Tetracarboxylic Dianhydride Research Articles

Perylene Tetracarboxylic Acid Crosslinked to Silica Matrix that Enables Ultrahigh Solid‐State Quantum Yield and Efficient Photon Recycling for Holographic Luminescent Solar Concentrators

Perylene derivatives possess large absorptivity and high quantum yields (QYs) and thus are promising luminophores for luminescent solar concentrators (LSCs). Unfortunately, severe aggregation‐caused quenching, poor solubility, and large reabsorption significantly reduce their solid‐state photoluminescence. To address these issues, perylene tetracarboxylic acid (PTCA) is prepared by hydrolyzing perylene tetracarboxylic dianhydride in sodium hydroxide, which is highly compatible with amino‐silane precursors for in situ sol–gel synthesis of the silica matrix. In this case, highly luminescent and transparent PTCA@silica composites are formed, in which PTCA mainly exists in the monomer species due to covalent crosslinking to silica network structures. Therefore, a near‐unity solid‐state QY of ≈90% is obtained even at elevated loadings and existence of reabsorption due to the preservation of monomer states and efficient photon recycling. To demonstrate their potentials in LSCs, large‐area LSCs () with laminated configuration are fabricated, yielding a high power conversion efficiency of 1.1%. To mitigate the escape‐cone losses, the LSCs can be integrated with holographic grating, reaching an ultrahigh edge‐emission efficiency of 90%.

Plasmon-Enhanced Electrochemiluminescence of PTP-Decorated Eu MOF-Based Pt-Tipped Au Bimetallic Nanorods for the Lincomycin Assay.

Plasmonic bimetal nanostructures can be employed to amplify electrochemiluminescence (ECL) signals. In this work, a high-performance ECL platform was constructed using a europium metal-organic framework (MOF) as a luminophore and Au-Pt bimetallic nanorods (NRs) as a plasma source. Due to the SPR effect of Au-Pt NRs, the aptasensor exhibits 2.6-fold ECL intensity compared to that of pure polyaniline (PANI)-decorated perylene tetracarboxylic dianhydride (PTCA)/Eu MOF. Moreover, decoration with PTP greatly enhances the conductivity and stability of Eu MOF, resulting in sizeable plasmon-enhanced electrochemical luminescence. The as-designed plasmon-enhanced ECL aptasensor displayed highly sensitive detection for lincomycin (Lin). The as-proposed aptasensor could quantify Lin from 0.1 mg/mL to 0.1 ng/mL with a limit of detection (LOD) of 0.026 ng/mL.

Designing and Synthesising Novel Benzophenone Biscyclic Imides Comprising Drug Moity with Investigating their Antimicrobial Activity

The present work involved designing and synthesizing of a series of new. compounds which their molecules are composed from two biologically active components namely sulfamethoxazole or β-lactam containing drugs and cyclic imides. The target new compounds were synthesized by two steps in the first one a series of six bis (N-drug phthalamic acid_4-yl) ketone (1-6) were prepared from the reaction of sulfamethoxazole or β-lactam containing drugs with benzophenone 3, 3′, 4, 4′ -tetracarboxylic dianhydride. In the second step, compounds (1-6) were introduced in dehydration reaction via fusion process producing the target compounds bis (N-drug phthalimidyl-4-yl) ketone (7-12). The antibacterial and antifungal high activities of the prepared compounds (7-12) were tested against (Bacillus subtilis, Klebsiella pneumoniae, Pseudomonas auroginosa and Staphylococcus aurus) and all compounds showed good to high antibacterial activity. However, the maximum inhibition zone was 38 mm against Staphyloccus aurus, 36 mm against Bacillus subtilis, 35 mm against Pseudomonas auroginosa, 28mm against Klebsiella pneumoniae and 19 mm against Rhizosporium fungi.

Электронные состояния зоны проводимости ультратонких пленок тиофен-фенилен со-олигомера и замещенного бифенила на поверхности послойно выращенного ZnO

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO substrate. This corresponds to the transfer of a negative charge from the СH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The СH3-PTTP-СH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 micrometers x 10 micrometers. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10–15 nm.

