Aromatic Bis Research Articles

Shedding light on the use of graphene oxide-thiosemicarbazone hybrids towards the rapid immobilisation of methylene blue and functional coumarins.

Coumarins, methylene blue derivatives, as well as related functional organic dyes have become prevalent tools in life sciences and biomedicine. Their intense blue fluorescence emission makes them ideal agents for a range of applications, yet an unwanted facet of the interesting biological properties of such probes presents a simultaneous environmental threat due to inherent toxicity and persistence in aqueous media. As such, significant research efforts now ought to focus on their removal from the environment, and the sustainable trapping onto widely available, water dispersible and processable adsorbent structures such as graphene oxides could be advantageous. Additionally, flat and aromatic bis(thiosemicarbazones) (BTSCs) have shown biocompatibility and chemotherapeutic potential, as well as intrinsic fluorescence, hence traceability in the environment and in living systems. A new palette of graphene oxide-based hierarchical supramolecular materials incorporating BTSCs were prepared, characterised, and reported hereby. We report on the supramolecular entrapping of several flat, aromatic fluorogenic molecules onto graphene oxide on basis of non-covalent interactions, by virtue of their structural features with potential to form aromatic stacks and H-bonds. The evaluations of the binding interactions in solution by between organic dyes (methylene blue and functional coumarins) and new graphene oxide-anchored Zn(ii) derivatised bis(thiosemicarbazones) nanohybrids were carried out by UV-Vis and fluorescence spectroscopies.

Organosoluble and colorless fluorinated poly(ether imide)s containing a bulky fluorene bis(ether anhydride) and various trifluoromethyl-substituted aromatic bis(ether amine)s: synthesis and characterization

Organosoluble and colorless fluorinated poly(ether imide)s containing a bulky fluorene bis(ether anhydride) and various trifluoromethyl-substituted aromatic bis(ether amine)s: synthesis and characterization

π-Extended benzo[1,2:4,5]di[7]annulene bis(dicarboximide)s - a new class of non-alternant polycyclic aromatic dicarboximides.

Aromatic dicarboximides are a class of molecules represented by the well-known rylene bis(dicarboximide)s, in particular perylene or naphthalene bis(dicarboximide)s, which show pronounced optoelectronic properties and are applied as color pigments, fluorescent dyes and organic semiconductors. Herein we extend the family of aromatic bis(dicarboximide)s and report the synthesis of the first series of non-alternant aromatic dicarboximides by twofold Pd-catalyzed [5 + 2] annulation. Characterization by UV/vis spectroscopy and cyclic voltammetry (CV) measurements give insight into the optoelectronic characteristics of the hitherto unexplored substance class of heptagon-containing imides. Theoretical studies by nucleus independent chemical shift (NICS) XY-scans and anisotropy of the induced current density (ACID) plots demonstrate the influence of both the non-alternant carbon framework and the imide moieties on aromaticity of the synthesized bisimides.

Aromatic Bis[aminomethylidenebis(phosphonic)] Acids Prevent Ovariectomy-Induced Bone Loss and Suppress Osteoclastogenesis in Mice.

Osteoporosis is a skeletal disease associated with excessive bone turnover. Among the compounds with antiresorptive activity, nitrogen-containing bisphosphonates play the most important role in antiosteoporotic treatment. In previous studies, we obtained two aminomethylidenebisphosphonates—benzene-1,4-bis[aminomethylidene(bisphosphonic)] (WG12399C) acid and naphthalene-1,5-bis[aminomethylidene(bisphosphonic)] (WG12592A) acid—which showed a significant antiproliferative activity toward J774E macrophages, a model of osteoclast precursors. The aim of these studies was to evaluate the antiresorptive activity of these aminobisphosphonates in ovariectomized (OVX) Balb/c mice. The influence of WG12399C and WG12592A administration on bone microstructure and bone strength was studied. Intravenous injections of WG12399C and WG12592A bisphosphonates remarkably prevented OVX-induced bone loss; for example, they sustained bone mineral density at control levels and restored other bone parameters such as trabecular separation. This was accompanied by a remarkable reduction in the number of TRAP-positive cells in bone tissue. However, a significant improvement in the quality of bone structure did not correlate with a parallel increase in bone strength. In ex vivo studies, WG12399C and WG12592A remarkably bisphosphonates reduced osteoclastogenesis and partially inhibited the resorptive activity of mature osteoclasts. Our results show interesting biological activity of two aminobisphosphonates, which may be of interest in the context of antiresorptive therapy.

