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Metal free 5,10,15,20-tetra( p -amino-phenyl)porphyrin (H 2 TAPP) with additional nitrogen atoms at the tetrapyrrole periphery was employed to construct a nitrogen-rich covalent organic framework ( H 2 P-Bph-COF ) with the help of 4,4′-biphenyldialdehyde under solvothermal condition. The abundant and periodically distributed N atoms in H 2 P-Bph-COF stabilize and uniformly disperse the Pd ions inside the COF structure, resulting in a remarkable catalytic activity towards the Suzuki-coupling reaction between bromoarenes and arylboronic acids under mild condition with high yield of 97.1–98.5%. The present result appears to extend the catalysis application of porphyrin-based COFs from radical or carbene participated oxidation reactions into the Suzuki-coupling reaction. [ABSTRACT FROM AUTHOR]

• A brand-new three-dimensional sulfonic-functionalized POPs (TP-PPOPs-SO 3 H) was successfully prepared. • TP-PPOPs-SO 3 H exhibited ultra-high adsorption capacity for both MB and CIP. • TP-PPOPs-SO 3 H exhibited extremely fast adsorption rate and excellent adsorption selectivity. • TP-PPOPs-SO 3 H could simultaneously capture multi-pollutants from a variety of water environments. • TP-PPOPs-SO 3 H possessed remarkable re-usability and outstanding industrial compatibility. The pollution of toxic organic dyes and unmetabolized antibiotics to environments was becoming increasingly serious, therefore, it was urgent to remove them. In this paper, a three-dimensional hypercrosslinked porphyrin-based porous organic polymer (TP-PPOPs) with 5,10,15,20-tetraphenylporphyrin and triptycene as monomers was designed and synthesized for the first time. By further reacting TP-PPOPs with chlorosulfonic acid, a new three-dimensional sulfonic acid functional material (TP-PPOPs-SO 3 H) with significantly improved electronegativity and hydrophilicity was obtained. Both reactions were mild and no expensive metal catalysts were required. Benefiting from the hypercrosslinked structure, stable three-dimensional rigid framework, abundant adsorption active sites and high specific surface area, TP-PPOPs-SO 3 H exhibited extremely fast adsorption rate, outstanding adsorption selectivity, extraordinary reusability and ultra-high adsorption capacity for MB and CIP, with the maximum adsorption capacities being 1283.33 mg·g−1 for MB and 485.39 mg·g−1 for CIP, respectively. The study of adsorption mechanism revealed that the ultra-high adsorption capacity of TP-PPOPs-SO 3 H on MB and CIP was mainly attributed to their strong electrostatic interaction and the extended π-conjugated frameworks and large specific surface area of TP-PPOPs-SO 3 H. [ABSTRACT FROM AUTHOR]

Highlights • A novel porphyrin-based porous organic polymer (PPOP) is designed and prepared. • Large surface area with adequately exposed catalytic active sites of the PPOP ensures its high peroxidase-like activity. • A versatile colorimetric biosensor for H 2 O 2 , glucose and three antioxidants detection with high sensitivity and stability is established with PPOP. • The distinguishing inhibitory behaviors of three antioxidants to PPOP imply different antioxidative mechanisms. Abstract As promising alternatives to natural enzymes, catalytically active nanomaterials (nanozymes) are of great interest due to their high activity, controlled synthesis, low-cost, and excellent stability against stringent conditions. Studies of the chemical interactions between antioxidants and nanozymes would provide valuable information about catalytic mechanisms, help to better understand some metabolic pathways and screen more effective artificial enzymes. In this work, a porphyrin-based porous organic polymer, named FePPOP-1 was synthesized via a Sonogashira–Hagihara coupling reaction between 1,3,5-triethynylbenzene and iron 5,10,15,20-tetrakis-(4′-bromophenyl)porphyrin (FeTBrPP). FePPOP-1 possesses large BET surface area as well as high thermal and chemical stability. The good peroxidase-like activity of FePPOP-1 was confirmed by catalyzing the oxidation reaction of 3,3′,5,5′-Tetramethylbenzidine (TMB) with H 2 O 2. A FePPOP-1 based colorimetric biosensor was then established for H 2 O 2 , glucose and three antioxidants [ascorbic acid (AA), gallic acid (GA) and tannic acid (TA)] detection with high sensitivity and stability. Moreover, the inhibitory effects of these three natural antioxidants on peroxidase-like activity of FePPOP-1 and the relative strength of their anti-oxidative capacity were comparatively investigated. The distinguishing inhibitory behavior of AA, GA and TA implied their different anti-oxidative mechanisms. [ABSTRACT FROM AUTHOR]