Two-dimensional lamellar polyimide/cardanol-based benzoxazine copper polymer composite coatings with excellent anti-corrosion performance.

The economic loss and environmental damage caused by metal corrosion is irreversible. Thus, effective methods, such as coating technologies are used to protect metal surfaces from corrosion. In this work, cardanol-based benzoxazine (CB) was synthesized by a solvent-free method using cardanol, paraformaldehyde and n-octylamine. A cardanol-based benzoxazine copper polymer (CBCP) with good mechanical properties was then prepared by CuCl2 catalysis and can be cured at room temperature. Subsequently, polyimide corrosion inhibitors with a two-dimensional sheet structure (pyromellitic dianhydride polyimide (PDPI) and 1,4,5,8-naphthalene tetracarboxylic dianhydride polyimide (NDPI)) were designed and prepared. Lastly, PDPI or NDPI was mixed with CBCP to obtain two-dimensional lamellar polyimide/cardanol-based benzoxazine copper polymer composite coatings. The Tafel curves and electrochemical impedance spectroscopy (EIS) measurements showed composite coatings with good corrosion resistance in different corrosive media. Compared to CBCP coating, the anticorrosion performance of the composite coatings improved obviously, especially the coating obtained with 0.5 wt% PDPI. It exhibits a high polarization resistance (3.874 × 109 Ω), a high protection efficiency (99.99% and 97.98%) and low corrosion rate (3.376 × 10−6 mm year−1). This work suggested a facile and eco-friendly strategy for preparing bio-based anticorrosive composite coatings from low cost and abundant cardanol and polyimide corrosion inhibitors, which will significantly promote their application in metal anticorrosion.

Conduction band electronic states of ultrathin thiophene-phenylene co-oligomer and substituted biphenyl films on the surface of layer-by-layer grown ZnO

The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene -CH3(CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO-substrate. This corresponds to the transfer of a negative charge from the CH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO-substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The CH3-PTTP-CH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 μmx10 μm. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10-15 nm. Keywords: thiophene-phenylene co-oligomers, biphenyl tetracarboxylic dianhydride, ultrathin films, ZnO, atomic layer deposition method, electronic properties, low-energy electron spectroscopy, interface potential barrier.

Closed-Cell Rigid Polyimide Foams for High-Temperature Applications: The Effect of Structure on Combined Properties.

Closed-cell rigid polyimide foams with excellent thermal stability and combined properties were prepared by thermal foaming of a reactive end-capped polyimide precursor powder in a closed mold. The precursor powder was obtained by thermal treatment of a polyester-amine salt (PEAS) solution derived from the reaction of the diethyl ester of 2,3,3′,4′-biphenyl tetracarboxylic dianhydride (α-BPDE) with an aromatic diamine mixture of p-phenylenediamine (PDA) and 2-(4-aminophenyl)-5-aminobenzimidazole (BIA) in the presence of an end-capping agent (mono-ethyl ester of nadic acid anhydride, NE) in an aliphatic alcohol. The effect of polymer mainchain structures on the foaming processability and combined properties of the closed-cell rigid polyimide foams were systematically investigated. The polyimide foams (100–300 kg/m3) with closed-cell rates of 91–95% show an outstanding thermal stability with an initial thermal decomposition temperature of ≥490 °C and a glass transition temperature of 395 °C. Polyimide foams with density of 250 kg/m3 exhibited compression creep deformation as low as 1.6% after thermal aging at 320 °C/0.4 MPa for 2 h.

Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.

Synthesis and characteristic of the ternary composite electrode material PTCDA/CNT@MPC and its electrochemical performance in sodium ion battery