The Thermal Stability and Mechanical Properties of Non-Segregating Blends of Polyimides with Copoly(Urethane-Imide)s

The series of compositions containing thermodynamically incompatible flexible blocks of aliphatic polyesters and rigid blocks of aromatic bis (urethane) imides in the volume of polymers was obtained on the basis of multiblock (segmented) poly (urethane-imides) and related aromatic polyimides. The series includes segmented poly (urethane-imides) with different relative content of flexible and rigid blocks, non-segregating mixtures of poly (urethane-imides) and thermoplastic partially crystalline polyimide, statistical copolymers of poly (urethane-imide) with imide, and non-segregating mixtures of statistical copolymers with thermoplastic polyimide. The derived polymer systems were studied using thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. The deformation and strength properties of film samples are determined. It is shown that the properties of the studied polymers change as their content of imides blocks increases, and the transition from thermoplastic poly (urethane-imide) elastomers to thermoplastic polyimides is observed.

Synthesis and characterization of new poly(diketone imide)s derived from 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride and various diamines

1,4-Bis(3,4-dicarboxybenzoyl)benzene dianhydride, an aromatic bis(ketone anhydride) monomer, was synthesized by the Friedel–Crafts reaction of terephthaloyl dichloride and o-xylene, followed by the oxidation of the intermediate tetramethylated compound and cyclodehydration of the resulting tetraacid. A series of new poly(diketone imide)s (PDKIs) were prepared from this dianhydride with various aromatic diamines via a conventional two-stage process that included ring-opening polyaddition to form the poly(amic acid)s followed by thermal or chemical imidization. Most of the PDKIs through chemical imidization were soluble in aprotic amide solvents, such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, m-cresol, and so on. The resulting PDKIs had good thermal property with the glass transition temperature of 203–275°C, the temperature at 5% weight loss of 500–539°C, and the residue of 51–60% at 800°C in nitrogen. Additionally, strong and flexible PDKI films obtained by thermal imidization exhibited outstanding mechanical property with the tensile strength of 88.8–158.5 MPa, tensile modulus of 1.9–3.5 GPa, and elongation at breakage of 7–21%.

Biological effects of aromatic bis[aminomethylidenebis(phosphonic)] acids in osteoclast precursors in vitro.

Nitrogen-containing bisphosphonates (N-BPs) inhibit bone resorption by preventing osteoclast activity. Most clinically usedBPs are hydroxybisphosphonates with the exception of incadronate, which belongs to the class of aminomethylidenebisphosphonic acids. The aim of this study was to evaluate the antiproliferative activity of two previously reported aminobisphosphonates (WG8185B2 and WG9001B) in combination with doxorubicin and cisplatin toward J774E cells (a model of osteoclast precursors in vitro). WG8185B2 and WG9001B BPs enhanced the cytotoxic activity of doxorubicin and cisplatin, especially when applied 24hr prior to cytostatics. The antiproliferative effect of studied BPs was related to the changes in cell cycle progression. WG8185B2 leads to significant accumulation of J774E cells in S phase, whereas WG9001B causes transient arrest in G2 /M phase, followed by an increase in the percentage of cells in S phase. Moreover, WG8185B2 and WG9001B BPs showed enhanced proapoptotic activity in osteoclast precursors, which was manifested by an increase in caspase-3 activity and percentage of apoptotic cells. In addition, both compounds influenced the motility of J774E cells. The exact molecular mechanism of action of examined BPs remains to be determined; however, results show an interesting biological activity of these compounds, which may be of interest in the context of antiresorptive therapy.

Thermal stability and structural anisotropy of semiaromatic poly(ester amides) from aromatic bis(2-oxazolines) and aliphatic dicarboxylic acids

Semiaromatic poly(ester amides) containing three different aromatic units and aliphatic spacers with five different chain lengths were investigated using various experimental methods, with a focus on the effect of structural changes in the mesogenic groups and the length of the flexible alkylene spacer on the observed physical properties. The results of thermal stabilities and crystallographic measurements indicate that the thermal stability is dependent on the content of the amorphous phase in the polymer. The results from the thermal stability, differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and optical microscopy of the poly(ester amides) containing aromatic moieties were compared to the dielectric properties recorded using dielectric relaxation spectroscopy (DRS). DRS contributed to the description of four relaxation regions detected by matching the temperature and frequency dependencies of the dielectric functions. For the poly(ester amides) containing biphenyl units, the presence of a liquid-crystalline (LC) phase was observed.

A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction.

