals as flexible, single-component, lightweight photothermal materials.

Photothermal therapy (PTT) is a promising tumor treatment strategy. However, developing organic photothermal agents (PTAs) with both high photothermal conversion efficiency (PCE) and simple synthesis remains a major challenge. Herein, we developed the charge-transfer complex nanoparticles (termed PER-TCQ), via supramolecular assembly of perylene (PER) as the electron donor and tetrachloro-1,4-benzoquinone (TCQ) as the electron acceptor. The strong charge-transfer interaction between PER and TCQ confers PER-TCQ nanoparticles with pronounced near-infrared (NIR) absorption. Upon 808nm laser irradiation, PER-TCQ achieved a high PCE of 66.1%. Its effective antitumor efficacy was consistently validated by in vitro and in vivo experiments, demonstrating the great promise of such programmable complexes as high-performance organic PTAs.

Förster energy transfer phenomena were observed in the system of anthracene (AN) - tetracene (TE) and anthracene (AN) - perylene (PE) doped in poly-N-isopropylacrylamide (PNIPA) gel, which exhibits volume-phase transfer phenomena. In the shrunken state, the energy transfer occurred slightly. By contrast, in the swollen state, we observed that energy transfer occurred efficiently from AN to TE or PE. In general, the energy transfer process depends on the concentration and distance between the energy donor and acceptor. The actual concentration and distances between probe molecules were estimated using equations for the Förster energy transfer. The average distance changes were ca. 1 nm during swollen–shrunken processes. We were able to use Förster energy transfer phenomena for quantitative elucidation at the molecular level.

Organic donor-acceptor (D-A) cocrystals are gaining attention for their potential applications in optoelectronic devices. This study explores the dynamics of charge transfer (CT) and triplet exciton formation in various D-A cocrystals. By examining a series of D-A cocrystals composed of coronene (COR), peri-xanthenoxanthene (PXX), and perylene (PER) donors paired with N,N-bis(3'-pentyl)perylene-3,4:9,10-bis(dicarboximide) (PDI), naphthalene-1,4:5,8-tetracarboxy-dianhydride (NDA), or pyrene-4,5,9,10-tetraone (PTO) acceptors, using transient absorption microscopy and time-resolved electron paramagnetic resonance spectroscopy, we find that the strength of the CT interaction influences the nature and yield of triplet excitons produced by CT state recombination. In particular, in the PER-PDI, COR-PTO, and PER-PTO cocrystals, localized triplet excitons are lower in energy than the CT state. By contrast, no localized triplet excitons are available to the CT states of the PXX-NDA, PER-NDA, and PXX-PTO cocrystals, and as a result, the CT states rapidly decay to ground state with no triplet formation. Moreover, density functional theory calculations show that the transition between delocalized CT states to a triplet state localized to a single donor or acceptor unit provides the source of spin-orbit coupling necessary when the triplet states are energetically accessible. These findings provide insights into the design of molecular materials with tailored exciton properties for optoelectronic applications.

The combination of photothermal therapy (PTT) and photodynamic therapy (PDT) has become an attractive tumor treatment modality, yet the facile design of photoimmunotheranostic agents with efficient near infrared (NIR) light-absorbing and immune-activating capabilities remains a tremendous challenge. Herein, we developed a NIR-activable organic charge transfer complex (CTC), with perylene (PER) as the electron donor and 4,5,9,10-tetrabromoisochromeno [6,5,4-def]isochromene-1,3,6,8-tetraone (Br4NDI) as the electron acceptor. Through further supramolecular assembly, the PER-Br4NDI nanoparticle (PBND NP) for spatiotemporally controlled photoimmunotherapy was constructed. The PBND NP exhibits superb NIR absorption, robust intermolecular charge transfer, and enhanced intersystem crossing. Upon NIR photoirradiation, the PBND NP effectively exerts photothermal and photodynamic effects with a remarkable photothermal conversion efficiency of 63.5 % and a high reactive oxygen species generation capability, which not only directly ablates primary tumors, but also dramatically suppresses distant tumor growth via promoted immunogenic cell death. Moreover, programmed cell death protein 1 antibody acts synergistically to block immune evasion and ultimately enhances cancer treatment efficacy. This work therefore sheds light on the design of organic CTCs for synergistic photoimmunotherapy.

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

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.

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

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.

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.

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.

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

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

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.

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.

Size control has been successfully achieved in inorganic materials, but it remains a challenge in polymer nanomaterials due to their polydispersity. Here, we report a facile approach to tailor the diameters of polyurethane (PU) nanoparticles (490 nm, 820 nm and 2.1 μm) via perylene bisimide (PBI) assisted self-assembly. The formed morphologies such as spindle, spherical and core–shell structures depend on the ratio of PBI and polymer concentrations. It is shown that the formation of PU nanoparticles is directed by π–π stacking of PBI and the morphology transition is not only affected by the amount of PBI incorporated, but also influenced by solvent, which controls the initial evaporation balance. Furthermore, the prepared PUs exhibit retained optical stability and enhanced thermal stability. The PUs, designed to have conjugated PBI segments in backbones, were synthesized via ring-opening and condensation reactions. Compared with the neat PU, gel permeation chromatography shows narrower molecular weight distribution. Fluorescence spectra and ultraviolet–visible spectra indicate retained maximum emission wavelength of PBI at 574 nm and 5.2% quantum yields. Thermal gravimetric analysis and differential scanning calorimetry reveal 79°C higher decomposition temperature and 22°C higher glass transition temperature. This study provides a new way to fabricate well-defined nanostructures of functionalized PUs.

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.