A three-dimensional composite carbon material ([email protected]) showing coaxial cable-like structure was prepared by carbon nanotubes (CNTs) and glucose through hydrothermal method. The ternary composite (PTCDA/[email protected]) was synthesized by coating a layer of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on the surface of [email protected] composite carbon material. The sodium ion battery was assembled using the ternary composite as the positive electrode material, and sodium metal as the negative electrode. The results show that the electrochemical performance of PTCDA/[email protected] composite is much better than that of pure PTCDA. The first discharge capacity is 131.2 mAh g−1 as the current density is 0.1 A g−1, which is close to its theoretical specific capacity of 135 mAh g−1. In particular, the battery shows better discharge properties at higher discharge current rate. When the current density reaches 10 A g−1, the PTCDA/[email protected] electrode material is still able to attain a superior capacity of 90.1 mAh g−1. This is due to the higher conductivity of [email protected] composite carbon material, which not only enhances the conductivity of PTCDA, but also increases the transport channel of ions, so as to increase the adsorption of sodium ions into the composite positive electrode. Therefore, the reversible capacity and cycle life of the composite electrode are significantly improved, which exhibit the excellent intercalation and de-intercalation performance for sodium ions and the charge-discharge rate performance.

Processable poly(ether ether ketone imide)s

New aromatic poly(ether ether ketone imide)s, [PEEKimide]s, were synthesized successfully from 1,3-bis-4′-(4″-aminophenoxy benzoyl) benzene and various commercially available aromatic dianhydrides, such as pyromellitic dianhydride (PMDA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic anhydride (OPDA) and 4,4′-(hexafluro isoproylidene) diphthalic anhydride (HFDA), by two step polycondensation method. These PEEKimides were characterized by FT-IR, solubility in organic solvents, inherent viscosity, DSC, TGA and WXRD. Inherent viscosities of the precursor poly(ether ether ketone amic acid)s were in the range of 0.23–0.40 dl/g in DMF, indicating formation of moderate to high molecular weights. These poly(ether ether ketone imide)s showed good solubility in polar aprotic solvents such as N,N-dimethylacetamide (DMAc), N-methyl 2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) and dimethyl sulphoxide (DMSO) and had glass transition temperatures in the range 245–279°C. Poly(ether ether ketone imide)s showed no weight loss below 280°C; temperatures for 10% weight loss (T10) were in the range of 406–483°C and char yields at 800°C were 17–34%, indicating their good thermal stability. All these poly(ether ether ketone imide)s were amorphous in nature, as per patterns of WXRD which exhibited diffuse broad halos at (2θ = 10–30°) and amorphous nature was reflected in polymer’s good solubility in common organic solvents.

Design, Synthesis and Antimicrobial Activity Evaluation of New Bisimidyl Sulfonamido Ketone Comprising Drug component

This work involved design and synthesis of four new compounds which their molecules contain three biologically active segments, including β-lactam containing drug, cyclic imide and sulfonamido group. Synthesis of the compounds was performed by several steps. In the first step, compound (1) bis[N-phenyl phthalamic acid] ketone was synthesized via reaction of aniline with benzophenone 3,3’,4,4’-tetra carboxylic dianhydride. In the second step, compound (1) was dehydrated by fusion to give the corresponding bis phthalimide (2) which in turn was introduced in reaction with chloro sulfonic acid. The third step involved producing compound (3), the corresponding bis phthalimidyl benzene sulfonyl chloride. Compound (3) is the important key compound from which the target compounds (4-7) were prepared through its reaction with different β-lactam containing drugs. Antibacterial and antifungal activities of compounds (4-7) were screened and the results indicated that they have high biological activity.

Soluble Biobased Polyimides from Diaminotruxinic Acid with Unique Bending Angles

Biobased diamines with unique bending angles, β- and δ-type truxinic acids, were prepared from functionalized 4-nitrocinnamic acid derivatives via solid-state photodimerization and further chemical modification. The obtained diamines were polymerized with tetracarboxylic acid dianhydrides to produce soluble polyimides via chemical imidization at a high efficiency. The obtained δ-type-based polyimides exhibited a high thermostability at 10% weight loss temperature of ∼415 °C and good solubility in organic solvents. Most of the polyimides were soluble in chloroform and dichloromethane, as well as polar organic solvents. Tensile test results showed that biopolyimide films from cyclobutanetetracarboxylic dianhydride exhibited ∼10.2% elongation at break, indicating high flexibility.

PTCDA Molecular Monolayer on Pb Thin Films: An Unusual π-Electron Kondo System and Its Interplay with a Quantum-Confined Superconductor.