Here we report a general method for the synthesis of polycyclic aromatic dicarboximides (PADIs) by palladium-catalyzed annulation of naphthalene dicarboximide to different types of aromatic substrates. Reaction conditions were optimized by systematic variation of ligand, solvent, and additive. It was shown that solvent has a decisive effect on the yield of the reaction products, and thus 1-chloronaphthalene as solvent afforded the highest yield. By applying the optimized reaction conditions, a broad series of planar carbo- and heterocycle containing PADIs were synthesized in up to 97% yield. Moreover, this approach could be applied to curved aromatic scaffold to achieve the respective bowl-shaped PADI. Two-fold annulation was accomplished by employing arene diboronic esters, affording polycyclic aromatic bis(dicarboximides). The optical and electrochemical properties of this broad series of PADIs were explored as well.

An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

A new expanded porphycene with 26 π-electrons has been prepared by the McMurry coupling of 1,4-bis(3,4-diethyl-2-pyrryl)benzene dialdehyde. Expansion of the porphycene framework provides a ligand capable of stabilizing a bis(rhodium) and a monoruthenium complex. These new porphycene derivatives absorb strongly in the NIR spectral region, with appreciable absorptivity up to 1300 nm. On the basis of their ground- and excited-state spectroscopic features and structural parameters, both the free-base system and the bis(rhodium) complex are considered to be Hückel-type aromatic systems. This conclusion is supported by DFT calculations.

Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

Combining the new aromatic bis(guanidine) ligand bis(tetramethylguanidino)toluene (TMG2tol) and different copper salts led to four new complexes. The molecular structures were analysed by X‐ray diffraction. Three of the complexes are active in biomimetic activation of oxygen. It is the first time a bis‐µ‐oxido species of an aromatic guanidine copper complex is analysed by Raman and UV/Vis spectroscopy. The formation and decay of the bis(µ‐oxido)dicopper species were investigated at low temperatures up to 273 K by UV/Vis spectroscopy with a stopped‐flow setup. The results showed that the Cu2O2 intermediate of an aromatic guanidine–copper complex decays much faster than most known bis(guanidine) complexes. Moreover, natural bond orbital (NBO) analyses revealed that the aromatic guanidine is the stronger donor compared to the aliphatic one.

Organosoluble and colorless fluorinated poly(ether imide)s derived from a highly contorted biphenyl-2,2′-diol bis(ether anhydride) and aromatic bis(ether amine)s with trifluoromethyl substituents

A series of new fluorinated aromatic poly(ether imide)s (PEIs) were prepared from highly contorted 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and various trifluoromethyl-containing bis(ether amine)s via chemical or thermal imidization. All the PEIs showed good solubility in a variety of organic solvents and could afford flexible, colorless, and transparent thin films via solution-casting. They showed cut-off wavelengths of Uv-vis absorptions below 380 nm and very low yellowness index (b* < 7.0). They also showed high thermal stability with the 10% weight loss temperature from 503 to 585 °C of in nitrogen or air atmosphere. The glass transition temperatures (Tgs) are recorded in the range of 194–254 °C by DSC. For a comparative study, another series of non-fluorinated PEIs derived from the same biphenyl-2,2′-diol bis(ether anhydride) with various bis(ether amine)s without the trifluoromethyl substituents were also synthesized and characterized.

Thermal and ultrasound induced gelation of bis(acyl-semicarbazides)—Investigations on the anion tuning and dye adsorbing properties of their gels

Herein we report the anion tuning and dye adsorbing properties of aromatic bis(acyl-semicarbazides) carrying aromatic core and substituents of varying alkyl chain length. Gelator with a specific spacer length (C10) was chosen to study the effect of stimuli such as temperature, ultrasound and anions on gel strength, mode of interaction and morphology. A three dimensional network structure composed of fibers of varying diameters were observed for gels obtained by thermal treatment whereas a lamellar aggregation resulted upon ultrasound treatment as noticed in SEM studies. Ultrasound induced gels (USIG) exhibited higher gel-sol transition temperature and strength than temperature induced gel as observed from dynamic oscillatory studies, FT-IR and XRD due to the differences in the modes of aggregation. The gels could be tuned in the presence of anions at different concentrations and addition of 5 equivalents of F− and AcO− induced gel-sol transition. In addition, these organogels adsorbed dyes such as crystal violet and rhodamine-B from water every effectively which was confirmed by visual method and quantified by UV–vis spectrophotometry.