Abstract With the development of dye production and printing industry, dyes wastewater has increased dramatically. The resulting environmental pollution problem is increasing seriously. In the present work, a porphyrin-based porous organic polymer (PPOPs-OH) was synthesized by using pyrrole and 2,6-dihydroxynaphthalene-1,5-dicarbaldehyde (DHNDA) as basic building block in situ. This method was cost- and time-efficient, without the participation of metal catalysts. Further reaction of PPOPs-OH with chlorosulfonic acid, a new sulfonic acid functional material (PPOPs-SO 3 H) was obtained with the increasing electronegativity and hydrophilicity. PPOPs-SO 3 H exhibit good adsorption capacity for methylene blue (MB) from water (980.4 mg g−1) and excellent selectivity for MB in the present of rhodamine B (RhB) and methyl orange (MO). Mechanism investigation revealed that electrostatic in comparison with π-π interaction is the prominent force in the absorption process. Recycling experiments found the absorption properties of PPOPs-SO 3 H did not reduce significantly after several cycles. As a consequence, our findings highlight an appealing opportunities for covalent organic polymers with their potential application as high-efficiency and robust adsorbents for pollutants removal and environmental protection. Graphical abstract POPs-SO 3 H obtained by facile one-pot synthesis exhibited excellent adsorption performance towards MB, and its maximum adsorption capacity is 980.4 mg g−1. Image 1 Highlights • PPOPs-SO 3 H was obtained by cost- and time-efficient method. • PPOPs-SO 3 H exhibit good adsorption ability for methylene blue and well selectivity. • MB adsorption kinetics and mechanism were investigated. • PPOPs-SO 3 H showed excellent sustainability and recyclability for dye removal. • PPOPs-SO 3 H possessed a applicability for wastewater treatments. [ABSTRACT FROM AUTHOR]

A new ferrocene–porphyrin derivative, namely 5,15-bisferrocenyl-porphyrinato zinc was designed and synthesized. Its self-assembly behavior in the absence and presence of 4,4′-bipyridine had been comparatively investigated. Depending on the intermolecular π–π interaction, the ferrocene–porphyrin self-assembled into lotus flower-like nanostructures in the absence of 4,4′-bipyridine. However, when the equivalent of 4,4′-bipyridine was added into the self-assembly solution of the ferrocene–porphyrin, nanobelts were obtained depending mainly on the Zn–N 4,4′-bipyridine coordination bonds between the zinc atom of the ferrocene–porphyrin and the nitrogen atom of the additional 4,4′-bipyridine. Further investigation about the nonlinear optical properties of both aggregates revealed that the nanostructures fabricated from the ferrocene–porphyrin exhibited saturation absorption in the absence of 4,4′-bipyridine and reverse saturation absorption in the presence of 4,4′-bipyridine. [ABSTRACT FROM AUTHOR]

Nanozymes have been widely utilized in colorimetric sensors and developing nanomaterials with multienzyme functions have more application prospects due to their cascaded catalytic efficiency. Here, a unique organic-inorganic nanocomposite CoFe 2 O 4 /H 2 PPOP was synthesized by depositing CoFe 2 O 4 nanocubes on a fully conjugated porphyrin-based porous organic polymer (H 2 PPOP) in situ. CoFe 2 O 4 /H 2 PPOP revealed outstanding tetra-enzyme-like activities, namely oxidase-like, peroxidase-like, catalase-like and superoxide dismutase-like activities. Compared with pure CoFe 2 O 4 nanocubes, the catalytic activities of CoFe 2 O 4 /H 2 PPOP were significantly boosted because of the large surface area and extended conjugated structure of H 2 PPOP, abundant active substances (CoFe 2 O 4) on the surface and the effective electronic transfer between CoFe 2 O 4 and H 2 PPOP. Based on the oxidase-like activity of CoFe 2 O 4 /H 2 PPOP, a colorimetric platform was constructed for Cr (VI) with a wide linear range (0.6–100 μM) and a low detection limit (26 nΜ). Further utilizing the double oxidase-like and peroxidase-like activities, a more sensitive colorimetric platform with a faster detection speed for Cr (VI) was realized with the LOD as low as 2 nΜ. This work opens up a new way to prepare multi-enzyme active nanozyme and excavates its potential for detecting environmental pollutants. Synergetic Catalytic Mechanism of CoFe 2 O 4 /H 2 PPOP [Display omitted] • A novel nanocomposite CoFe 2 O 4 /H 2 PPOP with four enhanced enzyme-mimic properties was synthesized. • The electron current-carrying process were speeded up by the formation of heterojunction constructure in CoFe 2 O 4 /H 2 PPOP. • Colorimetric platforms based on oxidase-like and double enzyme-like performances were established for detecting Cr (VI). [ABSTRACT FROM AUTHOR]