The hybridization of magnetism and superconductivity has been an intriguing playground for correlated electron systems, hosting various novel physical phenomena. Usually, localized d or f electrons are central to magnetism. In this study, by placing a PTCDA (3,4,9,10-perylene tetracarboxylic dianhydride) molecular monolayer on ultrathin Pb films, we built a hybrid magnetism/superconductivity (M/SC) system consisting of only sp electronic levels. The magnetic moments reside in the unpaired molecular orbital originating from interfacial charge transfers. We reported distinctive tunneling spectroscopic features of such a Kondo screened π electron impurity lattice on a superconductor in the regime of T_{K}≫Δ, suggesting the formation of a two-dimensional bound states band. Moreover, moiré superlattices with tunable twist angle and the quantum confinement in the ultrathin Pb films provide easy and flexible implementations to tune the interplay between the Kondo physics and the superconductivity, which are rarely present in M/SC hybrid systems.

Laser direct write of heteroatom-doped graphene on molecularly controlled polyimides for electrochemical biosensors with nanomolar sensitivity

Fabrication of heteroatom-doped graphene electrodes remains a challenging endeavor, especially on flexible substrates. Precise chemical and morphological control is even more challenging for patterned microelectrodes. We herein demonstrate a scalable process for directly generating micropatterns of heteroatom-doped porous graphene on polyimide with different backbones using a continuous-wave infrared laser. Conventional two-step polycondensation of 4,4′-oxydianiline with three different tetracarboxylic dianhydrides enabled the fabrication of fully aromatic polyimides with various internal linkages such as phenylene, trifluoromethyl or sulfone groups. Accordingly, we leverage this laser-induced polymer-to-doped-graphene conversion for fabricating electrically conductive microelectrodes with efficient utilization of heteroatoms (N-doped, F-doped, and S-doped). Tuning laser fluence enabled achieving electrical resistivity lower than ∼13 Ω sq−1 for F-doped and N-doped graphene. Finally, our microelectrodes exhibit superior performance for electrochemical sensing of dopamine, one of the important neurotransmitters in the brain. Compared with carbon fiber microelectrodes, the gold standard in electrochemical dopamine sensing, our F-doped high surface area graphene microelectrodes demonstrated 3 order of magnitude higher sensitivity per unit area, detecting dopamine concentrations as low as 10 nM with excellent reproducibility. Hence, our approach is promising for facile fabrication of microelectrodes with superior capabilities for various electrochemical and sensing applications including early diagnosis of neurological disorders.

In-depth characterization of self-healing polymers based on π-π interactions.

The self-healing behavior of two supramolecular polymers based on π–π-interactions featuring different polymer backbones is presented. For this purpose, these polymers were synthesized utilizing a polycondensation of a perylene tetracarboxylic dianhydride with polyether-based diamines and the resulting materials were investigated using various analytical techniques. Thus, the molecular structure of the polymers could be correlated with the ability for self-healing. Moreover, the mechanical behavior was studied using rheology. The activation of the supramolecular interactions results in a breaking of these noncovalent bonds, which was investigated using IR spectroscopy, leading to a sufficient increase in mobility and, finally, a healing of the mechanical damage. This scratch-healing behavior was also quantified in detail using an indenter.

Chain, Network and Framework Formation in Uranyl Ion Complexes with 1,1′‐Biphenyl‐3,3′,4,4′‐Tetracarboxylate

Abstract1,1′‐Biphenyl‐3,3′,4,4′‐tetracarboxylic acid dianhydride has been reacted with uranyl nitrate under solvo‐hydrothermal conditions and in the presence of different counterions to give three complexes of varying periodicity. [Co(en)3]‐ [UO2(bptc)(HCOO)] ⋅ 2.5H2O (1) crystallizes as a monoperiodic coordination polymer in which the bptc4− ligand is exclusively bound through formation of two 7‐membered chelate rings. The [Co(en)3]3+ counterion is essentially a hydrogen bond donor, forming 15 hydrogen bonds with carboxylate and water oxygen atoms. In [H2NMe2]2[UO2(bptc)] ⋅ 0.5H2O (2), half the ligand forms a 7‐membered chelate ring, and the other half bridges two uranium atoms, resulting in the formation of a diperiodic network with hcb topology, the H2NMe2+ counterions being located between the undulating sheets. [PPh4]4[(UO2)4(bptc)3] ⋅ 6H2O (3) contains a mixture of ligands forming either four 4‐membered or two 7‐membered chelate rings, the latter with further bridging, which gives a triperiodic framework displaying large channels, each of which contains two rows of PPh4+ counterions. These results are compared to those of previous studies with this ligand, and of similar studies of phthalate complexes of uranyl ion, in particular in relation to 7‐membered chelate ring formation.