Synthesis and characterization of advanced biobased thermoplastic nonisocyanate polyurethanes, with controlled aromatic-aliphatic architectures

The aim of this study was the elaboration of thermoplastic and biobased nonisocyanate polyurethanes (TNIPUs) based on different aromatic-aliphatic architectures. A rigid aromatic bis(cyclic carbonate) was synthesized from terephthalic acid, and subsequently used with various diamines for the preparation of TNIPUs. A two-step method was investigated to design advanced macromolecular architectures. All TNIPUs and corresponding intermediates were fully characterized. The influence of various parameters such as the ratio between the constituting building blocks and the chemical structure on NIPU properties was studied. Thermal and mechanical results show that the TNIPUs presenting the highest molar masses and the highest properties were synthesized from dimer diamine prepolymers. A high content of terephthalic acid and short-chain diamine increases the glass transition temperature and leads to good performances, with a balance between elongation and tensile strength properties. The final TNIPUs present biobased content up to 76%.

Fluorinated Poly(phenylquinoxaline)s with Low Dielectric Constants and High Hydrolytic Stability: Synthesis and Characterization

Two fluorinated polyphenylquinoxalines (FPPQs) have been prepared from the newly developed trifluoromethyl-containing aromatic bis(alpha-diketone) monomers (FTKs) and aromatic bis(o-diamine). The thermal, electrical, and hydrolytic properties of the FPPQs were investigated. The results reveal that the developed FPPQ films exhibit low dielectric constants of 2.78-2.85, which are closely related to their excellent hydrophobic nature. The FPPQ films also manifest excellent hydrolytic stability in the aqueous environment. Meanwhile, the intrinsically high thermal stability and electrical resistivity are maintained for the FPPQs.

Aromatic Gain in a Supramolecular Polymer

The synergy of aromatic gain and hydrogen bonding in a supramolecular polymer is explored. Partially aromatic bis(squaramide) bolaamphiphiles were designed to self-assemble through a combination of hydrophobic, hydrogen-bonding, and aromatic effects into stiff, high-aspect-ratio fibers. UV and IR spectroscopy show electron delocalization and geometric changes within the squaramide ring indicative of strong hydrogen bonding and aromatic gain of the monomer units. The aromatic contribution to the interaction energy was further supported computationally by nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) indices, demonstrating greater aromatic character upon polymerization: at least 30% in a pentamer. The aromatic gain-hydrogen bonding synergy results in a significant increase in thermodynamic stability and a striking difference in aggregate morphology of the bis(squaramide) bolamphiphile compared to isosteres that cannot engage in this effect.

Aromatic Gain in a Supramolecular Polymer

AbstractThe synergy of aromatic gain and hydrogen bonding in a supramolecular polymer is explored. Partially aromatic bis(squaramide) bolaamphiphiles were designed to self‐assemble through a combination of hydrophobic, hydrogen‐bonding, and aromatic effects into stiff, high‐aspect‐ratio fibers. UV and IR spectroscopy show electron delocalization and geometric changes within the squaramide ring indicative of strong hydrogen bonding and aromatic gain of the monomer units. The aromatic contribution to the interaction energy was further supported computationally by nucleus‐independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) indices, demonstrating greater aromatic character upon polymerization: at least 30 % in a pentamer. The aromatic gain–hydrogen bonding synergy results in a significant increase in thermodynamic stability and a striking difference in aggregate morphology of the bis(squaramide) bolamphiphile compared to isosteres that cannot engage in this effect.

Organotrifluoroborates as attractive self-assembling systems: the case of bifunctional dipotassium phenylene-1,4-bis(trifluoroborate).

The first structure of an aromatic bis(trifluoroborate) dipotassium salt, elucidated by the combination of crystallography, DFT calculations, topological and non-covalent interaction analysis, discloses a 3D network undergoing spontaneous self-assembly thanks to the massive participation of weak intra- and intermolecular interactions for which fluorine atoms proved to play a leading role.

SuFEx-based synthesis of polysulfates.

High-molecular-weight polysulfates are readily formed from aromatic bis(silyl ethers) and bis(fluorosulfates) in the presence of a base catalyst. The reaction is fast and proceeds well under neat conditions or in solvents, such as dimethyl formamide or N-methylpyrrolidone, to provide the desired polymers in nearly quantitative yield. These polymers are more resistant to chemical degradation than their polycarbonate analogues and exhibit excellent mechanical, optical, and oxygen-barrier properties.

SuFEx‐Based Synthesis of Polysulfates

AbstractHigh‐molecular‐weight polysulfates are readily formed from aromatic bis(silyl ethers) and bis(fluorosulfates) in the presence of a base catalyst. The reaction is fast and proceeds well under neat conditions or in solvents, such as dimethyl formamide or N‐methylpyrrolidone, to provide the desired polymers in nearly quantitative yield. These polymers are more resistant to chemical degradation than their polycarbonate analogues and exhibit excellent mechanical, optical, and oxygen‐barrier properties.