Abstract: Various nanostructures of 5,10,15,20-tetrakis(4-carboxyl phenyl)-porphyrin (H2TCPP) can be easily synthesized by a surfactant-assisted self-assembly (SAS) method at different temperatures. When the DMF solution of porphyrin monomer was injected into cetyltimethylammonium bromide (CTAB) aqueous solution by a syringe, diverse H2TCPP nanostructures dependent on the different temperatures, including hollow nanospheres, solid nanospheres and nanospheres with holes, were successfully obtained. As a result, the suitable concentration of the CTAB aqueous solution used to form nanostructues of porphyrin ranges from 0.15 to 0.2mM. The various morphologies of porphyrin nanostructures were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). UV–vis adsorption spectra showed that the micro-/nano-aggregate properties of porphyrin transformed from H-aggretates to J-aggregates during the process of self-assembly of porphyrin at different temperatures. Fluorescence spectra revealed a greater fluorescence quenching of various micro-/nano-aggregatess of porphyrin formed at different temperatures in aqueous solution, compared to the DMF solution of porphyrin monomer. [Copyright &y& Elsevier]

Recycling precious metals from electronic waste not only benefits environmental protection, but is also favorable for alleviating resource shortages. Ionic porous organic polymers, as one type of burgeoning material, are regarded as excellent adsorbents due to their high ion density, but their application in precious metal recovery is still very limited. Here, V-PPOP-Br, a highly stable and easy-to-build cationic porous organic polymer, was successfully prepared for the first time. By linking porphyrins with viologens, V-PPOP-Br obtained the characteristics of a hierarchical porous structure, a high ion density skeleton, and a rich nitrogen content, which gave it an ultrahigh adsorption capacity (Q max = 792.22 mg g−1) and rapid adsorption rate for Au(III). V-PPOP-Br also had an effective Au(III) recovery capability from SIM cards. Mechanism investigation confirmed that this remarkable adsorption performance was attributed to the interplay of ion exchange, redox reactions and coordination. Moreover, V-PPOP-Br had excellent recyclability and could maintain an ultrahigh adsorption efficiency of 81% after eight consecutive adsorption-desorption experiments. These excellent performances as well as the roughly calculated gold recycling economics ($37.37/g V-PPOP-Br) confirmed that it possesses promising potential as an ionic porous material for gold recovery. [Display omitted] • A porphyrin and viologen-linked cationic POP was prepared via Zincke reaction. • The V-PPOP-Br exhibited ultrahigh adsorption capacity for Au(III). • The mechanism was ascribed to the ion exchange, redox reaction, and coordination. • The V-PPOP-Br could selectively recover gold from the SIM card. • The V-PPOP-Br possessed great recyclability and practical application potential. [ABSTRACT FROM AUTHOR]

Abstract: (R)-Enantiomer of optically active metal free porphyrin, bearing four chiral citronellal units linked directly onto the meso positions of the porphyrin ring, and its zinc congener, namely (R)-meso-5,10,15,20-tetra-(2,6-dimethyl-5-heptenyl) porphyrin [(R)-H2T(C9H17)4P (1)] and (R)-meso-5,10,15,20-tetra-(2,6-dimethyl-5-heptenyl) porphyrinato zinc complex [(R)-ZnT(C9H17)4P (2)], have been designed and synthesized. These two compounds were characterized by a wide range of spectroscopic methods. In contrast to the CD silent of a similar compound N,N′,N″-Tris{21H,23H-5-p-Aminophenyl-10,15,20-tris-[p-(S)-3,7-dimethyloctoxyphenyl]porphyrin}-1,3,5-tricarboxamid, bearing the similar chiral units linked onto the meso positions of the porphyrin ring via meso-attached benzene, observation of a positive CD signal in the Soret absorption region of both porphyrin compounds, not only indicate effectively chiral information transfer from the chiral citronellal tails to porphyrin chromophore at the molecular level, but also reveal the effect of substituents position on the asymmetrical perturbation. In addition, both compounds were revealed to show good third-order nonlinear optical properties. [Copyright &y& Elsevier]