Preparation and properties of polyimide/carbon nanotube composite films with electromagnetic wave absorption performance

AbstractThe polyimide (PI)/carbon nanotube (CNT) films including 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride (BPDA), p‐phenylenediamine (p‐PDA), and CNTs were prepared, which have prominent electromagnetic (EM) wave absorption performance. Experimental analyses of the mechanical properties, thermal stabilities, coefficient of thermal expansion (CTE), the glass transition temperature (Tg), and EM parameter revealed the beneficial effects of the CNTs on the resulting composite films. In particular, when the content of CNTs is 6 wt%, the film shows the highest EM wave absorption performance, which exhibits the effective absorption bandwidth of 2.72 GHz with the matching thickness of only 2.0 mm. These results indicate that PI‐based films have a certain potential application in the area of EM wave‐absorbing materials.

Glutamic acid-assisted hydrothermal recrystallization to configure bamboo-like carbon nanotubes for improved triiodide reduction

Carbon nanotubes (CNTs) have been far and wide employed as the counter electrodes (CEs) in dye-sensitized solar cells because of their individual physical and chemical properties. However, the techniques available now, such as chemical vapor deposition, arc discharge and laser ablation for synthesizing CNTs, commonly suffer from rigorous operations and complicated steps, which make the process difficult to be controlled. Herein, we present a simple and facile glutamic acid-assisted hydrothermal recrystallization strategy to construct bamboo-like CNTs (GHP-BC- x ). Generally, the conventional organic dye 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) is used as a precursor and glutamic acid efficiently promotes the recrystallization of the perylene cores’ planar π-conjugated system in PTCDA under hydrothermal conditions and then self-assembles into one-dimensional nanorods with improved crystallization degree, finally resulting in the morphology of bamboo-like CNTs after carbonization. When applied as the counter electrodes, the GHP-BC-3 displays a remarkable power conversion efficiency of 8.25%, benefiting from the superb electrical conductivity and mass transfer dynamics, superior to that of Pt CE (7.62%).

Photophysical Properties of Thin Films of Perylene Modified with Tetracarboxylic Acid Dianhydride and Diimide Functional Groups

Photophysical Properties of Thin Films of Perylene Modified with Tetracarboxylic Acid Dianhydride and Diimide Functional Groups

Colorless Polyimides Derived from an Alicyclic Tetracarboxylic Dianhydride, CpODA.

An alicyclic tetracarboxylic dianhydride having cyclopentanone bis-spironorbornane structure (CpODA) was polycondensated with aromatic dianhydrides to form the corresponding poly(amic acid)s which possessed logarithmic viscosities in the range 1.47–0.54 dL/g. The poly(amic acid) was imidized by three methods: a chemical, a thermal, and a combined chemical and thermal process. In a thermal method, imidization temperature markedly influenced the film quality and molecular weight of the polyimide. When the poly(amic acid) was cured over the Tg of the corresponding polyimide, the flexible polyimide films were obtained and the molecular weights increased several times, which means that the post-polymerization took place. In spite of low-temperature cure below Tg flexible films with the imidization ratio of 100% were fabricated by a combined chemical and thermal imidization technique. The films possessed the decomposition temperatures in a range of 475–501 °C and Tgs over 330 °C. The high Tg results from a dipole–dipole interaction between the keto groups of the polymer chains as well as development of the rigid polyalicyclic unit. The polyimide films exhibited CTE between 17 and 57 ppm/K. All the films fabricated were entirely colorless and possessed the λcut-offs shorter than 337 nm. Notably, the films prepared by a chemical method exhibited outstanding optical properties.