Post-polymerization modification of aromatic polyimides via Diels-Alder cycloaddition

We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials.     

Design of selective molecularly imprinted sorbent for the optimized solid‐phase extraction of S‐pramipexole from the model multicomponent sample of human urine

The objective of this article was to design the selective molecularly imprinted sorbent dedicated to the solid‐phase extraction of S‐pramipexole from the complex matrix such as human urine. For that purpose, S‐2,6‐diamino‐4,5,6,7‐tetrahydrobenzothiazole was used as the template acting as the structural analog of S‐pramipexole and five various monomers were employed in the presence of ethylene glycol dimethacrylate to produce molecularly imprinted polymers. The binding capabilities of resulted polymers revealed that the highest imprinting effect was noted for polymer prepared from the itaconic acid. The comprehensive analysis of morphology and the characterization of binding sites showed not only negligible differences in the extension of surfaces of imprinted and nonimprinted polymers but also higher heterogeneity of binding sites in the imprinted material. Comprehensive optimization of the molecularly imprinted solid‐phase extraction allowed to select the most appropriate solvents for loading, washing, and elution steps. Subsequent optimization of mass of sorbent and volumes of solvents allowed to achieve satisfactory total recoveries of S‐pramipexole from the model multicomponent real sample of human urine that equals to 91.8 ± 3.2% for imprinted sorbent with comparison to only 37.1 ± 1.1% for Oasis MCX.     

Preparation and application of molecularly imprinted polymer solid‐phase microextraction fiber for the selective analysis of auxins in tobacco

As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.     

Coordination polymers and a dinuclear complex constructed from zinc(II) ions and fluorescein: iodine adsorption and optical properties

Abstract

1-D coordination polymers, ¹_∞[Zn(fl)₂]·2EtOH and ¹_∞[Zn(fl)₂]·2MeOH, and a dinuclear complex, [{Zn(fl)₂}₂(dienpip)]·4H₂O·4EtOH (dienpip?= N,N′-bis(2-aminoethyl)piperazine), were obtained using Zn(II) ions and fluorescein anions (fl). Thermal analysis shows stability of the polymers after solvent removal up to more than 400?°C. Crystallization solvent molecules were removed under reduced pressure with the preservation of the polymeric structure, ¹_∞[Zn(fl)₂]. Desolvated crystals were exposed to I₂ vapors and the crystal structure determination by X-ray diffraction confirmed the presence of I₂ molecules in the channels generated in crystals by the metal-organic framework. The iodine content, evaluated by X-ray diffraction, corresponds to the overall formula ¹_∞[Zn(fl)₂]·0.3I₂. The optical properties of the coordination polymers and the dinuclear complex have been investigated.     

A Conjugated Polymer Containing Arylazopyrazole Units in the Side Chains for Field‐Effect Transistors Optically Tunable by Near Infra‐Red Light

Optically tunable field‐effect transistors (FETs) with near infra‐red (NIR) light show promising applications in various areas. Now, arylazopyrazole groups are incorporated in the side chains of a semiconducting donor–acceptor (D‐A) polymer. The cis–trans interconversion of the arylazopyrazole can be controlled by 980 nm and 808 nm NIR light irradiation, by utilizing NaYF₄:Yb,Tm upconversion nanoparticles and the photothermal effect of conjugated D‐A polymers, respectively. This reversible transformation affects the interchain packing of the polymer thin film, which in turn reversibly tunes the semiconducting properties of the FETs by the successive 980 nm and 808 nm light irradiation. The resultant FETs display fast response to NIR light, good resistance to photofatigue, and stability in storage for up to 120 days. These unique features will be useful in future memory and bioelectronic wearable devices.     

Solid Amine Adsorbent Prepared by Molecular Imprinting and Its Carbon Dioxide Adsorption Properties

A carbon dioxide imprinted solid amine adsorbent (IPEIA‐R) with polyethylenimine (PEI) as a skeleton was conveniently prepared by using glutaraldehyde to cross‐link carbon dioxide‐preadsorbed PEI. As confirmed by FTIR, FT‐Raman, and ¹³C NMR spectroscopy, CO₂ preadsorbed on PEI could occupy the reactive sites of amino groups and act as a template for imprinting in the cross‐linking process. The imino groups formed from the cross‐linking reaction between glutaraldehyde and PEI could be reduced by NaBH₄ to form CO₂‐adsorbable amino groups. The adsorption results indicated that CO₂ imprinting and reduction of imino groups by NaBH₄ endowed the adsorbent with a higher CO₂ adsorption capacity. Compared with PEI‐supported mesoporous adsorbents, the solid amine adsorbent with PEI as a skeleton can avoid serious pore blockage and CO₂ diffusion resistance, even with a high amine content. The solid amine adsorbent with PEI as a skeleton showed a remarkable CO₂ adsorption capacity (8.56 mmol g^?1) in the presence of water at 25 °C, owing to the high amine content and good swelling properties. It also showed promising regeneration performance and could maintain almost the same CO₂ adsorption capacity after 15 adsorption–desorption cycles.     