Abstract: Two sandwich-type mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes, M(Pc)(TPP) [H2Pc=phthalocyanine; H2TPP=meso-tetra(phenyl)porphyrin] (M=Eu, Lu) (1, 2) were synthesized and the structure of Lu(Pc)(TPP) was characterized by X-ray single-crystal diffraction method. Crystal data: triclinic, space group , Z =2, C77H45Cl3LuN12, Mr =1419.57, a =12.573(5), b =12.911(5), c =22.935(5)Å, α =103.793(5)°, β =101.363(5)°, γ =93.682(5)°, V =3521(2)Å3, μ(Mo Kα)=1.196mm−1, F(000)=1426, R =0.0590, and wR =0.1639 for 9745 observed reflections with I > 2σ(I). X-ray analysis reveals that the coordination polyhedron adopts a slightly distorted square-antiprismatic structure around the metal center. Both phthalocyanine and porphyrin ligands are saucer-shaped, with the skew angle of the two ligand planes approximately 45°. The self-assembled nano-structures of both complexes 1 and 2 were systematically investigated by electronic absorption and Fourier transform infrared (FT-IR) spectroscopy, transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), and X-ray diffraction (XRD) techniques, revealing the effect of molecular structure on the dimension of self-assembled nano-structures. [Copyright &y& Elsevier]

Abstract: A mixed phthalocyaninato and porphyrinato triple-decker complex [Eu2(Pc)2(TClPP)] was synthesized and characterized by elemental analysis, FT-IR, UV, and X-ray structure determination. Its self-assembling properties in mixed chloroform/methanol solution were investigated by TEM, SEM and XRD techniques. Investigation revealing the availability of the single crystal, together with the molecular structure, renders it possible to investigate the formation mechanism as well as the molecular packing conformation of self-assembled nanostructures fabricated from this complex in a more confirmed manner. [ABSTRACT FROM AUTHOR]

Effective capture of pollutants from wastewater is crucial for protecting the environment and human health. An azo-based porous organic polymer (AzoPPOP) containing porphyrin and inorganics cage polyhedral oligomeric silsesquioxane units was synthesized via a catalyst-free coupling reaction. Results showed that AzoPPOP possess a high surface area, a hierarchically porous structure, good thermal stability, abundant adsorption sites, and an electronegative nature. Based on these properties, AzoPPOP had an extremely high adsorption capacity (1357.58 mg g−1) for RhB, a fast adsorption rate, and good selectivity. Study of the mechanism revealed that in addition to electrostatic interactions, the high specific surface area, existence of -NH 2 , and the strong π-π interaction between AzoPPOP and RhB also play important roles for the adsorption of RhB. AzoPPOP also displayed excellent adsorption properties for heavy metal ions (230.45, 192.24 and 162.11 mg g−1 for Ag+, Hg2+, and Pb2+, respectively). More importantly, simulation of the purification experiment of waste water and the recycling regeneration experiment revealed that AzoPPOP has good high-level recyclability and could remove multi-pollutants in one pass through a simple adsorption column. ga1 • A silsesquioxane-porphyrin-based POPs was prepared via a simple and mild method. • The AzoPPOP exhibited ultrahigh adsorption capacity for RhB and heavy metal ions. • Unique chemical properties endowed AzoPPOP with excellent adsorption properties. • The AzoPPOP could simultaneously remove multi-pollutants from wastewater. • The AzoPPOP possessed excellent recyclability and practical application potential. [ABSTRACT FROM AUTHOR]

We developed a novel electrochemical biosensor for uracil-DNA glycosylase (UDG) detection based on enzyme-free and substrate-free electrocatalytic signal amplification by porphyrin-based covalent-linked nanomaterial (OAPS-Por). This OAPS-Por could not only absorb much Thionine (Thi), but also possess obvious electrocatalytic activity toward the reduction of Thi without involvement of H 2 O 2. Sequentially, the functionalized OAPS-Por with Thi, Au nanoparticles and single-stranded DNA (OAPS-Por/Thi@AuNPs-ssDNA) was ingeniously designed as the signal probe. Meantime, the hairpin DNA (hDNA) with four uracil bases was immobilized on AuNPs/GCE via an Au–S bond. When UDG was present, the uracil in hDNA was removed and hairpin structure was unfolded. Next, the signal probes binded with the unfolded hDNA by DNA hybridization. The Thi in signal probes could generated an original electrochemical signal, which could be further amplified and output due to the robust electrocatalytic activities of OAPS-Por toward Thi. As a result, the as-constructed electrochemical biosensor had a broad linear range from 0.005 to 1 U mL-1. It also exhibited a low detection limit of 6.97 × 10-4 U mL-1. Moreover, this biosensor could be used to assay the inhibition of UDG (UGI) and the UDG activity in real samples (HeLa cell lysates and human blood serums), and demonstrated great prospect in clinical diagnostics and biomedical research. • A novel electrochemical biosensor is developed for sensitive detection of uracil-DNA glycosylase (UDG). • This biosensor is based on nonenzymatic nanomaterial (OAPS-Por) signal amplification. • OAPS-Por exhibited intrinsic electrocatalytic activity toward the reduction of absorbed Thi without involvement of H 2 O 2. • This biosensor shows low limit of detection and wide linear range of UDG activity. [ABSTRACT FROM AUTHOR]