Application of Linear and Branched Poly(Ethylene Glycol)‐Poly(Lactide) Block Copolymers for the Preparation of Films and Solution Electrospun Meshes

Poly(ethylene glycol)‐poly(lactide) (PEG‐PLA) block copolymers are processed to solvent cast films and solution electrospun meshes. The effect of polymer composition, architecture, and number of anchoring points for the plasticizer on swelling, degradation, and mechanical properties of these films and meshes is investigated as potential barrier device for the prevention of peritoneal adhesions. As a result, adequate properties are achieved for the massive films with a longer retention of the plasticizer PEG for star‐shaped block copolymers than for the linear triblock copolymers and consequently more endurable mechanical properties during degradation. For electrospun meshes fabricated using the same polymers, similar trends are observed, but with an earlier start of fragmentation and lower tensile strengths. To overcome the poor mechanical strengths and an occurring shrinkage during incubation, which may impair the coverage of the wound, further adaptions of the meshes and the fabrication process are necessary.

     

Synthesis,Structures, and Fluorescent Properties of Three Cobalt‐Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand

Three cobalt(II) coordination polymers, [Co₂(tatb)₂(2,2′‐bipy)₂ (H₂O)₂ · DMA · 2H₂O] ( 1 ), [Co₂(tatb)₂(1,10‐phen)₂(H₂O)₂ · 2H₂O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H₂O] ( 3 ) (H₃tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 4⁴‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated.     

Influence of Steric Hindrance of N‐Heterocyclic Ancillary Ligands on the Structure and Magnetic Properties of Manganese(II) Coordination Polymers

Three biphenyl‐3,5‐dicarboxylic acid (H₂ L ) based coordination polymers, namely, [Mn₃( L )₃(2,2′‐bpy)₂]_n ( 1 ), {[Mn( L )(phen)] · (MeOH)}_n ( 2 ), and [Mn( L )(dipt)]_n ( 3 ), (2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and dipt = 2,9‐dimethyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction and analyses of their magnetic properties. 1 is a trinuclear manganese structure with a 2D motifs, which can join by hydrogen bond bridges to give 3D supramolecular architectures. 2 has a dinuclear center forming a 1D supramolecular ladder chain. The mononuclear complex 3 displays 1D metal‐organic chains driven by μ₂‐ L linkers. Their structural differences were investigated, revealing that the influence of steric hindrance on the structures of acid‐based coordination polymers is realized through changing the N‐heterocyclic ancillaries of diverse steric hindrance. Obviously, with decreasing of the steric hindrance of the N‐donor ligand, complexes 1 – 3 show structures from 1D to 2D and mononuclear to multinuclear. Magnetic susceptibility measurements indicate that 1 and 2 have dominating antiferromagnetic couplings between metal ions, whereas compound 3 is paramagnetic.     

Synthesis and characterization of new fluorinated photoactive polyamides based on xanthene pendant: Evaluation of antibacterial and heavy metal ions removal behavior

A series of novel organosoluble polyamides (PAs) bearing different functional groups such as flexible ether, substituted imidazole, and xanthene rings and electron-withdrawing CF₃ groups were synthesized from diamines and various dicarboxylic acids. The structures of diamines and PAs were fully characterized by elemental analysis, Fourier transform infrared spectroscopy, and proton nuclear magnetic resonance spectroscopy. The PAs showed good solubility in aprotic and polar organic solvents, with high thermal stability exhibiting the glass transition temperatures (T_gs) and 10% weight loss temperatures (T₁₀%) in the range of 184–277°C and 410–480°C in N₂ atmosphere, respectively. These polymers showed fluorescence emission upon irradiation with UV light. Diamine compounds and two of synthesized polymers were also screened for antibacterial activity against gram-positive and gram-negative bacteria, and the obtained results for all four combinations showed good inhibition. Extraction capability for heavy metal ions such as Cr³⁺, Pb²⁺, Hg²⁺, Cd²⁺, and Co²⁺ from aqueous solutions was also tested at 25°C and pH 7–8.